REVIEW | doi:10.20944/preprints202312.0068.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Acid-base catalysis; Green catalytic transformation; Layered double hydroxides; Heterogeneous catalysis; Applications
Online: 1 December 2023 (10:03:56 CET)
Layered double hydroxides (LDHs) have emerged as promising catalysts for various acid-base catalytic reactions. Due to their unique structure and regulatable dual acid-base properties, they offer more environmentally friendly and sustainable alternatives to traditional liquid acid and base catalysts. This study introduces the structural composition, preparation methods, and acid-base catalytic properties of LDHs-based catalysts. Recent application progress of LDHs and rehydrated LDHs, LDHs-based metal nanocatalysts, and LDHs-based mixed metal oxide catalysts used as solid acid-base catalysts in acid-base green catalytic conversion is reviewed. The challenges and prospects of LDHs-based catalysts as green and sustainable catalysts are summarized and proposed.
ARTICLE | doi:10.20944/preprints202311.1281.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: geopolymer; metakaolin; adsorption; wastewater treatments; NH4+ removal
Online: 21 November 2023 (07:34:27 CET)
Elevated ammonium (NH4+) concentrations in untreated waterways contribute to eutrophication and dissolved oxygen depletion, which cause severe degradation of water quality. Ion exchange processes are a robust, low operational cost and efficient option for ammonium removal with zeolites being the most widely used. Geopolymers are a sustainable and low-cost option compared to zeolites that follows the same ion exchange technology. In the present study, a metakaolin-based porous geopolymer was synthetized, characterised and validated as adsorbent material. The laboratory batch tests showed a maximum adsorption capacity (Qm) of 18.35 mg/g being 27% higher than reference zeolites. Kinetics followed the Weber-Morris rate equation being the intraparticle diffusion the limiting process and continuous experiments indicated a maximum removal of 97% in the first hours. The material was validated in a wastewater treatment pilot plant where values in pH, electrical conductivity and NH4+ concentration were monitored. The obtained data indicated that the material achieved up to 80% NH4+ removal which is similar to traditional zeolites. The results demonstrate that this sustainable, low-cost and easy-to-install metakaolin-based geopolymer can be used effectively for NH4+ treatment.
ARTICLE | doi:10.20944/preprints202311.0994.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: self-propagating high-temperature synthesis; few-layer graphene; laser initiation; pyrotechnic composition
Online: 16 November 2023 (02:17:39 CET)
Carbonization of a biopolymer (lignin) in self-propagating high-temperature synthesis (SHS) led to the production of 2D graphene structures. With the help of modern analytical methods (Raman spectroscopy, X-ray diffraction) and electron microscopy, the resulting product was confirmed to have a few-layer 2D graphene structure. The predicted photovoltaic properties of the resulting few-layer graphene were implemented for laser ignition of a model pyrotechnic composition based on porous silicon. A phenomenological model of the formation mechanism of 2D graphene structures under the conditions of the SHS process is proposed.
ARTICLE | doi:10.20944/preprints202311.0611.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: high-frequency arc discharge; hydrogen reduction; silicon chlorides; germanium chlorides
Online: 9 November 2023 (11:20:32 CET)
The processes of hydrogen reduction of silicon and germanium chlorides under the conditions of high-frequency (40.68 MHz) counteracted arc discharge stabilized between two rod electrodes are investigated. The main gas-phase and solid products of plasma-chemical transformations are determined. Thermodynamic analysis of SiCl4 + H2 and GeCl4 + H2 systems for optimal process parameters was carried out. Using the example of hydrogen reduction of SiCl4 by the method of numerical modeling, gas-dynamic and thermal processes for this type of discharge are investigated. The impurity composition of gas-phase and solid reaction products is investigated. The possibility of single-stage production of high-purity Si and Ge mainly in the form of compact ingots, as well as high-purity chlorosilanes and trichlorogermane, is shown.
ARTICLE | doi:10.20944/preprints202310.2044.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: carbon dioxide hydrogenation; methanol synthesis; nanomaterials; heterogeneous catalysis; metal-support interaction
Online: 31 October 2023 (09:17:30 CET)
The increading emission of carbon dioxide to the atmosphere has urged the scientific community to investigate alternatives to alleviate such emissions being the principal contributor to the greenhouse gas effect. One major alternative is carbon capture and utilisation (CCU) towards the production of value-added chemicals using diverse technologies. This work aims at the study of the catalytic potential of different cobalt-derived nanoparticels for methanol syntheis from carbon dioxide hydrogenation. Thanks to its abundance and cost-efficacy, cobalt can serve as an economical catalyst compared to noble-metal-based catalysts. In this work, we present a systematic comparison among different cobalt and cobalt oxide nanocomposites in terms of their efficiency as catalysts for carbon dioxide hydrogenation to methanol as well as how different supports can enhance their catalytic capacity. The oxygen vacancies in the cerium oxide act as carbon dioxide adsorption and activation sites, which facilitates a higher methanol production yield.
ARTICLE | doi:10.20944/preprints202310.1287.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: lead ions (Pb+2); Zn-Fe LDH/PANI; Carbon paste electrode (CPE); differential pulse voltammetry (DPV); Zn/Mg/Fe LDH; Atomic absorption spectrophotometer (ASS); cytotoxicity
Online: 19 October 2023 (13:38:55 CEST)
The requirement for developing tools capable of detecting and monitoring heavy metals (HMs) has recently taken on more significance due to worries about their toxic effect on human health and aquatic habitats. In this study, a simple electrochemical sensing carbon paste electrode (CPE) based on composite of Zinc/Iron layered double hydroxide (LDH) and polyaniline (PANI) was developed for the determination of lead ions in aquatic solutions. For this purpose, Zn-Fe LDH/PANI was prepared and characterized by Fourier transform infrared (FTIR), X ray diffraction (XRD), and scanning electron microscopy (SEM). Modified carbon electrode based Zn-Fe LDH/PANI was electrochemically characterized compared with unmodified electrode in FCN as a redox probe using cyclic voltammetry (CV). Thus, Zn-Fe LDH/PANI was utilized as sensing material for the electrochemical determination of lead ions using differential pulse voltammetry (DPV). Zn-Fe LDH/PANI/CPE show limits of detection (LOD) and quantification (LOQ) of 167.8 nM and 559.4 nM, respectively. Zn/Mg/Fe LDH was prepared using co-precipitation method and characterized by XRD, FTIR, SEM and BET, used for removal of Pb+2 ions. Removal process was investigated at different conditions as pH, metal ion concentrations, starting adsorbent dose at first and contact time. Zn/Mg/Fe LDH was evaluated as an effective adsorbent material for lead ions elimination in aquatic solutions, with capacity of adsorption 700 mg/g. The elimination of lead ions on Zn/Mg/Fe LDH fitted the pseudo first-order kinetics model and the isotherm was matched with Langmuir model. Studies revealed that the ideal removal conditions were pH = 5.0, an adsorbent mass of 0.05 g, and 20 ml of 50 ppm metal ion concentration at 60 min. The Zn-Fe LDH/PANI composite also showed potential anti-cancer properties against lung cancer cells (A549) while maintaining safety for normal lung fibroblast cells (WI-38). Collectively, advancements in electrochemical sensors offer promising solutions for lead ion detection, with wide-reaching applications in wastewater treatment and cytotoxicity assessment. These innovations have the potential to enhance environmental monitoring and public health safety.
ARTICLE | doi:10.20944/preprints202310.0673.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: ZnO anodes; nanoflowers; CNT dispersants; electrical conduction network; lithium-ion batteries
Online: 11 October 2023 (07:28:25 CEST)
The demand for high-energy-density batteries necessitates novel anode materials. Transition metal oxides (TMOs) show promise due to their high capacity, sustainability, and cost-effectiveness. However, TMO-based anodes face challenges related to expansion and conductivity. This study presents a two-step dilution crystallization method to fabricate porous ZnO nanoflowers at a moderate temperature. In-situ integration with carbon nanotube dispersants enhances conductivity and reduces agglomeration. The resulting composite anode exhibits impressive initial discharge capacity (2314.2 mAh g-1) and cycling stability (580.5 mAh g-1 over 50 cycles). This study provides a facile approach for next-generation anode materials.
ARTICLE | doi:10.20944/preprints202310.0644.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Glycerol; Acetalization; Solketal; catalysis; MOF-808
Online: 11 October 2023 (05:08:19 CEST)
Glycerol is the main residue in the biodiesel production industry; therefore, their valorisation is crucial. Acetalization of glycerol towards fuel additives as solketal (2,2-dimethyl-1,3-dioxolan-4-methanol) is of high interest, promoting circular economy since it can be added to the biodiesel or even fossil-diesel to improve their quality and efficiency. Straightforward prepared metal-organic framework (MOF) materials of MOF-808 family were applied to the valorisation of glycerol for the first time. In particular, MOF-808(Hf) revealed to be an effective heterogeneous catalyst to produce solketal under moderate conditions: small amount of the MOF material (only 4wt% of glycerol), ratio 1:6 of glycerol/acetone and temperature of 60 ºC. The high efficiency of MOF-808(Hf) was associated with the high amount of acid centres present in its structure. Furthermore, its structural characteristics such as window opening cavities size and pore diameters showed to be ideal to reuse this material during at least ten consecutive reaction cycles without losing activity (conversion > 90% and selectivity > 98%). Remarkably, it was not necessary the washing or other activation treatment of the MOF-808(Hf) catalyst between cycles (no pore blockage occurred) and it maintained structural integrity after the ten cycles, confirming to be a sustainable heterogeneous catalyst to the glycerol valorisation.
REVIEW | doi:10.20944/preprints202310.0427.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Recycling; Plastic wastes; Chemical recycling; Depolymerization; Closed-loop recycling
Online: 8 October 2023 (05:28:37 CEST)
Ranging from traditional food packaging, clothing, and furniture to the current small and large electronic devices and automobiles, plastics serve to fulfill diverse demands in our daily lives. However, the global plastic waste generation is dramatically escalating, currently standing at approximately 150 million metric tonnes annually. While some of regenerated plastics recycled by mechanical methods can be used as their parent plastics, cost and energy savings are limited by multiple preliminary processes such as plastic sorting, shredding, washing, and drying. Moreover, the continuous mechanical recycling process degrades the physical properties of the materials. In this context, chemical recycling is emerging as a promising alternative method due to its high efficiency, simple preliminary steps, reducing reliance on fossil resources, and conversion of plastic waste into value-added chemicals. This review provides a state-of-the-art overview of contemporary chemical recycling of polymeric materials via i) depolymerization: “polymers to small valuable molecules” and ii) closed-loop cycles: “polymers to monomers, and/or to polymers”, by encompassing both traditional/advanced depolymerization chemistries and the remaining challenges. These recycling approaches are contextualized within the present industrial technologies, key design principles, and specific recycling case studies related to distinct polymeric materials.
ARTICLE | doi:10.20944/preprints202310.0308.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: activated carbon; biomass; carbon composites; spent coffee; Aloe-Vera; corncob; zinc oxide, H2S, hydrogen sulfide, adsorption
Online: 6 October 2023 (05:05:45 CEST)
Biomass exploitation is a global trend due to the circular economy and the environmentally friendly spirit. Numerous applications are now based on the use of biomass derived products. Hydrogen sulfide (H2S) is a highly toxic and environmentally hazardous gas, which emitted from various processes. Thus, the efficient removal of this toxic hazardous gas following cost effective processes is an essential requirement. In this study, we present the synthesis and characterization of biomass-derived activated-carbon/zinc-oxide (ZnO@AC) composites from different biomass sources as potential candidates for H2S sorption. The synthesis involved a facile method for activated carbon production via pyrolysis and chemical activation of biomass precursors (spent coffee, Aloe-Vera waste leaves, and corncob). Activated carbon production was followed by the incorporation of zinc oxide nanoparticles into the porous carbon matrix using a simple melt impregnation method. The synthesized ZnO@AC composites were characterized using X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and nitrogen porosimetry. The H2S removal performance of the ZnO@AC composites was evaluated through sorption experiments using a handmade apparatus. Our findings demonstrate that the Aloe-Vera, Spent-coffee, and Corncob derived composites exhibit superior H2S sorption capacity up to 106 mgH2S/gads., 66 mgH2S/gads., and 47 mgH2S/gads. respectively.
ARTICLE | doi:10.20944/preprints202310.0247.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Scientific Machine Learning; Perfume Engineering; Graph Neural Networks; Fragrances; Consumer Feedback
Online: 5 October 2023 (05:40:18 CEST)
In this research, we present a comprehensive methodology to categorize perfumes based on their fragrance profiles and subsequently aid in creating innovative odoriferous molecules using advanced neural networks. Drawing from data on Parfumo and the Good Scents Company webpage (Parfumo, 2008; The Good Scents Company, 2021), the study employs sophisticated web scraping techniques to gather diverse perfume attributes. Following this, a k-means algorithm is applied for perfume clustering, paving the way for recommending similar scents to consumers. The process then bridges customer preferences to molecular design by incorporating their feedback into generating new molecules via graph neural networks (GNNs). Through converting the Simple Molecular Input Line Entry System (SMILES) representation into graph structures, the GNN facilitates the creation of new molecular designs attuned to consumer desires. The proposed approach offers promising avenues for consumers to pinpoint similar perfume choices, incorporating feedback, and for manufacturers to conceptualize new fragrant molecules with a high likelihood of market resonance.
ARTICLE | doi:10.20944/preprints202309.0795.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Artificial Intelligence; Machine Learning; Thermostability; Molecular Dynamics Simulation; Extended Sequence; Directed Evolution
Online: 12 September 2023 (16:57:22 CEST)
The combination of wet-lab experimental data on multi-site combinatorial mutations and machine learning is an innovative method in protein engineering. In this study, we present an improved innovative sequence–activity relationship (innov'SAR) methodology based on novel descriptors and digital signal processing (DSP) to construct a predictive model. In this improved approach, 21 experimental (R)-selective amine transaminases from Aspergillus terreus (AT-ATA) were used as an input to predict higher thermostability than that predicted using the existing data. We successfully improved the determination coefficient (R2) of the model from 0.66 to 0.92. In addition, root mean square deviation (RMSD) and root mean square fluctuation (RMSF) were estimated and conformation analysis based on molecular dynamics simulations was performed to verify the enhanced thermal stability of the screened mutants. The improved innov'SAR algorithm enhanced the predictive accuracy, suggesting a method for modifying the stability of AT-ATA, which may help in directed evolutionary screening and open up new avenues for protein engineering.
REVIEW | doi:10.20944/preprints202309.0781.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: biodegradable plastics; renewable resources; polylactic acid (PLA); UV-barrier properties; photosensitive packaging
Online: 12 September 2023 (10:30:55 CEST)
Plastic materials have revolutionized modern life, particularly in the domain of food packaging, owing to their versatility, lightweight nature, and ease of processing. However, the environmental ramifications of non-degradable plastics have raised concerns. Polylactic acid (PLA), derived from renewable sources, presents a sustainable alternative due to its biodegradability and exceptional barrier, mechanical, and safety properties. Nevertheless, the high UV transmittance of PLA limits its use for photosensitive food and pharmaceutical packaging, where UV radiation can lead to nutritional loss and spoilage. Various methods have been explored to enhance the UV-blocking capabilities of PLA, including the integration of inorganic nanoparticles and surface coatings. Despite advancements, these approaches often compromise the inherent transparency of PLA. Incorporating large conjugated groups can maintain transparency but introduces additional challenges. This paper reviews modification methods to enhance PLA's UV-barrier properties and anticipates its expanded utility in food and drug packaging, promoting UV resistance and diversifying PLA's applications.
ARTICLE | doi:10.20944/preprints202309.0397.v2
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: hydrothermal carbonization; cellulose; ammonium sulfate; thiourea; doping; supercapacitor carbon
Online: 7 September 2023 (11:45:43 CEST)
Hydrothermal carbonization of cellulose was examined at 240 ℃ for 1 h. Ammonium sulfate and thiourea were selected as the doping sources of inorganic nitrogen and organic nitrogen for the preparation of supercapacitor carbon. The effect of boric acid on the properties of the resulting hydrochar after KOH activation was examined. The results showed that the proportion of functional groups and the specific surface area of the activated hydrochar would be reduced after the addition of boric acid, and the pore-forming process of the micropores would be inhibited. The hydrochar obtained from the reaction of cellulose and organic nitrogen compounds had better pore size distribution and electrochemical properties after activation. The largest specific surface area (952.27 m2 g-1) was obtained when only thiourea was used as the only doping source. In the three-electrode system, the specific capacitance resulting activated hydrochar reached 236.25 F g-1 at a current density of 1 A g-1. After 20,000 cycles of charging and discharging at a current density of 10 A g-1, the capacitance retention rate reached 99.96%. Therefore, this study proves that the supercapacitor carbon with good electrochemical properties could be obtained by the direct reaction of cellulose with organic nitrogen compounds.
ARTICLE | doi:10.20944/preprints202308.1521.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: ultrasound pre-treatment; microwave hydro-distillation; thyme; essential oil; thymol
Online: 22 August 2023 (09:37:49 CEST)
In this paper, the extraction of essential oil (EO) from thyme by consecutive use of ultrasound and microwave treatments is presented. The aim of the study was to apply an ultrasound pre-treatment of thyme leaves to enhance the thymol content and the extraction yield of the EO obtained by microwave-assisted hydro-distillation (MWHD). Compared with the conventional hydro-distillation (CHD), the consecutive use of ultrasound and microwave treatments resulted in a 72% lower extraction time. When the ultrasound pre-treatment (using the ultrasonic processor with an amplitude of 70%) was applied, the EO content was 23% higher compared to the extraction without pre-treatment. The EO samples were analyzed by GC/MS. The results showed that the major component, thymol, varied from 43.54% (by CHD) to 65.94% (by consecutive use of ultrasound and microwave treatments).
ARTICLE | doi:10.20944/preprints202308.0783.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Essential oil; Solid-phase microextraction; Gas chromatography; antioxidant activity; ABTS; ATR-FTIR
Online: 10 August 2023 (10:13:23 CEST)
Scientific advancements in the food industry have resulted in the discovery of natural substances that can serve various functions in food. Essential oils, in particular, can act as food preservatives or flavoring agents due to their abundance of natural antioxidants, which possess preservative properties. In this study, the composition of Thymus vulgaris essential oil was determined using GC-MS and HS-SPME. The essential oil obtained from Thymus vulgaris L. through hydro-distillation yielded approximately 4%. GC/MS analysis of the essential oil identified 11 components, with a predominant presence of oxygenated monoterpenes (56.97%). Notably, carvacrol (37.63%) and thymol (17.35%) were present in significant amounts, accounting for 54.98% of the overall composition. The in vitro antioxidant activity of the essential oil was evaluated using three methods. The DPPH free radical scavenging test yielded an IC50 of 0.51±0.11 mg mL-1. The β-carotene/linoleic acid bleaching test resulted in an IC50 of 2.58±0.10 mg mL-1. Finally, the ABTS assay indicated relatively lower antioxidant activity compared to ascorbic acid.
REVIEW | doi:10.20944/preprints202308.0838.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: advanced oxidation processes; organic pollutants; wastewater pollution; antibiotics removal; photocatalysis
Online: 10 August 2023 (09:08:18 CEST)
Simultaneously with the development of industrial society, wastewater with organic pollutants has caused various environmental problems. The most majority of organic pollutants in water and wastewater are persistent, reason which can cause serious problems for human health, animal health, and for the whole environment. Therefore, efficient treatment methods for wastewater with highly concentration of organic compounds are immediately necessary. During the last years, the prescribed and non-prescribed consumption of antibiotics has grown a lot worldwide. Big quantities of antibiotics are discharged into wastewater because their incomplete absorption by living organisms, but at small concentrations present in aquatic environments represents a major risk for the human health and environment protection. The paper presents the main advantages and disadvantages of advanced oxidation processes, but also current state and new perspectives in the field of environment protection. Advanced oxidation processes (AOPs) are often used in the field of treatment of different types of wastewater. AOPs are based on physicochemical processes that create significant structural changes in chemical species, their commercialization at a wide scale may result in cost reductions that are desirable for environmental applications. The majority of antibiotics may be eliminated using physicochemical processes, such as photo-Fenton, photolysis, ozonation, electrooxidation, heterogeneous catalysis, and other bio processes. In comparison to conventional chemical processes, AOPs provide superior oxidation efficiency, ideal operating costs, and zero secondary pollutants.
ARTICLE | doi:10.20944/preprints202307.1556.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: bimetallic catalyst; Raman spectroscopy; TPR; palladium hydride; chemisorption; DRIFTS; STEM-EDX
Online: 25 July 2023 (10:03:28 CEST)
PdRe/Al2O3 catalysts are highly selective for hydrogenation of furfural to furfuryl alcohol (FAL). Moreover, synergy between the metals can result in greater specific activity (higher turnover frequency, TOF) than exhibited by either metal alone. Bimetallic catalyst structure depends strongly on the metal precursors employed and their addition sequence to the support. In this work, PdRe/Al2O3 catalysts were prepared by: (i) co impregnation (CI) and sequential impregnation (SI) of Al2O3 using HReO4 and Pd(NO3)2, (ii) SI using NH4ReO4 and [Pd(NH3)4(NO3)2], (iii) HReO4 addition to a reduced and passivated Pd/Al2O3 catalyst, and (iv) impregnation with the double complex salt (DCS), [Pd(NH3)4(ReO4)2]. Raman spectroscopy and temperature-programmed reduction (TPR) evidence larger supported PdO crystallites in catalysts prepared using Pd(NO3)2 than [Pd(NH3)4(NO3)2]. Surface [ReO4]- species detected by Raman exhibit TPR peak temperatures from ranging 85 to 260°C (versus 375°C for Re/Al2O3). After H2 reduction at 400°C, the catalysts were characterized by chemisorption, temperature-programmed hydride decomposition (TPHD), CO diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and scanning transmission electron microscopy (STEM) with energy-dispersive x-ray (EDX) spectroscopy. The CI catalyst containing supported Pd-Re alloy crystallites had a TOF similar to Pd/Al2O3 but higher (61%) FAL selectivity. In contrast, catalysts prepared by methods (ii-iv) containing supported Pd-Re nanoparticles exhibit higher TOFs and up to 78% FAL selectivity.
ARTICLE | doi:10.20944/preprints202307.1545.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Sugarcane bagasse; Steam explosion; Enzymatic hydrolysis; Fermentation; Lactic acid
Online: 24 July 2023 (08:10:50 CEST)
This work aimed at producing lactic acid (LA) from sugarcane bagasse after steam explosion at 195 ºC for 7.5 and 15 min. Enzymatic hydrolysis was carried out with Novozymes’ Cellic CTec3 and/or Cellic HTec3, whereas fermentation was performed with Bacillus coagulans DSM2314. Water-washing of pretreated solids before enzymatic hydrolysis improved both hydrolysis and fermentation yields. The presence of xylo-oligosaccharides (XOS) in substrate hydrolysates reduced hydrolysis efficiency, but their effect on fermentation was negligible. The presence of fermentation inhibitors in C5 streams was circumvented by adsorption on activated carbon powder with no detectable sugar losses. High carbohydrates-to-LA conversions (Yp/s) of 0.88 g·g-1 were obtained from enzymatic hydrolysates of water-washed steam-exploded materials that were produced at 195°C, 7.5 min and the use of centrifuged-but-never-washed pretreated solids decreased Yp/s by 16%. However, when the detoxified C5 stream was added at a 10% ratio, Yp/s was raised to 0.93 g·g-1 for an LA productivity of 2.55 g·L-1·h-1. Doubling the pretreatment time caused a decrease in Yp/s to 0.78 g·g-1, but LA productivity was the highest (3.20 g·L-1·h-1). For pretreatment at 195°C for 7.5 min, elimination of water washing seemed feasible, but the use of longer pretreatment times made it mandatory to eliminate fermentation inhibitors.
REVIEW | doi:10.20944/preprints202307.1520.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Bio hydrogen; Thermochemical conversion; Biomass; Syngas; gasification
Online: 24 July 2023 (02:16:38 CEST)
The utilization of lignocellulosic biomass as an alternative energy source presents a promising opportunity to achieve a future energy system that is clean and free from CO2 emissions. To realize this potential, it is crucial to develop effective techniques for converting biomass and organic solid waste into secondary energy sources. Among the available options, hydrogen production stands out due to its numerous advantages, including its cleanliness, versatility in conversion and utilization technologies, high energy efficiency, and dense energy content per unit weight. This article offers a comprehensive overview of different conversion pathways and important technologies for generating hydrogen from biomass and organic solid waste. It specifically focuses on the thermochemical conversion process, which shows promise as an economically viable approach. While certain thermochemical conversion processes are still in the developmental phase, utilizing organic biomass for hydrogen production is widely recommended due to its ability to yield higher amounts of end products and its compatibility with existing facilities. However, it should be noted that this method necessitates a substantial amount of energy due to its endothermic nature. The article also explores alternative hydrogen conversion technologies and their potential for utilizing organic biomass as a feedstock, while addressing the challenges and limitations associated with these methods.
ARTICLE | doi:10.20944/preprints202307.1360.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Tannin; Furfuryl alcohol; Polyvinyl alcohol; Foam; Insole
Online: 19 July 2023 (16:17:43 CEST)
The exploitation of bio-based foams implies an increase in the use of renewable biological resources to reduce the rapid consumption of petroleum-derived resources. Both tannins and furfuryl alcohol are derived from forestry resources and are therefore considered as attractive precursors for the preparation of tannin-furanic foams. In addition, toughening modification of tannin-furanic foams using polyvinyl alcohol (PVOH) resulted in a more flexible network-like structure, which imparts excellent flexibility to the foams with acquirement of relative properties that are even close to those of polyurethane foams, which are the most used polymers for fabrication of insoles for athletes. In addition, the addition of PVOH did not affect the thermal insulation of the foams, resilience and elongation at break, while reducing the brittleness of the samples and improving the mechanical properties. Also the observation of the morphology of the foam indicated that the compatibility between PVOH and tannin-furanic resin is good, and the cured foam does not show fragmentation or collapse, while the bubble pore structure is uniform. The developed flexible foam derived from biomass resources endowed the foam good thermal insulation properties and high mechanical properties, and the samples exhibited suitable physical parameters to be used as flexible insoles for athletes.
ARTICLE | doi:10.20944/preprints202307.1334.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: hematite electroreduction; boehmitic bauxite; Al extraction; reductive leaching; red mud; bauxite residue; magnetite; waste utilization
Online: 19 July 2023 (10:44:46 CEST)
Reductive leaching in the Bayer cycle using of iron (2+) allows Al extraction to be significantly increased by magnetization of Al-goethite and Al-hematite. However, the use of expensive iron (2+) salts or iron powder as a source of iron (2+) leads to a significant increase in production costs. In this work, the feasibility of a new method, the reductive leaching of bauxite using an electrolysis process, was investigated. Reduction of iron minerals of boehmitic bauxite in both Bayer solution and purely alkaline solutions were carried out. Experiments were performed using a plate cathode and a bauxite suspension in alkaline solution, as well as using a bulk cathode with a stainless-steel mesh at the bottom of the cell as the current supply. During the electrolysis process, the potential of the cathode relative to the reference electrode was measured as a function of current at different concentrations of solid (100-300 g L–1) and suspension temperatures (95-120 °C). It is shown that the current efficiency using suspension and plate cathode with the predominant deposition of Fe doesn’t exceed 50% even with the addition of magnetite to increase the contact of solid phase with the current supply. With the use of a bulk cathode, the reduction of iron minerals leads predominantly to the formation of magnetite with the efficiency of using electric current more than 80%. As a result of preliminary desilication and electroreduction it is possible to extract more than 97% of Al from bauxite, and to increase the iron content in the bauxite residue to 57-58%.
ARTICLE | doi:10.20944/preprints202307.0755.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Citrus reticulata peel waste; chitosan; Congo red; green adsorbents
Online: 12 July 2023 (03:22:18 CEST)
This study revealed the synthesis of cross-linked chitosan/Citrus reticulata peel waste (C/CRPW) composites that could be used as low-cost and green bio-adsorbents for the removal of Congo red (CR) dye from aqueous solutions. C/CRPW composites containing different amounts of Citrus reticulata peel waste (CRPW) and chitosan were prepared and cross-linked with glutaraldehyde. The composites were characterized by FESEM, FTIR, and BET. The C/CRPW composites as a new type of bio-adsorbents displayed superior adsorption capability toward anionic CR molecules and the adsorption capacities increased by incorporation of CRPW. Effects of different ambient conditions such as contact time, pH, adsorbent dosage, initial adsorbate concentration, and temperature were fully studied. The conditions which obtained 43.57 mg/g of the highest adsorption capacity were conducted at pH 4, initial concentration of 100 mg/L, adsorbent dosage of 2.0 g/L, and contact time of 24 hours at 328 K. The adsorption data was found to follow the pseudo-second-order kinetic model and the Freundlich isotherm model. According to the findings of this investigation, it was observed that the C/CRWP composites can be used as adsorbents due to their advantages of simple preparation process, environmentally friendly, renewable, efficient, and low-cost.
ARTICLE | doi:10.20944/preprints202307.0410.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: g-C3N4; melamine cyanurate; Pd catalysts; single atom catalysts; hydrogen storage; LOHC; dehydrogenation
Online: 6 July 2023 (10:22:07 CEST)
In this work, the use of graphite-like carbon nitride (g-C3N4) with improved texture characteristics for the synthesis of supported palladium catalysts of dehydrogenation of nitrogen-containing heterocycles was studied. This process is key to the creation of liquid organic carrier technology (LOHC) using N-heterocycles as reversibly hydrogenated/dehydrogenated substrates. For the preparation of g-C3N4-mca supports with advanced textural characteristics, well-established technology of the melamine cyanurate complex carbonization and standard techniques of adsorption precipitation together with wet impregnation were used for the synthesis of Pd-containing systems. The activity of the synthesized catalysts was studied in decahydroquinoline dehydrogenation. The high weight content of extractable hydrogen (7.2 wt %) and the high extraction rate, respectively, make it possible to consider these substances as the most promising N-heterocyclic compounds for this technology. It was shown that an increase in the specific surface area of g-C3N4 allows for achieving a slightly lower, but comparable fineness of palladium particles for the 1 wt% Pd/MCA-500 sample, compared to the standard 1 wt% Pd/C. In this case, the catalytic activity of 1 wt% Pd/MCA-500 in dehydrogenation of both substrates exceeded the analogous parameter for catalysts supported by nitrogen free supports. This regularity is presumably associated with the electron-donor effect of surface nitrogen, which favorably affects the dehydrogenation rate as well as the stability of catalytic systems.
ARTICLE | doi:10.20944/preprints202307.0412.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: hydrothermal synthesis; gel dehydration; SrZrO3–SrTiO3; solid solution; crystallisation; cubic structure; orthorhombic structure
Online: 6 July 2023 (09:11:05 CEST)
In recent decades, perovskite-type compounds (ABB′O3) have been exhaustively studied due to their unique ferroelectric properties. In this work, a systematic study aiming to prepare fine particles in the binary system SrZrO3–SrTiO3 was conducted under hydrothermal conditions in a KOH (5 M) solution at 200 °C for 4 h under a constant stirring speed of 130 rpm. The precursors employed were SrSO4 powder (< 38 μm size) and coprecipitated hydrous gels of Zr(OH)4•9.64 H2O (Zr-gel) and Ti(OH)4•4.5H2O (Ti-gel), which were mixed according to the stoichiometry of the SrZr1-xTixO3 in the compositional range of 0.0>x>100.0 mol% Ti4+. The XRD results revealed the formation of two crystalline phases rich in Zr4+, an orthorhombic structured SrZr0.93Ti0.07O3 and a cubic structured SrZr0.75Ti0.25O3 within the compositional range of 0.1–0.5 mol of Ti4+. A cubic perovskite-structured solid solution, SrTi1-xZrxO3, was preferentially formed within the compositional range of 0.5>x>0.1 mol% Ti4+. The SrZrO3 and SrZr0.93Ti0.07O3-rich phases had particle sizes averaging 3 m with a cubic morphology. However, a remarkable reduction in the particle size occurred on solid solutions prepared with hydrous Ti-gel over contents of 15 mol% Ti4+ in the reaction media, resulting in the formation of nanosized particles agglomerates with cuboidal shape self-assembled via a 3D hierarchical architecture, the sizes of these particles varied in the range between 141.0–175.5 nm. The limited coarsening of the particles is discussed based on the Zr-gel and Ti-gel dehydration capability differences that occurred under hydrothermal processing.
ARTICLE | doi:10.20944/preprints202306.1453.v2
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Scopolamine; Crystallization; Magnetic field; Physical properties; Hydrogen bond
Online: 21 June 2023 (15:38:53 CEST)
In this paper, a quick and efficient method for preparation of scopolamine hydrobromide with high purity was introduced, named as magnetic field induced crystallization. Based on the solubility difference between scopolamine and scopolamine hydrobromide, salifying crystallization was selected and then treated with the synergistic effect of magnetic field to achieve the aim of scopolamine purification. The effects of crystallization solvents and magnetic field intensity on the crystallization process of scopolamine hydrobromide, as well as the influnence of magnetic field on the crystal growth direction were investigated. The results revealed that after treatment under magnetic field, the shortened induction time (25.64%-75.46%), the increased purity of crystals (0.95%-2.92%) and the improved recovery rate (4.51%-10.78%) were achieved. Furthermore, we also found that magnetic field could destroy the hydrogen bond in the solution, and change the physical properties of the mother liquid, so as to promote the nucleation formation and crystal growth. The above experiments suggested that the external magnetic field has the potential to be a feasible method for scopolamine preparation.
ARTICLE | doi:10.20944/preprints202306.1026.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Petrochemical; Continuous Process; Advanced Process Control; Change Point Detection; Model Parameter Estimation
Online: 14 June 2023 (09:11:16 CEST)
Most petrochemical plants still maintain a Proportional-Integral-Differential controller(PID) system, which is a feedback control system. However, gradually, the PID system is being extended and introduced to the Advanced Process Controller (APC) system, which is an integrated control system of feedforward and feedback that predicts external influences in advance. In the process of conducting on-site plant tests and calculating APC model parameter for the application of APC systems, a problem arises that Model Parameter are implemented differently depending on the proficiency of APC engineers. To minimize this problem, a technique for estimating APC model parameter without a plant test is required. In order to estimate the APC model parameter, it is necessary to train on dynamic interval data. In this paper, we use statistical techniques such as PELT, Linear Kernel, and Radial Basis Function Kernel of Change Point Detection (CPD) to extract dynamic data with minimum Mean Absolute Error (MAE) from time series data of a real petrochemical plant. Then, the hyper parameter is fixed and the APC model parameter is estimated by learning the dynamic section data. By applying the estimated APC model parameter to the APC Model Tool and measuring the fitting rate, it was confirmed that it is possible to estimate the APC model parameter with excellent control performance without plant test.
ARTICLE | doi:10.20944/preprints202305.2271.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: macroporous cryogel; catalase; entrapment; oxidation of ethanol; hydrogen peroxide; molecular oxygen, air; flow-through reactor; batch type reactor
Online: 31 May 2023 (14:47:38 CEST)
In this article, the biocatalytic oxidation of ethanol into acetaldehyde was studied using a catalase entrapped within monolithic polyampholyte cryogel, p(APTAC-co-AMPS), derived from an anionic monomer, 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPS), and a cationic monomer, (3-acrylamidopropyl) trimethylammonium chloride (APTAC) as catalyst. Macroporous polyampholyte cryogels containing various amounts of catalase were synthesized in situ under cryo-polymerization conditions at a molar ratio of monomers [APTAC]:[AMPS] = 75:25 mol.% in the presence of 10 mol.% cross-linking agent, N,N-methylenebisacrylamide (MBAA). The conversion of ethanol into acetaldehyde in good-to-high yields was observed in flow-through and batch type reactors under optimal conditions: at T = 10-20 C, pH = 7.1, [C2H5OH]:[H2O2] = 50:50 vol.%. According to SEM image the pore sizes of p(AMPS-co-APTAC) cryogel vary from 15 to 55 μm. The catalytic activity of catalase entrapped within monolithic polyampholyte cryogel in the conversion of ethanol into acetaldehyde was evaluated through the determination of such kinetic parameters as Michaelis constant (Km), the maximum enzymatic rate (Vmax), activation energy (Ea), turnover number (TON) and turnover frequency (TOF). The catalase encapsulated within monolithic polyampholyte cryogel exhibits a high conversion of ethanol into acetaldehyde. The advantages and disadvantages of flow-through and batch type reactors were highlighted.
ARTICLE | doi:10.20944/preprints202305.2206.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: boehmite; atmospheric leaching; alkali; hematite reduction; red mud valorization; Mössbauer spectroscopy
Online: 31 May 2023 (08:44:12 CEST)
The Bayer process is the maim method of alumina production worldwide. The use of low-quality bauxites for alumina production results in the formation of a significant amount of technogenic waste - bauxite residue (BR). The Bayer reductive method is one possible way to eliminate BR stockpiling, but it requires high-pressure leaching at temperatures higher than 220 °C. In this research, the possibility of boehmitic bauxite atmospheric pressure leaching at both the first and second stages or high-pressure leaching at the second stage with the simultaneous reduction of hematite was investigated. Bauxite and solid residue after NaOH leaching were characterized using XRD, SEM-EDS, and Mössbauer spectroscopy methods. The first stage of leaching under atmospheric pressure with the addition of Fe(II) species in a strong alkali solution (330-400 g L–1 Na2O) results in a partial reduction of the iron minerals and an extraction of more than 60% of Si and 5-25% of Al (depending on caustic modulus of solution) after 1 h. The obtained desilicated bauxite was subjected to atmospheric leaching at 120 °C in a strong alkali solution (350 g L-1) or high-pressure leaching at 160-220 °C using the Bayer process mother liquor in order to obtain a concentrate with a magnetite content higher than 83 wt. %.
ARTICLE | doi:10.20944/preprints202305.1420.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Alkylation reaction; deep eutectic solvent; mild; response surface methodology
Online: 19 May 2023 (09:52:53 CEST)
The synthesis 2-tert-butyl-4-methylphenol is of great significance because of its widely application in industry, and the development of highly efficient catalyst is necessary to the alkylation of p-cresol and tert-butyl alcohol. Here, an efficient and mild method was established, caprolactam was chosen as hydrogen-bonding acceptor, p-toluenesulfonic acid was employed as hydrogen-bonding donor, and deep eutectic solvent (DES) was prepared to catalyze the alkylation reaction. The structure of the DES catalyst was characterized by 1H NMR spectra, thermogravimetric analysis and fourier transform infrared spectra (FT-IR). In addition, response surface design based on Box-Behnken method was employed to optimize the alkylation reaction process parameters, the study of reaction kinetics was also carried out subsequently. The recycle performance of the catalyst was evaluated by recovery experiments, and a good result was obtained. Comparing with the literature reported, we here provide a mild method to the synthesis of 2-tert-butyl-4-methylphenol.
COMMUNICATION | doi:10.20944/preprints202305.1371.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: ionic liquid; deep eutectic solvent; cyclodextrin; sorbent disc; water environment
Online: 19 May 2023 (04:04:11 CEST)
With the development of health service, animal husbandry, aquaculture and chemical industry, more and more pollutants are discharged into the water environment, including antibiotics and heavy metal ions. These hazard substances pose a great threat to environment safety and human health. As two kinds of new green solvents, ionic liquids (ILs) and deep eutectic solvents (DESs) are widely used in various fields including separation and environmental engineering, which are attracting huge attention from academia and industry. In this study, the optimal ionic liquid and deep eutectic solvent were selected and their complex with β-cyclodextrin (β-CD) were firstly prepared by simple and effective inclusion way. After necessary characterization and analysis, two kinds of complex were applied to prepare a special sorbent disc with two different sides by adding diluent (excipient) and pressing under 5~15 MPa. As the result, the IL and DES could be stably immobilized on the disc and play the key role in selective adsorption for targets. Besides that, the experiments of different hazardous substances achieved the expected results. Based on this study, the complex disc showed a lot of merits in the separation performance, easy preparation and use, simple operation, and good stability. It was believed to be a useful tool for water purification and detection.
ARTICLE | doi:10.20944/preprints202304.0872.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: glycerol; glycerol carbonate; carbon dioxide; 2-cyanopyridine; CuO/Al2O3
Online: 25 April 2023 (03:40:08 CEST)
A series of supported CuO-based nanoparticle catalysts were prepared by impregnation method and used for the synthesis of glycerol carbonate from glycerol and CO2 in the presence of 2-cyanopyridine as a dehydrant and DMF as a solvent. The effects of supports (activated alumina, silicon dioxide, graphene oxide, graphene, and activated carbon), CuO loading amount, calcination temperature, and reaction parameters on the catalytic activity of catalyst were investigated in detail. XRD, FTIR, SEM, BET, and CO2-TPD were used for the characterization of the prepared catalysts. It is found that CuO/Al2O3 shows a higher catalytic activity, which depends on the CuO loading amount and calcination temperature. The surface area and amount of basic sites of the catalyst exhibit crucial effect on the catalytic activity of CuO/Al2O3. Furthermore, there is a synergistic effect between the catalyst and 2-cyanopyridine that the former has higher activation ability for glycerol and the latter acts not only as a dehydrant, but also as a promoter for CO2 activation. Recycling experiments reveal that this catalyst can be reused at least five cycles without any inactivation. Based on the experiment results and FTIR characterization, a possible reaction mechanism for the carbonylation of glycerol and CO2 is proposed.
ARTICLE | doi:10.20944/preprints202304.0716.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: amine impregnation; inverse vulcanization; adsorption; mercury removal; sustainability; sulfur polymers
Online: 21 April 2023 (10:14:56 CEST)
Mercury (Hg (II)) contamination is indefatigable global hazard which causes severe permanent damages to human health. Extensive research has been carried out to produce mercury adsorbents however they are still facing certain challenges limiting their upscaling. Herein we reported the synthesis of novel amine impregnated inverse vulcanized copolymer for effective mercury removal. Poly(S-MA) was prepared using sulfur and methacrylic acid employing inverse vulcanization method following by functionalization. The polyethylenime (PEI) was impregnated on poly(S-MA) to increase the adsorption active sites. The developed adsorbent was then characterized using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). FTIR confirmed formation of copolymer and successful impregnation of PEI and SEM revealed composite porous morphology of the copolymer. Amine impregnated copolymer (amine@poly(S-MA)) outperformed poly(S-MA) in mercury as it showed 20 % superior performance with 44.7 mg/g maximum adsorption capacity. The adsorption data best fits the pseudo second order which indicates that the chemisorption is most influential mechanism in this case indicating the involvement of NH2 in mercury removal. The adsorption is mainly monolayer on homogenous surface as indicated by 0.76 value of Redlich-Peterson exponent (g) which describes the adsorption nature advent from R2 value of 0.99.
ARTICLE | doi:10.20944/preprints202304.0455.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: photovoltaics; air-source heat pumps; self-consumption; TRNSYS; hybrid installations
Online: 17 April 2023 (10:58:53 CEST)
Nowadays Air-Source Heat Pumps (ASHP) in combination with a Photovoltaic (PV) installation are a very promising option for a necessary and urgent energy transformation in European Union (EU). It is extremely important to develop solutions that will help maximize the use of energy generated from renewable energy sources (RES). Such issues include the problem of insufficient use of generated electricity in PV on-grid microinstallations in residential buildings. This paper's aim is to analyze the results of one-year-round operation of a PV array grid-connected hybrid installation with ASHP for domestic hot water (DHW) preparation in a residential building in Cracow, Poland in the context of increasing self-consumption (SC) of PV energy. Models of systems are built and simulated in Transient System Simulation Tool 18 (TRNSYS) software. Simulations were carried out for different scenarios involving different building electricity consumption profiles, PV system capacity and specified runtime management of ASHP. The novelty of this study lies in the evaluation of the impact of a certain range of conditions on the energy performance of the system, in particular on SC. The results showed that the use of ASHP, with specified runtime management, results in an increase in monthly SC values from 7 to 18%, and annual SC values up to 13%. Also determining the appropriate size of the used PV system depending on whether it is present ASHP in the installation is crucial to increase the value of the SC parameter. Overall, this study provides valuable insights into the potential benefits of PV panels and ASHP operating together, in particular on SC values.
ARTICLE | doi:10.20944/preprints202303.0529.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Peroxymonosulfate activation; Copper ferrite; Photocatalyst; Benzotriazole
Online: 30 March 2023 (12:37:40 CEST)
The development of oxidation processes with generating powerful radicals is the most interesting and thought-provoking dimension of peroxymonosulfate (PMS) activation. In this study, a magnetic spinel CuFe2O4 was successfully prepared by a facile, non-toxic, cost-efficient co-precipitation method with the synergetic effect of photocatalytic PMS oxidation against recalcitrant benzotriazole (BTA) pollutant. The high particle dispersion and large surface area (201.898 m2/g) provided a high photocatalytic activity with CuFe2O4. The obtained results from the central composite design (CCD) analysis confirmed the optimum degrading rate of BTA reached 81.4% at the optimum operational condition of CuFe2O4= 0.4 g/L, PMS= 2 mM, BTA= 20 mg/L after 70 min irradiation time. As such, the active species capture experiments revealed the presence of •OH, SO4•‒, O2•‒ and h+ species in CuFe2O4/UV/PMS system where SO4•‒ was dominated for BTA photodegradation. The combination of photocatalysis and PMS activation enhanced the consumption of metal ions in redox cycle reactions, thus preventing metal leaching and maintain the recyclability with reasonable mineralization efficiency which achieved more than 40% total organic carbon removal after four batch experiments. A retardant effect on BTA oxidation was observed with comparing the water’s common anion constituents as HCO3‒ > Cl‒ > NO3‒ > SO2‒. Results from intermediates identification showed that the transformation pathway of BTA developed as the deprotonation, hydrolysis and ring cleavage processes promoting the practical potential of photo-absorbing CuFe2O4 catalyzed PMS which can be a promising method due to convenient magnetic separation form the solution.
BRIEF REPORT | doi:10.20944/preprints202303.0267.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Plastics recovery; plastics recycling; waste plastics; polyesters; polyamides; cleantech; green energy
Online: 15 March 2023 (02:39:29 CET)
Plastic waste constitutes one of the most important sources of pollution worldwide. Despite the growing recycling trend, nowadays there are no effective technologies that can compensate for the continuous increase in plastic production. Polyesters and polyamides are one of the most produced single-use plastics, mainly used in manufacturing textiles and soft drinks bottles. Today, only a very low fraction of these polymers can be recycled. It can be done by exploiting two leading technologies: mechanical and chemical recycling. Mechanical recycling represents, nowadays, the most used industrial application. However, it can treat a very narrow range of waste materials due to the impossibility of removing dyes and the deterioration of mechanical properties due to the incompatibility of different plastic materials. Another critical limit of this recycling technology is the limited number of recycling loops that can be done due to the thermal degradation that occurs during the extrusion process. The second possibility is chemical recycling, which allows the depolymerization of the original product to recover the monomers directly. The main drawbacks are the long reaction times and the many solvents needed to achieve high-purity products. Therefore, chemical recycling is economically feasible, only for big companies that can produce the virgin polymer in situ. In this work, a new technology has been patented. This process is constituted of three main steps. The first one is the distillation-assisted cyclodepolymerization (DA-CDP), introduced as a modification of the CDP process. In this unit, cyclic oligomers together with high molecular weight compounds have been produced. Then, after polymer purification, it is possible to achieve the same molecular weight of the initial polymer in less than 30 minutes, exploiting the ring-opening polymerization (ROP) in the next step.
ARTICLE | doi:10.20944/preprints202303.0206.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: glycyl-L-alanine iodide; polymorphism; crystal structure; cyclic dipeptides; optical second harmonic generation; pyroelectricity
Online: 13 March 2023 (02:28:08 CET)
The crystal structure of a polymorph of Glycyl-L-alanine HI.H2O was synthesized from chiral cyclic Glycyl-L-alanine dipeptide, known to show molecular flexibility in different environments. The space group is polar (P21) and therefore pyroelectricity and optical second harmonic generation properties are allowed by symmetry. We report a pyroelectric coefficient as high as 45 µC/m2K occurring at 345 K, one order of magnitude smaller than the semi-organic ferroelectric Triglycine Sulphate (TGS) crystal. Furthermore, the polymorph displays a nonlinear optical effective coefficient of 0.14 pm/V, around 14 times smaller than the value from a phase-matched inorganic Barium Borate (BBO) single crystal.
ARTICLE | doi:10.20944/preprints202303.0172.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Adsorption kinetics; pseudo-second-order model; nonlinear method; linear method
Online: 9 March 2023 (09:34:58 CET)
Initial periods of adsorption kinetics play an important role in estimating the initial adsorption rate and rate constant of adsorption process. Several adsorption processes rapidly occur, and the experimental data of adsorption kinetics under the initial periods can contain potential errors. The pseudo-second-order (PSO) kinetic model has been popularly applied in the field of adsorption. The use of the nonlinear optimization method to obtain the parameters of the PSO model can minimize error functions during modelling compared to the linear method. However, the nonlinear method has limitations in that it cannot directly recognize potential errors in the experimental points of time-dependent adsorption, especially under the initial periods. In this study, for the first time, the different linear types (Types 1–6) of the PSO model are applied to discover the error points under the initial periods. The result indicated that the fitting method using its linear equations (Types 2–5) is really helpful for identifying the error (doubtful) experimental points from the initial periods of adsorption kinetics. The imprecise points lead to low adjusted R2 (adj-R2), high reduced χ2 (red-χ2), and high Bayesian information criterion (BIC) values. After removing those points, the experimental data were adequately fitted with the PSO model. statistical analyses demonstrated that the nonlinear method must be used for modelling the PSO model because its red-χ2 and BIC were lower than the linear method. Type 1 has been extensively applied in the literature because of its very high adj-R2 (0.9999) and its excellent fitting to experimental points. However, its application should be limited because the potential errors from experimental points were not identified by this type. For comparison, the other kinetic models (i.e., pseudo-first-order, pseudo-nth-order, Avrami, and Elovich) are applied. The modelling result using the nonlinear forms of those models indicated that the fault experimental points from the initial periods were not detected.
REVIEW | doi:10.20944/preprints202302.0521.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Lithium-sulfur batteries; Catalysis; High-entropy materials; Active sites
Online: 28 February 2023 (13:44:20 CET)
The emergence of various electronic devices and equipment such as electric vehicles and drones requires higher energy density energy storage devices. Lithium-sulfur batteries (LSBs) are considered as the most promising new generation energy storage system owing to high theoretical specific capacity and energy density. However, the severe shuttle behaviors of soluble lithium polysulfides (LiPSs) and the slow redox kinetics lead to low sulfur utilization and poor cycling stability, which seriously hinder the commercial application of LSBs. Therefore, various catalytic materials have been employed to solve these troublesome problems. High entropy materials (HEMs), as advanced materials, can provide unique surface and electronic structures that expose plentiful catalytic active sites, which opens new ideas for the regulation of LiPSs redox kinetics. Notwithstanding many instructive reviews in the land of LSBs, while this review aims to offer a complete and shrewd summary of the current progresses in HEMs-based LSBs, including in-depth interpretation of design principles and mechanistic electrocatalysis functions as well as pragmatic perspectives.
ARTICLE | doi:10.20944/preprints202302.0334.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: surface roughening; heat pipe; annealing twin; texture
Online: 20 February 2023 (09:06:52 CET)
Thin-wall heat pipe is an efficient heat transfer component, which has been widely used in the field of heat dissipation of high-power electronic equipment in recent years. In this study, the orange peel morphology defect of thin-wall heat pipes after bending deformation was analyzed both for the macro 3D profile and for the micro-formation mechanism. The results show that after high temperature sintering treatment, the matrix grains of heat pipe are coarsened seriously and formed a strong Goss texture, while a certain annealing twins with the unique Copper orientation are retained. The distribution of Schmid factor value subjected to the uniaxial stress indicate the inhomogeneity of intergranular deformation exist among the annealing twins and matrix grains. The annealing twin exhibit a “hard-oriented” component during the deformation; thus, it plays a role as barrier and hinder the slipping of dislocation. As the strain accumulates, part of the annealing twins may protrude from the surface of heat pipe, forming a large-scale fluctuation of the surface as the so called the “orange peel” morphology. The 3D profile shows the bulged twins mostly perpendicular to the drawing direction, with about 200-300μm in width and 10-20μm in height.
ARTICLE | doi:10.20944/preprints202302.0292.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: ChatGPT; heterogeneous catalysis; CO2 hydrogenation; reliability
Online: 17 February 2023 (03:11:31 CET)
ChatGPT is an AI language model trained on vast amounts of text data, including scientific papers, providing a comprehensive understanding of catalysis. However, its reliability in catalysis research is unknown. To evaluate reliability, we compared a ChatGPT-generated review article on heterogeneous catalysts for higher alcohols synthesis by CO2 hydrogenation to published peer-reviewed papers. Although the ChatGPT review article covers most necessary parts, it lacks sufficient discussion of the reaction mechanism. The core sections are too general, being not specific enough to the topic, and contain errors. The lack of citations further increases unreliability. While ChatGPT can provide much content on catalysis, it is insufficient and inaccurate for research on specific topics.
ARTICLE | doi:10.20944/preprints202302.0186.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: flue gases; carbon dioxide; membrane; cascade; process design
Online: 10 February 2023 (07:50:32 CET)
The present paper deals with the complex study of the CO2 capture from combined heat power plant flue gases using the efficient technological scheme design – membrane cascade type of «Continuous Membrane Column». In contrast to well-known multi-step or multi-stage process designs, the cascade type of separation unit provides several advantages. That apparatus conceptually refers to the distillation columns. Here, the separation process is implemented in it by creating two counter current flows. In one of them is depleted by the high-permeable component in a continuous mode, meanwhile the other one is enriched. Taking into account, that the circulating flows rate overcome the withdrawn ones, there is a multiplicative growth in separation efficiency. A comprehensive study of the CO2 capture using membrane cascade type of «Continuous Membrane Column» includes the determination of optimal membrane material characteristics, the sensitivity study of the process and feasibility evaluation. It was clearly demonstrated that proposed process provides the efficient CO2 capture, which meets the modern requirements in terms of CO2 content (≥ 95 mol.%), recovery rate (≥ 90 %) and residual CO2 concentration (≤ 2 mol.%). Moreover, it was observed, that it is possible to process CO2 with purity up to 99.8 mol.% at the same recovery rate. This allows use of this specific process design in the CO2 pretreatment operations in the production of high-purity carbon dioxide.
ARTICLE | doi:10.20944/preprints202301.0002.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Graphene; copper oxide nanoparticles; nanohybrid; trichloroethylene; Rhodamine B; water remediation.
Online: 3 January 2023 (04:30:54 CET)
In this work Cu2O nanoparticles (NPs) were created in-situ on graphene functionalized with Thermomyces lanuginosus lipase (G@TLL) where site-oriented supported TLL acted as template and binder in the presence of copper salt by tailorable synthesis under mild conditions, producing a heterogeneous catalyst. Cu2O NPs was confirmed by XRD and XPS. The TEM microscopy showed that the nanoparticles were homogeneously distributed over the G@TLL surface with sizes of 53 nm and 165nm. This G@TLL-Cu2O hybrid was successfully used in the degradation of toxic organic compounds such as trichloroethylene (TCE) and Rhodamine B (RhB). In the case of TCE, the hybrid presented a high catalytic capacity, degrading 60 ppm of product in 60 min in aqueous solution and room temperature without the formation of other toxic subproducts. In addition, a TOF value of 7.5 times higher than the unsupported counterpart (TLL-Cu2O) was obtained, demonstrating the improved catalytic efficiency of the system in the solid-phase. The hybrid also presented an excellent catalytic performance for the degradation of Rhodamine B (RhB) obtaining a complete degradation (48ppm) in 50 min in in aqueous solution and room temperature and with the presence of a green oxidant as H2O2.
ARTICLE | doi:10.20944/preprints202212.0388.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: alumina; Bayer process; bauxite; seeded precipitation; coarse gibbsite; agglomeration.
Online: 21 December 2022 (06:56:02 CET)
The addition of active seed for increasing the precipitation rate leads to the formation of fine Al(OH)3 particles that complicates separation of solid from the mother liquor. In this study, the enhanced precipitation of coarse Al(OH)3 from sodium aluminate solution using active agglomerated seed was investigated. Aluminum salt (Al2(SO4)3) were used for active agglomerated seed precipitation at the initial of the process. About 50% of precipitation rate was obtained when these agglomerates were used as a seed in the amount of 20 g L–1 at 25 °C within 10 h. The agglomerated active seed and precipitate samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR). SEM images showed that agglomerates consist of flake-like particles that can be stick together by bayerite (β-Al(OH)3) acting as a binder. The precipitation temperature above 35 °C and the high concentration of free alkali (αk > 3) lead to the agglomerates refinement that can be associated with the bayerite dissolution.
ARTICLE | doi:10.20944/preprints202212.0371.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: production of H2; numerical simulation; optimization
Online: 21 December 2022 (01:46:03 CET)
The annual energy matrix has been changing in the last years because of the necessity of less dependence on fossil fuels, which are running out on the planet. Therefore, a study was started to simulate the most efficient production of H2 through COMSOL Multiphysics®, as it is a gas that in the future will be essential to supply the world's energy necessities, due to its easy to get and insert in piped gas pipes. From this study, we were able to present an optimization of parameters that presents good indications of how to obtain efficient hydrogen production in an idealized reactor.
ARTICLE | doi:10.20944/preprints202212.0181.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: nanocomposites; ultralong carbon nanotubes; catalytic chemical vapor deposition; purification; catalyst removal; water vapor treatment; thermal analysis; Raman spectroscopy
Online: 9 December 2022 (13:11:58 CET)
Ultralong carbon nanotubes (UCNTs) are highly demanded for nanocomposites applications because of their magnificent physical and chemical properties. UCNTs are synthesized by catalytic chemical vapor deposition (CCVD) method and, before using as fillers in nanocomposites, should be purified from residual catalyst and non-CNT particles without significant destruction or scissoring of UCNTs. The role of water vapor for purification of UCNTs is investigated, the importance of water assistance in this process is confirmed. It was shown that wet air treatment of products of UCNTs CCVD synthesis under mild conditions can be used to decrease sufficiently residual catalyst content without significant carbon losses in comparison with the results obtained with dry air, while the residual iron content was shown to influence heavily on the subsequent oxidation of different forms of carbons, including UCNTs. The increasing of D/G ratio of Raman spectra after wet air treatment of products of UCNTs CCVD synthesis makes it possible to conclude that iron catalyst particles transform into iron oxides and hydroxides that caused inner structural strains and destruction of carbon shells improving removal of the catalyst particles by subsequent acid treatment. UCNTs purification with water assistance can be used to develop economically and ecologically friendly methods for obtaining fillers for nanocomposites of different applications.
ARTICLE | doi:10.20944/preprints202211.0105.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: alkali leaching; red mud; high-iron waste; disposal; Al-goethite; conversion; magnetite
Online: 7 November 2022 (04:30:13 CET)
Bauxite residue (BR), also known as red mud, is a by-product of the production of alumina via the Bayer process. Because of the high sodium oxide and other impurities content, this material is not used to obtain iron or other iron-containing products. In this paper, the hydro-chemical conversion of goethite (FeOOH) to magnetite (Fe3O4) in high-iron BR from the Friguia alumina refinery (Guinea) by Fe2+ ions in highly concentrated alkaline media was studied. The simultaneous extraction of Al and Na made it possible to obtain a product containing more than 96% Fe3O4. The results show that the magnetization of Al-goethite and Al-hemetite accelerates the dissolution of the Al from the iron mineral solid matrix and from the desilication product (DSP). After ferrous sulfate (FeSO4·7H2O) was added directly at the FeO:Fe2O3 molar ratio of 1:1 at 120 °C for 150 min in the solution with the 360 g L-1 Na2O concentration, the alumina extraction ratio reached 96.27% for the coarse bauxite residue size fraction (Sands) and 87.06% for fine BR obtained from red mud. The grade of iron (total iron in the form of iron element) in the residue can be increased to 69.55% for Sands and 58.31% for BR. The solid residues obtained after leaching were studied by XRD, XRF, TG-DTA, VSM, Mössbauer spectroscopy and SEM to evaluate the conversion and leaching mechanisms and the recovery ratio of Al from different minerals. The iron-rich residues can be used in the steel industry or as a pigment.
REVIEW | doi:10.20944/preprints202209.0048.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: removal; PAHs; heavy metals; marine sponges; bacterial consortium
Online: 5 September 2022 (07:43:34 CEST)
Toxic materials in waste generally contain several components of global trending pollutant categories, especially PAHs and heavy metals. Bioremediation technology for managing waste utilizing microorganisms (bacteria) has not been fully capable of breaking down these toxic materials simple and environmentally friendly chemical products. This study examines the potential application of a marine sponge symbiont consortium with high performance and efficiency in removing PAHs and heavy metal contaminants. The method is carried out through a review of some related research articles by the author and published by other re-searchers. The study results concluded that bioremediation technology development GTP, can be carried out to improve remediation efficiency. Several types of marine sponge symbiont bacteria, hydrocarbonoclastic (R-1), metalloclastic (R-2), and metallohydro-carbonoclastic (R-3), have the potential to be applied to improve the removal performance of waste. Bacterial screening be done to find and categorize R-1 bacteria, R-2; R-3 to remediate GTP. Develop of R-1 bacteria, R-2; R-3 forms of the mobile formulation are needed in the future. A crystalline consortium of bacteria preparations is needed so that they can be quickly mobilized to locations exposed to GTP. Marine sponge symbiont bacteria be traced mainly to marine sponges whose body surface is covered with mucus.
ARTICLE | doi:10.20944/preprints202207.0052.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: alumina; catalysis; gasoline fraction of oil; hydrotreating; rare earth element; zeolite
Online: 4 July 2022 (10:39:29 CEST)
The oil produced in the oil fields of the Republic of Kazakhstan contains a high percentage of sulfur. Synthesis and improvement of the properties of catalytic systems for the production of fuels with high octane number and low sulfur content is currently an urgent task for Kazakhstan. In this study, catalytic systems with a new composition based on zeolites with the addition of rare-earth metals (E) and phosphorus (P) have been prepared and tested in the process of the catalytic hydrotreating of straight-run gasoline and gasoline of catalytic cracking. In case of NiO-MoO3-E-P-HZSM-HY-Al2O3 catalyst, the octane rating of the gasoline after hydro-processing was increased to 88-90, which is much higher than for other catalysts. The octane number of straight-run gasoline up to 400°C is a maximum of 90 (Research Method) and 83.7 (Motor Method). At the same time, the sulfur content in the resulting gasoline decreases from 0.0088% to 0.0011%. In the case of catalytic cracking gasoline, the sulfur content is reduced from 0.0134% to 0.0012%. The smallest residual sulfur content in the final product, 0.0005% is revealed in case of catalyst CoO-WO3-E-P-HZSM-HY-Al2O3, and it is 2-4 times lower than for catalysts CoO-MoO3-E-P-HZSM-HY-Al2O3 and NiO-MoO3-E-P-HZSM-HY-Al2O3. These amounts of sulfur residue in raw materials is lower than that required by the Euro-5 Standard. The surface of the prepared catalysts was 211.0-274.0 m2/g, diameter of pores d ≈ 1.5-2.5 nm and d ≈ 7.0 nm. The total pore volume of the catalysts was not higher than 0.28-0.41 ml/g. The catalysts developed in this study can be used for hydrotreating raw materials and producing high-octane gasoline with a low sulfur content, corresponding in its characteristics to the Euro-5 Standard.
ARTICLE | doi:10.20944/preprints202207.0019.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: catalysts; iron oxides; cobalt; oxygen; oxidation; phenol; magnetic composites
Online: 1 July 2022 (16:42:17 CEST)
The development and improvement of methods for the synthesis of environmentally friendly catalysts based on base metals is currently an urgent and promising task of modern catalysis. Catalysts based on nanoscale magnetite and maghemite have fast adsorption-desorption kinetics and high chemical activity. The purpose of this work was to obtain magnetic composites, determine their physicochemical characteristics and verify their activity in the process of liquid-phase oxidation of phenol with oxygen. Magnetic nanocomposites were obtained by chemical co-deposition of salts of ferrous and trivalent iron. The synthesized magnetic composites were studied by X-ray diffractometry, energy dispersive X-ray fluorescence and Mössbauer spectroscopy, IR-Fourier spectroscopy, elemental analysis. To increase the catalytic activity in oxidative processes, the magnetite surfaces were modified using cobalt nitrate salt. Further, CoFe2O4 was stabilized by adding polyethylenimine (PEI) as a surfactant. Preliminary studies of the oxidation of phenol with oxygen, as the most typical environmental pollutant were carried out on the obtained Fe3O4, CuFe2O4, CoFe2O4/PEI catalysts. The spectrum of the reaction product shows the presence of CH in the aromatic ring and double C=C bonds, stretching vibrations of the C=O groups of carbonyl compounds; the band at 3059 cm–1 corresponds to the presence of double C=C bonds, the band at 3424 cm–1 hydroquinone compounds. The band at 1678 cm–1 and the intense band at 1646 cm–1 refer to vibrations of the С=О bonds of the carbonyl group of benzoquinone. Peaks at 1366 cm–1 and 1310 cm–1 can be related to the vibrations of C–H and C–C bonds of the quinone ring. Thus it was demonstrated that produced magnetic composites based on iron oxide are quite effective in the oxidation of phenol with oxygen.
COMMUNICATION | doi:10.20944/preprints202207.0008.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: fullerene, graphene, molybdenum disulfide, carbon nanotubes, catalysts, density functional theory, enzymes, honeybee biomimicry, drones, depollution, doubly-charged negative ions
Online: 1 July 2022 (08:12:59 CEST)
The Sulfur Dioxide (SO2) compound is a primary environmental pollutant worldwide, whereas elemental Sulfur (S) is a global commodity possessing a variety of industrial as well as commercial functions. The chemical relationship between poisonous SO2 and commercially viable elemental S has motivated this investigation using Density Functional Theory calculation of the relative transition state barriers for the 2-step Dehydro-sulfurization oxidation-reduction reaction. Additionally, doubly-charged nanoscale platelet Molybdenum Disulfide (MoS2), Armchair (6,6) Carbon Nanotube, 28-atom Graphene nanoflake (GR-28), and Fullerene C-60 are utilized as catalysts. The optimal heterogeneous and homogeneous catalysis pathways of the 2-step oxidation-reduction from SO2 to elemental S are further inspired by the biomimicry of the honeybee species multi-step bio-catalysis of pollen conversion to organic honey. Potential applications include environmental depollution, the mining of elemental sulfur, and the functionalization of novel technologies such as the recently patented aerial and amphibious Lynchpin TM drones.
ARTICLE | doi:10.20944/preprints202206.0362.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: catalytic converters; waste gases; phosphating; oxidation
Online: 27 June 2022 (10:49:57 CEST)
Iron and chromium based alloys have found wide application in various fields of science and technology. Primary carrier based on Fe-Cr-Al alloy is used in block catalysts for high-temperature hydrocarbon conversion, in production of block metal catalysts for neutralization of toxic gases released during operation of internal combustion engines, as well as those present in smoke emissions from enterprises. Influence of thermal action on Fe-Cr-Al alloy foil and stability of secondary carrier on its surface was studied. Elemental composition of the surface layer of X15U5 alloy foil does not remain constant during heating and depends on the thermal treatment mode. Some of the elements come to surface and elemental composition of surface layer can differ significantly from that observed in the bulk of foil sample. This implies the possibility of changing the adhesive and adsorption properties of the foil surface, as well as the need to take this fact into account when supporting a secondary carrier and active phase to the foil. Applied technique of phosphating and supporting a secondary carrier to the foil surface makes it possible to obtain a sufficiently stable coating. There is no shedding of the secondary carrier from foil surface during high-temperature treatment in air.
ARTICLE | doi:10.20944/preprints202206.0109.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Layered Double Hydroxides (LDH); mechano-chemical / co-precipitation synthesis; organic alkalis (tetramethylammonium hydroxides); memory effect; Claisen-Schmidt condensation; self-cyclohexanone condensation
Online: 8 June 2022 (03:23:29 CEST)
Using of the organic base tetramethylammonium hydroxides (TMAH) is a viable, cheap and fast route, for the MgZnAl-LDH type materials synthesis by both co-precipitation and mechano-chemical methods. TMAH provided several advantages as smaller quantity of water required in the washing step compared to the use of inorganic alkalis, prevention of LDH contamination with alkali cations, acting as template molecule in texture tailoring along with disadvantages as its presence in small quantities in the resulting layered materials. Regardless the use of organic / inorganic bases and co-precipitation / mechano-chemical methods, zincite stable phase was found in all the synthesized solids. The basicity of catalysts followed the trend: mixed oxides > reconstructed > parent LDH. The memory effect of LDH is supported only by the presence of Mg and Al cations, while Zn remains as zincite stable phase. The catalytic activities for Claisen-Schmidt condensation of benzaldehyde with cyclohexanone provided values higher than 90% after 2h, with a total selectivity in 2,6-dibenzylidenecyclohexanone, while in self-condensation of cyclohexanone no more than 7.29% after 5h. These behaviors depended on catalysts basicity as well as the planar rigidity of the compound.
REVIEW | doi:10.20944/preprints202203.0011.v2
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: colloids; interface; formulation; surfactant; cosmetics; petroleum; food; paint; pharmaceutics; emulsions; foams; dispersions; HLDN
Online: 2 March 2022 (07:30:26 CET)
Formulation is an ancient concept, although the word has been used only recently. The first formulations made our civilization advance by inventing bronze, steel, and gunpowder; then, it was used in medieval alchemy. When chemistry became a science and with the golden age of organic synthesis, the second formulation period began. This made it possible to create new chemical species and new combinations “à la carte.” However, the research and developments were still carried out by trial and error. Finally, the third period of formulation history began after World War II, when the properties of a system were associated with its ingredients and the way they were assembled or combined. Therefore, the formulation and the systems’ phenomenology were related to the generation of some synergy to obtain a commercial product. Winsor’s formulation studies in the 1950s were enlightening for academy and industries that were studying empirically surfactant-oil-water (SOW) systems. One of its key characteristics was how the interfacial interaction of the adsorbed surfactant with oil and water phases could be equal by varying the physicochemical formulation of the system. Then, Hansen’s solubility parameter in the 1960s helped to reach a further understanding of the affinity of some substances to make them suitable to oil and water phases. In the 1970s, researchers such as Shinoda and Kunieda, and different groups working in Enhanced Oil Recovery (EOR), among them Schechter and Wade’s group at the University of Texas, made formulation become a science by using semiquantitative correlations to attain specific characteristics in a system (e.g., low oil-water interfacial tension, formulation of a stable O/W or W/O emulsion, or high-performance solubilization in a bicontinuous microemulsion system at the so-called optimum formulation). Nowadays, over 40 years of studies with the hydrophilic-lipophilic deviation equation (HLD) have made it feasible for formulators to improve products in many different applications using surfactants to attain a target system using HLD in its original or its normalized form, i.e., HLDN. Thus, it can be said that there is still current progress being made towards an interdisciplinary applied science with numerical guidelines. In the present work, the state-of-the-art of formulation in multiphase systems containing two immiscible phases like oil and water, and therefore systems with heterogeneous or micro-heterogeneous interfaces, is discussed. Surfactants, from simple to complex or polymeric, are generally present in such systems to solve a wide variety of problems in many areas. Some significant cases are presented here as examples dealing with petroleum, foods, pharmaceutics, cosmetics, detergency, and other products occurring as dispersions, emulsions, or foams, that we find in our everyday lives.
ARTICLE | doi:10.20944/preprints202111.0573.v2
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: ofloxacin; rate-law; pseudo-order; half-life time; homogeneous catalysis; heterogeneous catalysis; photodegradation
Online: 15 December 2021 (08:24:46 CET)
Ofloxacin is a highly efficient and widely used antibiotic drug. It is classified as a refractory pollutant due to its poor biodegradability. Consequently, it is commonly found in water sources, requiring efficient methods for its removal. Advanced Oxidation Processes (AOPs) offer efficient alternatives since those yield complete degradation not achieved in adsorption or membrane processes. Previous studies suggest ofloxacin degradation follows a pseudo-first or -second order processes, whereas for full removal of refractory pollutants – lower pseudo-orders are required. Monitoring the actual “pseudo-order” degradation kinetics of ofloxacin is needed to evaluate any proposed AOP process. This study presents a simple procedure to evaluate pseudo-orders of AOPs. Photolysis of 20 mM ofloxacin solutions follow pseudo-zero order kinetics, with half-life times (t1/2) of approx. 60 min. TiO2 heterogenous catalyst show to have no influence at low concentration (0.2 mg L-1) but a significant reduction of half-life time (t1/2 = 20 min) and increase in pseudo-order (0.8) is measured at 2.0 mg L-1. Similar results are obtained with homogenous catalysis by 2.0 mg L-1 H2O2. The combination of H2O2 and TiO2 catalysts shows additional reduction in half-time life with increase in the pseudo-order to 1.2. The conclusions are (1) heterogenous and homogenous photocatalysis can effectively degrade ofloxacin, (2) combined photocatalysis yields higher pseudo-order, being less prone to achieve full removal, (3) analysis of specific pseudo-orders in AOPs of refractory pollutants helps to further elucidate the efficiency of the processes.
ARTICLE | doi:10.20944/preprints202111.0571.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Aminoglutethimide; Multicomponent solid form; Eutectic Mixure; Solubility
Online: 30 November 2021 (13:22:31 CET)
Here, we report the synthesis and experimental characterization of three drug-drug eutectic mixtures of drug aminoglutethimide (AMG) with caffeine (CAF), nicotinamide (NIC) and ethenzamide (ZMD). The eutectic mixtures (AMG-CAF, AMG-NIC and AMG-ZMD) demonstrate significant melting point depressions ranging from 99.2 to 127.2 °C compared to the melting point of the drug AMG (151°C) and also show significantly higher aqueous solubilities than that of the AMG. The results presented include the determination of the binary melt phase diagrams and accompanying analytical characterization via X-ray powder diffraction, FT-IR spectroscopy and Scanning electron microscopy.
ARTICLE | doi:10.20944/preprints202111.0481.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: plastic waste; chemical recycling; mathematical modelling; carbon feedstock; circular economy; open-loop recycling; acrylonitrile butadiene styrene; polystyrene; toluene
Online: 25 November 2021 (15:26:23 CET)
The inherent value and use of hydrocarbon from waste plastics and solvents can be extended through open-loop chemical recycling as this process converts plastic to range of non-plastic materials. This process is enhanced by first creating plastic-solvent-combinations from multiple sources which are then streamlined through single process stream. We report on the relevant mechanics for streamlining industrially relevant polymers such as polystyrene (PS), polypropylene (PP), high-density polyethylene (HDPE) and acrylonitrile butadiene styrene (ABS) into chemical slurries mixed with various organic solvents such as toluene, xylene and cyclohexane. The miscibility of the polymer feedstock within the solvent was evaluated using the Relative Energy Difference method, and the dissolution process was evaluated using the “Molecular theories in a continuum framework” model. These models were used to design a batch process yielding 1 tonne/h slurry by setting appropriate assumptions including constant viscosity of solvents, disentanglement-controlled dissolution mechanism and linear increase of the dissolved polymer’s mass fraction over time. Solvent selection was found to be the most critical parameter for the dissolution process. The characteristics of the ideal solvent are high affinity to the desired polymer and low viscosity. This work serves as a universal technical guideline for open-loop chemical recycling of plastics avoiding the growth of waste plastic in a circular economy framework.
ARTICLE | doi:10.20944/preprints202111.0413.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: bauxite residue; red mud; scandium; acid leaching; kinetics; shrinking core model; waste utilization.
Online: 23 November 2021 (09:07:23 CET)
One of the potential sources of rare-earth elements (REEs) is the solid waste from alumina industry - bauxite residue, known as “red mud” (RM). The main REEs from the raw bauxite are concentrated in RM after the Bayer leaching process. The earlier worldwide studies were focused on the scandium (Sc) extraction from RM by concentrated acids to enhance the extraction degree. This leads to the dissolution of major oxides (Fe2O3 and Al2O3) from RM. This article studies the possibility of selective Sc extraction from alkali fusion red mud (RMF) by diluted nitric acid (HNO3) leaching at pH ≥ 2 to prevent co-dissolution of Fe2O3. RMF samples have been analyzed by X-ray fluorescence spectrometry (XRF), X-ray diffraction (XRD), electron probe microanalysis (EPMA), and inductively coupled plasma mass spectrometry (ICP-MS). Sc extraction has been found to be 71.2 % at RMF leaching by HNO3 at pH=2 and at 80 °C during 90 min. The kinetic analysis of experimental data by the shrinking core model has shown that Sc leaching process is limited by the interfacial diffusion and the diffusion through the product layer. The apparent activation energy (Ea) was 19.5 kJ/mol. We have established that according to EPMA of RMF, Sc is associated with iron minerals; it could act as the product layer. The linear dependence of Sc extraction of magnesium (Mg) extraction has been revealed. This fact indicates that Mg can act as a leaching agent of Sc presented in RMF by ion-exchangeable phase.
ARTICLE | doi:10.20944/preprints202111.0238.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: volatile suspended solids; anaerobic digestion; hydrogen; sour cabbage; microaeration
Online: 12 November 2021 (17:04:00 CET)
In the article, were checked influences of microaeration, pH, and VSS (Volatile Suspended Solid) for sour cab-bage anaerobic digestion. Results fermentation of sour cabbage under the condition of small oxygen addition are presented in this research can be classified as dark fermentation or hydrogenotrophic anaerobic digestion. The investigations were carried out for two concentrations 5 g VSS /L and 10 g VSS /L of sour cabbage at pH 6.0. The oxygen flow rates (OFR) for 5 g VSS /L were in the range of 0.53 to 3.3 mL/h for obtaining 2% to 8% of oxygen. In cases of low pH and microaeration, ethylene production was observed at a level below 0.05% in biogas. The highest volume of hydrogen for 5 g VSS/L was obtained for flow rate 0.58 O2 mL/h, giving hydrogen concentration in biogas in the range of 0 to 20%. For VSS 5 g/L and oxygen flow rate 0.58 mL/h; 0.021 L of hydrogen is produced per gram of VSS. In this case, VSS 10 g/L and oxygen flow rate 1.4 mL/h at pH 6.0, 0.03 L of hydrogen is generated per gram. Microaeration from 0.58 mL/h to 0.87 mL/h was propitious for hydrogen production at 5 g VSS/L of sour cabbage and 1.4 mL/h for 10 g/L. Another relevant factor is the volatile suspended solid factor of sour cabbage that caused optimal hydrogen production at VSS 89.32%.
ARTICLE | doi:10.20944/preprints202111.0220.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: β-Ga2O3 crystal; optical floating zone; saturable absorber; Q-switch
Online: 12 November 2021 (12:09:07 CET)
β-Ga2O3 crystal have attracted great attentions in the fields of photonics and photoelectronics because of its ultra wide-band gap and high thermal conductivity. Here, pure β-Ga2O3 crystal was successfully grown by optical floating zone (OFZ) method, and used as saturable absorbers to realize a passively Q-switched all-solid-state 1μm laser for the first time. By placing the as-grown β-Ga2O3 crystal into the resonator of Nd:GYAP solid-state laser, a Q-switched pulses at the center wavelength of 1080.4 nm are generated under a output coupling of 10%. The maximum output power is 191.5 mW while the shortest pulse width is 606.54 ns, and the maximum repetition frequency is 344.06 kHz. The maximum pulse energy and peak power are 0.567 μJ and 0.93 W, respectively. Our experimental results show that β-Ga2O3 crystal has great potential in the development of all-solid-state 1μm pulsed laser.
ARTICLE | doi:10.20944/preprints202110.0157.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Adsorption; Cane Papyrus; Oily water; Produced water; Isotherm; Kinetic
Online: 11 October 2021 (11:53:37 CEST)
High quantities of wastewater produced from producing natural gas and oil from the aquifer, which called produced water. The produced water was comprised of dissolved solids, suspended solids, emulsified oil, and organic and inorganic compounds. That should be treated it's before disposal because it causes harm to the environment. This study takes the produced water from the southern Iraqi oilfield drilling company to adsorption by the Cane papyrus as natural and low-cost adsorbent. The analysis completed by using Fourier transforms infrared spectroscopy, EDX spectra and Scanning Electron Microscopic (SEM) for Cane papyrus. Investigating the effect of many parameters such as adsorbent dosage, temperature, solution pH, mixer speed and contact time. The Langmuir, Freundlich, Temkin and Harkins-Henderson isotherm models were tested, the results were 0.998,0.966, 0.931 and 0.966 respectively. The Langmuir model was more suitable described the adsorption process than the other models. The kinetics results were, 0.984 for Pseudo-first-order, 0.938 for Pseudo-second order is, 0.979 for Intra particle diffusion study and 0.912 for the Elovich model, the Pseudo-first-order kinetic equation best described the kinetics of the reaction. The thermodynamics study effect temperature changes on the thermodynamic parameters such as standard free energy change (∆G°), standard enthalpy change (∆H°) and standard entropy change (∆S°). The experimental data obtained demonstrated that Cane papyrus is a suitable adsorbent for removing oil from produced water.
ARTICLE | doi:10.20944/preprints202109.0398.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Preparation of Off-Site Consequence Analyses; Chemicals Control Act; Risk Assessment; Paint Manufacturing Plant; Plating Industry Plant
Online: 23 September 2021 (10:18:56 CEST)
: Chemical accidents can occur anywhere. The need for chemical management in Korea was realized following the 2012 Gumi hydrofluoric acid accident in 2012. The Chemicals Control Act was enacted in 2015. This system evaluates the risks (high, medium, low) and consequent safety management at all plants that handle hazardous chemical substances. However, the system was criticized as excessive when most plants were designated high-risk without considering their size. Thus, laboratories and hospitals handling very small quantities were subject to regulation. Accordingly, in 2021 Korea revised the system to include off-site consequence analyses and a Korean-style risk analysis. Plants handling very small quantities, such as laboratories and hospitals, were exempt from regulation. In this study, plating and paint manufacturing companies, which were classified as high-risk in the previous system, even though they were medium-size business plants, were re-evaluated as low-risk plants. In the Korean-style risk analysis, it is possible to see at a glance what is lacking in the plants, such as cooperation between local residents and local governments and the construction of safety facilities according to the type of accident scenario. The revised system is a reasonable regulation for medium business plants.
ARTICLE | doi:10.20944/preprints202106.0325.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Poultry litter; Carbon nanotubes; Catalyst; Experimental conditions; Adsorption
Online: 11 June 2021 (14:59:33 CEST)
Pakistan being an agricultural country is raising 146.5 million commercial and domestic poultry birds which generate around 544,831 tons of waste. This waste finds its final disposal in agricultural land as soil fertilizer or disposal site amendment. The uncontrolled use of poultry litter for this purpose results in environmental impacts such as the emission of methane, a greenhouse gas. However, other options like thermochemical conversion of this waste can offer a better solution wherein poultry litter can be used as low-cost carbon sources for the synthesis of Carbon Nanotubes (CNTs). In this study, efforts have been made to utilize this cheap and plenty of available carbon source for synthesis of CNTs in the presence of Ni/Mo/MgO as a catalyst, through pyrolysis. The optimum mole ratio of catalyst (4:0.2:1) was found to yield more carbon product. Furthermore, process parameters such as temperature, time, polymer & catalyst weight were also optimized. The best possible process parameters that resulted (pyrolysis time (12 min), temperature (825◦C), and catalyst weight (100 mg) good yield of CNTs . The structure and morphology of produced nanotubes were confirmed through X-ray Diffractometer (X-RD) & Scanning Electron Microscopy (SEM). The environmental application of the nanotubes was tested in synthetic chromium solution in the lab using a batch experiment. Different experimental conditions (pH, adsorbent dosage and contact time) were optimized to enhance the adsorption of Cr (VI) by carbon nanotubes and UV-Visible spectrophotometer was used at 540nm to measure the absorbance of Cr (VI). Results show that up to 81.83% of Cr (VI) removal was achieved by using 8 mg of CNTs at pH 3 with 400 rpm at 180 min of contact time. Thus, it was concluded that poultry litter can be a useful source for the synthesis of CNTs and thereby removal of Cr (VI) from industrial tanneries wastewater.
ARTICLE | doi:10.20944/preprints202106.0213.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Rectangular channels; Twisted tape inserts; Laminar flow; Forced convection; Water; Heat enhancement; Pressure drop; Performance evaluation criteria
Online: 8 June 2021 (11:09:04 CEST)
Heat enhancement is a topic of great interest nowadays due to its different application in industries. Porous material also known as metallic foam plays a major role in heat enhancement at the expenses of pressure drop. Flow in channels demonstrate the usefulness of this technology in heat extraction. In our current study, a porous strip attached to the channels walls is proposed as an alternative for heat enhancement. The thickness of the porous strip was varied for different Reynolds number. By maintaining laminar regime and using water as fluid, we determined an optimum thickness of porous material leading to the highest performance evaluation criterion. In our current study with the aspect ratio being the porous strip thickness over the channel width, an aspect ratio of 0.2 is found to be the alternative. A 40% increase in heat enhancement is detected in the presence of porous strip when compared to a clear channel case for a Reynolds number equal to 200 and improve further as the Reynolds number increase accordingly.
ARTICLE | doi:10.20944/preprints202101.0635.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Powder; AlSiMg; Ti64; N700; microstructure; high-resolution electron microscopy
Online: 29 January 2021 (17:21:56 CET)
This paper presents an advanced microstructural analysis of the AlSiMg, Ti64 and N700 powders used for additive manufacturing. The internal microstructure of the regular and irregular powder grains were characterized down to atomic resolution by using scanning electron microscopy and high resolution scanning transmission electron microscopy.The accretionary forms on top of the irregular AlSiMg powder grains exhibit a slightly coarse microstructure with a network of eutectic Si consisting of nano-crystallites, suggestinga slower cooling than the grain itself that contain a predominately amorphous Si network. A nm thin amorphous C layer on the surface of some Ti64 plasma atomized powder grains promoted the attachment of satellites and growth of envelopes. In case of gas atomized N700 powder grains, we identified thin oxide and carbon amorphous layers as well as metal segregations at the interface between the grain body and the accretionary forms.
ARTICLE | doi:10.20944/preprints202101.0422.v1
Online: 21 January 2021 (14:19:33 CET)
We present new results in positron annihilation lifetime spectroscopy (PALS), thermo-optical dilatometry and microscopy, which are indicating a strong correlation between grain-boundaries and mass transport during the sintering process of carbonyl iron powder. In this particular system we were able to show that the change in particle shape and size with increasing temperature yields an anisotropy in shrinkage, which manifests itself in a higher shrinkage perpendicular to the compaction axis. In the intermediate stage of sintering, where the major mass transport occurs, the average distance between two grain boundaries could be determined to (3,73 ± 0,18) μm at T = 744°C. This is in good agreement with previous calculations of positron pathways in defect free particles. Furthermore, due to sintering temperatures far above the annealing temperature of dislocations in iron, the existence of dislocations in the bulk of the particles is very unlikely. These claims are reflected by the collected positron data, which exhibit a clear grain boundary signal of ∼ 250ps while no vacancy or dislocation signal (typically ∼ 160 ps) is evident in the intermediate stage of sintering.
ARTICLE | doi:10.20944/preprints202012.0231.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Plasma, zinc oxide, photocatalysis, nanomaterials.
Online: 9 December 2020 (15:51:59 CET)
In this work, zinc oxide (ZnO) nanoparticles were modified in a circulating fluidized bed through argon and hydrogen (Ar-H) alternative-current (AC) arc plasma, which shows the characteristics of non-equilibrium and equilibrium plasma at the same time. In addition, a circulating fluidized bed with two plasma jets was used for cyclic processing. The catalytic degradation performance on Rhodamine B (Rh B) by Ar-H plasma modified ZnO and pure ZnO was tested in aqueous media to identify the significant role of hydrogen atoms in Rh B degradation mechanism. Meanwhile, the effects of plasma treatment time on the morphology, size and photocatalytic performance of ZnO were also investigated. The results demonstrated that ZnO after 20 minutes-treatment by Ar-H plasma showed Rh B photocatalytic degradation rate is ten times greater than that of pure ZnO, and the reaction follows a first-kinetics for the Rh B degradation process. Furthermore, the photocatalyst cycle experiment curve exhibited that the modified ZnO still displays optimum photocatalytic activity after five cycles of experiment. The improvement of photocatalytic activity and luminescence performance attributes to the significant increase of the surface area, and the introduction of hydrogen atoms on the surface also could enhance the time of carrier existence where the hydrogen atoms act as shallow donors.
REVIEW | doi:10.20944/preprints202010.0378.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Carbon dioxide capture; Deep eutectic solvents; Ionic liquids.
Online: 19 October 2020 (11:59:37 CEST)
Carbon dioxide capture and storage (CCS) is highly expected to be mitigating the discharges of carbon dioxide in a surrounding environment. Solvents are an integral part of CCS. So far, several solvents have been explored the interest of meeting the requirements such as accessibility, non-harmfulness, biocompatibility, recyclability, and inexpensiveness. However, most solvents face failure in fulfilling the requirements due to many factors, so, this review paper gives a brief discussion about another category of solvent, an analogue of ionic liquids (ILs) named deep eutectic solvent (DES). Extensive research has been done on DES in recent years because of their various attractive advantages, i.e., non-poisonousness, biodegradability, cheap cost and easy preparation, that make them as a promising green solvent for many industrial procedure and application, for instance, polymer synthesis, biodiesel treatment, green chemistry, electrochemistry etc. Therefore, this manuscript mainly focusses on CO2 capturing through DES in oil and gas field. In addition, the preparation and chemical structures of this novel solvent (DES) is also discussed. Moreover, a detailed study based on experimental solubility of CO2 in DESs is also reported in this article.
ARTICLE | doi:10.20944/preprints202010.0104.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Fe3O4; Ag; TiO2 nanoparticles; Degradation; 2, 4-dichlorophenol
Online: 5 October 2020 (17:51:13 CEST)
In this research, first a binary nanocomposite of magnetic recyclable photocatalyst Fe3O4/TiO2, was synthesized by sol gel technique. Then, in order to enhance the photocatalytic activity of the synthesized nanocomposite, it was deposited by silver nanoparticles for using in degradation of organic pollutants 2, 4-dichlorophenol (2, 4-DCP) under visible light. A range of analytical techniques including XRD, FESEM/EDX, DRS, VSM and N2 physisorption were employed to reveal the crystal structure, morphology and property of the nanocomposites. We obtained 32% and 55% degradation of 2, 4-DCP under visible light after 180 min irradiation in the presence of Fe3O4/TiO2 and Fe3O4/TiO2/Ag respectively. Thus, the excellent visible light photocatalytic activity of Fe3O4/TiO2/Ag sample can be attributed to the surface plasmon resonance effect of Ag nanoparticles deposited on Fe3O4/TiO2 nanocomposite.
ARTICLE | doi:10.20944/preprints202010.0103.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Ag nanoparticles; Plasmonic photocatalysts; Fe3O4; Oxidation; 2, 4-DCP
Online: 5 October 2020 (17:49:27 CEST)
In this work, pure TiO2 and binary nanocomposites of Fe3O4/TiO2 and Ag/TiO2 were synthesized in order to improve photocatalytic performance of these samples for degradation of 2, 4-dichlorophenol (2, 4-DCP) as an organic pollutant. A range of analytical techniques including XRD, DRS, SEM/EDX, and elemental mapping were employed to reveal the crystal structure, morphology and property of the nanocomposites. XRD data demonstrated that the prepared samples are purely in TiO2 anatase phase and cubic spinel Fe3O4 exist in the synthesized nanocomposite. We calculated the TiO2 crystal size from XRD patterns, in the range of 8.35-11.09 nm. The presence of Ag, Fe, O, and Ti atoms in the synthesized nanocomposites was confirmed by SEM/EDX. We obtained 30.43, 32.02 and 42.40 % degradation of 2, 4-DCP (100 ml 2, 4-DCP 40 ppm and 0.01 g catalyst) for pure TiO2, Fe3O4/TiO2 and Ag/TiO2, respectively, after 180 min of irradiation under visible light. Similar conditions were employed for 2, 4-DCP degradation under UV irradiation, we obtained 53.05, 51.00 and 71.50 % degradation of 2, 4-DCP pure TiO2, Fe3O4/TiO2 and Ag/TiO2, respectively. Thus, the synthesized binary nanocomposites exhibited higher photocatalytic activity compared to pure TiO2 under visible light.
COMMUNICATION | doi:10.20944/preprints202008.0701.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: carbon dioxide; molybdenum carbide; methanol; copper; alkali; dopant
Online: 31 August 2020 (05:03:06 CEST)
Mitigation of Anthropogenic CO2 emissions possess a major global challenge for modern societies. Herein catalytic solutions are meant to play a key role. Among the different catalysts for CO2 conversion Cu supported on molybdenum carbide is receiving increasing attention. Hence, in the present communication we show the activity, selectivity and stability of fresh-prepared -Mo2C catalysts and compare the results with those of Cu/Mo2C, Cs/Mo2C and Cu/Cs/Mo2C in CO2 hydrogenation reactions. The results showed that all the catalysts were active and the main reaction product was methanol. The results showed that copper-cesium and molybdenum effectively interact and that cesium promoted the formation of metallic Mo. While, the incorporation of copper is positive to improve the activity and selectivity to methanol, the presence of Mo0 phase was detrimental for the conversion and selectivity. Moreover, the catalysts promoted by cesium underwent redox surface transformations during the reaction that diminished their catalytic performance. The molybdenum phase in Cu/Mo2C changes during reaction leading to metallic molybdenum and tuning the catalytic activity.
ARTICLE | doi:10.20944/preprints202008.0427.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: chromium; reduction; oxalic acid
Online: 20 August 2020 (05:40:51 CEST)
The direct Cr (VI) reduction process by oxalic acid was conducted and the results showed that the Cr (VI) was efficiently reduced by oxalic acid at high reaction temperature and high dosage of oxalic acid. The reduced product, Cr (III), was easily generated stable complex compounds (Cr(HC2O4)3) with oxalate, which displayed a negative effect on the reduction process. The high reaction temperature and high acidic medium could destroy the stable structure of a complex compound to release oxalate, and facilitate the reduction of Cr (VI). Generally, the present study provided a versatile strategy for Cr (VI) reduction, exhibiting a bright application future for real wastewater treatment.
BRIEF REPORT | doi:10.20944/preprints202005.0355.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: microplastics; analysis; waste treatment; food; diet
Online: 23 May 2020 (04:58:22 CEST)
This preprint is focused in the presence of plastics and microplastics in food. We will discuss how many we eat, and how they arrive to the food, and why. We will treat many other things, such as the waste treatment in Europe and in Spain, with updated data; how much plastic waste is generated; what are microplastics and how they are analyzed, I will tell about the experience we have at the University of Alicante (UA); how they can be removed and we will estimate how many we eat over the course of a year.
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: adsorption; lead; biocomposite; alginate; Ficus carica L.
Online: 7 May 2020 (08:03:17 CEST)
In this study, fig leaves, zeolite and alginate were used to prepare a biocomposite for the adsorption of Pb(II) ions from aqueous solutions. Effects of various parameters on the biosorption process such as pH, temperature, initial lead concentration and contact time have been investigated. Maximum uptake of Pb(II) ions (85%) has been achieved at pH 6, with 25 mg/L of initial concentration and at a temperature of 288.15 K. Among the applied models, the data correlated well with Freundlich and D-R models and it was established that the biosorption was physical in nature. The amount of adsorbed lead per gram of sorbent was found to be 150.3 mg/g. Thermodynamic parameters showed the exothermic heat of biosorption and the feasibility of the process. Results have suggested that the prepared biosorbent possesses promising biosorption potential.
ARTICLE | doi:10.20944/preprints202002.0266.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: deep eutectic solvents; absorption; biogas; dimethyl disulfide; green solvents; desulfurization
Online: 18 February 2020 (11:10:40 CET)
The paper presents a synthesis of deep eutectic solvents (DESs) based on choline chloride (ChCl) as hydrogen bond acceptor and phenol (Ph), glycol ethylene (EG), and levulinic acid (Lev) as hydrogen bond donors in 1:2 molar ratio. DESs were successfully used as absorption solvents for removal of dimethyl disulfide from (DMDS) from model biogas steam. Several parameters affecting the absorption capacity and absorption rate has been optimized including kind of DES, temperature, the volume of absorbent, model biogas flow rate, and initial concentration of DMDS. Furthermore, reusability and regeneration of DESs by means of adsorption and nitrogen barbotage followed by the mechanism of absorptive desulfurization by means of density functional theory (DFT) as well as FT-IR analysis were investigated. Experimental results indicate that the most promising DES for biogas purification is ChCl:Ph, due to high absorption capacity, relatively long absorption rate, and easy regeneration. The research on the absorption mechanism revealed that van der Waal interaction is the main driving force for DMDS removal from model biogas.
ARTICLE | doi:10.20944/preprints202002.0129.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Graphene; Nanocomposite; photocatalyst; water splitting; hydrogen
Online: 10 February 2020 (15:20:21 CET)
The present study focuses on the synthesis, characterization, and investigation of a p-n heterojunction photocatalysis. Titanium dioxide (TiO2) can’t alone induce the photocatalytic water splitting due to its wide bandgap, which decreases its catalytic activity in the visible light. To make redshift of absorptivity for the TiO2, Nickel (Ni)-doped Graphene (rGO) supported TiO2 was synthesized. Several characterization techniques have been employed to validate the composition and the light absorption ability of the prepared photocatalysts including TEM, SEM, EDS, XRD, XPS, and UV-Vis spectroscopy. The characterization revealed successful doping of the Ni and TiO2 on the rGO nanosheet. Moreover, the UV-Vis spectroscopy indicated a significant shift of light absorption toward the visible spectrum. The photon-induced evolution of H2 was remarkably enhanced using the prepared Ni-rGO/TiO2 nanocomposite. Furthermore, the optimum ratio of rGO: TiO2: Ni in the hybrids was 10:1:4, while the higher Ni ratio would decrease the photocatalytic activity. The stability of the photocatalyst was also verified during 8 cycles of photocatalytic reactions. The kinetic study revealed the nature of the integrated reaction and the controlling step governing the reaction sequence. .
ARTICLE | doi:10.20944/preprints202001.0348.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: PEBAX; Ag; olefin; membrane; nanoparticle
Online: 29 January 2020 (04:35:25 CET)
PEBAX-2533/metal salt/Al salt membranes were prepared for mixed olefin/paraffin separation. PEBAX-2533 with 80% ether group and 20% amide group was suggested as the polymer matrix for comparison of separation performance according to the functional group ratio in copolymer PEBAX. In addition, Al salts were used to stabilize metal ions for a long time as additives. High permeance was expected with the proportion of high ether groups since these functional groups provided relatively permeable regions. As a result, the PEBAX-2533 composite membrane showed a selectivity of 5 (propylene/propane) with 10 GPU. However, the permeance of membrane was not unexpectedly improved and the selectivity was reduced. The result was analyzed by SEM, FT-RAMAN and TGA, including FT-IR. The reduction in separation performance was determined by FT-IR. From these results, in order to stabilize the metal ions interacting with the polymer through Al(NO3)3, it was concluded that specific ratio of amide group was needed in PEBAX as polymer matrix.
ARTICLE | doi:10.20944/preprints202001.0046.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: CO2; diethyl carbonate; ethanol; dehydrating agent; catalyst
Online: 5 January 2020 (16:58:11 CET)
Excessive CO2 emissions and alternative energy fuels are two major difficult issues. The utilization of CO2 into fine chemicals is an optimal route. Diethyl carbonate (DEC) is an extremely versatile chemical intermediate. DEC is used in gasoline, pharmaceutical, chemical and other fields. DEC synthesis from CO2 and ethanol is a typical green synthetic route. Ni-Cu@Na3PW12O40 catalysts were synthesized by two novel methods of supported and mixed. The catalyst prepared by mixed method showed nice catalytic performance. It was confirmed that water removal was the key to improving conversion efficiency. In the presence of dehydrating agent of ethylene, ethanol conversion increased from ca. 3% to ca. 40%. Propylene oxide (PO) was participated in the reaction and ethanol conversion continued to reach to ca.90% while DEC selectivity dropped by half. Under optimal conditions, our Ni-Cu@Na3PW12O40 catalyst effectively solved the two major issues above.
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: ASP flooding; low permeability oil layer; partial quality tool; maximum injection pressure; oil recovery
Online: 13 November 2019 (03:38:54 CET)
In order to solve the problem of the poor oil displacement effect of high molecular weight alkali/surfactant/polymer (ASP) solution in low permeability reservoirs, Daqing Oilfield uses a partial quality tool to improve the oil displacement effect in low permeability reservoirs. Without changing the oil displacement capability of high molecular weight ASP solution in high permeability oil layers, the ASP solution is actively sheared in low permeability oil layers by using a partial quality tool to increase the injection capability of the solution and improve the overall oil recovery. In order to study the ability of the partial quality tool to improve the oil displacement effect, firstly, the matching degree of high molecular weight ASP solution to low permeability cores is studied, and the ability of quality control tools to change the molecular weight is studied. Then, experimental research on the pressure and oil displacement effect of high molecular weight ASP solution before and after the actions of the partial quality tool is carried out. The results show that ASP solutions with molecular weights of 1900 × 104 and 2500 × 104 have a poor oil displacement effect in low permeability reservoirs. After the action of the partial quality tool, the injection pressure is reduced by 5.22 MPa, and the oil recovery is increased by 7.79%. The injection pressure of the ASP solution after shearing by the partial quality tool is lower than that of the ASP solution with the same molecular weight and concentration without shearing, but the oil recovery is lower. On the whole, the use of the partial quality tool can obviously improve the oil displacement effect in low permeability reservoirs.
ARTICLE | doi:10.20944/preprints201911.0049.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: silk fibroin nanoparticles; cocoon degumming; bombyx mori; ionic liquids ultrasound; autoclave
Online: 6 November 2019 (09:30:22 CET)
In recent years, numerous research studies have shown the excellent characteristics of silk fibroin nanoparticles as a vehicle for drugs delivery and it is foreseeable that their production could reach industrial scale in the coming years. For this reason, it is essential to know all the parameters that affect the formation of nanoparticles in order to standardize the process. Several studies have stated that the process used for sericin removal (degumming) from silk cocoons has a strong impact in the silk fibroin integrity and their mechanical properties after processing it into biomaterials. In this work, silk cocoons were degummed following four standard methods: autoclaving, short alkaline (Na2CO3) boiling, long alkaline (Na2CO3) boiling and ultrasounds. The resultant silk fibroin fibers were dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate and used for nanoparticle synthesis by rapid desolvation in polar organic solvents. The relative efficiencies of the degumming processes and the integrity of the resulting fibroin fibers obtained were analyzed by weight loss, optical microscopy, thermogravimetric analysis, infrared spectroscopy and SDS-PAGE. Particle sizes and morphology were analyzed by Dynamic Light Scattering and Field Emission Scanning Electronic Microscopy. The results showed that the different treatments had a remarkable impact on the integrity of the silk fibroin chains, as confirmed by gel electrophoresis which can be correlated with particle mean size and size distribution changes. The study confirm that all the parameters of the process must be controlled in order to reach an optimum reproducibility of the nanoparticle production.
ARTICLE | doi:10.20944/preprints201911.0027.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: hydrogen; amorphous; silicon carbide; alumina; chemical vapor deposition
Online: 3 November 2019 (18:14:26 CET)
An amorphous silicon carbide (SiC) membrane with H2 permeance of 1.2E-7 mol･m-2･s-1･Pa-1 and excellent H2/CO2 selectivity of 2600 at 673 K was successfully synthesized on a Ni-gamma-alumina-coated alpha-alumina porous support by counter diffusion chemical vapor deposition (CDCVD) using silacycrobutane (SCB) at 788 K. The dominant permeation mechanism for He and H2 in the temperature range 323-673 K was activated diffusion. The SiC active layer was formed in Ni-gamma-Al2O3 intermediate layer. The thermal expansion coefficients mismatch between SiC active layer and Ni-gamma-Al2O3-coated alpha-Al2O3 porous support was eased by the low decomposition temperature of SiC source and membrane structure.
ARTICLE | doi:10.20944/preprints201911.0009.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: ammonia borane; ptni/g-c3n4; hydrogen storage; dehydrogenation
Online: 1 November 2019 (11:27:00 CET)
Graphite carbon nitride (g-C3N4) supported PtNi alloy nanoparticles (NPs) were fabricated via a facile and simple impregnation and chemical reduction method and explored their catalytic performance towards hydrogen evolution from ammonia borane (AB). Interestingly, the resultant Pt0.5Ni0.5/g-C3N4 catalyst affords superior performance, including 100% conversion, 100% H2 selectivity, yielding the extraordinary initial total turnover frequency (TOF) of 250.8 molH2 min-1 (molPt)-1 for hydrogen evolution from AB at 10 °C, a relatively low activation energy of 38.09 kJ mol−1, and a remarkable reusability (at least 10 times), which surpass most of the noble metal heterogeneous catalysts. This notably improved activity is attributed to the charge interaction between PtNi NPs and g-C3N4 support. Especially, the nitrogen-containing functional groups on g-C3N4, serving as the anchoring sites for PtNi NPs, may be beneficial for becoming a uniform distribution and decreasing the particle size for the NPs. Our work not only provides a cost-effective route for constructing high-performance catalysts towards the hydrogen evolution of AB but also prompts the utilization of g-C3N4 in energy fields.
ARTICLE | doi:10.20944/preprints201909.0250.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: ch4 temperature-programmed reduction; methane combustion; pd/zro2 catalyst; reduction; calcination
Online: 21 September 2019 (09:36:45 CEST)
The improvement of the methane combustion activity was observed in cyclic temperature-programmed and isothermal reactions over Pd/ZrO2 catalysts by simple reduction/re-oxidation treatment. The catalytic activity increased during the initial stages of isothermal reaction, and the light-off temperature was lowered as the number of cycles increased in the cyclic temperature-programmed reaction. To reveal the origin of activation, variations in the reduction properties after the activation period were carefully investigated through CH4 temperature-programmed reduction (TPR) measurements. From the CH4-TPR results, it was confirmed that the reduction temperature decreased significantly after activation. The observation of the CH4-TPR peak at relatively low temperatures is directly proportional to the catalytic activity of CH4 combustion. It was therefore concluded that repeated reduction/re-oxidation occurred in the reactant stream, and this phenomenon allowed the combustion reaction to proceed more easily at lower temperatures.
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: hypercrosslinked polymer; p-hydroxy-phthalic acid; pollutants; adsorption; biodegradation
Online: 17 September 2019 (11:36:51 CEST)
Adsorption is an effective strategy for the removal of pollutants from the wastewater. Herein, a 2-hydroxyterephthalic acid (HTC) modified hypercrosslinked polymer (HTC-HCP) is successfully synthesized via Friedel-Crafts reactions, and used as an adsorbent for the different types of pollutants including organic contaminants and heavy metal ions from wastewater. Excellent adsorption capacities are observed for amines (aniline, p-methylaniline (p-MA), p-chloroaniline (p-CA), and p-aminobenzoic acid (p-ABA)), phenols (phenol, p-chlorophenol (4-CP) Bisphenol A (BPA), 1-Naphthol (1-NP)), dyes (rhodamine B (RhB) and methyl orange (MO)), and metal ions (Pb2+, Hg2+, and Cd2+). The resulting polymers exhibited excellent adsorption performance towards these pollutants. Especially, the removal rate of aniline is above 95% in the concentration of 2.5 mg/L in 40 min at 25 °C. The interaction mechanism has been investigated, and confirmed by FTIR and the theoretical calculation results. It is due to surface complexation and chemisorption between adsorbent and adsorbate. The polymer exhibits good performance such as high adsorption capacity, high separation efficiency, biodegradable properties, and easy regeneration, suggesting that its potential technological applications for the removal of organic compounds and heavy metal ions from actual industrial effluent.
ARTICLE | doi:10.20944/preprints201908.0086.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: carbonylation of glycerol; glycerol carbonate; CO2; nanoparticle catalyst; CuO; CeO2
Online: 7 August 2019 (03:43:55 CEST)
Two important types of metal oxide nanoparticle catalysts Copper (II) oxide (CuO) and Cerium oxide (CeO2) are prepared by a suitable method which was traditional precipitation (PT) method at calcination temperature of 400oC for 5h and used for the synthesis of glycerol carbonate GC (C4H6O4) from the direct reaction by the carbonylation of Glycerol GL (C3H8O3) with Carbone Dioxide. The precipitation (PT) was an important route for the preparation of nanoparticles catalyst. The effects of performance of (CuO and CeO2) nanoparticle catalysts on the conversion of glycerol GL, yield of glycerol carbonate GC, selectivity of glycerol carbonate are researched. XRD, XPS, BET, FT-IR, CO2-TPD, H2-TPR are used for the characterization of the prepared catalysts. Comparing the optimal performance between them under reaction conditions were 150 oC, 4MPa (40 bar.), 5h, and both CuO and CeO2 catalyst amount 37.6 % (based on ratio of glycerol weight) by using 2-pyridinecarbonitrate (C6H4N2) as dehydrating agent and dimethylformamide (DMF), (C3H7NO) as solvent. The glycerol conversion (XGL), glycerol carbonate yield (YGC) and glycerol carbonate selectivity (SGC) over 0.7g CuO are 57.151%, 47.524%, and 83.156%, respectively, and glycerol carbonate yield over 0.7 CeO2 is 36.2185% or 35.076%, and the yield of GC could reach as high as 78.234% over 1.73g CeO2, the both catalysts could be easily regenerated by washing with methanol and water after a reaction and then dried at 60 oC overnight after that calcination at 400 oC for 5h without loss of activity after five recycling times, In addition to, the (ICP- MS) results confirmed that the leaching of CuO and CeO2 was below the detection limit.
ARTICLE | doi:10.20944/preprints201907.0249.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: vehicle; shell thickness, coating; focused ion beam; containing cross-linking agents
Online: 23 July 2019 (07:36:14 CEST)
This research was conducted to manufacture thermally expandable microspheres (TEMs) for vehicles’ underbody coating and to apply them on an industrial scale. TEMs heat resistance was studied depending on the ratios of a cross-linking agent and an initiator. This research focused on the content of a cross-linking agent and how it affected the results. The TEMs’ outer shell was thickened to solve the problem of the foam expansion ratio’s reduction that occurred due to the shrinkage after the maximum expansion (Tmax) was reached. After foaming, the cross-sectional thickness and surface of the sample with thickened outer shell were observed. The TEMs with the thickened shell showed the least shrinkage, which indicated excellent shrinkage stability, even after prolonged exposure to heat.
ARTICLE | doi:10.20944/preprints201907.0232.v1
Online: 22 July 2019 (07:46:54 CEST)
This paper focused on the oxidative leaching process of vanadium from vanadium-chromium reducing residue in alkaline medium with MnO2. The effect of experimental parameters including reaction time, reaction temperature, dosage of MnO2, dosage of NaOH, and liquid-to-solid ratio on the leaching efficiency of vanadium had been studied. The results indicated that MnO2 was an efficient oxidant for leaching out of vanadium. The leaching efficiency of vanadium was up to 97.25% under optimal reaction conditions: reaction temperature of 90 ℃, reaction time of 60 min, dosage of MnO2 at 50 wt.%, concentration of NaOH at 30 wt.% and liquid-to-solid at 5:1 mL/g.
ARTICLE | doi:10.20944/preprints201907.0160.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: solar thermal systems; phase change materials; thermoplastic elastomer; mechanical property; photo-thermal performance
Online: 11 July 2019 (11:54:58 CEST)
Traditional phase change composites usually suffer poor mechanical property and easy collapsing in the phase changing process. Herein, a highly flexible phase change composite is fabricated using thermoplastic elastomer as the basic gel and the expanded graphite/paraffin as the filler. This new phase change composite shows a tensile strength of 2.1 MPa and a breaking elongation of 220%. It has a melting enthalpy of 145.4 J•g-1 and a thermal conductivity of 2.2 W•m-1•K-1 with 70% of expanded graphite/paraffin. The thermoplastic elastomer based phase change composite exhibits great reversible property after 200 heating/cooling cycles. This flexible phase change composite demonstrates good photo-thermal energy charging/discharging property and shows great potential to be applied in the solar thermal energy systems.
ARTICLE | doi:10.20944/preprints201907.0087.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: pinning-depinning; evaporation; chemically stripe-patterned surfaces; lattice Boltzmann
Online: 5 July 2019 (04:40:38 CEST)
The liquid-vapor phase change lattice Boltzmann method is used to investigate the pinning-depinning mechanism of the contact line during droplet evaporation on the stripe-patterned surfaces in 3D space. Considering the curvature of the contact line and the direction of the unbalanced Young’s force, the local force balance theory near the stripe boundary is proposed to explain the steady state of the droplets on the stripe-patterned surfaces. An equation is proposed to evaluate the characteristic contact angle of the stabilized droplets. During the evaporation of the droplet, the stick-slip-jump behavior and the CCR-Mixed-CCA mode can be well captured by the lattice Boltzmann simulation. When the contact line is pinned to the stripe boundary, the contact line in the direction perpendicular to the stripes is slowly moving while the curvature of the contact line is gradually increasing. The gradually increasing curvature of the contact line accelerates the movement of the contact line, and the final contact line is detached from the stripe boundary. The research results provide theoretical support and guidance for the design, improvement and application of patterned surfaces in the field of micro-fluidic and evaporation heat transfer.
ARTICLE | doi:10.20944/preprints201906.0284.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: TEM; underbody coating; UBC; FIB; thermally expandable microspheres
Online: 27 June 2019 (07:52:13 CEST)
This research was conducted to manufacture thermally expandable microspheres (TEMs) for vehicles’ underbody coating and to apply them on an industrial scale. TEMs heat resistance was studied depending on the ratios of a cross-linking agent and an initiator. This research focused on the content of a cross-linking agent and how it affected the results. The TEMs’ outer shell was thickened to solve the problem of the foam expansion ratio’s reduction that occurred due to the shrinkage after the maximum expansion (Tmax) was reached. After foaming, the cross-sectional thickness and surface of the sample with thickened outer shell were observed. The TEMs with the thickened shell showed the least shrinkage, which indicated excellent shrinkage stability, even after prolonged exposure to heat.
ARTICLE | doi:10.20944/preprints201906.0055.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Supercritical carbon dioxide, Modeling, Acid, Artificial intelligence, Solubility
Online: 7 June 2019 (12:18:48 CEST)
In the present work, a novel and the robust computational investigation is carried out to estimate solubility of different acids in supercritical carbon dioxide. Four different algorithms such as radial basis function artificial neural network, Multi-layer Perceptron artificial neural network, Least squares support vector machine and adaptive neuro-fuzzy inference system are developed to predict the solubility of different acids in carbon dioxide based on the temperature, pressure, hydrogen number, carbon number, molecular weight, and acid dissociation constant of acid. In the purpose of best evaluation of proposed models, different graphical and statistical analyses and also a novel sensitivity analysis are carried out. The present study proposed the great manners for best acid solubility estimation in supercritical carbon dioxide, which can be helpful for engineers and chemists to predict operational conditions in industries.
ARTICLE | doi:10.20944/preprints201903.0068.v2
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: germanium; supported liquid membrane; transport; Cyanex 923; modeling
Online: 29 May 2019 (04:54:50 CEST)
A transport process was studied from an aqueous solution containing oxalic acid and 100 mg/L Ge using a flat sheet supported liquid membrane (FSSLM) system. Cyanex 923 immobilized in a polytetrafluoroethylene membrane was employed as a carrier. The solution chemistry and related diagrams were applied to study the transport of germanium. The effectual parameters such as oxalic acid, carrier concentration, and strip reagent composition were evaluated in this study. Based on the results, the oxalic acid concentration of 0.075 mol/L and the carrier concentration of 20 %v/v were the condition in which the efficient germanium transport occurred. Among strip reagents, NaOH (0.04-0.1 mol/L) had the best efficiency to transport germanium through the SLM system. Furthermore, the permeation model was obtained to calculate the mass transfer resistances of the membrane (Δm) and feed (Δf) phases. According to the results, the values of 1 and 1345 s/cm were evaluated for Δm and Δf, respectively.
ARTICLE | doi:10.20944/preprints201905.0298.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: silver nanoparticles; nano-TiO2; nano- ZnO; nanohybrids; antibacterial
Online: 24 May 2019 (12:44:36 CEST)
This work emphasizes to use silver decorative method to enhance the antibacterial activity of TiO2 and ZnO nanoparticles. These silver decorated nanoparticles (hybrid nanoparticles) were synthesized by using sodium borohydride as a reducing agent, with the weight ratio of Ag precursors: oxide nanoparticles = 1: 30. The morphology and optical property of these hybrid nanoparticles were investigated using transmission electron microscopy (TEM) and UV–vis spectroscopy. The agar-well diffusion method was used to evaluate their antibacterial activity against both Staphylococcus aureus and Escherichia coli bacteria, with or without light irradiation. The TEM images indicated clearly that silver nanoparticles (AgNPs, 5-10 nm) were well deposited on the surface of nano-TiO2 particles (30-60 nm). Besides, smaller AgNPs (< 2 nm) were dispersed on the surface of nano-ZnO particles (20-50 nm). UV-vis spectra confirmed that the hybridization of Ag and oxide nanoparticles led to shift the absorption edge of oxide nanoparticles to the lower energy region (visible region). The antibacterial tests indicated that both oxide pure nanoparticles did not exhibit inhibitory against bacteria, with or without light irradiation. However, the presence of AgNPs in their hybrids, even at low content (< 40 mg/mL) leads to a good antibacterial activity and the higher inhibition zones under light irradiation as compared to that in dark was observed.
ARTICLE | doi:10.20944/preprints201905.0045.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: fuel cell; carbon nanotube; catalyst; platinum-ruthenium
Online: 6 May 2019 (10:05:30 CEST)
Due to low working temperature, high energy density and low pollution, proton exchange fuel cells have been investigated under different operating conditions in different applications. Using platinum catalyst in methanol fuel cell leads to increasing the cost of this kind of fuel cells which is considered as a barrier to commercialism of this technology. For this reason, a lot of efforts have been made to reduce the loading of the catalyst required on different supports. In this study, carbon black (CB) and carbon nanotubes (CNT) have been used as catalyst supports of the fuel cell as well as using the double-metal combination of platinum-ruthenium (PtRu) as anode electrode catalyst and platinum (Pt) as cathode electrode catalyst. The performance of these two types of the electro-catalyst in oxidation reaction of methanol has been compared based on electrochemical tests. Results showed that the carbon nanotubes increase the performance of the micro-fuel cell by 37% at maximum power density, compared to the carbon black. Based on thee-electrode tests of chronoamperometry and voltammetry, it was found that oxidation onset potential of methanol for CNT has been around 20% less than CB, leading to the kinetic improvement of the oxidation reaction. In addition, the active electrochemical surface area of catalyst has been increased up to 90% by using CNT compared to CB which shows the significant rise of the electrocatalytic activity in CNT supported catalyst with 62% increase in current density of methanol oxidation reaction respect to CB supported one. Moreover, the resistance of CNT supported sample to poisonous intermediate species has been found 3% more than CB supported one. According to the chronoamperometry test results, it was concluded that the performance and sustainability of NCT electro-catalyst shows remarkable improvement compared to CB electro-catalyst in long term.
ARTICLE | doi:10.20944/preprints201904.0177.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: lipid peroxidation; membrane elasticity; mesoporous silica nanoparticles; myricetin; myricitrin; nanomechanics; protective effects of flavonoids; quercetin
Online: 16 April 2019 (09:54:03 CEST)
Flavonoids, polyphenols with anti-oxidative activity have high potential as novel therapeutics for neurodegenerative disease, but their applicability is rendered by their poor water solubility and chemical instability under physiological conditions. In this study, this is overcome by delivering flavonoids to model cell membranes (unsaturated DOPC) using prepared and characterized biodegradable mesoporous silica nanoparticles, MSNs. Quercetin, myricetin and myricitrin have been investigated in order to determine the relationship between flavonoid structure and protective activity towards oxidative stress i.e. lipid peroxidation induced by addition of hydrogen peroxide and/or Cu2+ ions. Among investigated flavonoids, quercetin showed the most enhanced and prolonged protective anti-oxidative activity. The nanomechanical (Young modulus) measurement of the MSNs treated DOPC membranes during lipid peroxidation confirmed attenuated membrane damage. By applying combination of experimental techniques (AFM, force spectroscopy, ELS, DLS), this work generated detailed knowledge about the effects of flavonoid loaded MSNs on the elasticity of model membranes, especially under oxidative stress conditions. Results from this study will pave the way towards the development of innovative and improved markers for oxidative stress-associated neurological disorders. In addition, the obtained could be extended to designing effective delivery systems of other high potential bioactive molecules with an aim to improve human health in general.
ARTICLE | doi:10.20944/preprints201904.0020.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Hydrotreating, mesoporous sulfide materials, waste Jatropha biomass, drop-in biofuels, upgrading technology
Online: 1 April 2019 (13:51:53 CEST)
The bio-oil was largely produced by thermal pyrolysis of Jatropha-derived biomass wastes (denoted as Jatropha bio-oil) using a Pilot Plant with a capacity of 20 kg h-1 at Thailand Institute of Scientific and Technological Research (TISTR), Thailand. Jatropha bio-oil is an unconventional type of bio-oil, which is mostly composed of fatty acids, fatty acid methyl esters, fatty acid amides and derivatives, and consequently it contained large amounts of heteroatoms (oxygen ~ 20 wt.%, nitrogen ~ 5 wt.%, sulfur ~ 1000 ppm.). The heteroatoms, nitrogen especially, are highly poisonous to the metal or sulfide catalysts for upgrading of Jatropha bio-oil. To overcome this technical problem, we reported a stepwise strategy for hydrotreating of 100 wt% Jatropha bio-oil over mesoporous sulfide catalysts of CoMo/γ-Al2O3 and NiMo/γ-Al2O3 to produce drop-in transport fuels, such as gasoline- and diesel-like fuels. This study is very different from our recent work on co-processing of Jatropha bio-oil (ca. 10 wt%) with petroleum distillates to produce a hydrotreated oil as a diesel-like fuel (Chen et al., Catalysts 2018, 8, 59; http://dx.doi.org/10.3390/catal8020059). Jatropha bio-oil was pre-treated through a slurry-type high pressure reactor under severe condition, resulting in a pre-treated Jatropha bio-oil with relatively low amounts of heteroatoms (oxygen < 20 wt.%, nitrogen < 2 wt.%, sulfur < 500 ppm.). The light and middle distillates of pre-hydrotreated Jatropha bio oil was then separated by distillation at temperature below 240 oC, and the temperature of 240-360 oC. Deep hydrotreating of light distillates over sulfide CoMo/γ-Al2O3 catalyst was performed on a batch-type high pressure reactor at 350 oC and 7 MPa of H2 gas for 5 h. The hydrotreated oil was a gasoline-like fuel, which contained 29.5 vol.% of n-paraffins, 14.4 vol.% of iso-paraffins, 4.5 vol.% of olefins, 21.4 vol. % of naphthene compounds and 29.6 wt.% of aromatic compounds, and little amounts of heteroatoms (nearly no oxygen and sulfur, and less than 50 ppm of nitrogen), corresponding to an octane number of 44, and it would be suitable for blending with petro-gasoline. The hydrotreating of middle distillates over sulfide NiMo/γ-Al2O3 catalyst using the same reaction condition produced a hydrotreating oil with diesel-like composition, low amounts of heteroatoms (no oxygen and less than 50 ppm of sulfur and nitrogen), and a cetane number of 60, which would be suitable for use in drop-in diesel fuel.
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: polyethylene; nanocomposites; silver nanoparticles; Fe3O4-Ag hybrid nanoparticles; antibacterial activity
Online: 19 March 2019 (07:54:54 CET)
We report here the synthesis of uniform nanospheres-like silver nanoparticles (AgNPs, 5-10 nm) and the dumbbell-like Fe3O4-Ag hybrid nanoparticles (FeAgNPs, 8-16 nm) by the use of seeding growth method in the presence of oleic acid (OA)/oleylamine (OLA) as surfactants. The antibacterial activity of pure nanoparticles and nanocomposites by monitoring the bacterial lag–log growth has been investigated. The electron transfer from AgNPs to Fe3O4NPs which enhances the biological of silver nanoparticles has been proven by nanoscale Raman spectroscopy. The lamellae structure in the spherulite of FeAgNPs/PE nanocomposites seems play the key role to the antibacterial activity of nanocomposites, which has been proven by nanoscale AFM-IR. An atomic force microscopy coupled with nanoscale infrared microscopy (AFM-IR) is use to highlight the distribution of nanoparticles on the surface of nanocomposite at the nanoscale. The presence of FeAgNPs in PE nanocomposites has a better antibacterial activity than that reinforced by AgNPs due to the faster Ag+ release rate from the Fe3O4-Ag hybrid nanoparticles and the ionization of AgNPs in hybrid nanostructure.
ARTICLE | doi:10.20944/preprints201903.0159.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Taguchi method; experimental design; optimization; scandium; extraction; sulfuric acid
Online: 15 March 2019 (09:34:01 CET)
Bauxite residue is the voluminous by-product of alumina production after Bayer process. Its high alkalinity causes disposal problems and harmful environmental impacts. However, the residue contains significant amounts of valuable elements such as rare earth elements including scandium. Greek bauxite residue contains a high amount of scandium close to its main resources. Taking into account scandium limited availability coupled with its high demand in modern technology, bauxite residue could be considered as a potential resource for scandium recovery. In this study, the optimization of scandium extraction from bauxite residue with sulfuric acid is investigated using Taguchi methodology. Based on previous studies acid molarity, leaching time, solid/liquid ratio and reaction temperature were selected as control parameters for the selective Sc recovery. Method optimization targeted the highest concentration of scandium combined with the lowest concentration of iron without taking into account applications constraints. The predicted values resulted by Taguchi methodology were affirmed by a confirmation experiment conducted at optimal conditions. Regression analysis provided the respective equations to be applied on several conditions depending on different applications.
ARTICLE | doi:10.20944/preprints201903.0134.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: Carbon-coated separator; polysulfide; shuttle effect; lithium-sulfur batteries
Online: 12 March 2019 (10:02:03 CET)
Lithium sulfur (Li–S) batteries are expected to be very useful for next-generation transportation and grid storage because of their high energy density and low cost. However, their low active material utilization and poor cycle life limit their practical application. The use of a carbon-coated separator in these batteries serves to inhibit the migration of the lithium polysulfide intermediate and increases the recyclability. We report the extent to which the electrochemical performance of Li–S battery systems depends on the characteristics of the carbon coating of the separator. Carbon-coated separators containing different ratios of carbon black (Super-P) and vapor-grown-carbon-fibers (VGCF) were prepared and evaluated in Li–S batteries. The results showed that larger amounts of Super-P on the carbon-coated separator enhanced the electrochemical performance of Li–S batteries; for instance, the pure Super-P coating exhibited the highest discharge capacity (602.1 mAh g-1 at 150 cycles) with a Coulombic efficiency exceeding 95%. Furthermore, the separators with the pure Super-P coating had a smaller pore structure, and hence limited polysulfide migration, compared to separators containing Super-P/VGCF mixtures. These results indicate that it is necessary to control the porosity of the porous membrane to control the movement of the lithium polysulfide.
ARTICLE | doi:10.3390/sci1010013.v1
Subject: Chemistry And Materials Science, Chemical Engineering Keywords: hybrid phosphite; crystal structure; thermal behavior; biological activities; antimicrobial; micro-organisms
Online: 12 March 2019 (00:00:00 CET)
A novel hybrid phosphite [(C4N2H14)Co(H2PO3)4·2H2O] was synthesized with 1,4- diaminobutane (dabn) as a structure-directing agent using slow evaporation method. Single crystal X-ray diffraction analysis showed that it crystallizes in the triclinic system (S.G: P-1, #2) with the following unit cell parameters (Å, °) a = 5.4814 (3), b = 7.5515 (4), c = 10.8548 (6), α = 88.001 (4), β = 88.707 (5), γ = 85.126 (5). The crystal structure was built up from corner-sharing [CoO6]-octahedrons, forming chains parallel to , which are interconnected by H2PO3 pseudo-pyramid units. The diprotonated 1,4-diaminobutane molecules, residing between the parallel chains, interacted with the inorganic moiety via hydrogen bonds leading thus to the formation of the 3D crystal structure. The Fourier transform infrared result exhibited characteristic bands corresponding to the phosphite group and the organic molecule. The thermal decomposition of the compound consists mainly of the loss of the organic moiety and the water molecules. The biological tests exhibited significant activity against Candida albicans and Escherichia coli strains in all used concentrations, while less activity was pronounced when tested against Staphylococcus epidermidis and Saccharomyces cerevisiae, while there was no activity against the nematode model Steinernema feltiae.