REVIEW | doi:10.20944/preprints202011.0398.v1
Subject: Chemistry, Electrochemistry Keywords: bioelectrocatalysis; nanostructured electrodes; protein engineering; bioelectrosynthesis; photo-bioelectrocatalysis
Online: 16 November 2020 (08:32:45 CET)
Bioelectrocatalysis has become one of important research fields in electrochemistry and provided a firm base for an important technology for application to various bioelectrochemical devices such as biosensors, biofuel cells, and biosupercapacitors. The understanding and technology in bioelectrocatalysis have been greatly improved by introducing nanostructured electrode materials and protein-engineering methods over the last few decades. Recently, the electro-enzymatic production of renewable energy resources and useful organic compounds (bioelectrosynthesis) also attracts worldwide attention. In this review, we summarize recent progress in applications of enzymatic bioelectrocatalysis.
Fri, 4 September 2020
ARTICLE | doi:10.20944/preprints202009.0077.v1
Subject: Chemistry, Electrochemistry Keywords: ionic imprinted polypyrrole; zinc oxide nanorods; mercury ions; diazonium salts; electrochemical sensor
Online: 4 September 2020 (03:28:26 CEST)
A biomimetic, ion-imprinted polymer (IIP) was prepared by electropolymerization of pyrrole at the surface of gold electrodes decorated with vertically grown ZnO nanorods. The vertical growth of the nanorods was achieved via an ultrathin aryl monolayer grafted by reduction of diazonium salt precursor. Pyrrole was polymerized in the presence of L-cysteine as chelatant agent and Hg(II) (template). Hg(II)-imprinted polypyrrole (PPy) was also prepared on bare gold electrode in order to compare the two methods of sensor design (Au-ZnO-IIP vs Au-IIP). Non-imprinted PPy was prepared in the same conditions, however in the absence of any Hg2+ template. The strategy combining diazonium salt modification and ZnO nanorod decoration of gold electrodes permitted to increase considerably the specific surface and thus to improve the sensor performances. The limit of detection (LOD) of the designed sensor was ~1 pM, the lowest value ever reported in literature. The dissociation constants between PPy and Hg2+ were estimated at [Kd1 = (7.89 ± 3.63) mM and Kd2 = (38.10 ± 9.22) pM]. The sensitivity of the designed sensor was found to be 0.692 ± 0.034 μA/pM. The Au-ZnO-IIP was found to be highly selective towards Hg(II) compared to cadmium, lead and copper ions. This sensor design strategy could open up new horizons in monitoring toxic heavy metal ions in water and therefore contribute to enhance environmental quality.
Wed, 26 August 2020
ARTICLE | doi:10.20944/preprints202008.0564.v1
Subject: Chemistry, Electrochemistry Keywords: Li-ion battery; computer simulation; numerical method; software
Online: 26 August 2020 (07:45:40 CEST)
This code provides computational facilities to simulate current versus time during the charging of Li-ion cells at desire constant voltage by considering multiscale physical phenomena. This code only considers a powder of active materials (at microscale or nanoscale) and a small part of electrolyte around it as a half cell. Then it is extended to a complete cell by applying correct boundary conditions. This code is very useful by modifying code parameters to understand the effect of the complex shape of active materials powder (surface area and powder size), kind of electrolyte, and the applied voltages on the charging response of Li-ion cell. As a summary, a microscale approach to the design of Li-ion cells has been provided via this code.
Thu, 23 July 2020
ARTICLE | doi:10.20944/preprints202007.0561.v1
Subject: Chemistry, Electrochemistry Keywords: perfluorooctanoic acid; emerging contaminant; defluorination; platinum; electro-oxidation
Online: 23 July 2020 (12:36:19 CEST)
Perfluorooctanoic acid (PFOA), C7F15COOH, has been widely employed over the past fifty years, causing an environmental problem due to its dispersion and low biodegradability. Furthermore, the high stability of this molecule, conferred by the high strength of the C-F bond makes it very difficult to remove. In this work, electrochemical techniques are applied for PFOA degradation in view to study the influence of the cathode on defluorination. For this purpose, boron doped diamond (BDD), Pt, Zr and stainless steel have been tested as cathodes working with BDD anode at low electrolyte concentration (3.5 mM) to degrade PFOA at 100 mg/L. Among these cathodic materials, Pt improves the defluorination reaction. The electro-degradation of a PFOA molecule starts by a direct exchange of one electron at the anode and then follows a complex mechanism involving reaction with hydroxyl radicals and adsorbed hydrogen on the cathode. It is assumed that Pt acts as an electrocatalyst, enhancing PFOA defluorination by the reduction reaction of perfluorinated carbonyl intermediates on the cathode. The defluorinated intermediates are then more easily oxidized by HO• radicals. Hence, high mineralization (xTOC: 76.1%) and defluorination degrees (xF-: 58.6%) were reached with Pt working at current density j = 7.9 mA/cm2. This BDD-Pt system reaches a higher efficiency in terms of defluorination for a given electrical charge than previous works reported in literature. Influence of the electrolyte composition and initial pH are also explored.
Mon, 20 July 2020
REVIEW | doi:10.20944/preprints202007.0459.v1
Subject: Chemistry, Electrochemistry Keywords: current-potential curve; multi-enzymatic cascades; multi-analyte detection; mass-transfer-controlled amperometric response; potentiometric coulometry
Online: 20 July 2020 (08:16:47 CEST)
Bioelectrocatalysis provides the intrinsic catalytic-functions of redox enzymes to non-specific electrode reactions and is the most important and basic concept for biosensors. This review starts by describing fundamental characteristics of bioelectrocatalytic reactions in mediated and direct electron transfer types from a theoretical viewpoint and summarizes amperometric biosensors based on multi-enzymatic cascades and for multi-analyte detection. The review also introduces prospective aspects of two new concepts of biosensors: mass-transfer-controlled (pseudo)steady-state amperometry at microelectrodes with enhanced enzymatic activity without calibration curves and potentiometric coulometry at enzyme/mediator-immobilized biosensors for absolute determination.
Tue, 14 July 2020
ARTICLE | doi:10.20944/preprints202007.0298.v1
Subject: Chemistry, Electrochemistry Keywords: Carbon nanotube; Functionalization; Heteroatoms; Electrochemically active surface; Oxygen reduction reaction; Corrosion stability; Alkaline media
Online: 14 July 2020 (11:16:31 CEST)
The influence of the type and amount of oxygen (O), nitrogen (N), and/or phosphorus (P) heteroatoms on the surface of carbon nanotube (CNT) on stability and catalytic activity in the oxygen reduction reaction (ORR) was investigated in alkaline media. It is shown that the functionalization of CNT leads to the growth of the electrochemically active surface and to an increase in the activity in ORR. At the same time, a decrease in stability is observed after the functionalization of CNT under accelerated corrosion testing in an alkaline media. These results are most significant on CNT after functionalization in HNO3 due to the formation of a large number of structural defects. However, the subsequent doping by N and / or P atoms provides a further activity increase and enhances the corrosion stability of CNT. Thus, as shown by the studies of characteristic parameters (SEAS, E1/2, corrosion stability), CNT doped with N and NP are a promising catalytic system that can be recommended for use as fuel cell cathodes. An important condition for effective doping is the synthesis of carboxyl and carbonyl oxygen containing group on the surface of CNT.
Fri, 3 July 2020
ARTICLE | doi:10.20944/preprints202007.0031.v1
Subject: Chemistry, Electrochemistry Keywords: spin dependent electrochemistry; water splitting; nickel; chirality; OER
Online: 3 July 2020 (09:09:56 CEST)
Results are presented concerning the influence on the water splitting process of enantiopure tartaric acid present in bulk solution. Stainless steel and electrodeposited nickel are used as working electrode (WE) surface. The latter is obtained by electrodeposition on the two poles of a magnet. The influence and role played by the chiral compound in solution has been assessed by comparing the current values, in cyclic voltammetry (CV) experiments, recorded in the potential range at which oxygen evolution reaction (OER) occurs. In the case of tartaric acid and nickel WE a spin polarization of about 4 % is found. The use of the chiral environment (bulk solution) and ferromagnetic chiral Ni electrode allows for observing the OER at a more favourable potential: about 50 mV (i.e. a cathodic, less positive, shift of the potential at which the oxygen evolution is observed).
Fri, 10 April 2020
ARTICLE | doi:10.20944/preprints202004.0169.v1
Subject: Chemistry, Electrochemistry Keywords: black Si; antireﬂection; photo-anode; water splitting9
Online: 10 April 2020 (07:51:31 CEST)
The fabrication and characterisation of photo-anodes based on black-Si (b-Si) are presented using a photo-electrochemical cell in NaOH solution. Black-Si was fabricated by maskless dry plasma etching and was conformally coated by tens-of-nm of TiO2 using atomic layer deposition (ALD) with a top layer of CoOx cocatalyst deposited by pulsed laser deposition (PLD). Low reﬂectivity R < % of Black-Si over the entire visible and near-IR (λ < 2 µm) spectral range is favourable in better absorption of light while an increased surface area facilities larger current densities. Photoelectrochemical performance of the heterostructured photoanode is discussed in terms of n-n junction between b-Si and TiO2.
Mon, 24 February 2020
ARTICLE | doi:10.20944/preprints202002.0345.v1
Subject: Chemistry, Electrochemistry Keywords: platinum electrocatalys; PtCu/C; oxygen electroreduction; methanol electrooxidation; catalyst activity; durability; fuel cell life tests; de-alloyed catalysts; PEM FC
Online: 24 February 2020 (03:56:11 CET)
Behavior of supported alloyed and de-alloyed platinum-copper catalysts, which contained 14% - 27% wt. of Pt, was studied in the reactions of methanol electrooxidation (MOR) and oxygen electroreduction (ORR) in 0.1 M HClO4 solutions. Alloyed PtCux/C catalysts were prepared by a multistage sequential deposition of copper and platinum onto a Vulcan XC72 dispersed carbon support. De-alloyed PtCux-y/C catalysts were prepared by PtCux/C materials pretreatment in acid solutions. The effects of the catalysts initial composition and the acid treatment condition on their composition, structure, and catalytic activity in MOR and ORR were studied. Functional characteristics of platinum-copper catalysts were compared with those of commercial Pt/C catalysts when tested, both in an electrochemical cell and in H2/Air membrane-electrode assembly (MEA). It was shown that the acid pretreatment of platinum-copper catalysts practically does not have negative effect on their catalytic activity, but it reduces the amount of copper passing into the solution during the subsequent electrochemical study. The activity of platinum-copper catalysts in the MOR and the current-voltage characteristics of the H2/Air PEMFC MEAs measured in the process of their life tests were much higher than those of the Pt/C catalysts.
Fri, 21 February 2020
ARTICLE | doi:10.20944/preprints202002.0297.v1
Subject: Chemistry, Electrochemistry Keywords: light alloys; magnesium; corrosion; vanadate; phosphate; fluoride; inhibition; conversion coating
Online: 21 February 2020 (02:21:19 CET)
The anodic polarization response of magnesium alloy AZ31 was characterized during exposure to aerated 0.1M NaCl solutions with millimolar additions of NaVO3, Na3PO4, Na2HPO4, NaF and various pairings to assess their ability to inhibit corrosion kinetics and retard localized corrosion. Each of the candidate inhibitors reduced the corrosion rate of the alloy to some degree. A Na3PO4 - NaVO3 pair produced a powerful inhibiting response decreasing the corrosion rate to about 10-7 A/cm2, which was two orders of magnitude lower than the uninhibited control case. A Bliss Independence assessment indicated that this inhibitor pair acted synergistically. A Na2HPO4 - NaVO3 pair reduced the corrosion rate to 10-6 A/cm2 but was not assessed to be acting synergistically. The NaVO3 - NaF pair did not reduce the corrosion rate significantly compared to the control case and was an antagonistic pairing. SEM imaging showed film formation due to exposure, which appears to be the origins of the observed inhibition. The resistance to localized corrosion was assessed as the difference in the breakdown potential and the corrosion potential with larger values indicating a lower probability of localized corrosion during free corrosion exposures. Effects of the inhibitors on this characteristic were mixed, but each of the inhibitor pairs yielded potential differences in excess of 100mV. A conceptual conversion coating process based on a mixture of vanadate and phosphate compounds were demonstrated. A fluoride-bearing formulation produced coatings whose total impedance was increased by a factor or 2 compared to an uncoated control. A fluoride-free formulation produced coatings whose corrosion resistance was increased by more than a factor of 3.
Sun, 16 February 2020
REVIEW | doi:10.20944/preprints202002.0215.v1
Subject: Chemistry, Electrochemistry Keywords: hydrogen evolution reaction; catalysis; supported catalysts; single atom catalysts
Online: 16 February 2020 (12:57:18 CET)
Hydrogen evolution reaction (HER) is one of the most important reaction in electrochemistry. This is not only because it is the simplest way to produce high purity hydrogen and the fact that it is the side reaction in many other technologies. HER actually shaped current electrochemistry because it was in focus of active research for so many years (and it still is). The number of catalysts investigated for HER is immense, and it is impossible to overview them all. In fact, it seems that the complexity of the field overcomes the complexity of HER. The aim of this review is to point out some of the latest developments in HER catalysis, current directions and some of the missing links between a single crystal, nanosized supported catalysts and, recently emerging, single atom catalysts for HER
Mon, 3 February 2020
REVIEW | doi:10.20944/preprints202002.0031.v1
Subject: Chemistry, Electrochemistry Keywords: direct-electron transfer-type bioelectrocatalysis; nanostructures; mesoporous electrodes, curvature effect; protein engineering; bi-directional bioelectrocatalysis; hydrogenase; fructose dehydrogenase; bilirubin oxidase; formate dehydrogenase; ferredoxin-NADP+ reductase
Online: 3 February 2020 (13:34:02 CET)
Direct electron transfer (DET)-type bioelectrocatalysis, which couples electrode reactions and catalytic functions of redox enzymes without any redox mediator, is one of the most intriguing subjects studied over the past decades in the field of bioelectrochemistry. In order to realize the DET-type bioelectrocatalysis and to improve the performance, nanostructures of the electrode surface have to be carefully tuned for each enzyme. In addition, enzymes can also be tuned by protein engineering approach for the DET-type reaction. This review summarizes the resent progresses in this field of the research, while taking into consideration of the importance of nanostructure of electrodes as well as redox enzymes. Described are basic concepts and theoretical aspects of DET-type bioelectrocatalysis, significance of nanostructures as scaffolds for DET-type reactions, protein engineering approached for DET-type reactions, and concepts and facts of bidirectional DET-type reactions, from a cross-disciplinary viewpoint.
Sun, 12 January 2020
ARTICLE | doi:10.20944/preprints202001.0118.v1
Subject: Chemistry, Electrochemistry Keywords: ZnO-NPs; corrosion; synthesis; carbon steel; convolvulus; leaf; extract
Online: 12 January 2020 (13:53:53 CET)
This paper studies the use of zinc oxide nanoparticles (ZnO-NPs) synthesized using an extract of convolvulus leaves and expired ZnCl2, as an efficient inhibitor for carbon steel corrosion in 1M HCl solution. ZnO-NPs are characterized by Fourier-transform infrared spectrophotometer (FTIR) and UV–Vis analysis. The technique of weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) has also been used to investigate the prevention of carbon steel corrosion in 1M HCl. The results showed that the efficiency of restraint increased when the concentration of ZnO-NPs was raised to 91% and that the inhibition efficiency is still high despite its decrease at high temperature, and it acts as a mixed-type inhibitor A sample of carbon steel with the protective inhibitor layer on top was immersed for 20 hours and observed; an increase in the charge transfer resistance (Rct) and stability of the inhibitor was noticed after 6 hours. Adsorption isotherm models demonstrated that the inhibitor adsorption mechanism on the carbon steel surface followed Langmuir, more than Freundlich and Temkin, behavior. The thermodynamic parameters showed that the adsorption process is a mixed adsorption, spontaneous, and exothermic. The results illustrated that the acid medium was a strong inhibitor of carbon steel corrosion. Scanning electron microscope (SEM) showed that the ZnO-NPs formed a good protective film on the carbon steel surface.
Fri, 20 December 2019
ARTICLE | doi:10.20944/preprints201912.0267.v1
Subject: Chemistry, Electrochemistry Keywords: adsorption; coatings; poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate); corrosion tests; atomic force microscopy
Online: 20 December 2019 (07:00:55 CET)
Poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) named further PVBA was investigated as protective coating for copper corrosion in 0.9 % NaCl solution using electrochemical measurements such as, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization associated with Atomic Force Microscopy (AFM). The PVBA coating on the copper surface (Cu-PVBA) was modeled in methanol containing PVBA. Its inhibitory properties against corrosion was comparatively discussed with those of the copper sample treated in methanol without polymer (Cu-Me) and of untreated sample (standard copper). A protective performance of PVBA coating of 80 % was computed from electrochemical measurements, for copper corrosion in NaCl solution. Also, AFM images designed a specific surface morphology of coated surface with PVBA, clearly highlighting a polymer film adsorbed on the copper surface, which presents certain deterioration after corrosion, but metal surface was not significantly affected compared to those of untreated samples or treated in methanol, in the absence of PVBA.
Tue, 19 November 2019
ARTICLE | doi:10.20944/preprints201911.0211.v1
Subject: Chemistry, Electrochemistry Keywords: polypyrrole; diazonium; multiwalled carbon nanotubes; chelator; heavy metal ions; electrochemical sensors
Online: 19 November 2019 (03:50:04 CET)
Highly sensitive multicomponent materials designed for the recognition of hazardous compounds request a detailed knowledge of interfacial chemistry. It is a key parameter in the construction of the sensing (macro)molecular architectures. In this work, multi-walled carbon nanotubes (in short, CNTs) were deposited on diazonium-modified flexible ITO electrodes prior to electropolymerization of pyrrole. This three step process, including diazoniumelectroreduction, deposition of CNTs and electropolymerization, provided adhesively bonded polypyrrole-wrapped CNT composite coatings on aminophenyl-modified flexible ITO sheets. The aminophenyl (AP) groups were attached to ITO by electroreduction of the in situ generated aminobenzenediazonium compound in aqueous, acidic medium. For the first time, polypyrrole (PPy) was electrodeposited in the presence of both benzenesulfonic acid (dopant) and ethylene glycol-bis(2-aminoethylether)-tetraacetic acid (EGTA) which acts as a chelator. The flexible electrodes were characterized by XPS, Raman and scanning electron microscopy (SEM) which provided strong supporting evidence for the wrapping of CNTs by the electrodeposited PPy. Indeed, the diameter of the nanotubes increased from 2-9 nm to ~24-35 nm for one voltammetric cycle and further to ~29-45 nm for 5 cycles. The PPy/CNT/NH2-ITO films generated by this strategy exhibit significantly improved stability and higher conductivity compared to a similar PPy coating without any embedded CNTs as assessed by from electrochemical impedance spectroscopy measurements. The potentiometric response was linear in the 10-8−3×10-7 mol.L-1Pb(II) concentration range and the detection limit was 2.9×10-9 mol.L-1 at S/N=3. The EGTA was found to drastically improve selectivity forPb(II) over Cu(II). To account for this improvement, density functional theory (DFT) was employed to calculate the EGTA-metal ion interaction energy which was found to be -374.6 and -116.4 kJ/mol for Pb(II) and Cu(II), respectively, considering solvation effects. This work demonstrates the power of a subtle combination of diazonium coupling agent, CNTs, chelators and conductive polymers to design high-performance electrochemical sensors for environmental applications.
Sun, 17 November 2019
REVIEW | doi:10.20944/preprints201911.0204.v1
Online: 17 November 2019 (13:28:21 CET)
Developing sustainable and renewable energy sources is critical as higher and higher global energy and environmental challenges arise. Hydrogen has the highest mass/energy density of any fuel and is considered one of the best sources of clean energy. Water splitting is regarded as one of the most promising solutions for hydrogen production on a large scale. Highly efficient, durable and cost-effective catalysts for hydrogen evolution reaction (HER) are critical in the realization of this goal. Among many materials proposed, graphene-based materials offer some unique properties for HER catalysis. In this review, we present recent progress on development of graphene-based electrocatalysts toward HER throughout the past few years.
Wed, 16 October 2019
ARTICLE | doi:10.20944/preprints201910.0177.v1
Subject: Chemistry, Electrochemistry Keywords: oxide ion conductivity; perovskite oxide; molecular dynamics simulation; ceramics electrolyte
Online: 16 October 2019 (04:55:22 CEST)
The molecular dynamics simulation has been used to investigate the structural and transport properties of (Ba0.5-xSrx)La0.5InO3-δ (x=0, 0.1, 0.2) oxygen-ion conductor. The previous studies reported that the ionic conductivity of Ba-doped LaInO3 decreases because Ba dopant forms narrow oxygen path in the lattice, which could hinder the diffusion of oxygen ion. In this study, we reveal the mechanism to improve the ionic conductivity by Ba and Sr co-doping on La site in LaInO3 perovskite oxide. The results show that the ionic conductivity of (Ba0.5-xSrx)La0.5InO3-δ increases with increasing numbers of Sr ions, which oxygen diffusion paths including Sr ion have larger critical radius than Ba ions. The RDF calculations showed the heights of peak in composition including Sr ions is lower and broaden, so oxygen ions moved easily into other oxygen sites.
Tue, 10 September 2019
Subject: Chemistry, Electrochemistry Keywords: titanium dental implant; vitamin D3; bioactive coating; anticorrosion protection; EIS; DFT
Online: 10 September 2019 (11:35:26 CEST)
In recent years extensive studies have been continuously undertaken on the design of bioactive and biomimetic dental implant surfaces due to the need for improvement of the implant-bone interface properties. In this paper, the titanium dental implant surface was modified by a bioactive vitamin D3 coating prepared by self-assembly process. Surface characterization of the modified implant was performed by field emission scanning electron microscopy (FE-SEM), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), and contact angle measurements (CA). Implant’s electrochemical stability during exposure to an artificial saliva solution was monitored in situ by electrochemical impedance spectroscopy (EIS). Experimental results obtained were corroborated by means of quantum chemical calculations at the density functional theory level (DFT). The formation mechanism of the coating onto the titanium implant surface was proposed. During a prolonged immersion period, the bioactive vitamin D3 coating effectively prevented the underlying titanium from corrosive attack (polarization resistance in order of 107 Ω cm2) with ~95% protection effectiveness.
Sun, 8 September 2019
ARTICLE | doi:10.20944/preprints201909.0087.v1
Subject: Chemistry, Electrochemistry Keywords: heterostructured Fe2O3-MnO; oxygen evolution reaction; alkaline water splitting; electrochemical synergy
Online: 8 September 2019 (16:16:26 CEST)
For efficient electrode development in an electrolysis system, Fe2O3, MnO, and heterojunction Fe2O3-MnO materials were synthesized via a simple sol-gel method. These particles were coated on a Ni-foam electrode, and the resulting material was used as an electrode to be used during an oxygen evolution reaction (OER). A 1000-cycle OER test in a KOH alkaline electrolyte indicated that the heterojunction Fe2O3-MnO/NF electrode exhibited the most stable and highest OER activity: it exhibited a low overvoltage (n) of 370 mV and a small Tafel slope of 66 mV/dec. X-ray photoelectron spectroscopy indicated that the excellent redox performance contributed to the synergy of Mn and Fe, which enhanced the OER performance of the Fe2O3-MnO/NF electrode. Furthermore, the effective redox reaction of Mn and Fe indicated that the structure maintained stability even under 1000 repeated OER cycles.
Mon, 12 August 2019
ARTICLE | doi:10.20944/preprints201908.0134.v1
Subject: Chemistry, Electrochemistry Keywords: aluminium alloy; corrosion inhibitor; alkaline environment; impedance analysis; adsorption; dihydroxybenzene
Online: 12 August 2019 (03:58:57 CEST)
Selection of efficient corrosion inhibitors requires detailed knowledge regarding interaction mechanism, which depends on the type and amount of functional groups within the inhibitor molecule. Position of functional groups between different isomers is often overlooked but not less important since factors like steric hinderance may significantly affect the adsorption mechanism. In this study we have presented how different dihydroxybenzene isomers interact with aluminium alloy 5754 surface, reducing its corrosion rate in bicarbonate buffer (pH = 11). We have shown the highest inhibition efficiency among tested compounds belongs to catechol at 10 mM concentration, although differences were moderate. Utilization of novel impedance approach to adsorption isotherm determination allowed to confirm that while resorcinol chemisorbs on aluminium surface, catechol and quinol follows ligand exchange model of adsorption. Unlike catechol and quinol, the protection mechanism of resorcinol is bound to interaction with insoluble aluminium corrosion products layer and was only found efficient at concentration of 100 mM (98.7%). The aforementioned studies were confirmed with scanning electron microscopy and x-ray photoelectron spectroscopy analyses. There is a significant increase of the corrosion resistance offered by catechol at 10 mM after 24 h exposure in electrolyte: from 63 to 98%, with only negligible changes in inhibitor efficiency observed for resorcinol at the same time. However, in the case of resorcinol a change in electrolyte color was observed. We have revealed that the differentiating factor is the keto-enol tautomerism. The NMR studies of resorcinol indicate the keto form in structure in presence of NaOH, while the chemical structure of catechol does not change significantly in alkaline environment.
Mon, 10 June 2019
REVIEW | doi:10.20944/preprints201906.0077.v1
Subject: Chemistry, Electrochemistry Keywords: aqueous electrolyte; corrosion; iron-air; metal-air batteries; silicon-air; stationary energy storage
Online: 10 June 2019 (11:24:23 CEST)
Abstract: Metal-air batteries provide a most promising battery technology given their outstanding potential energy densities, which are desirable for both stationary and mobile applications in a ‘beyond lithium-ion’ battery market. Silicon- and iron-air batteries underwent less research and development compared to lithium- and zinc-air batteries. Nevertheless, in the recent past, the two also-ran battery systems made considerable progress and attracted rising research interest due to the excellent resource-efficiency of silicon and iron. Silicon and iron are among the top five of the most abundant elements in the earth’s crust, which ensures almost infinite material supply of the anode materials, even for large scale applications. Furthermore, primary silicon-air batteries are set to provide one of the highest energy densities among all batteries, while iron-air batteries are frequently considered as a highly rechargeable system with decent performance characteristics. Considering fundamental aspects for the anode materials, i.e., the metal electrodes, in this review, we will first outline the challenges, which explicitly apply to silicon- and iron-air batteries and prevented them from a broad implementation so far. Afterwards, we provide an extensive literature survey regarding state-of-the-art experimental approaches, which are set to resolve the aforementioned challenges and might enable the introduction of silicon- and iron-air batteries into the battery market in the future.
Thu, 4 April 2019
ARTICLE | doi:10.20944/preprints201904.0056.v1
Subject: Chemistry, Electrochemistry Keywords: Co-B/SiC composite coatings; electrodeposition; hard coatings; wear volume
Online: 4 April 2019 (12:52:34 CEST)
In the present paper, Co-B/SiC composite coatings were obtained via electrodeposition from colloidal suspensions with different concentrations of SiC particles and subsequent heat treatments at 350 °C. The composition, morphology and structure of the Co-B/SiC composite coatings were analyzed using glow discharge spectrometry (GDS), scanning electron microscopy (SEM) coupled with energy-dispersive spectroscopy (EDS) and X-ray diffraction (XRD). Hardness and tribological properties were also studied. The results showed that an increase in the SiC concentration in the colloidal suspensions resulted in both an increase in the SiC content and a decrease in the B content in the obtained Co-B/SiC coatings. The Co-B/SiC coatings were adherent, glossy and soft and exhibited a homogeneous composition in all thicknesses. By contrast, an increase in the SiC particle content of the Co-B/SiC composite coating from 0 to 2.56 at.% SiC reduced the hardness of the film from 680 to 360 HV and decreased the wear volume values from 1180 to 23 mm3 N-1 m-1, respectively (that is, the wear resistance increased). Moreover, when the Co-B/SiC coatings with SiC content ranging from 0 to 2.56 at.% SiC were subjected to a heat treatment process, the obtained coating hardness values were in the range of 1200 to 1500 HV and the wear volume values were in the range of 382 to 19 mm3 N-1 m-1.
Mon, 1 April 2019
ARTICLE | doi:10.20944/preprints201904.0016.v1
Subject: Chemistry, Electrochemistry Keywords: Li-ion battery; electrode; porous structure; virtual structure; machine learning; simulation; physico-chemical model; optimization
Online: 1 April 2019 (13:35:13 CEST)
We have proposed a data-driven approach for designing mesoscale porous structures of Li-ion battery electrode with three-dimensional virtual structures and machine learning techniques. Over 2,000 artificial 3D structures assuming positive electrode composed of random packed spheres as active material particles are generated, and charge/discharge resistance has been evaluated using simplified Physico-chemical model. In this model, resistance from Li diffusion in active material particles (diffusion resistance), transfer resistance of Li+ in electrolyte (electrolyte resistance) and reaction resistance on the interface between active material and electrolyte are simulated based on mass balance of Li, Ohm’s law in and linearized Butler-Volmer equation, respectively. Using these simulation results, regression models via Artificial Neural Network (ANN) have been created in order to predict charge/discharge resistance from porous structure features. In this study, porosity, active material particle size and volume fraction, pressure in the compaction process, electrolyte conductivity, and binder volume fraction are adopted as features, associated with controllable process parameters for manufacturing battery electrode. As results, the predicted electrode resistance by ANN regression model is good agreement with the simulated values. Furthermore, sensitivity analysis and optimization of the process parameters have been carried out. The proposed data-driven approach could be a solution as a guiding principle for manufacturing battery electrode.
Thu, 7 March 2019
ARTICLE | doi:10.20944/preprints201903.0097.v1
Subject: Chemistry, Electrochemistry Keywords: Te nanotubes decorated with Pt nanoparticles; fuel cell neutral pH; oxygen reduction reaction; methanol oxidation reaction; X-ray photoelectron spectroscopy.
Online: 7 March 2019 (13:49:46 CET)
In fuel-cell technological development, one of the most important objectives is to minimize the amount of Pt, the most employed material as oxygen reduction and methanol oxidation electro-catalyst. In this paper we report the synthesis and characterization of Te nanotubes (TeNTs) decorated with Pt nanoparticles, readily prepared from stirred aqueous solutions of PtCl2 containing a suspension of TeNTs and ethanol acting as a reducing agent, avoiding the use of any hydrophobic surfactants as capping stabilizing substance. The as obtained TeNTs decorated with Pt nanoparticles (TeNTs/PtNPs) have been fully characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area diffraction patterns (SAD), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). We demonstrate that the new material can be successfully employed in fuel cell either as anodic (for methanol oxidation reaction) and cathodic (for oxygen reduction reaction) electrode with high efficiency in terms of related mass activities and on-set improvement. Remarkably, the cell operates in aqueous electrolyte buffered at pH 7.0, thus avoiding acidic or alkaline conditions that may lead e. g. to Pt dissolution (at low pH) and paving the way for the development of biocompatible devices and on chip fuel cells.
Mon, 4 March 2019
ARTICLE | doi:10.20944/preprints201903.0043.v1
Online: 4 March 2019 (13:30:34 CET)
Removal of hexavalent chromium had attracted much more attention as it was a hazardous contaminant. Electrochemical reduction technology was applied to removal chromium (VI) from wastewater. The mechanism and parameters affect the reduction process were investigated. The results showed that the reduction efficiency was significantly affected by the concentration of H2SO4, current density and reaction temperature. And the reduction efficiency was up to 86.45% at concentration of H2SO4 of 100g/L, reaction temperature of 70 ℃, current density at 50 A/m2, reaction time at 180 min and stirring rate of 500 rpm. The reduction process of chromium (VI) was followed pseudo-first-order equation, and the reduction rate could be expressed as Kobs = k [H2SO4]1• [j] 4•exp-4170/RT.
Thu, 20 December 2018
ARTICLE | doi:10.20944/preprints201811.0572.v2
Subject: Chemistry, Electrochemistry Keywords: PCFCs/PCECs; Ruddlesden-Popper phases; symmetrical cells; proton-conducting electrolytes
Online: 20 December 2018 (05:23:10 CET)
Reversible protonic ceramic cells (rPCCs) combine two different operation regimes, fuel cell and electrolysis cell modes, which allow reversible chemical-to-electrical energy conversion at reduced temperatures with high efficiency and performance. Here we present novel technological and materials science approaches, enabling a rPCC with symmetrical functional electrodes to be prepared using a single sintering step. The response of the cell fabricated on the basis of P–N–BCZD|BCZD|PBN–BCZD (where BCZD = BaCe0.5Zr0.3Dy0.2O3–δ, PBN = Pr1.9Ba0.1NiO4+δ, P = Pr2O3, N = Ni) is studied at different temperatures and water vapor partial pressures (pH2O) by means of volt-ampere measurements, electrochemical impedance spectroscopy and distribution of relaxation times analyses. The obtained results demonstrate that symmetrical electrodes exhibit classical mixed-ionic/electronic conducting behavior with no hydration capability at 750 °C; therefore, increasing the pH2O values in both reducing and oxidizing atmospheres leads to some deterioration of their electrochemical activity. At the same time, the electrolytic properties of the BCZD membrane are improved, positively affecting the rPCC’s efficiency. The electrolysis cell mode of the rPCC is found to be more appropriate than the fuel cell mode under highly humidified atmospheres, since its improved performance is determined by the ohmic resistance, which decreases with pH2O increasing.
Mon, 26 November 2018
ARTICLE | doi:10.20944/preprints201811.0572.v1
Subject: Chemistry, Electrochemistry Keywords: PCFCs/PCECs; ruddlesden-popper phases; symmetrical cells; proton-conducting electrolytes
Online: 26 November 2018 (06:42:08 CET)
Reversible protonic ceramic cells (rPCCs) combine two different operation regimes, fuel and electrolysis modes, which allow reversible chemical-to-electrical energy conversion at reduced temperatures with high efficiency and performance. Here we present novel technological and materials science approaches, enabling a rPCC with symmetrical functional electrodes to be prepared using a single sintering step. The response of the cell fabricated on the basis of P–N–BCZD|BCZD|PBN–BCZD (where BCZD = BaCe0.5Zr0.3Dy0.2O3–δ, PBN = Pr1.9Ba0.1NiO4+δ, P = Pr2O3, N = Ni) is studied at different temperatures and water vapor partial pressures by means of volt-ampere measurements, electrochemical impedance spectroscopy and distribution of relaxation times analyses. The obtained results demonstrate that symmetrical electrodes exhibit classical mixed-ionic/electronic conducting behavior with no hydration capability at 750 °C; therefore, increasing the pH2O values in both reducing and oxidizing atmospheres leads to some deterioration of their electrochemical activity. At the same time, the electrolytic properties of the BCZD membrane are improved, positively affecting the rPCC’s efficiency. The electrolysis mode of the rPCC is found to be more efficient than the fuel cell mode under highly humidified atmospheres, since its performance is determined by the ohmic resistance, which decreases under respectively less humid conditions.
Tue, 20 November 2018
ARTICLE | doi:10.20944/preprints201811.0492.v1
Subject: Chemistry, Electrochemistry Keywords: single atom catalysis; carbon-supported catalysts; platinum-group metals; aberration-corrected scanning transmission electron microscopy
Online: 20 November 2018 (09:19:06 CET)
Nanoparticles of platinum-group metals (PGM) on carbon supports are widely used as catalysts for a number of chemical and electrochemical conversions on laboratory and industrial scale. The newly emerging field of single atom catalysis focuses on the ultimate level of metal dispersion, i.e. atomically dispersed metal species anchored on the substrate surface. However, the presence of single atoms in traditional nanoparticle-based catalysts remains largely overlooked. In this work we use aberration-corrected scanning transmission electron microscope to investigate four commercially available nanoparticle-based PGM/C catalysts (PGM = Ru, Rh, Pd, Pt). We show that in addition to nanoparticles, single atoms are also present on the surface of carbon substrates. These observations raise questions about the role that single atoms play in conventional nanoparticle PGM/C catalysts. We critically discuss the observations with regard to the quickly developing field of single atom catalysis.
Mon, 12 November 2018
ARTICLE | doi:10.20944/preprints201811.0285.v1
Subject: Chemistry, Electrochemistry Keywords: proton exchange membrane water electrolysis; anode catalyst; oxygen evolution reaction; iridium; tin oxide
Online: 12 November 2018 (11:03:24 CET)
We have developed IrOx/M-SnO2 (M = Nb, Ta, and Sb) anode catalysts, IrOx nanoparticles uniformly dispersed on M-SnO2 supports with fused-aggregate structures, which make it possible to evolve oxygen efficiently, even with a reduced amount of noble metal (Ir) in proton exchange membrane water electrolysis. Polarization properties of IrOx/M-SnO2 catalysts for the oxygen evolution reaction (OER) were examined at 80 °C in both 0.1 M HClO4 solution (half cell) and a single cell with a Nafion® membrane (thickness = 50 μm). While all catalysts exhibited similar OER activities in the half cell, the cell potential (Ecell) of the single cell was found to decrease with the increasing apparent conductivities (σapp, catalyst) of these catalysts: an Ecell of 1.61 V (voltage efficiency of 92%) at 1 A cm-2 was achieved in a single cell by the use of an IrOx/Sb-SnO2 anode (highest σapp, catalyst) with a low Ir-metal loading of 0.11 mgIr cm-2 and Pt supported on graphitized carbon black (Pt/GCB) as the cathode, with 0.35 mgPt cm−2. In addition to the reduction of the ohmic loss in the anode catalyst layer, the increased electronic conductivity contributed to decreasing the OER overpotential due to the effective utilization of the IrOx nanocatalysts on the M-SnO2 supports, which is an essential factor in improving the performance with low noble metal loadings.
Mon, 5 November 2018
REVIEW | doi:10.20944/preprints201811.0089.v1
Subject: Chemistry, Electrochemistry Keywords: diaminomaleonitrile; diaminofumaronitrile; monosubstitution; bisubstitution; symmetric; asymmetric; photoisomerization; internal charge transfer
Online: 5 November 2018 (08:07:40 CET)
Diaminomaleonitrile (DAMN) is an electron-rich ligand which is commonly used in the synthesis of purines, amides and Schiff base ligands. In the last case lies the interest in this molecule, given its symmetry and apparent facility to form various ligands and complexes of interest in fields such as organic solar cells and catalysis among others. Nevertheless, its bisubstitution with aldehydes displays certain difficulty due to the double conjugated presence of the nitrile group (C≡N) in its structure, which significantly affect its coordination behavior by modulating the chemical reactivity of its amines. In addition to presenting a practical resume of guidelines for the preparation of different bisubstituted compounds from DAMN, this paper reviews the possibility of attaining a precise characterization by simple spectroscopic techniques. We provide an additional discussion for one of these techniques (commonly reported but often overlooked), given its potential to provide both the symmetry and E/Z configuration of the product. We hope the comprehensive evidence discussed and shown in this review will be helpful to further develop and understand the products derived of this interesting molecule in their broad applications.
Thu, 1 November 2018
ARTICLE | doi:10.20944/preprints201810.0765.v1
Subject: Chemistry, Electrochemistry Keywords: Photoelectrochemical water splitting; Silicon/MoS2 junction; Atomic Layer Deposition; Mixed-phase metal chalcogenides
Online: 1 November 2018 (18:09:09 CET)
We describe the direct formation of mixed-phase (1T and 2H) MoS2 layers on Si as a photocathode via atomic layer deposition (ALD) for application in the photoelectrochemical (PEC) reduction of water to hydrogen. Without typical series-metal interfaces between Si and MoS2, our p-Si/SiOx/MoS2 photocathode showed efficient and stable operation in hydrogen evolution reactions (HERs). The resulting performance could be explained by spatially genuine device architectures in three dimensions (that is, laterally homo and vertically heterojunction structures). The ALD-grown MoS2 overlayer with the mixed-phase 1T and 2H homojunction passivates light absorber and surface states and functions as a monolithic structure for effective charge transport within MoS2. It is also beneficial in the operation of p-i-n heterojunctions with inhomogeneous barrier heights due to the presence of mixed-phase cocatalysts. The effective barrier heights reached up to 0.8 eV with optimized MoS2 thicknesses, leading to a 670 mV photovoltage enhancement without employing buried Si p-n junctions. The fast-transient behaviors via light illumination show that the mixed-phase layered chalcogenides can serve as efficient cocatalysts by depinning the Fermi levels at the interfaces. A long-term operation of ~ 70 h was also demonstrated in a 0.5 M H2SO4 solution.
Thu, 25 October 2018
ARTICLE | doi:10.20944/preprints201810.0605.v1
Subject: Chemistry, Electrochemistry Keywords: photoelectrochemical cell; hydrogen evolution reaction (HER); metal free catalyst; cobalt selenide catalyst
Online: 25 October 2018 (11:59:07 CEST)
Photoelectrochemical water splitting is a promising field for sustainable energy production using hydrogen. Development of efficient catalysts is essential for resourceful hydrogen production. The most efficient catalysts reported to date have been extremely precious rare-earth metals. One of the biggest hurdles in this research area is the difficulty of developing highly efficient catalysts comparable to the noble metal catalysts. Here, we report that non-noble metal dichalcogenide (Co3Se4) catalysts made using a facile one-pot electrodeposition method, showed highly efficient photoelectrochemical activity on a Si photocathode. To enhance light collection and enlarge its surface area even further, we implemented surface nano-structuring on the Si surface. The nano-structured Si photoelectrode has an effective area greater than that of planar silicon and a wider absorption spectrum. Consequently, this approach exhibits reduced overvoltage as well as increased photo-catalytic activity. Such results show the importance of controlling the optimized interface between the surface structure of the photoelectrode and the electrodeposited co-catalyst on it to improve catalytic activity. This should enable other electrochemical reactions in a variety of energy conversion systems.
Thu, 18 October 2018
ARTICLE | doi:10.20944/preprints201810.0395.v1
Subject: Chemistry, Electrochemistry Keywords: sodium rechargeable battery; polymer electrolyte; Nafion; cycle stability; electrochemical stability
Online: 18 October 2018 (04:16:01 CEST)
The possibilities of manufacturing batteries with Nafion 117 membranes in the Na+-form intercalated by mixtures of non-aqueous organic solvents used both as electrolyte, separator and binder were investigated. Electrochemical stability of various organic solvent mixtures based on N,N-dimethylacetamide, ethylene carbonate, propylene carbonate, tetrahydrofuran was characterized. It was shown that sodium battery based on Nafion-Na membrane intercalated by mixture of ethylene carbonate ‑ propylene carbonate with Na3V1.9Fe0.1(PO4)3/C positive electrode is characterized by a discharge capacity of ca. 110 mAh g-1 (C/10) at room temperature and shows the ability to cycle for a long time. Batteries with Nafion membrane electrolytes, containing N,N-dimethylacetamide were characterized by capacity fading during cycling, which is due to the interaction of N,N-dimethylacetamide and a negative sodium electrode.
Thu, 27 September 2018
ARTICLE | doi:10.20944/preprints201809.0532.v1
Subject: Chemistry, Electrochemistry Keywords: metal doping; nickel-based catalyst; transition metals; synthesis; hydrogen oxidation reaction; exchange current density; alkaline medium; DFT; hydrogen binding energy; hydroxide binding energy
Online: 27 September 2018 (04:59:46 CEST)
Carbon supported nanoparticles of monometallic Ni catalyst and binary Ni-Transition Metal (Ni-TM/C) electrocatalytic composites were synthesized via chemical reduction method, where TM stands for the doping elements Fe, Co, and Cu. The chemical composition, structure and morphology of the Ni-TM/C materials were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDS). The electrochemical properties towards hydrogen oxidation reaction in alkaline medium were studied using the rotating disc electrode and cycling voltammetry methods. A significant role of the TM dopant in the promotion of the hydrogen electrooxidation kinetics of the binary Ni-TM/C materials were revealed. A record-high in exchange current density value of 0.060 mA cm2Ni was measured for Ni3Fe1/C, whereas the monometallic Ni/C counterpart has only shown 0.039 mA cm2Ni. In order to predict the feasibility of the electrocatalysts for hydrogen chemisorption, density functional theory was applied to calculate the hydrogen binding energy and hydroxide binding energy values for bare Ni and Ni3TM1.
Mon, 17 September 2018
COMMUNICATION | doi:10.20944/preprints201809.0297.v1
Subject: Chemistry, Electrochemistry Keywords: silicon nanowire (SiNW), hydrogen evolution reaction (HER), reduced graphene oxide
Online: 17 September 2018 (10:09:06 CEST)
Silicon-based photoelectrochemical (PEC) conversion system has recently gained attention with its ability to provide cost-efficient and superior photoresponsive behavior in regard to other various semiconductor photoelectrodes. Carbon-based co-catalysts have always shared the spotlight for being rendered as alternative metal-free electrocatalysts intended for hydrogen evolution reaction (HER). In particular, a representative carbon-derived material, reduced Graphene Oxide (rGO) has attracted much attention as a non-metal catalyst for efficient and durable HER. Herein, we have deposited rGO on silicon nanowire (SiNW) structure which shows the highest reduction in the overpotential for HER up to date. This could be attributed to the synergistic effects of rGO and SiNW with unique anisotropic morphology, facile tuning capabilities, and scalable fabrication methods. Combined with nanostructured photocathode, rGO deposited SiNW showed better applied bias photon to current conversion efficiency of 3.16%, which is 158 times higher than that of bare planar Si system. In regard to this development we believe that rGO-SiNW photoelectrodes would pave the way for state-of-the-art highly efficient non-metal catalysts for energy conversion technologies.
Tue, 11 September 2018
REVIEW | doi:10.20944/preprints201809.0188.v1
Subject: Chemistry, Electrochemistry Keywords: origins of life; prebiotic chemistry; mineral catalysis; sulfide minerals; mineral diversity; density functional theory; electrocatalysis
Online: 11 September 2018 (08:39:51 CEST)
Prebiotic organic synthesis reactions catalyzed by Earth-abundant metal sulfides are key processes for understanding the evolution of biochemistry from inorganic molecules, yet the catalytic functions of sulfides have remained poorly explored in the context of the origins of life. Past studies on prebiotic chemistry have mostly focused on a few types of metal sulfide catalysts, such as FeS or NiS, which form limited types of products with inferior activity and selectivity. To explore the potential of metal sulfides on catalyzing prebiotic chemical reactions, here, the chemical diversity (variations in chemical composition and phase structure) of 304 natural metal sulfide minerals in a mineralogy database was surveyed and approaches to rationally predict the catalytic functions of metal sulfides are discussed based on advanced theories and analytical tools of electrocatalysis such as proton-coupled electron transfer, structural comparisons between enzymes and minerals, and in-situ spectroscopy. To this end, we introduce a model of geo-electrochemistry driven prebiotic synthesis for chemical evolution, as it helps us to predict kinetics and selectivity of targeted prebiotic chemistry under “chemically messy conditions”. We expect that combining the data-mining of mineral databases with experimental methods and theories developed in the field of electrocatalysis will facilitate the prediction and verification of catalytic performance under a wide range of pH and Eh conditions, and aid in the rational screening of mineral catalysts involved in the origins of life.
Tue, 4 September 2018
ARTICLE | doi:10.20944/preprints201809.0062.v1
Subject: Chemistry, Electrochemistry Keywords: Nernst voltage; activation overvoltage; concentration loss; equilibrium potential; exchange current density; net current density
Online: 4 September 2018 (11:56:23 CEST)
Normally, the Nernst voltage calculated from the concentration of the reaction gas in the flow channel is considered to be the ideal voltage (reversible voltage) of the oxyhydrogen fuel cell, but actually it will cause a concentration gradient when the reaction gas flows from the flow channel through the gas diffusion layer to the catalyst layer. The Nernst voltage loss in fuel cells in most of the current literature is thought to be due to the difference in concentration of reaction gas in the flow channel and concentration of reaction gas on the catalyst layer at the time when the high net current density is generated. Based on the Butler-Volmer equation in oxyhydrogen fuel cell, this paper demonstrates that the Nernst voltage loss is caused by the concentration difference of reaction gas in flow channel and on the catalytic layer at the time when equilibrium potential (Galvanic potential) of each electrode is generated.
Tue, 31 July 2018
ARTICLE | doi:10.20944/preprints201807.0605.v1
Subject: Chemistry, Electrochemistry Keywords: arrayed flexible chloride sensor; wireless sensing system; hysteresis voltage; selectivity coefficient; dynamic microfluidic
Online: 31 July 2018 (05:16:24 CEST)
Water quality monitoring was an important objective in the surroundings. In this study, we investigated the sensing characteristics of the arrayed flexible chloride sensor with XBee wireless sensing system. The sensitivity and linearity of the wireless chloride sensing devices were 91.6 mV/pCl and 0.988, respectively. The hysteresis voltages were 50.14 mV and 36.71 mV during the cycles of 1 M → 10−1 M → 1 M → 10−3 M → 1 M and 1 M → 10−3 M → 1 M → 10−1 M → 1 M, respectively. The selectivity coefficients of the ClO− ion, ClO4− ion, NO3− ion and I− ion for Cl− ion were 5.0 × 10−2, 1.0 × 10−1, 5.9 × 10−3 and 5.6×10−1, respectively. The sensing characteristics of real time measurement were investigated for dynamic microfluidic. The arrayed flexible chloride sensor was integrated with the microfluidic device, syringe pump and wireless sensing system. The sensitivity and linearity were 273.1 mV/pCl and 0.978 at 35 μL/min, respectively.
Fri, 20 July 2018
ARTICLE | doi:10.20944/preprints201807.0392.v1
Subject: Chemistry, Electrochemistry Keywords: electrodeposition; platinum; highly oriented pyrolytic graphite; 2D growth
Online: 20 July 2018 (16:08:11 CEST)
We discuss the electrodeposition of two-dimensional (2D) Pt-nanostructures on HOPG achieved under constant applied potential versus a Pt counter electrode (Eappl = ca. - 2.2 V vs RHE). The deposition conditions are discussed in terms of the electrochemical behavior of the electrodeposition precursor (H2PtCl6). We performed cyclic voltammetry (CV) of the electrochemical Pt deposit on HOPG and on Pt substrates to study the relevant phenomena that affect the morphology of Pt deposition. Under conditions where the Pt deposition occurs and H2 evolution is occurring at the diffusion-limited rate (- 0.3 V vs RHE), Pt forms larger structures on the surface of HOPG, and the electrodeposition of Pt is not limited by diffusion. This indicates the need for large overpotentials to direct the 2D growth of Pt. Investigation of the possible effect of Cl- showed that Cl- deposits on the surface of Pt at low overpotentials, but strips from the surface at potentials more positive than the electrodeposition potential. The CV of Pt on HOPG is a strong function of the nature of the surface. We propose that during immersion of HOPG in the electrodeposition solution (3 mM H2PtCl6, 0.5 M NaCl, pH 2.3) Pt islands are formed spontaneously, and these islands drive the growth of the 2D nanostructures.
Mon, 2 July 2018
ARTICLE | doi:10.20944/preprints201807.0009.v1
Subject: Chemistry, Electrochemistry Keywords: Bi-functional catalyst; hydrothermal synthesis; OER/ORR; nickel ferrite; Ni FeLDH
Online: 2 July 2018 (10:47:25 CEST)
This article reports the two-step synthesis of NiFeOx nanomaterials, their characterisation and bifunctional electrocatalytic activity measurements in alkaline electrolyte for metal-air batteries. The samples were mostly in layered double hydroxide at the initial temperature, but upon heat treatment, they were converted to NiFe2O4 phases. The electrochemical behaviour of the different samples was studied by linear sweep voltammetry and cyclic voltammetry on the glassy carbon electrode. The OER catalyst activity was observed for low mass loadings (0.125 mg cm−2), whereas high catalyst loading exhibited the best performance on the ORR side. The sample heat treated at 250 °C delivered the highest bi-functional oxygen evolution and reduction reaction activity (OER/ORR) thanks to its thin-holey nanosheet like structure with higher nickel oxidation state at 250 °C. This work further helps to develop low-cost electrocatalyst development for metal-air batteries.
Fri, 22 June 2018
COMMUNICATION | doi:10.20944/preprints201806.0354.v1
Subject: Chemistry, Electrochemistry Keywords: Graphene; Mn3O4; Nanocomposites; Energy storage and conversion; Supercapacitors
Online: 22 June 2018 (10:53:49 CEST)
Mn3O4 /graphene nanosheets (GNS) composites serve as very excellent electrode materials for supercapacitors. They can fully combine the advantages of two materials such as graphene and metal oxide. Meanwhile, they can improve not only the specific energy and specific power of the materials, but also the cyclic stability of the materials. The results of the cyclic voltammetry and constant current charge discharge test on the composite electrode material have shown that the Mn3O4 /GNS powder sample has good capacitive performance. When the scanning rate is 5~50mV, the specific capacity retention rate of the composite electrode is 80.3% and 88% respectively. Mn3O4 nanoparticles, with the highest ratio of network coated GNS, exhibit a specific capacitance value of 957.6 F g−1 at a current density of 2 A g−1 in 1 M Na2SO4 solution. Besides, its network structure demonstrates high specific capacity and multiplying performance.
Wed, 13 June 2018
ARTICLE | doi:10.20944/preprints201806.0215.v1
Subject: Chemistry, Electrochemistry Keywords: Copper; Phosphoric acid; 3D Nanostructures; 1-dodecanethiol SAMs
Online: 13 June 2018 (15:33:35 CEST)
A novel and simple method to improve the corrosion resistance of copper by constructing a 3D 1-dodecanethiol self-assembled monolayers (SAMs) in 3.5% NaCl solution is reported in this study. Several drops of 1% H3PO4 solution are thinly and uniformly distributed on copper surface to form a 3D nanostructure constituted by Cu3(PO4)2 nanoflowers. The anticorrosion properties of 1-dodecanethiol SAMs on copper surface and on copper surface treated with H3PO4 solution were evaluated. Results demonstrated that 1-dodecanethiol SAMs on bare copper surface exhibit good protection capacity, whereas a copper surface pretreated with H3PO4 solution can substantially enhance the corrosion resistance of 1-dodecanethiol SAMs.
Tue, 12 June 2018
REVIEW | doi:10.20944/preprints201806.0186.v1
Subject: Chemistry, Electrochemistry Keywords: Magnetoelectrochemistry; CISS; spin; chirality; spin-dependent electrochemistry
Online: 12 June 2018 (10:42:16 CEST)
Magneto-electrochemistry (MEC) is a unique paradigm in science, where electrochemical experiments are carried out as a function of an applied magnetic field, creating a new horizon of potential scientific and technological applications. Over the time, detailed understanding of this research domain was developed to identify and rationalize the possible effects exerted by a magnetic field on the various microscopic processes occurring in an electrochemical system, such as: electrolyte properties governed by charge-transfer process (electric conductivity, viscosity, and diffusivity), mass transfer, electrochemical kinetics and on the structure/quality of products formed either at the working electrode or in the electrochemical cell. Particularly, magnetic field controlled chiral architecture obtained from deposited metal, alloys and catalyst and their excellent enantio-recognition in experimental frame is highly appealing. Interestingly, Hall effect was also demonstrated in electrolytic medium via an impressive experimental technique which is being employed for further theoretical understanding in the field of magneto-electrochemical science. Later, a highly reproducible local temperature variation was observed in electrochemical electrolytes exposed to perpendicular magnetic and electric fields. However, until recent studies, none of the above mentioned reports considered the possibility of a spin-dependent related charge-transfer process. Recent experimental and theoretical studies reveal that electron’s transmission through chiral molecules is spin-selective and this effect has been referred to as chiral-induced spin-selectivity (CISS) effect. The CISS effect pave the way for the building up of a system characterized by a net magnetic moment exploiting the spin-filtering ability of chiral molecules. This interplay between chirality and magnetism may shed light on fundamental scientific aspects underlying the enantio-recognition and highly efficient electron-transfer that occurs in biological process.
Mon, 11 June 2018
ARTICLE | doi:10.20944/preprints201806.0151.v1
Subject: Chemistry, Electrochemistry Keywords: electrode nanomaterials; magnesium-tin intermetallics; magnesium-ion batteries; Sn-119 Mössbauer spectroscopy
Online: 11 June 2018 (10:55:38 CEST)
A study is reported on the electrochemical alloying-dealloying properties of Mg2Sn intermetallic compounds. 119Sn Mössbauer spectra of β-Sn powder, thermally alloyed cubic-Mg2Sn and an intermediate MgSn nominal composition are used as references. The discharge of a Mg/micro-Sn half-cell led to significant changes in spectra line shape that are explained by a multiphase mechanism involving the coexistence of c-Mg2Sn, distorted Mg2-δSn and Mg-doped β-Sn. Capacities and capacity retention were improved by using nanoparticulate tin electrodes. This material reduces significantly the diffusion lengths for magnesium and contains surface SnO and SnO2, which are partially electroactive. The half-cell potentials were suitable to be combined versus MgMn2O4 cathodes. Energy density and cycling properties of the resulting full Mg-ion cells are also scrutinized.
Wed, 6 June 2018
ARTICLE | doi:10.20944/preprints201806.0099.v1
Online: 6 June 2018 (15:37:29 CEST)
In this work the influence of the structure forming agent on the composition, morphology and oxygen reduction reaction (ORR) activity of Fe-N-C catalysts was investigated. As structure forming agent (SFA), dicyandiamide (DCDA) (nitrogen source) or oxalic acid (oxygen source) or mixtures thereof were used. For characterization, cyclic voltammetry and rotating disc electrode (RDE) experiments were performed in 0.1 M H2SO4. In addition to this, N2 sorption measurements and Raman spectroscopy were performed for the structural characterization. The role of metal, nitrogen and carbon sources within the synthesis of Fe-N-C catalysts has been pointed out before. Here, we show that the optimum in terms of ORR activity is achieved if both N- and O-containing SFAs are used in almost similar fractions. All catalysts display a redox couple, whereat its position depends on the fractions of SFAs. The SFA has also a strong impact on the morphology: Catalysts that were prepared with a larger fraction of N-containing SFA revealed a higher order in graphitization, indicated by bands in the 2nd order range of the Raman spectra. Nevertheless, the optimum in terms of ORR activity is obtained for the catalyst with highest D/G band ratio. Therefore, the results indicate that the presence of an additional oxygen-containing SFA is beneficial within the preparation.
Thu, 24 May 2018
ARTICLE | doi:10.20944/preprints201805.0331.v1
Subject: Chemistry, Electrochemistry Keywords: conjugated polymer; selenophene; fluorine; carbazole band; gap; Suzuki coupling
Online: 24 May 2018 (05:32:43 CEST)
In this study, two donor-acceptor (D-A) type conjugated polymers namely PQSeCz and PQSeFl were designed and synthesized. Selenophene was incorporated as a π -bridge, quinoxaline as an acceptor unit while carbazole and fluorene were used as the donor units. Polymers were synthesized via palladium catalyzed Suzuki polymerization reaction. All molecules were characterized by 1H and 13C NMR Spectroscopy. The weight and number average molecular weights of the two polymers were determined by gel permeation chromatography (GPC). Electrochemical and spectroelectrochemical characterizations of the polymers were performed to investigate their optoelectronic properties. Oxidation potentials were 1.15 V/ 0.82 V and 1.11 V/ 0.82 V for PQSeCz and PQSeFl respectively, while reduction potentials were -1.26 V /-1.14 V and -1.48 V/ -1.23 V, respectively. In the visible region, maximum absorption wavelengths for the two polymers were 551 nm and 560 nm, respectively. Optical band gaps (Egop) were found from the lowest energy π – π∗ transition onsets as 1.71 eV and 1.58 eV, respectively. Both polymers showed good solubility in common solvents.
Tue, 22 May 2018
COMMUNICATION | doi:10.20944/preprints201805.0285.v1
Subject: Chemistry, Electrochemistry Keywords: electrochemical oscillation; vanadium; chronopotentiometry
Online: 22 May 2018 (05:22:36 CEST)
The electrochemical oscillation was first observed in the charging process of anolyte in VRFBs. The chronopotentiometry with current ramp results could be used to judge the appearance of electrochemical oscillation. The electrochemical oscillation could be explained in terms of the competition between the growth and the chemical dissolution of V2O5 film in the H2SO4 solution. It was possible to regular the extra power consumption resulted by the electrochemical oscillation. This work might provide new focus on the charging process of the VRFBs and guide for new methods on energy saving.
Mon, 23 April 2018
REVIEW | doi:10.20944/preprints201804.0300.v1
Subject: Chemistry, Electrochemistry Keywords: SEPM; SECM; SICM; biosensors; high-resolution imaging; ion channels; microelectrode arrays
Online: 23 April 2018 (17:30:49 CEST)
This review discusses a broad range of recent advances (2013-2017) of chemical imaging using electrochemical methods, with a particular focus on techniques that have been applied to study cellular processes, or techniques that show promise for use in this field in the future. Non-scanning techniques such as microelectrode arrays (MEAs) offer high time-resolution (< 10 ms) imaging, however at reduced spatial resolution. In contrast, scanning electrochemical probe microscopies (SEPMs) offer higher spatial resolution (as low as a few nm per pixel) imaging, with images collected typically over many minutes. Recent significant research efforts to improve the spatial resolution of SEPMs using nanoscale probes, and to improve the temporal resolution using fast scanning have resulted in movie (multiple frame) imaging with frame rates as low as a few seconds per image. Many SEPM techniques lack chemical specificity or have poor selectivity (defined by the choice of applied potential for redox-active species). This can be improved using multifunctional probes, ion-selective electrodes and tip-integrated biosensors, although additional effort may be required to preserve sensor performance after miniaturization of these probes. We discuss advances to the field of electrochemical imaging, and technological developments which are anticipated to extend the range of processes that can be studied. This includes imaging cellular processes with increased sensor selectivity and at much improved spatiotemporal resolution than has been previously customary.
Fri, 13 April 2018
ARTICLE | doi:10.20944/preprints201804.0174.v1
Subject: Chemistry, Electrochemistry Keywords: Perovskite materials; energy; band-gap; photo-efficiency.
Online: 13 April 2018 (06:41:48 CEST)
In a world where conventional sources of energy are fast depleting, the quest for alternative energy sources may hold the key for the survival of humanity. In the present work, emphasis has been given to the idea of producing energy from perovskite based solar cells. In order to bring this idea into fruition, a unique and novel nano structured perovskite material n-propyl ammonium lead chloride (C3H7NH3+PbCl3⁻) was prepared through a unique co-precipitation route using n-propyl amine (n-C3H7NH2) and hydrochloric acid as the starting precursors with aqueous solution of Pb(CH3COO)23H2O. Finally acetic acid was added to the solution and this solution was allowed to concentrate and then gradually cooled down to room temperature. After math, the synthesized material was spin-coated on TiO2 film to fabricate the solar cell. The device was then undergone systematic analysis using XRD, SEM, UV and Photo Conversion to get a transparent idea regarding its structural, electrical and optical properties. When experimentally applied, this perovskite-based solar cell has shown energy conversion efficiency (η) of around 6.01 % which is noticeably good. Thus it can be concluded that this material is promising for fabrication of vastly efficient solar cells. This technology can be tried in large scale as an alternative of conventional energy in the near future.
Mon, 9 April 2018
ARTICLE | doi:10.20944/preprints201804.0097.v1
Subject: Chemistry, Electrochemistry Keywords: WO3; electrocatalysts; alkaline; Pd-W alloy; oxygen reduction reaction; reduction-oxidation method
Online: 9 April 2018 (04:06:25 CEST)
In this paper, we first report that WOx contained nanoalloys exhibit stable electrocatalytic performance in alkaline media, though bulk WO3 are easy to be dissolved in NaOH solutions. Carbon supported oxide-rich Pd-W alloy nanoparticles (PdW/C) with different Pd:W atom ratios were prepared by reduction-oxidation method. Among the catalysts, the oxide-rich Pd0.8W0.2/C (Pd/W = 8:2, atom ratio) exhibits the highest catalytic activity for oxygen reduction reaction. The X-ray photoelectron spectroscopy data shows that ~40% of Pd atoms and ~60% of the W atoms are in their oxides form. The Pd 3d5/2 peaks in oxide-rich Pd-W nanoalloys are positive shift compared with that of Pd/C, which indicates the electronic structure of Pd is affected by the strong interaction between Pd and W/WO3. Compare to Pd/C, the onset potential of oxygen reduction reaction at the oxide-rich Pd0.8W0.2/C is positive shifted. The current density (mA·mg Pd−1) at the oxide-rich Pd0.8W0.2/C is ~1.6 times of that at Pd/C. The oxide-rich Pd0.8W0.2/C also exhibits higher catalytic stability than Pd/C, which demonstrate that it is a prospective candidate for the cathode of fuel cells operated with alkaline electrolyte.
Fri, 24 November 2017
ARTICLE | doi:10.20944/preprints201711.0162.v1
Subject: Chemistry, Electrochemistry Keywords: Zn–Ni plating; Zn–Fe plating; anti-corrosion performance; Mo addition; alloy formation
Online: 24 November 2017 (16:30:38 CET)
Zn–Ni plating is indispensable in various industries because of its high corrosion resistance. However, Ni has been reported to trigger allergies; thus, an alternative Ni-free plating is desired. Zn–Fe plating is considered to be a promising candidate, albeit its corrosion resistance still needs to be improved. The corrosion resistance of Zn–Fe plating is expected to increase by the addition of Mo as the third alloying element as it is more noble than Zn and Fe. In this study, Zn–Fe–Mo plating with a corrosion resistance nearly equivalent to that of the Zn–Ni plating was fabricated. Zn–Fe–Mo plating was electrically deposited from continuously agitated plating baths prepared by mixing ZnSO4, FeSO4, Na2MoO4, Na3C6H5O7, and Na2SO4 using Fe or Ni plates as the substrate. The surface morphology, composition, crystal phase, and electronic state of Mo of the platings were investigated by SEM-EDS, XRD, and XPS. The anti-corrosion performance was evaluated by Tafel extrapolation method. Formation of plating comprising a Mo containing alloy phase was found to be crucial for improving corrosion resistance. The Zn–Fe–Mo plating demonstrates promise for replacing anti-corrosion Zn–Ni platings.
ARTICLE | doi:10.20944/preprints201711.0161.v1
Subject: Chemistry, Electrochemistry Keywords: copper; carbonous nanomaterial; composite coating; heat-dissipation material; nanodiamond
Online: 24 November 2017 (16:18:35 CET)
Carbonous nanomaterials are promising additives for composite coatings for heat-dissipation materials because of their excellent thermal conductivity. Here, copper/carbonous nanomaterial composite coatings were prepared using nanodiamond (ND) as the carbonous nanomaterial. The copper/ND composite coatings were electrically deposited onto copper substrates from a continuously stirred copper sulfate coating bath containing NDs. NDs were dispersed by ultrasonic treatment, and the initial bath pH was adjusted by adding sodium hydroxide solution or sulfuric acid solution before electrodeposition. The effects of various coating conditions—the initial ND concentration, initial bath pH, stirring speed, electrical current density, and the amount of electricity—on the ND content of the coatings were investigated. Furthermore, the surface of the NDs was modified by hydrothermal treatment to improve ND incorporation. A higher initial ND concentration and a higher stirring speed increased the ND content of the coatings, whereas a higher initial bath pH and a greater amount of electricity decreased it. The electrical current density showed a minimum ND content at approximately 5 A/dm2. Hydrothermal treatment, which introduced carboxyl groups onto the ND surface, improved the ND content of the coatings. A copper/ND composite coating with a maximum of 3.85 mass% ND was obtained.
Mon, 8 May 2017
ARTICLE | doi:10.20944/preprints201705.0054.v1
Subject: Chemistry, Electrochemistry Keywords: E-tongue; E-nose; data fusion; variable selection; patter recognition; beer
Online: 8 May 2017 (08:57:56 CEST)
Multi-sensor data fusion of E-tongue and E-nose can provide a more comprehensive and more accurate analysis results. However, it also brings some redundant information, it is a hot issue to reduce the feature dimension for pattern recognition. In this paper, the taste-olfactory data fusion based on E-tongue and E-nose combined with Support Vector Machine (SVM) was used to classify five different beers. First, the taste and olfactory feature information were obtained based on E-tongue and E-nose. Second, the original feature data of single system were fused, then Principal Component Analysis (PCA) was applied to extract principal components, Genetic Algorithm-Partial Least Squares (GA-PLS) was used to select the characteristic variables, 20 subsets were generated with those variables based on the best Variable Importance of Projection (VIP) score. Finally, the classification models based on SVM were established, also c and g of SVM were calculated by Grid Search (GS), Genetic Algorithm (GA), and Particle Swarm Optimization (PSO), the classification results of all subsets were obtained. The results showed that the classification accuracy using data fusion was much higher over single E-tongue and single E-nose, and the variable selection method by VIP had the best classification performance in #12 subset coupled with GA-SVM.
Tue, 4 April 2017
ARTICLE | doi:10.20944/preprints201704.0018.v1
Subject: Chemistry, Electrochemistry Keywords: nanomaterials; non-enzymatic glucose biosensors; nanocomposites; electrodeposition; titanium dioxide nanocomposite; XPS; EIS.
Online: 4 April 2017 (09:27:36 CEST)
The performance of modified electrode of nanocomposite film consisting of polypyrrole-chitosan-titanium dioxide (Ppy-CS-TiO2) has been explored as non-enzymatic glucose biosensors. The synergy effect of TiO2 nanoparticles and conducting polymer on the current response of electrode resulted in higher sensitivity for nanocomposite modified electrode. The incorporation of TiO2 nanoparticles in the nanocomposite films were confirmed by XPS spectra. The FESEM and HR-TEM provided more evidences for the presence of TiO2 in Ppy-CS structure. Glucose biosensing properties were determined by amperommetry and cyclic voltammetry (CV) methods. The interfacial properties of nanocomposite electrodes were studied by electrochemical impedance spectroscopy (EIS). The developed biosensors showed a good sensitivity over the liner range of 1-14 mM with a detection limit of 614 μM for glucose. It also exhibited good selectivity and long term stability with no interference effect. The Ppy-CS-TiO2 nanocomposites film presented high electron transfer kinetics.
Tue, 20 September 2016
ARTICLE | doi:10.20944/preprints201609.0072.v1
Subject: Chemistry, Electrochemistry Keywords: Pb-acid batteries, electrolyte additives, battery energy capacity, electrolyte additive concentration
Online: 20 September 2016 (15:39:49 CEST)
The paper presents a method to assess the effect of electrolyte additives on the energy capacity of Pb-acid batteries. The method applies to any chemically unreactive additive, including suspensions and gels. The approach is thermodynamically based and it leads to the definition of a region of admissible concentrations –the battery’s admissible range– where the battery can undergo an indefinite number of charge/discharge cycles without suffering permanent damage. An experimental procedure to determine this range is presented. The obtained results provide a way to assess the potential of electrolyte additives to improve the energy capacity of Pb-acid batteries. The same results also provide a means to determine the additive concentration that produces the maximum energy capacity increase of the battery. The paper closes with an example of application of the proposed approach to a practical case.
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