This review focuses on an extensive synopsis of the recent improvements in the field of CO2 hydrogenation over structured zeolites including their properties, synthesis methods, and characterization approaches. The role of bimodal mesoporous structures surface oxygen vacancies, and the Si/Al ratio in improving catalytic activity is highlighted. The porosity, thermal stability, and structural integrity are also discussed in the review along with how structured zeolites are affected by electrical and plasma interactions. The synthesis methods are analyzed in detail by comparing the benefits and drawbacks of the bottom-up techniques, such as hard templating, soft templating, and non-templating on the one side; and the top-down approaches, e.g. dealumination, desilication, and recrystallization on the other. This review also draws attention to the necessity of overcoming the difficulties arising from these synthesis techniques, for example, micropore-induced diffusion restrictions and morphological constraints, employing innovative approaches and optimization strategies. Conventional and advanced characterization techniques are pointed out in this respect as crucial for understanding the catalytic mechanism and the dynamic behavior, hence, beneficial in the advancements of research on structured zeolites with higher efficiency and activity. The review ends with a perspective that highlights the necessity of further research in the improvement of synthesis approaches and characterization procedures of the structured zeolites to increase their catalytic activity in CO2 hydrogenation, a critical process of paramount importance in the global effort to reduce excessive carbon emissions and combat climate change..

Additives can improve the efficiency of anaerobic digestion by increasing biogas production, reducing air pollution, and preventing total ammoniacal nitrogen (TAN) inhibition. Biological or chemical supplementation can also improve the economic efficiency of anaerobic digestion. However, the effects of specific additives on biogas production can vary depending on the type of supplement used. This research utilizes the additives on an industrial scale and monitors the optimization of the anaerobic digestion operating parameters after their addition. The various AD additives were examined in a sufficient cycle of operation for three biogas plants located in northern Greece. In this manner, the effectiveness was investigated in multiple initial feeds and unstable operating situations caused by the seasonality of specific feedstocks. The existing operation state in the three biogas plants was recorded before and after adding the supplements. In all three cases, lower concentration levels were observed in many of the examined trace elements. Introducing additives proved to be a stabilization factor in AD performance and inhibition mediator.

In the light of current justified international concerns about pollution caused by both greenhouse gases and by current agricultural practices, as well as the management of livestock manure, zeolite rocks with a prevalent zeolite content (a mineral endowed with peculiar chemical-physical properties), are widely used worldwide. They have a high extraction potential and represent an effective and scientifically proven means of pollution control. Moreover, based on the results of countless laboratory and field experiments, zeolitites (in particular Italian chabazite) rich in potassium (K) but low in sodium (Na) and with high drainage and water retention properties, have an effective potential for environmental protection, reduction of fertilizers and irrigation water, and increase of agronomic production. In agriculture and horticulture, in particular, the permanent correction of agricultural soils and growing media with appropriate amounts of zeolitites makes it possible to reduce the input of synthetic fertilizers and water as well, in order to substantially increase yields in quantity and quality. However, there are few scientific articles describing the use of zeolite in agriculture and its benefits for farmers. This review is aimed at gaining a better insight into the application of zeolitites in agriculture, particularly in difficult climatic situations, and to provide more information on how these minerals can ensure both the reduction of the use of fertilizers and the increase of plant protection. In addition, details and explanations are provided on the term 'zeolitite' used in order to ensure higher quality agricultural products.

The addition of biocarriers can improve the biological processes appearing in a bioreactor since their surface allows the immobilization, attachment, protection, and growth of microorganisms. In addition, the development of a biofilm layer allows the colonization of microorganisms in the biocarriers. The structure, composition, and roughness of the biocarriers' surface are crucial factors that affect the development of the biofilm. In the current work, the aluminosilicate zeolites 13X and ZSM-5 were examined as the main building components of the biocarrier scaffolds, using bentonite, montmorillonite, and halloysite nanotubes as inorganic binders in various combinations. 3D printing was utilized to form pastes into monoliths that underwent heat treatment. The 3d-printed biocarriers were subjected to a mechanical analysis, including density, compression, and nanoindentation tests. Furthermore, the 3d-printed biocarriers were morphologically and structurally characterized using nitrogen adsorption at 77 K (LN2), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The stress-strain response of the materials being studied was obtained through nanoindentation tests combined with finite element analysis (FEA). These tests were also utilized to simulate the lattice geometries under compression loading conditions to investigate their deformation and stress distribution in relation to experimental compression testing. The results indicated that the 3d-printed biocarrier 13X/halloysite nanotubes was endowed with high specific surface area and extended mesoporous structure. Due to these assets, its bulk density was one of the lowest observed amongst the biocarriers derived from the various combinations of materials. The biocarriers based on the 13X zeolite exhibited the highest mechanical stability and appropriate morphological features. The 13X/halloysite nanotubes scaffold exhibits a moderate hardness value compared to the rest, while it presents the highest value of modulus of elasticity. In conclusion, Aluminosilicate zeolites and their combination with clays and inorganic nanotubes afford 3d-printed biocarriers of various textural and structural properties, which can be utilized to improve biological processes.

Lewis acid zeolites play an important role in industrially important green reactions closely related to fine chemicals and biomass conversion. Titanium-doped TS-1 zeolite is a milestone Lewis acid zeolite, which widely uses in industrially significant green oxidation processes with hydrogen peroxide as an oxidant under mild conditions. TS-1 Zeolites are normally synthesized in basic condition under hydrothermal treatment. Up to now, it is still not successful to synthesize active TS-1 Lewis acid zeolite by using inorganic alkali, e.g. NaOH or KOH as base, which are cheaper and more stable compared with quaternary ammonium hydroxide or organic amines used in the traditional synthesis. Here, inorganic base of NaOH was firstly employed in synthesizing active TS-1 zeolites. The crucial factor was the control of adverse effects of sodium cations on the incorporation of active titanium cations. A higher catalytic activity could be achieved by further reducing the size of the TS-1 crystal by seed-added strategy, which could approach the catalytic activity of commercial catalyst while the production cost was much lower than the commercial TS-1 catalysts, indicating great commercial potential and the possibility of preparing other cheap Lewis acid catalysts by using inorganic alkali.

Starting from the environmental issues related to global warming, climate change and reduction of greenhouse gas emissions, this review paper describes how CO₂ recycling can represent a challenging strategy suitable to explore new concepts and opportunities for catalytic and industrial development. In this view, the production of dimethyl ether (DME) from catalytic hydrogenation of CO₂ appears as a viable technology, able to meet also the ever-increasing need for alternative environmentally-friendly fuels and energy carriers. Basic considerations on thermodynamic aspects controlling DME production from CO₂ are presented, then summarizing the main catalytic systems developed in such a field. Special attention is paid on the role assumed during last years by zeolite-based systems, either in the methanol-to-DME dehydration step or in the one-pot CO₂-to-DME hydrogenation. On the whole, the productivity of DME results significantly to be dependent on several catalyst features, linked not only to the metal-oxide phase responsible for CO₂ activation/hydrogenation, but also to specific properties of the zeolites (i.e., topology, porosity, surface area, acidity, interaction with active metals, distributions of metal particles, …) influencing activity and stability of hybridized bifunctional heterogeneous catalysts.

Binderless zeolite macrostructures in the form of ZK-4 microspheres were prepared using anion exchange resin beads as shape directing macrotemplates. The particles were synthesized under hydrothermal conditions at different temperatures and treatment times. The influence of the different synthesis parameters was investigated by X-ray diffraction, scanning electron microscopy, fluorescence X, nitrogen adsorption measurements and ²⁹Si solid NMR. Fully crystalline spheres similar in size and shape to the original resin beads were obtained by a hydrothermal treatment at the highest temperatures (150 - 180 °C) for a short treatment time of 24 h. The synthesized microspheres showed to be promising in the molecular decontamination of Volatile Organic Compounds (VOCs).

The feasibility of using zeolites, synthesized from components found in municipal solid waste fly ash (MSW-FA), as sorbents for the recovery of nutrients (nitrate and phosphate) and heavy metals is critically assessed in this review. The inherent drawbacks of utilising a highly contaminated, variable, and relatively Al- and Si-dilute source such as MSW-FA to synthesize zeolites are discussed, and different methods to extract and decontaminate zeolite precursor materials from MSW-FA are considered. Ways to synthesize tailored zeolites and how their properties as well as the operational conditions impact the adsorption of cations such as ammonium and heavy metals are summarized. The use of surface-modified zeolites to adsorb nitrate and phosphate is also reviewed. And subsequently, approaches to utilise directly or recover for reuse the adsorbed compounds are considered, discussing potential challenges and mitigating measures related to leaching of unwanted compounds from the zeolites. Moreover, the possibility to regenerate the adsorption capacity of the zeolites for multiple adsorption cycles is considered. In the final chapter of the review a more general discussion of the main challenges and existing research gaps is provided, giving directions for recommended studies.

Fine chemicals are produced in small annual volume batch processes (often <10,000 tonnes per year), with a high associated price (usually > $10/kg). As a result of their usage in the production of speciality chemicals, in areas including agrochemicals, fragrances and pharmaceuticals, their necessity will remain high for the foreseeable future. This review article assesses current methods used to produce fine chemicals with heterogeneous catalysts, including both well-established methods as well as newer experimental methods. A wide range of methods utilising microporous and mesoporous catalysts has been explored, including their preparation and modification before use in industry. Their potential drawbacks, as well as benefits, have been analysed, with their feasibility compared to newer, recently emerging catalysts. The field of heterogeneous catalysis for fine chemical production is a dynamic and ever-changing area of research. This deeper insight into catalytic behaviour and material properties will produce more efficient, selective, and sustainable processes in the fine chemical industry. The findings from this article will provide an excellent foundation for further exploration and a critical review in this field of fine chemical production using micro- and mesoporous heterogeneous catalysts.