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Catalysts with no hazardous or toxic components are required for the selective hydrogenation of acetylenic bonds in the synthesis of pharmaceuticals, vitamins, nutraceuticals, and fragrances. The present work demonstrates that a high selectivity to alkene can be reached over a Pd-Fe-O/SiO2 system prepared by the co-impregnation of a silica support with a solution of the metal precursors (NH4)3[Fe(C2O4)3] and [Pd(NH3)4]Cl2 followed by thermal treatment in hydrogen or in air at 400 °C. A DRIFT spectroscopic study of CO adsorption revealed large shifts in the position of the Pdn+-CO bands for this system, indicating the strong effect of Fen+ on the Pd electronic state, resulting in a decreased rate of double C=C bond hydrogenation and an increased selectivity of alkyne hydrogenation to alkene. The prepared catalysts consisted of mono- and bimetallic nanoparticles on an SiO2 carrier and exhibited a selectivity as high as that of the commonly used Lindlar catalyst (which contains such hazardous components as lead and barium), while the activity of the Fe-Pd-O/SiO2 catalyst was an order of magnitude higher. The hydrogenation of a triple bond over the proposed Pd-Fe catalyst opens the way to selective hydrogenation over nontoxic catalysts with a high yield and productivity. Taking into account a simple procedure of catalyst preparation, this direction provides a rationale for the large-scale implementation of these catalysts.

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To meet the increasing needs of fuels, especially non-fossil fuels, the production of "bio-oil" is proposed and many efforts have been undertaken to find effective ways to transform bio-wastes into valuable substances to obtain the fuels and simultaneously reduce carbon wastes, including CO2. This work is devoted to the gasification of sugar cane bagasse to produce CO in the process assisted by CO2. The metals were varied (Fe, Co, or Ni), along with their amounts, in order to find the optimal catalyst composition. The materials were investigated by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), and electron diffraction, and were tested in the process of CO2-assisted gasification. The catalysts based on Co and Ni demonstrate the best activity among the investigated systems: the conversion of CO2 reached 88% at ~800 °C (vs. 20% for the pure sugarcane bagasse). These samples contain metallic Co or Ni, while Fe is in oxide form.

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Currently, microwave radiation is widely used in various chemical processes in order to intensify them and carry out processes within the framework of "green" chemistry approaches. In the last 10 years, there has been a significant increase in the number of scientific publications on the application of microwaves in catalytic reactions and synthesis of nanomaterials. It is known that heterogeneous catalysts obtained under microwave activation conditions have many advantages, such as improved catalytic characteristics and stability, and the synthesis of nanomaterials is accelerated several times compared to traditional methods used to produce catalysts. The present review article is to summarize the results of modern research on the use of microwave radiation for the synthesis of heterogeneous catalytic nanomaterials and discusses the prospects for research in the field of microwave-induced liquid-phase heterogeneous catalysis in hydrogenation.

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Because of the growing demand for high-quality fuels, the light cycle oil fraction improvement including cetane number improvement is important. The main way to reach this improvement is the ring opening of cyclic hydrocarbons, and a highly effective catalyst should be found. Cyclohexane ring openings are a possible option to investigate the catalyst activity. In this work, we investigated rhodium-loaded catalysts prepared using the commercially available industrial supports: single-component ones, SiO2 and Al2O3; and mixed oxides CaO + MgO + Al2O3 and Na2O + SiO2 + Al2O3. The catalysts were prepared by incipient wetness impregnation and investigated by N2 low-temperature adsorption-desorption, XRD, XPS, DRS UV-Vis and DRIFT spectroscopy, SEM, and TEM with EDX. The catalytic tests were performed in cyclohexane ring opening in the range of 275-325 °C. The best result was demonstrated by the sample 1Rh/CaMgAlO: the selectivity to n-hexane was about 75% while the cyclohexane conversion was about 25% at 275 °C. The space-time yield was up to 12 mmoln-hexane gcat-1h-1.

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Phase equilibria in the In-Pd-Sn system were investigated by a combination of key experiments and thermodynamic modeling. Partial isothermal sections at 500 °C and 800 °C of the In-Pd-Sn system for Pd contents above 66 at.% have been plotted experimentally using scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM/EDX) and X-ray diffraction (XRD). The solubility of the third component in binary compounds InPd3 and Pd3Sn was determined. The new ternary compound τ1 was found in Pd contents ranging from 20 to 25 at.% and at Sn contents varying from 5 to approximately 17 at.% Sn. This compound crystallizes in an Al3Ti-type tetragonal structure. Isostructural InPd2 and Pd2Sn phases from the In-Pd and Pd-Sn binary compositions form a continuous phase field in the ternary system at both temperatures. The temperatures of the solidus, liquidus, and phase transitions of the alloys along the Pd-In50Sn50 line were measured using DTA/DSC. Thermodynamic calculation of the In-Pd-Sn ternary system is performed using the CALPHAD method using the Thermo-Calc® software. The thermodynamic properties of the disordered fcc and liquid phases were described by the Redlich-Kister-Muggianu model. To describe intermetallic phases, namely, InPd3, Pd3Sn, τ1 and Pd2(InxSn1-x), a two-sublattice models was used. Thermodynamic description of the In-Pd-Sn system obtained in this study is in good agreement both with our results and the published experimental data.

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Hydrolytic lignin is one of the non-demanded carbon materials. Its CO2-assisted conversion is an important way to utilize it. The use of the catalysts prepared by metal deposition on the surface of hydrolytic lignin makes it possible to apply milder conditions of the conversion process with CO2 and to improve the economic indicators. The development of methods of deposition of the active phase is a problem of high importance for any heterogeneous catalytic processes. This work aimed at investigating the influence of the conditions of iron deposition on the surface of hydrolytic lignin on the process of CO2-assisted conversion of lignin. Different Fe precursors (Fe(NO3)3, FeSO4, Fe2(SO4)3), solvents (water, isopropanol, acetone, and ethanol), and concentrations of the solution were used; the properties of Fe/lignin composites were estimated by SEM, EDX, TEM, XRD methods and catalytic tests. All the prepared samples demonstrate a higher conversion compared to starting lignin itself in the carbon dioxide-assisted conversion process. The carbon dioxide conversion was up to 66% at 800 °C for the sample prepared from Fe(NO3)3 using a twofold water volume compared to incipient wetness water volume as a solvent (vs. 39% for pure lignin).

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The formation of complexes and transformations of nitrogen oxides (NO, N2O) on strong Lewis acid sites of HZSM-5, H[Ga]ZSM-5, ZnO/HZSM-5 zeolites and dealuminated mordenites was investigated by diffuse-reflectance IR spectroscopy. Adsorbed N2O that is formed by disproportionation of NO is capable of oxidizing CO and CH4 molecules to CO2. The behaviour of strong Lewis acid sites in zeolites and cationic forms of zeolites in the NO disproportionation and CO or CH4 oxidation was comparatively studied.

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Catalytic conversion of carbohydrates into value-added products and platform chemicals became a trend in recent years. Microwave activation used in the processes of carbohydrate conversion coupled with the proper choice of catalysts makes it possible to enhance dramatically the efficiency and sometimes the selectivity of catalysts. This mini-review presents a brief literature survey related to state-of-the-art methods developed recently by the world research community to solve the problem of rational conversion of carbohydrates, mostly produced from natural resources and wastes (forestry and agriculture wastes) including production of hydrogen, synthesis gas, furanics, and alcohols. The focus is made on microwave technologies used for processing carbohydrates. Of particular interest is the use of heterogeneous catalysts and hybrid materials in processing carbohydrates.

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Decomposition of N2O on modified zeolites, crystalline titanosilicalites, and related amorphous systems is studied by the catalytic and spectroscopic methods. Zinc-containing HZSM-5 zeolites and titanosilicalites with moderate Ti/Si ratios are shown to exhibit a better catalytic performance in N2O decomposition as compared with conventionally used Cu/HZSM-5 zeolites and amorphous Cu-containing catalysts. Dehydroxylation of the HZSM-5 zeolite by calcination at 1120 K results in an enhancement of the N2O conversion. The mechanism of the reaction and the role of coordinatively unsaturated cations and Lewis acid sites in N2O decomposition are discussed on the basis of the spectroscopic data.

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Ozonolysis is used for oxidation of a model cyclic molecule-decalin, which may be considered as an analog of saturated cyclic molecules present in heavy oil. The conversion of decalin exceeds 50% with the highest yield of formation of acids about 15-17%. Carboxylic acids, ketones/aldehydes, and alcohols are produced as intermediate products. The methods of UV-visible, transmission IR, attenuated total reflection IR-spectroscopy, NMR and mass-spectrometry were used to identify reaction products and unravel a possible reaction mechanism. The key stage of the process is undoubtedly the activation of the first C-H bond and the formation of peroxide radicals.

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Reduction of CO2 with hydrogen into CO was studied for the first time on alumina-supported Co and Fe catalysts under supercritical conditions with the goal to produce either CO or CH4 as the target products. The extremely high selectivity towards methanation close to 100% was found for the Co/Al2O3 catalyst, whereas the Fe/Al2O3 system demonstrates a predominance of hydrogenation to CO with noticeable formation of ethane (up to 15%). The space-time yield can be increased by an order of magnitude by using the supercritical conditions as compared to the gas-phase reactions. Differences in the crystallographic phase features of Fe-containing catalysts cause the reverse water gas shift reaction to form carbon monoxide, whereas the reduced iron phases initiate the Fischer-Tropsch reaction to produce a mixture of hydrocarbons. Direct methanation occurs selectively on Co catalysts. No methanol formation was observed on the studied Fe- and Co-containing catalysts.

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The nonoxidative conversion of ethanol to acetaldehyde under thermal and microwave heating was studied on mixed oxide ZnO-CuO-SiO2 catalysts modified with additives of tungsten carbide nanoparticles. The results revealed that the WC-modified catalyst exhibited superior activity and selectivity under microwave heating conditions. It is assumed that when microwave heating is used, hot zones can appear at the contact points of WC nanoparticles and active centers of the mixed oxide ZnO-CuO-SiO2 catalyst, which intensively absorb microwave energy, allowing the more efficient formation of acetaldehyde at moderate temperatures. Thermodynamic calculations of equilibrium concentrations of reagents and products allowed us to identify the optimal conditions for effective acetaldehyde production. The initial catalyst and the catalyst prepared by the coprecipitation of the oxides with the addition of WC were characterized by physicochemical methods (TPR-H2, XRD, DRIFTS of adsorbed CO). The active centers of the oxide catalyst can be Cu+ cations.

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The formation of complexes and disproportionation of nitrogen oxides (NO, N2O) on cationic forms of LTA, FAU, and MOR zeolites was investigated by diffuse-reflectance IR spectroscopy. N2O is adsorbed on the samples under study in the molecular form and the frequencies of the first overtone of the stretching vibrations ν10-2 and the combination bands of the stretching vibrations with other vibrational modes for N2O complexes with cationic sites in zeolites (ν30-1 + ν10-1, ν10-1 + δ0-2) are more significantly influenced by the nature of the zeolite. The presence of several IR bands in the region of 2400-2600 cm-1 (the ν10-1 + δ0-2 transitions) for different zeolite types was explained by the availability of different localization sites for cations in these zeolites. The frequencies in this region also depend on the nature of the cation (its charge and radius). The data can be explained by the specific geometry of the N2O complex formed, presumably two-point adsorption of N2O on a cation and a neighboring oxygen atom of the framework. Adsorption of CO or CH4 on the samples with preliminarily adsorbed N2O at 20-180 °C does not result in any oxidation of these molecules. NO+ and N2O3 species formed by disproportionation of NO are capable of oxidizing CO and CH4 molecules to CO2, whereas NOx is reduced simultaneously to N2 or N2O. The peculiarities in the behavior of cationic forms of different zeolites with respect to adsorbed nitrogen oxides determined by different density and localization of cations have been established.

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Nowadays, there is a demand in the production of nontoxic multifunctional magnetic materials possessing both high colloidal stability in water solutions and high magnetization. In this work, a series of water-dispersible natural humate-polyanion coated superparamagnetic magnetite nanoparticles has been synthesized via microwave-assisted synthesis without the use of inert atmosphere. An impact of a biocompatible humate-anion as a coating agent on the structural and physical properties of nanoparticles has been established. The injection of humate-polyanion at various synthesis stages leads to differences in the physical properties of the obtained nanomaterials. Depending on the synthesis protocol, nanoparticles are characterized by improved monodispersity, smaller crystallite and grain size (up to 8.2 nm), a shift in the point of zero charge (6.4 pH), enhanced colloidal stability in model solutions, and enhanced magnetization (80 emu g-1).

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Novel catalytic nano-sized materials based on LaCoO(x) perovskite nanoparticles incapsulated in the mesoporous matrix of zirconia were prepared, characterized by physicochemical methods and tested in complete methanol oxidation. LaCoO(x) nanoparticles were prepared inside the mesopores of ZrO(2) by decomposition of bimetallic La-Co glycine precursor complexes. The catalysts have been studied by diffuse-reflectance FTIR-spectroscopy using such probe molecules as CO, CD(3)CN and CDCl(3) to test low-coordinated metal ions. At low temperatures of decomposition of complexes (up to 400°C), low-coordinated Co(3+) ions predominate in the LaCoO(x) nanoparticles, whereas basically Co(2+) ions are found upon increasing the decomposition temperature to 600°C. The novel nano-sized perovskite catalysts exhibit a very high catalytic activity in the abatement of volatile organic compounds present in air, like methanol and light hydrocarbons.

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