In this work, we studied the role of zinc in the composition of supported iron-containing catalysts for the hydrogenation of CO2. Various variants of incipient wetness impregnation of the support were tested to obtain catalyst samples. The best results are shown for samples synthesized by co-impregnation of the support with a common solution of iron and zinc precursors at the same molar ratio of iron and zinc. Catalyst samples were analyzed by various methods: Raman, DRIFT-CO, TPR-H2, XPS, and UV/Vis. The introduction of zinc leads to the formation of a mixed ZnFe2O4 phase. In this case, the activation of the catalyst proceeds through the stage of formation of the metastable wustite phase FeO. The formation of this wustite phase promotes the formation of metallic iron in the composition of the catalyst under the reaction conditions. It is believed that the presence of metallic iron is a necessary step in the formation of iron carbides—that is, active centers for the formation and growth of chain in the hydrocarbons. This leads to an increase in the activity and selectivity of the formation of hydrocarbons in the process of CO2 hydrogenation.
A new reality of the 21st century is the transition to a new type of economy and energy concepts characterized by the replacement of existing petrochemical routes to a bio-based circular economy. The needs for new strategies in obtaining basic products from bio-based resources with minimum CO2 traces has become mandatory. In this review, recent trends in the conversion of biomass-derived molecules, such as simple monomeric sugars and cellulose, to industrially important C5 and C6 sugar alcohols on heterogeneous catalysts based on non-noble metals are discussed focusing on the influence of catalyst structures and reaction conditions used on the substrate conversion and product selectivity. The challenges and prominent ideas are suggested for the further development of catalytic hydrogenation of naturally abundant carbohydrates to value-added chemicals on non-noble metal catalysts.
Active and stable catalysts are essential for effective hydrogenation of gaseous CO2 into valuable chemicals. This work focuses on the structural and catalytic features of single metals, i.e., Co and Ni, as well as bimetallic CoNi alloy catalysts synthesized via combustion of reactive sol-gels. Different characterization methods were used for studying the relationships between the structure, composition, and catalytic activity of the fabricated materials. All catalysts exhibited highly porous sponge-like microstructure. The outermost surfaces of the CoNi alloys were more saturated with Co, while a stoichiometric Co/Ni ratio was observed for the particle’s bulk. Catalytic properties of the as-synthesized powders were studied in the CO2 hydrogenation reaction at 300 °C for over 80 h of time on stream. All the catalysts demonstrated exceptional selectivity with respect to CH4 formation. However, the combination of elemental Co and Ni in a single phase resulted in a synergistic effect in bulk alloy catalysts, with activity twofold to threefold that of single-metal catalysts. The activity and stability of the CoNi3 catalyst were higher than those previously reported for Ni-based catalysts. The reasons for this behavior are discussed.
The state of palladium and copper on the surface of the PdCl2–CuCl2/γ-Al2O3 nanocatalyst for the low-temperature oxidation of CO by molecular oxygen was studied by various spectroscopic techniques. Using X-ray absorption spectroscopy (XAS), powder X-ray diffraction (XRD), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), freshly prepared samples of the catalyst were studied. The same samples were also evaluated after interaction with CO, O2, and H2O vapor in various combinations. It was shown that copper exists in the form of Cu2Cl(OH)3 (paratacamite) nanophase on the surface of the catalyst. No palladium-containing crystalline phases were identified. Palladium coordination initially is comprised of four chlorine atoms. It was shown by XAS that this catalyst is not capable of oxidizing CO at room temperature in the absence of H2O and O2 over 12 h. Copper(II) and palladium(II) are reduced to Cu(I) and Pd(I,0) species, respectively, in the presence of CO and H2O vapor (without O2). It was found by DRIFTS that both linear (2114 cm−1, 1990 cm−1) and bridging (1928 cm−1) forms of coordinated CO were formed upon adsorption onto the catalyst surface. Moreover, the formation of CO2 was detected upon the interaction of the coordinated CO with oxygen. The kinetics of CO oxidation was studied at 18–38 °C at an atmospheric pressure for CO, O2, N2, and H2O (gas) mixtures in a flow reactor (steady state conditions).