The green and sustainable electrocatalytic conversion of nitrogen-containing compounds to ammonia is currently in high demand in order to replace the eco-unfriendly Haber–Bosch process. Model catalysts for the nitrate reduction reaction were obtained by electrodeposition of metal Co, Fe, and bimetallic Fe/Co nanoparticles from aqueous solutions onto a graphite substrate. The samples were characterized by the following methods: SEM, XRD, XPS, UV–vis spectroscopy, cyclic (and linear) voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. In addition, the determination of the electrochemically active surface was also performed for all electrocatalysts. The best electrocatalyst was a sample containing Fe-nanoparticles on the layer of Co-nanoparticles, which showed a Faradaic efficiency of 58.2% (E = −0.785 V vs. RHE) at an ammonia yield rate of 14.6 μmol h−1 cm−2 (at ambient condition). An opinion was expressed to elucidate the mechanism of coordinated electrocatalytic action of a bimetallic electrocatalyst. This work can serve primarily as a starting point for future investigations on electrocatalytic conversion reactions to ammonia using model catalysts of the proposed type.
22 February 2023 in Journal of Chemical Technology & Biotechnology
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).
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.
Green and sustainable electrocatalytic conversion of nitrogen-containing compounds to ammonia are currently in high demand in order to replace the eco-unfriendly Haber-Bosch process. Model catalysts for the nitrate reduction reaction were obtained by electrodeposition of metal Co, Fe and bimetallic Fe/Co nanoparticles from aqueous solutions onto a graphite substrate. The samples were characterized by the following methods: SEM, XRD, XPS, UV-vis spectroscopy, cyclic (and linear) voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Besides, the determination of electrochemically active surface was also performed for all electrocatalysts. The best electrocatalyst was a sample containing Fe-nanoparticles on the layer of Co-nanoparticles, which showed the Faradaic efficiency 58.2% (E=-0.785 V vs. RHE) at the ammonia yield rate of 14.6 μmol h-1 cm-2. An opinion was expressed on elucidation of the mechanism of coordinated electrocatalytic action of a bimetallic electrocatalyst. This work can serve primarily as a starting point for future investigations on electrocatalytic conversion reactions to ammonia using model catalysts of the proposed type.
Copper-containing catalysts supported on different commercial oxide supports (SiO2, Al2O3, and mixed oxide supports) were prepared by the incipient wetness impregnation method and investigated for the selective hydrogenation of methyl esters (methyl butyrate, methyl hexanoate, methyl stearate) to fatty alcohols. Characterization techniques, including transmission (TEM) and scanning electron microscopy (SEM), X-ray diffraction (XRD), N2 adsorption–desorption isotherms, and the temperature-programmed hydrogen reduction (H2-TPR) method, were utilized and revealed the relationship between catalyst properties and its structure. The best results of catalytic activity were obtained in the presence of the Cu catalyst supported on SiO2 with co-precipitated Al2O3, where the conversion of esters was above 50% with a selectivity for the corresponding alcohols of 40–70%. This efficient and inexpensive Cu-based catalyst can be widely used in industrial production, which is conducive to promoting the development of non-precious metal catalysts in the biomass industry.