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The influence of the reaction medium on the surface structure and properties of a Ni-based catalyst used for the reductive transformations of O-, N-, and S-containing aromatic substrates under hydrogen transfer conditions has been studied. The catalysts were characterized by XRD, XPS, and IR spectroscopy and TEM methods before and after the reductive reaction. It has been shown that the conversion of 1-benzothiophene causes irreversible poisoning of the catalyst surface with the formation of the Ni2S3 phase, whereas the conversion of naphthalene, 1-benzofuran, and indole does not cause any phase change of the catalyst at 250 °C. However, after the indole conversion, the catalyst surface remains enriched with N-containing compounds, which are evenly distributed over the surface. [ABSTRACT FROM AUTHOR]

Mixed Co-Ni bimetallic systems with the structure of a solid substitution solution have been synthesized using the supercritical antisolvent precipitation (SAS) method, which uses supercritical CO2 as an antisolvent. The systems obtained have been characterized in detail using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Fourier-transform infrared (FTIR) spectroscopy, and magnetostatic measurements. It has been found that Co-enriched systems have a defective hexagonal close-packed (hcp) structure, which was described by a model which embedded cubic fragments of packaging into a hexagonal close-packed (hcp) structure. It has been shown that an increase in water content at the precipitation stage leads to a decrease in the size of cubic fragments and a more uniform distribution of them in Co-enriched systems. It has also been shown that mixed systems have the greatest coercivity in the line of samples. Ni-enriched bimetallic systems have a cubic close-packed (ccp) structure with modified crystal lattice parameters. [ABSTRACT FROM AUTHOR]

Transfer hydrogenation (TH) is considered as one of the most promising ways to convert biomass into valuable products. This study aims to demonstrate the performance of high-loaded Ni-based catalysts in the TH of phenolic compounds such as guaiacol and dimethoxybenzenes. The experiments were carried out under supercritical conditions at 250 °C using 2-PrOH as the only hydrogen donor. Ni-SiO2 and NiCu-SiO2 were synthesized using the eco-friendly original method based on supercritical antisolvent coprecipitation. It has been found that guaiacol is rapidly converted into 2-methoxycyclohexanol and cyclohexanol, while the presence of Cu impedes the formation of the latter product. Transformations of dimethoxybenzene position isomers are slower and result in different products. Thus, 1,3-dimethoxybenzene loses oxygen atoms transform into methoxycyclohexane and cyclohexanol, whereas the saturation of the aromatic ring is more typical for other isomers. The Cu addition increases specific catalytic activity in the TH of 1,2-and 1,3-dimethoxybenzene compared to the Cu-free catalyst. [ABSTRACT FROM AUTHOR]

Mixed Ni-Al oxide catalytic precursors with different elemental ratios (20, 50, and 80 wt.% Ni0) were synthesized using green supercritical antisolvent co-precipitation (SAS). The obtained oxide precursors and metal catalysts were characterized in detail by X-ray diffraction (XRD) analysis, atomic pair distribution function (PDF) analysis, CO adsorption, and high-resolution transmission electron microscopy (HRTEM). It was found that the composition and structure of the Ni-Al precursors are related to the Ni content. The mixed Ni1−xAlxO oxide with NiO-based crystal structure was formed in the Ni-enriched sample, whereas the highly dispersed NiAl2O4 spinel was observed in the Al-enriched sample. The obtained metal catalysts were tested in the process of anisole H2-free hydrogenation. 2-PrOH was used as a hydrogen donor. The catalyst with 50 wt.% Ni0 demonstrated the highest activity in the hydrogenation process. [ABSTRACT FROM AUTHOR]

This paper describes the chemical engineering aspects for the preparation of highly active and stable nanocomposite photocatalysts based on N-doped TiO2. The synthesis is performed using titanium oxysulfate as a low-cost inorganic precursor and ammonia as a precipitating agent, as well as a source of nitrogen. Mixing the reagents under a control of pH leads to an amorphous titanium oxide hydrate, which can be further successfully converted to nanocrystalline anatase TiO2 through calcination in air at an increased temperature. The as-prepared N-doped TiO2 provides the complete oxidation of volatile organic compounds both under UV and visible light, and the action spectrum of N-doped TiO2 correlates to its absorption spectrum. The key role of paramagnetic nitrogen species in the absorption of visible light and in the visible-light-activity of N-doped TiO2 is shown using the EPR technique. Surface modification of N-doped TiO2 with copper species prevents its intense deactivation under highly powerful radiation and results in a nanocomposite photocatalyst with enhanced activity and stability. The photocatalysts prepared under different conditions are discussed regarding the effects of their characteristics on photocatalytic activity under UV and visible light. [ABSTRACT FROM AUTHOR]

Binary Ni–Cu heterogeneous catalysts are known to demonstrate excellent activity in conventional hydrogenation of phenolic compounds, and Cu addition facilitates hydrodeoxygenation (HDO). In this study, we aimed to show the effect of Cu on the specific catalytic activity and selectivity of Ni–Cu catalysts in transfer hydrogenation, in which 2-PrOH was used as a solvent and an H donor. Catalytic transformations of anisole were studied in sub- and supercritical alcohol at 150 and 250 °C. The catalysts were prepared using an environmentally friendly supercritical antisolvent coprecipitation method, which makes it possible to obtain well-dispersed particles (less than 7 nm) at high metal loading (up to 50 wt.%). When copper is added, deactivation of the catalyst in transformations of anisole, including HDO, is observed. The experimental data and the appropriate kinetic analysis demonstrate that there is a decrease in the rate of anisole conversion accompanied by an increase in the concentration of acetone formed during the dehydrogenation of 2-PrOH. [ABSTRACT FROM AUTHOR]