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Highly dispersed Ni‐TiO2 catalyst has been studied in the process of preparation and under catalytic transfer hydrogenation reaction conditions in supercritical 2‐propanol (250°C, 70 bar) using electron spin resonance in situ. Electron spin resonance in situ has been used to study the process of the catalyst passivation and subsequent reduction of the oxide layer in the gas flow. Reduction of the NiO layer on the surface of passivated Ni nanoparticles has been detected in supercritical 2‐propanol, which is in agreement with kinetic modeling data. It has been found that the reduction of the nickel oxide layer in supercritical 2‐propanol occurs at a lower temperature compared with the reduction in hydrogen flow, according to in situ electron spin resonance study. [ABSTRACT FROM AUTHOR]

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]

A new ring opening reaction was found while attempting to isolate the imines from ortho‐heteroatom substituted anilines and camphor‐like bicyclic ketones. The benzoazoles containing a cyclopentanemethyl group at position 2 of the heterocycle were isolated instead of the expected imines. The detailed study of the transformation, including EPR experiments, revealed the most probable radical mechanism. The proposed reaction pathways were confirmed by quantum chemical calculations. The dichotomy of 1–2 and 2–3 bonds cleavage is discussed together with the evaluation of the stereochemical outcome of the reactions. The benzoazoles obtained via the new reaction are of particular interest for the medicinal chemistry. [ABSTRACT FROM AUTHOR]

Five crude oil samples with different physical properties have been studied with respect to asphaltene stability. The attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopic imaging approach of n-heptane-induced precipitation has been used to monitor crude oil behaviour under dilution with a flocculation agent. For each sample, the dynamics of asphaltene precipitation has been observed by applying this chemical imaging method. Based on these data, the stability of crude oil samples has been compared and the correlation between asphaltene stability and crude oil properties has been proposed. [ABSTRACT FROM AUTHOR]

The wax appearance temperature (WAT), being one of the key characteristics of waxy crude oil and other waxy substances, is used for the necessary assessment of the phase stability of materials during various technological processes. However, the determination of this parameter as well as peculiarities of wax formation under high gas pressure suffers from the lack of suitable techniques for this task. To address this issue, an attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) method has been applied for the first time to measure the WAT of waxy crude oil under high gas pressure. Carbon dioxide (CO2), nitrogen, and natural gas were used in the study due to their widespread applicability as injection gases in enhanced oil recovery methods. The S2/S1 versus temperature method based on changes in the band of rocking vibrations of the CH2 group was applied to determine WAT. It was found that the ATR FT-IR method based on the proposed dependence S2/S1 versus temperature gives lower WAT values compared to those observed by viscometry, magnetic resonance imaging inspection, and cross-polarized microscopy methods for the waxy crude oil studied. A detailed analysis was carried out using variable-temperature ATR FT-IR spectra of waxy crude oil in the temperature region near the WAT. Essentially different dynamics of wax crystal formation in waxy oil sample and model paraffin solution were demonstrated during the cooling process. The results obtained by high-pressure ATR FT-IR showed that CO2 and natural gas reduce the WAT, while nitrogen has virtually no effect. In addition, for the studied oil, it was found that high pressure of CO2 and natural gases leads to a visual decrease in the amount of wax crystals precipitated, but not to the complete disappearance of microcrystals at a certain temperature and pressure. The results obtained proved that ATR FT-IR can be an effective method for proper determinations of WAT under high-pressure conditions similar to those met in practice. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Base-free transfer hydrogenation of menthone by primary and secondary alcohols as a hydrogen donor under sub- and sc conditions. • The similar H -donor activity of all alcohols under non-catalytic sc conditions. • Only secondary alcohols demonstrate a high H -donor activity in the presence of Raney® Ni under subcritical conditions. • A quasi-equilibrium of isomeric menthone/isomenthone mixture reached via enolization under sc conditions. Abstract The base-free transfer hydrogenation (THR) of menthone with six aliphatic alcohols as hydrogen source has been developed under sub- and supercritical conditions. Under sc conditions (at 350 °C and 78–210 atm) without any catalyst, all alcohols demonstrated the similar H -donor activity, which was high enough. The menthone conversion was about 64 ± 5% for 5 h of the reaction, whereas the selectivity on menthol reached 92–99% for all alcohols except MeOH (73%). The non-catalytic THR at 250 °C was very slow and the conversion in the most active 2-PrOH was only 7.0–7.5% for 9 h of the reaction. Under subcritical conditions at 150 °C, the non-catalytic menthone reduction was negligible in all alcohols. But in secondary 2-PrOH and 2-BuOH, the base-free THR catalyzed by Raney® nickel results in excellent conversion and selectivity of menthol at 150 °C, whereas no conversion of menthone was observed in primary alcohols under the same reaction conditions. A quasi-equilibrium of isomeric menthone/isomenthone mixture reached via enolization was evaluated under sub- and supercritical conditions and the Gibbs energies of the isomerization in each alcohol were calculated. [ABSTRACT FROM AUTHOR]

Highlights: [•] Different forms of SiO2 react slowly with methanol at 350°C to give mainly TMOS. [•] Some N-unsubstituted benzazoles increase considerably the amount of reacted SiO2. [•] The key role of heterocycles is nucleophilic assistance to the reaction. [•] Azole ring of heterocycles is methylated by MeOH during the reaction. [•] Both SiO2-surface and TMOS catalyze the methylation of benzazole. [ABSTRACT FROM AUTHOR]

• The Al-Si oxides were synthesized for the first time via supercritical antisolvent precipitation of Al-Si-containing sols. • The alumina and silicon-doped alumina obtained by the SAS method were shown to be mesoporous and thermal stable materials. • The alumina composed of X-ray amorphous particles (2-5 nm) forming a narrow pores size distribution (3-5 nm). A method of alumina and silica sols precipitation in supercritical CO 2 has been developed for the first time to prepare alumina and silica doped alumina. The silicon content of samples is varied within the range from 0 to 30 mol. %. The approach suggested can be considered as a development of supercritical antisolvent (SAS) method that is widely used to prepare powders from solutions but not sols. The alumina and silicon-doped alumina obtained are shown to be mesoporous materials with narrow size distribution in the range of 3–5 nm. The high-temperature treatment of the sample containing 10 mol. % of Si results in the formation of γ-Al 2 O 3 phase followed by its transition into the δ -Al 2 O 3 phase at 1200 °C without α-Al 2 O 3 phase formation. It is demonstrated that the gradual introduction of silica into the alumina allows one to fine-tune the strength and amount of acid sites existing in oxides. [ABSTRACT FROM AUTHOR]

Sub- and supercritical alcohols are known as effective hydrogen donors. In this work, transfer hydrogenation (TH) of furfural with C 1 -C 4 alcohols has been studied under sub- and supercritical conditions. In the range of 230–275 °C, the observed activation energy of catalyst-free transformations of furfural into furfuryl alcohol and some minor byproducts has been shown to be 98 ± 8, 64 ± 4 and 79 ± 6 kJ/mol for EtOH, 1-PrOH and 2-PrOH, respectively. The use of a Ni/γ-Al 2 O 3 catalyst results in higher rate constants compared to the catalyst-free TH. Nevertheless, the selectivity to furfuryl alcohol in the presence of the catalyst does not exceed 50% vs 70–80% for the catalyst-free transformations. Thus, this study shows the high donor potential of alcohols in TH under both catalytic and catalyst-free conditions. A special attention is paid to primary alcohols, because they are highly demanded as H-donors due to economic and environmental reasons. [Display omitted] • Primary C 1 -C 4 alcohols demonstrate high donor activity in furfural TH. • Catalyst-free TH of furfural and 1-PrOH has lower activation energy than 2-PrOH. • Selectivity to furfuryl alcohol of catalyst-free furfural TH reaches 70–80%. • Use of Ni/γ-Al 2 O 3 results in higher rate constants but the lower selectivity. [ABSTRACT FROM AUTHOR]

Transfer hydrogenation of anisole in 2-PrOH has been studied as a model reaction for lignocellulose processing. The reaction was studied over high-loaded Ni-based catalysts synthesized via supercritical antisolvent precipitation of a Ni precursor and sols of four oxides: Al 2 O 3 , SiO 2 , TiO 2 , and ZrO 2. It was demonstrated that the oxide support significantly affects the structure of the catalysts, their activity, and selectivity. The best performance in the transfer hydrodeoxygenation of anisole was shown by Ni supported on alumina at 250 °C, which was explained by the highest dispersion of Ni0 particles in this catalyst and by the highest concentration of acid centers. [Display omitted] • Well-dispersed high-loaded Ni catalysts were synthesized by SAS method. • Obtained catalysts show excellent activity in transfer hydrogenation of anisole. • Acid sites and the smaller Ni particles facilitate hydrodeoxygenation of anisole. [ABSTRACT FROM AUTHOR]

[Display omitted] • Poisoning titration is precise approach to quantify Raney® Ni active centers. • Effect of 15 poisons (thiols, amines, acids) on catalyst activity measured. • TOF of Raney® Ni probed by thiophenol titration was 2.4 h–1 at 82 °C. • C–S bond cleavage of thiophenol did not occur during poisoning of Raney® Ni. For the first time, the poisoning effect of 15 different chemical compounds on Raney® nickel catalyst has been comparatively studied in the transfer hydrogenation of camphor using 2-PrOH as a solvent and a hydrogen donor. It has been shown that thiophenol, HCl and H 3 PO 4 demonstrate the strongest poisoning action under the reaction conditions: no camphor conversion was observed at 5 mol.% of poison-to-nickel ratio. A strong chemical binding of thiophenol molecules to the catalyst surface without C S bond cleavage was proved by XRF, TPD methods, CHNS analysis, and FTIR spectroscopy. It was shown that the poisoning titration with thiophenol is an effective and convenient tool to calculate the number of active sites for Ni based catalysts directly, measuring catalytic activity in target chemical reaction, which was defined correspondently as 2.4 h−1 and 9.6 × 10–5 mole for Raney® nickel catalyst in the transfer hydrogenation. [ABSTRACT FROM AUTHOR]