Characteristics and catalytic activity in hydrogen production from formic acid of Au catalysts supported on porous N-free (Au/C) and N-doped carbon (Au/N-C) have been compared with those of Au/SiO₂ and Au/Al₂O₃ catalysts. Among the catalysts examined, the Au/N-C catalyst showed the highest Au mass-based catalytic activity. The following trend was found at 448 K: Au/N-C > Au/SiO₂ > Au/Al₂O₃, Au/C. The trend for the selectivity in hydrogen production was different: Au/C (99.5%) > Au/Al₂O₃ (98.0%) > Au/N-C (96.3%) > Au/SiO₂ (83.0%). According to XPS data the Au was present in metallic state in all catalysts after the reaction. TEM analysis revealed that the use of the N-C support allowed obtaining highly dispersed Au nanoparticles with a mean size of about 2 nm, which was close to those for the Au catalysts on the oxide supports. However, it was by a factor of 5 smaller than that for the Au/C catalyst. The difference in dispersion could explain the difference in the catalytic activity for the carbon-based catalysts. Additionally, the high activity of the Au/N-C catalyst could be related to the presence of pyridinic type nitrogen on the N-doped carbon surface, which activates the formic acid molecule forming pyridinium formate species further interacting with Au. This was confirmed by density functional theory (DFT) calculations. The results of this study may assist the development of novel Au catalysts for different catalytic reactions.

Porous nitrogen-doped and nitrogen-free carbon materials possessing high specific surface areas (400–1000 m² g⁻¹) were used for deposition of Ni by impregnation with nickel acetate followed by reduction. The nitrogen-doped materials synthesized by decomposition of acetonitrile at 973, 1073, and 1173 K did not differ much in the total content of incorporated nitrogen (4–5 at%), but differed in the ratio of the chemical forms of nitrogen. An X-ray photoelectron spectroscopy study showed that the rise in the synthesis temperature led to a strong growth of the content of graphitic nitrogen on the support accompanied by a reduction of the content of pyrrolic nitrogen. The content of pyridinic nitrogen did not change significantly. The prepared nickel catalysts supported on nitrogen-doped carbons showed by a factor of up to two higher conversion of formic acid as compared to that of the nickel catalyst supported on the nitrogen-free carbon. This was related to stabilization of Ni in the state of single Ni²⁺ cations or a few atoms clusters by the pyridinic nitrogen sites. The nitrogen-doped nickel catalysts possessed a high stability in the reaction at least within 5 h and a high selectivity to hydrogen (97%).

Two-dimensional black phosphorus (BP) has attracted great attention as a perspective material for various applications. The chemical functionalization of BP is an important pathway for the preparation of materials with improved stability and enhanced intrinsic electronic properties. Currently, most of the methods for BP functionalization with organic substrates require either the use of low-stable precursors of highly reactive intermediates or the use of difficult-to-manufacture and flammable BP intercalates. Herein we report a facile route for simultaneous electrochemical exfoliation and methylation of BP. Conducting the cathodic exfoliation of BP in the presence of iodomethane makes it possible to generate highly active methyl radicals, which readily react with the electrode’s surface yielding the functionalized material. The covalent functionalization of BP nanosheets with the P–C bond formation has been proven by various microscopic and spectroscopic methods. The functionalization degree estimated by solid-state ³¹P NMR spectroscopy analysis reached 9.7%.

The synthesis, characterization, experimental X-ray photoelectron spectra (XPS) and density-functional theory (DFT) investigations on solid solutions of Mo_1−xRe_xS₂ (x = 0.05, 0.10, 0.15 and 0.20) are reported herein.

Ni supported on N-doped carbon is rarely studied in traditional catalytic reactions. To fill this gap, we compared the structure of 1 and 6 wt% Ni species on porous N-free and N-doped carbon and their efficiency in hydrogen generation from gaseous formic acid. On the N-free carbon support, Ni formed nanoparticles with a mean size of 3.2 nm. N-doped carbon support contained Ni single-atoms stabilized by four pyridinic N atoms (N₄-site) and sub-nanosized Ni clusters. Density functional theory calculations confirmed the clustering of Ni when the N₄-sites were fully occupied. Kinetic studies revealed the same specific Ni mass-based reaction rate for single-atoms and clusters. The N-doped catalyst with 6 wt% of Ni showed higher selectivity in hydrogen production and did not lose activity as compared to the N-free 6 wt% Ni catalyst. The presented results can be used to develop stable Ni catalysts supported on N-doped carbon for various reactions.

Single-walled carbon nanotubes (SWCNTs) with their high surface area, electrical conductivity, mechanical strength and elasticity are an ideal component for the development of composite electrode materials for batteries. Red phosphorus has a very high theoretical capacity with respect to lithium, but has poor conductivity and expends considerably as a result of the reaction with lithium ions. In this work, we compare the electrochemical performance of commercial SWCNTs with red phosphorus deposited on the outer surface of nanotubes and/or encapsulated in internal channels of nanotubes in lithium-ion batteries. External phosphorus, condensed from vapors, is easily oxidized upon contact with the environment and only the un-oxidized phosphorus cores participate in electrochemical reactions. The support of the SWCNT network ensures a stable long-term cycling for these phosphorus particles. The tubular space inside the SWCNTs stimulate the formation of chain phosphorus structures. The chains reversibly interact with lithium ions and provide a specific capacity of 1545 mAh·g⁻¹ (calculated on the mass of phosphorus in the sample) at a current density of 0.1 A·g⁻¹. As compared to the sample containing external phosphorus, SWCNTs with encapsulated phosphorus demonstrate higher reaction rates and a slight loss of initial capacity (~7%) on the 1000th cycle at 5 A·g⁻¹.