The elucidation of the ring–opening reaction mechanism is a critical step towards improving the catalytic performance for the conversion of biomass into value–added chemicals. Herein, we focused on the stepwise C−O bond hydrogenolysis mechanism of oxygen–containing heterocycles (O‐heterocycles) into α,ω‐diols, in particular THFA to 1,5‐PeD, over selective Ni−La(OH)₃ in hydrogen–donor isopropanol. A mechanistic study was carried out on a structurally well–defined Ni−La(OH)₃, where the mechanism was elucidated using a combination of kinetic and ¹³C NMR isotope labeling experiments. It was suggested that both Ni nanoparticles and La(OH)₃ support play a critical role in the reaction mechanism, where basic hydroxide species of the support initially deprotonate the CH₂OH and −OH modified furan, tetrahydrofuran and tetrahydropyran rings, adsorbing them chemically on the catalyst surface. This step is followed by a direct hydride attack on the second carbon atom of these rings, which is proposed to be the key step for ring cleavage, as indicated by the increased deuteration at this position. In addition to the direct hydrogenolysis using gaseous H₂, it is assumed that a catalytic transfer hydrogenolysis reaction (CTH) reaction of THFA is proposed to proceed via the dehydrogenation of isopropanol over isolated Ni species, forming hydrogen species that can be adsorbed on the Ni surface or desorb as H₂ molecules.

We report on surface defects, electronic structure, and visible luminescence in pristine and Co-doped ZnO nanocrystals (NCs) by combining experimental characterization with density functional theory (DFT) calculations. Co doping notably reduced the crystallite size (25–18 nm) and nearly doubled the dislocation density (δ), indicating a decline in crystal quality. X-ray photoelectron spectroscopy (XPS) confirmed the incorporation of Co ions in a high-spin Co2+ (3d7, e4t23) configuration, with no detectable traces of Co3+ or metallic Co0 clusters. Photoluminescence (PL) spectra exhibited a dominant blue emission (2.7–2.8 eV), primarily due to electron transitions from the conduction band to zinc vacancy (VZn) acceptor states, further enhanced by Co-induced defects. A strong correlation between the experiment and DFT (Perdew–Burke–Ernzerhof generalized gradients approximation + U with mBJ corrections) elucidates the defect states responsible for visible emission. Our findings show how local atomic defects tune the optical properties and highlight the potential of Co-doped ZnO nanocrystals for blue light-emitting diode applications.

The oxidation of hydrocarbons of different structures under the same conditions is an important stage in the study of the chemical properties of both the hydrocarbons themselves and the oxidation catalysts. In a 50% H₂O₂/Cu₂Cl₄·2DMG/CH₃CN system, where DMG is dimethylglyoxime (Butane-2,3-dione dioxime), at 50 °C under the same or similar conditions, we oxidized eleven RH hydrocarbons of different structures: mono-, bi- and tri-cyclic, framework and aromatic. To compare the composition of the oxidation products of these hydrocarbons, we introduced a new quantitative characteristic, “distributive oxidation depth D(O), %” and showed the effectiveness of its application. The adiabatic ionization potentials (AIP) and the vertical ionization potentials (VIP) of the molecules of eleven oxidized and related hydrocarbons were calculated using the DFT method in the B3LYP/TZVPP level of theory for comparison with experimental values and correlation with D(O). The same calculations of AIP were made for the molecules of the oxidant, solvent, DMG, related compounds and products. It is shown that component X, which determines the mechanism of oxidation of hydrocarbons RH with AIP(Exp) ≥ AIP(X) = 8.55 ± 0.03 eV, is a trans-DMG molecule. Firstly theoretically estimated experimental values of AIP(trans-DMG) = 8.53 eV and AIP(cis-DMG) = 8.27 eV.

The oxidative C-C cleavage of a C₁₈ substrate is an important transformation in synthetic organic chemistry, facilitating the synthesis of valuable C₈-C₉ acids widely used in many industries. Through a comparative analysis of the catalytic and physicochemical properties of catalysts, comprising mono- (Pd or Au) and bimetallic (PdAu) nanoparticles deposited on oxides, oxyhydroxides and graphite-like carbon material Sibunit (Cp), it was shown that the efficiency of the catalyst in the oxidative cleavage of 9,10-dihydroxystearic acid relies on the nature of the active component, the support and the average size of metal nanoparticles (NPs). The dependency of 9,10-DSA conversion on the average size of metal NPs shows the structural sensitivity of the oxidative cleavage reaction. Notably, catalysts with an average size of gold particles less than 3 nm exhibit the highest activity. The nature of the active component and the support material are crucial factors determining the process selectivity. Among the catalysts studied, the most effective for the oxidative cleavage of 9,10-DSA is a material based on Au NPs deposited on Cp.