Inorganic Chemistry Frontiers最新文献

The development of direct methanol fuel cell technology is expected to ease the excessive consumption of non-renewable fossil fuels, which puts forward a new request for the exploration of advanced Pt-alternative electrocatalysts toward the methanol oxidation reaction (MOR). Here, we demonstrate a facile and robust bottom-up method for the spatial construction of three-dimensional (3D) porous rhodium–copper alloy nanoflowers stereoassembled on Ti₃C₂T_x MXene nanosheets (RhCu NF/Ti₃C₂T_x) through an in situ soft-chemistry process. With the synergistic contributions from the distinctive structural merits, such as the 3D nanoflower-shaped configuration, abundant porosity, bimetallic alloy and strain effects, and excellent metallic conductivity, the resultant RhCu NF/Ti₃C₂T_x nanoarchitectures manifest significantly boosted electrocatalytic MOR performance under alkaline conditions, which is more competitive than that of conventional particle-shaped Rh catalysts dispersed on Ti₃C₂T_x nanosheets, graphene, carbon nanotubes, carbon black and commercial Pt/carbon black and Pd/carbon black catalysts.

Manganese dioxide is considered an ideal cathode candidate material for aqueous zinc-ion batteries. However, its poor conductivity and nanostructural degeneration impede its further application. Herein, a 3 × 3 tunnel-structured τ-MnO₂ cathode material was synthesized through the addition of excessive Mg²⁺. During its preparation, a portion of Mg²⁺ was embedded into the 3 × 3 tunnel of τ-MnO₂ to stabilize the microstructure, while another portion of Mg²⁺ formed a new phase, i.e., Mg₂(OH)₃Cl·4H₂O, adjoining τ-MnO₂, resulting in a cathode material with heterointerface synergy between τ-MnO₂ and Mg₂(OH)₃Cl·4H₂O. The charge arrangement of the heterointerface between τ-MnO₂ and Mg₂(OH)₃Cl·4H₂O enabled more active sites and accelerated ion-diffusion kinetics. The introduction of Mg₂(OH)₃Cl·4H₂O increased the proportion of Mn(IV) and suppressed the structural instability caused by Jahn–Teller distortion, thereby improving the electrochemical performance of the τ-MnO₂ cathode (capacity retention of 86.7% after 1800 cycles at 1 A g⁻¹).

Aqueous Mg–air batteries are promising candidates for large-scale energy storage, but their practical application is significantly hindered by water-induced parasitic reactions and the chunk effect. In this study, taurine (Tau) is an effective electrolyte additive for aqueous Mg–air batteries utilizing various magnesium anodes. The non-sacrificial Tau molecules, possessing both donor and acceptor groups, disrupt the inherent hydrogen bond network of H₂O and replace solvated H₂O in the Mg²⁺ solvation sheath, forming dynamic adsorption on Mg and creating a hydrophobic electric double layer. Consequently, taurine inhibits H₂O attack on Mg, promoting uniform Mg stripping. An appropriate amount of Tau not only enhances the discharge activity of the AZ31 anode but also suppresses its self-discharge phenomenon, achieving a surprising effect of simultaneously boosting voltage and anode utilization. Therefore, 0.2 M Tau was identified as the optimal electrolyte concentration and successfully incorporated in Mg–air batteries utilizing various routine Mg anodes (such as VW83, VW103, and LA103Z). The results demonstrate that Tau effectively enhances the discharge properties for Mg–air batteries employing various magnesium anodes.

Correction for ‘Unexpected in crystallo reactivity of the potential drug bis(maltolato)oxidovanadium(IV) with lysozyme’ by Maddalena Paolillo et al., Inorg. Chem. Front., 2024, 11, 6307–6315, https://doi.org/10.1039/D4QI01528B.

Sulfoxides, a class of pharmaceuticals and fine chemicals of significant importance, are readily peroxidized to sulfones in the H₂O₂ system. Altering the intermediate oxygen species is the key to achieving selectivity regulation. Herein, Zr(OH)₄ was used to support Mo species, after calcining at 500 °C, obtaining a unique amorphous composite oxide with Mo uniformly dispersed in the ZrO₂ matrix (Mo_aZr_0.8O_x-500). Mo_aZr_0.8O_x-500 demonstrates enhanced catalytic proficiency, enabling the synthesis of sulfoxides within 30 minutes at 30 °C. Reactive oxygen species (ROS) quenching experiments and EPR spectra indicate that Mo_aZr_0.8O_x-500 possesses the ability to rapidly and directly participate in the heterolytic cleavage of H₂O₂ to produce ¹O₂ without passing through the intermediate ˙O²⁻, preventing the peroxidation of sulfoxides to sulfones. Additionally, the prevalence of basic sites in Mo_aZr_0.8O_x-500 is conducive to proton transfer, which plays a significant role in the heterolytic cleavage of H₂O₂. Furthermore, Mo_aZr_0.8O_x-500 exhibits excellent reproducibility, scalability, and broad substrate applicability. This study provides new insights into the selective regulation of the sulfide oxidation reaction, as well as the preparation of amorphous solid solution.