Electrochemical reduction of CO 2 to chemicals and fuels is an interesting and attractive way to mitigate greenhouse gas emissions and energy shortages. In this work, we report the use of atomic In catalysts for CO 2 electroreduction to CO. The atomic In catalysts were anchored on N-doped carbon (In A /NC) through pyrolysis of In-based metal−organic frameworks (MOFs) and dicyandiamide. It was discovered that In A /NC had outstanding performance for selective CO production in the mixed electrolyte of ionic liquid/ MeCN. It is different from those common In-based materials, in which formate/ formic acid is formed as the main product. The faradaic efficiency (FE) of CO and total current density were 97.2% and 39.4 mA cm -2 , respectively, with a turnover frequency (TOF) of ∼40 000 h −1 . It is one of the highest TOF for CO production to date for all of the catalysts reported. In addition, the catalyst had remarkable stability. Detailed study indicated that In A /NC had higher double-layer capacitance, larger CO 2 adsorption capacity, and lower interfacial charge transfer resistance, leading to high activity for CO 2 reduction. Control experiments and theoretical calculations showed that the In−N site of In A /NC is not only beneficial for dissociation of COOH* to form CO but also hinders formate formation, leading to high selectivity toward CO instead of formate.

Deciphering the sophisticated interplay between thermodynamics and kinetics of high‐temperature lithiation reaction is fundamentally significant for designing and preparing cathode materials. Here, the formation pathway of Ni‐rich layered ordered LiNi0.6Co0.2Mn0.2O2 (O‐LNCM622O) is carefully characterized using in situ synchrotron radiation diffraction. A fast nonequilibrium phase transition from the reactants to a metastable disordered Li1−x(Ni0.6Co0.2Mn0.2)1+xO2 (D‐LNCM622O, 0 < x < 0.95) takes place while lithium/oxygen is incorporated during heating before the generation of the equilibrium phase (O‐LNCM622O). The time evolution of the lattice parameters for layered nonstoichiometric D‐LNCM622O is well‐fitted to a model of first‐order disorder‐to‐order transition. The long‐range cation disordering parameter, Li/TM (TM = Ni, Co, Mn) ion exchange, decreases exponentially and finally reaches a steady‐state as a function of heating time at selected temperatures. The dominant kinetic pathways revealed here will be instrumental in achieving high‐performance cathode materials. Importantly, the O‐LNCM622O tends to form the D‐LNCM622O with Li/O loss above 850 °C. In situ XRD results exhibit that the long‐range cationic (dis)ordering in the Ni‐rich cathodes could affect the structural evolution during cycling and thus their electrochemical properties. These insights may open a new avenue for the kinetic control of the synthesis of advanced electrode materials.

Cobalt nitride (Co-N) thin films prepared using a reactive magnetron sputtering process are studied in this work. During the thin film deposition process, the relative nitrogen gas flow (RN2) was varied. As RN2 increases, Co(N), Co4N, Co3N and CoN phases are formed. An incremental increase in RN2, after emergence of Co4N phase at RN2 = 10%, results in a linear increase of the lattice constant (a) of Co4N. For RN2 = 30%, a maximizes and becomes comparable to its theoretical value. An expansion in a of Co4N, results in an enhancement of the magnetic moment, to the extent that it becomes even larger than pure Co. Such larger than pure metal magnetic moment for tetra-metal nitrides (M4N) have been theoretically predicted. Incorporation of N atoms in M4N configuration results in an expansion of a (relative to pure metal) and enhances the itinerary of conduction band electrons leading to larger than pure metal magnetic moment for M4N compounds. Though a higher (than pure Fe) magnetic moment for Fe4N thin films has been evidenced experimentally, higher (than pure Co) magnetic moment is evidenced in this work.

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Catalysts for photochemical reactions underlie many foundations in our lives, from natural light harvesting to modern energy storage and conversion, including processes such as water photolysis by TiO2. Recently, metal–organic frameworks (MOFs) have attracted large interest within the chemical research community, as their structural variety and tunability yield advantages in designing photocatalysts to address energy and environmental challenges. Here, we report a series of novel multivariate metal–organic frameworks (MTV-MOFs), denoted as MTV-MIL-100. They are constructed by linking aromatic carboxylates and AB2OX3 bimetallic clusters, which have ordered atomic arrangements. Synthesized through a solvent-assisted approach, these ordered and multivariate metal clusters offer an opportunity to enhance and fine-tune the electronic structures of the crystalline materials. Moreover, mass transport is improved by taking advantage of the high porosity of the MOF structure. Combining these key advantages, MTV-MIL-100­(Ti,Co) exhibits a high photoactivity with a turnover frequency of 113.7 molH2 gcat. –1 min–1, a quantum efficiency of 4.25%, and a space time yield of 4.96 × 10–5 in the photocatalytic hydrolysis of ammonia borane. Bridging the fields of perovskites and MOFs, this work provides a novel platform for the design of highly active photocatalysts.