Oxygenate-induced structural evolution of high-entropy electrocatalysts for multifunctional alcohol electrooxidation integrated with hydrogen production.

High-entropy compounds have been emerging as promising candidates for electrolysis, yet their controllable electrosynthesis strategy remains a formidable challenge because of the ambiguous ionic interaction and codeposition mechanism. Herein, we report a oxygenates directionally induced electrodeposition strategy to construct high-entropy materials with amorphous features, on which the structural evolution from high-entropy phosphide to oxide is confirmed by introducing vanadate, thus realizing the simultaneous optimization of composition and structure. The representative P-CoNiMnWVOx shows excellent bifunctional catalytic performance toward alkaline hydrogen evolution reaction and ethanol oxidation reaction (EOR), with small potentials of -168 mV and 1.38 V at 100 mA cm-2, respectively. In situ spectroscopy illustrates that the electrochemical reconstruction of P-CoNiMnWVOx induces abundant Co-O species as the main catalytic active species for EOR and follows the conversion pathway of the C2 product. Theoretical calculations reveal the optimized electronic structure and adsorption free energy of reaction intermediates on P-CoNiMnWVOx, thereby resulting in a facilitated kinetic process. A membrane-free electrolyzer delivers both high Faradaic efficiencies of acetate and H2 over 95% and superior stability at100 mA cm-2 during 120 h electrolysis. In addition, the unique composition and structural advantages endow P-CoNiMnWVOx with multifunctional catalytic activity and realize multipathway electrosynthesis of formate-coupled hydrogen production.

Pt-decorated spinel MnCo2O4 nanosheets enable ampere-level hydrazine assisted water electrolysis.

Coupling hydrazine oxidation reaction (HzOR) with hydrogen evolution reaction (HER) has been widely concerned for high efficiency of green hydrogen preparation with low energy consumption. However, the lacking of bifunctional electrodes with ampere-level performance severely limits its industrialization. Herein, we put forward an efficient active site anchored strategy for MnCo2O4 nanosheet arrays on nickel foam (NF) by introducing Pt species (denoted as Pt-MnCo2O4/NF), which is standing for excellent bifunctional electrodes. The Pt-MnCo2O4/NF delivers ultralow potentials of -195 mV and 350 mV at 1000 mA cm-2 as well as robust stability for HzOR and HER, respectively. The study of in-situ Raman and reaction kinetics reveal that the formation of key adsorbed *NH2 and *N2H4 intermediates and the rapidly oxidization of intermediates with a fast interfacial charge transfer on Pt-MnCo2O4/NF. Remarkably, the Pt-MnCo2O4/NF assembled two-electrode hydrazine assisted water electrolyzer realizes current density of 100 mA cm-2 and 1000 mA cm-2 at 0.16 V and 0.62 V with over 80 h stability. This work provides a promising way to design efficient electrodes for energy-saving H2 generation under ampere-level current density.

Engineering cobalt molybdate nanosheet arrays with phosphorus-modified nickel as heterogeneous electrodes for highly-active energy-saving water splitting.

Electrochemical urea electrolysis has been regarded as a promising strategy to replace traditional water-splitting technology to achieve hydrogen fuel due to its cost savings and high energy efficiency. Designing efficient bifunctional electrocatalysts easily is important but still faces significant challenges. Herein, an interface engineering strategy is used to construct a hybrid material by coupling cobalt molybdate (CoMoO4) nanosheet arrays with phosphorus-modified nickel (P-Ni) particles on copper foam (P-Ni@CoMoO4/CF) through the hydrothermal and in-situ electrodeposition process. Benefiting from the abundant catalytic active sites, low charge transfer resistance, and synergistic coupling effect, the optimal P-Ni@CoMoO4/CF electrocatalyst presents a superior bifunctional activity for urea oxidation reaction (UOR) and hydrogen evolution reaction (HER). In detail, a small overpotential of 125 mV and a low potential of 1.36 V is required to attain the current density of 100 mA cm-2 for HER and UOR, respectively. In the process of urea electrolysis, the P-Ni@CoMoO4/CF-based electrolyzer provides a current density of 100 mA cm-2 with an overall voltage of 1.50 V, about 170 mV less than that in a traditional water electrolyzer. The high performance of P-Ni@CoMoO4/CF outperforms many recently reported electrodes, suggesting its promising application in energy-saving hydrogen production. Our work proposes a novel idea for the rational design and exploitation of low-cost and robust bifunctional electrodes for electrocatalysis.