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-CoNiMnWVO x 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-CoNiMnWVO x induces abundant Co–O species as the main catalytic active species for EOR and follows the conversion pathway of the C 2 product. Theoretical calculations reveal the optimized electronic structure and adsorption free energy of reaction intermediates on P-CoNiMnWVO x , thereby resulting in a facilitated kinetic process. A membrane-free electrolyzer delivers both high Faradaic efficiencies of acetate and H 2 over 95% and superior stability at100 mA cm −2 during 120 h electrolysis. In addition, the unique composition and structural advantages endow P-CoNiMnWVO x with multifunctional catalytic activity and realize multipathway electrosynthesis of formate-coupled hydrogen production.

中文翻译：

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氧诱导的多功能醇电氧化与制氢相结合的高熵电催化剂的结构演化


高熵化合物已成为电解的有希望的候选者，但由于不明确的离子相互作用和共沉积机制，其可控电合成策略仍然是一个巨大的挑战。在此，我们报道了一种含氧化合物定向诱导电沉积策略来构建具有非晶特征的高熵材料，通过引入钒酸盐证实了从高熵磷化物到氧化物的结构演化，从而实现了成分和结构的同时优化。代表P-CoNiMnWVO x对碱性析氢反应和乙醇氧化反应（EOR）表现出优异的双功能催化性能，在100 mA cm时具有-168 mV和1.38 V的小电位−2 ， 分别。原位光谱表明 P-CoNiMnWVO 的电化学重构x诱导丰富的Co-O物种作为EOR的主要催化活性物种，并遵循C的转化途径2产品。理论计算揭示了 P-CoNiMnWVO 上反应中间体的优化电子结构和吸附自由能x ，从而导致促进的动力学过程。无膜电解槽可提供醋酸盐和 H 的高法拉第效率2超过 95% 且在 100 mA cm 时具有出色的稳定性−2 120小时电解过程中。此外，独特的成分和结构优势赋予P-CoNiMnWVO x具有多功能催化活性，可实现甲酸耦合制氢的多途径电合成。