Hydrazine-assisted water splitting is a promising strategy for energy-efficient hydrogen production, yet challenges remain in developing effective catalysts that can concurrently catalyze both hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR) in acidic media. Herein, we report an effective bifunctional catalyst consisting of Rh clusters anchored on Co₃O₄ branched nanosheets (Rh-Co₃O₄ BNSs) synthesized via an innovative arginine-induced strategy. The Rh-Co₃O₄ BNSs exhibit unique Rh-O-Co interfacial sites that facilitate charge redistribution between Rh clusters and Co₃O₄ substrate, thereby optimizing their valence electronic structures. When the current density reaches 10 mA cm-2, the Rh-Co3O4 BNSs require the working potentials of only 32 mV for HER and 0.26 V for HzOR, far surpassing commercial Pt/C. Furthermore, the Rh-Co3O4 BNSs can work efficiently for hydrazine-assisted water electrolysis with a low voltage of 0.34 V at 10 mA cm-2 and an excellent stability. Theoretical calculations reveal that the optimized valence electronic structure within interfacial Rh-O-Co sites not only reduces the adsorption energy barrier of Co3O4 for H* in HER; but also optimizes the hydrazine adsorption in HzOR and lowers the free energy change of potential-determining step, where the facilitated dehydrogenation is observed in in situ Raman spectra. This work provides a viable approach for designing efficient bifunctional catalysts for future hydrazine-assisted hydrogen production.

中文翻译：

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不对称的 Rh-O-Co 桥位点为肼辅助制氢提供了卓越的双功能催化


肼辅助水分解是一种很有前途的节能制氢策略，但开发能够在酸性介质中同时催化析氢反应 （HER） 和肼氧化反应 （HzOR） 的有效催化剂仍然存在挑战。在此，我们报道了一种有效的双功能催化剂，该催化剂由锚定在锚定在 Co₃O₄ 支链纳米片 （Rh-Co₃O₄ BNS） 上的 Rh 簇组成，该催化剂通过创新的精氨酸诱导策略合成。Rh-Co₃O₄ BNS 表现出独特的 Rh-O-Co 界面位点，可促进 Rh 团簇和 Co₃O₄ 衬底之间的电荷再分布，从而优化其价电子结构。当电流密度达到 10 mA cm-2 时，Rh-Co3O4 BNS 需要的 HER 工作电位仅为 32 mV，HzOR 的工作电位仅为 0.26 V，远超商用 Pt/C。此外，Rh-Co3O4 BNS 可以高效地用于肼辅助水电解，在 10 mA cm-2 下具有 0.34 V 的低电压和出色的稳定性。理论计算表明，界面 Rh-O-Co 位点内优化的价电子结构不仅降低了 Co3O4 对 HER 中 H* 的吸附能垒;而且还优化了 HzOR 中的肼吸附，并降低了电位确定步骤的自由能变化，其中在原位拉曼光谱中观察到促进脱氢。这项工作为设计用于未来肼辅助制氢的高效双功能催化剂提供了一种可行的方法。