The design of dual-functional catalysts for the oxygen evolution reaction and ethanol oxidation reaction is essential for improving hydrogen production efficiency, and one of the strategies to improve catalytic performance is the incorporation of high-valence metals. However, the generation of high-valence metals has always been a challenge in the field of catalysis, and elucidating the involved mechanisms is also difficult. Herein, we synthesized a metal–organic framework (MOF) material on nickel foam (NF) using a straightforward one-step hydrothermal technique and subsequently transformed it into a metal oxide hydroxide through activation, denoted as Co₁Ni_0.5Mn₁BDC@NF-A. The catalyst with Mn enhanced exhibits a curved sheet-like morphology, arranged in an ordered layered structure, with abundant active surfaces. Mn induces additional production of Ni³⁺ and Co³⁺ to accelerate the OER/EOR process. The catalyst exhibits outstanding electrochemical performance in both the OER, with an overpotential of 298 mV at 100 mA cm⁻², and the EOR, with a potential of 1.30 V at 100 mA cm⁻², demonstrating superior performance compared to other Ni-based and Co-based catalysts. Furthermore, to reach 100 mA cm⁻², the combined EOR–HER process requires only 1.39 V, while the combined OER–HER process requires just 1.54 V. The remarkable performance is attributed to the inclusion of Mn, which can promote the transformation of morphology, mainly transforming the catalyst from disordered stacking to an ordered staggered arrangement, exposing more active sites. More importantly, XPS testing shows that Mn reduces the binding energy of the Ni/Co(II) to Ni/Co(III) transition by adjusting the hybridization effect between Ni 3d, Co 3d and O 2p orbitals, promoting the generation of Ni³⁺ and Co³⁺ for enhanced reaction kinetics. In summary, this work presents a simple yet effective strategy for the generation of high-valence transition metals, which can be used to accelerate the OER and EOR processes, thus offering promising prospects for advancing hydrogen production technology.

中文翻译：

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添加 Mn 促进高比例的 Ni3+ 和 Co3+ 以增强析氧反应和乙醇氧化反应

用于析氧反应和乙醇氧化反应的双功能催化剂的设计对于提高制氢效率至关重要，而提高催化性能的策略之一是掺入高价金属。然而，高价金属的生成一直是催化领域的挑战，阐明其机制也很困难。在此，我们使用简单的一步水热技术在泡沫镍（NF）上合成了一种金属有机骨架（MOF）材料，随后通过活化将其转化为金属氧化物氢氧化物，表示为Co ₁ Ni _0.5 Mn ₁ BDC@NF -A。 Mn增强的催化剂呈现出弯曲的片状形貌，排列有序的层状结构，具有丰富的活性表面。 Mn 诱导额外产生 Ni ³⁺和 Co ³⁺以加速 OER/EOR 过程。该催化剂在OER（100 mA cm ^-2下的过电位为298 mV ）和EOR（100 mA cm ^-2下的电位为1.30 V）中均表现出出色的电化学性能，与其他镍基催化剂相比表现出优异的性能和钴基催化剂。此外，为了达到100 mA cm ^-2，组合的EOR-HER过程仅需要1.39 V，而组合的OER-HER过程仅需要1.54 V。其卓越的性能归因于Mn的加入，Mn可以促进形貌，主要是将催化剂从无序堆积转变为有序交错排列，暴露出更多的活性位点。更重要的是，XPS测试表明，Mn通过调节Ni 3d、Co 3d和O 2p轨道之间的杂化效应，降低了Ni/Co( II )向Ni/Co( III )转变的结合能，促进Ni ³的生成⁺和 Co ³⁺以增强反应动力学。总之，这项工作提出了一种简单而有效的高价过渡金属生成策略，可用于加速 OER 和 EOR 过程，从而为推进制氢技术提供了广阔的前景。