Jun Ke, Jiaxi Zhang*, Longhai Zhang, Shunyi He, Chengzhi Zhong, Li Du, Huiyu Song, Xiaoming Fang*, Zhengguo Zhang and Zhiming Cui*,
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引用次数: 0
摘要
在铁镍基氧化物中掺入高价金属已被广泛认为是促进碱性氧进化反应（OER）的有效方法，但由于缺乏对真实结构的鉴定，相应的结构-性能关系仍不清楚。在本研究中，我们揭示了掺杂 M 的铁镍氧化物（M 为 Mo、V 和 W）的表面演化过程，并阐明了 M 的溶解在增强氧演化动力学中的作用。以 Mo 为例，将高价金属 Mo 掺杂到 FeNiOx 中，观察其在 OER 过程中的浸出行为。通过结合原位拉曼分析、电化学测量和第一原理计算，揭示了以 MoO42- 形式存在的 Mo 的电解导致晶格氧的优先去除，从而促进了 OH 的吸附步骤，并触发了晶格氧介导的促进 OER 的机制。因此，优化后的 FeNiMoOx 在达到 10 mA/cm2 时的过电位仅为 235 mV，与 1.53 V 时的 FeNiOx 相比，比活性提高了 30 倍。我们的研究结果从另一个角度揭示了高价金属溶解与碱性 OER 性能之间错综复杂的关系，阐明了溶解引起的结构变化对促进 OER 机制的关键作用。
Role of High-Valence Metal Dissolution in Oxygen Evolution Kinetics of the Advanced FeNiOx Catalysts
The incorporation of high-valence metals into FeNi-based oxides has been widely accepted as an efficient approach for facilitating the alkaline oxygen evolution reaction (OER), but the corresponding structure–property relationship remains unclear due to the lack of identification of the real structure. In this study, we reveal the surface evolution processes of M-doped FeNi oxides (M is Mo, V, and W) and elucidate the role of M dissolution in enhancing oxygen evolution kinetics. Taking Mo as an example, the high-valence metal Mo was doped into FeNiOx and its leaching behavior was observed during OER. By combining in situ Raman analysis, electrochemical measurement, and first-principles calculation, it was unveiled that the electro-dissolution of Mo, in the form of MoO42–, led to preferential removal of lattice oxygen, thereby facilitating the adsorption step of OH and triggering the lattice oxygen-mediated mechanism for promoting OER. Consequently, the optimized FeNiMoOx displayed an overpotential of only 235 mV to reach 10 mA/cm2 and a 30-fold enhancement in specific activity compared with that of FeNiOx at 1.53 V. Our findings provide a different perspective on the intricate association between dissolution of high-valence metal and alkaline OER performance, elucidating the key role of the dissolution-induced structure change on promoting the OER mechanism.
期刊介绍：
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.
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