厦门大学张华团队报道了相工程通过晶格氧机制促进O-O耦合，以增强磷化镍铁上的析氧。相关研究成果发表在2024年12月25日出版的《美国化学会杂志》。

镍铁基催化剂因其在碱性条件下的析氧反应（OER）中的高效性而受到认可，但驱动其优异性能的潜在机制尚不清楚。

该文中，研究人员揭示了掺磷镍铁纳米催化剂（NiFeP）上OER的分子机制，和OER的结构-中间体-性能关系。NiFeP表现出卓越的活性和稳定性，在1 M KOH中电流密度10 mA cm^–2时的过电位仅为210 mV，在阴离子交换膜水电解槽中1 A cm^–2电流密度下的电池电压为1.68 V。

研究人员使用壳分离纳米粒子增强拉曼光谱，辅以微分电化学质谱和密度泛函理论，对NiFeP上OER过程中活性位点和中间体的演变进行了原位探测和关联。这些结果提供了OER通过晶格氧介导机制进行的直接证据。值得注意的是，磷掺杂在稳定活性β-Ni（Fe）OOH相方面起着关键作用，这有助于*OH脱质子化和随后的O-O偶联形成*OO中间体。

研究结果加深了对OER机制的理解，为设计具有更高效率和耐用性的下一代OER催化剂提供了明确的途径。

附：英文原文

Title: Phase Engineering Facilitates O–O Coupling via Lattice Oxygen Mechanism for Enhanced Oxygen Evolution on Nickel–Iron Phosphide

Author: Zheng-Xin Qian, Ge-Hao Liang, Liang-Fei Shen, Ge Zhang, Shisheng Zheng, Jing-Hua Tian, Jian-Feng Li, Hua Zhang

Issue&Volume: December 25, 2024

Abstract: Nickel–iron-based catalysts are recognized for their high efficiency in the oxygen evolution reaction (OER) under alkaline conditions, yet the underlying mechanisms that drive their superior performance remain unclear. Herein, we revealed the molecular OER mechanism and the structure-intermediate-performance relationship of OER on a phosphorus-doped nickel–iron nanocatalyst (NiFeP). NiFeP exhibited exceptional activity and stability with an overpotential of only 210 mV at 10 mA cm–2 in 1 M KOH and a cell voltage of 1.68 V at 1 A cm–2 in anion exchange membrane water electrolyzers. The evolution of active sites and intermediates during OER on NiFeP was in situ probed and correlated using shell-isolated nanoparticle-enhanced Raman spectroscopy, complemented by differential electrochemical mass spectrometry and density functional theory. These results provide direct evidence that OER proceeds via the lattice oxygen-mediated mechanism. Remarkably, phosphorus doping plays a critical role in stabilizing the active β-Ni(Fe)OOH phase, which facilitates the *OH deprotonation and the subsequent O–O coupling to form *OO intermediates. Our findings offer a deeper understanding of the OER mechanism, providing a clear pathway for designing next-generation OER catalysts with improved efficiency and durability.

DOI: 10.1021/jacs.4c15847

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c15847