近日，复旦大学张立明团队报道了晶格O-O配体的铁掺入氢氧化物增强水氧化电催化。相关论文于2025年8月18日发表在《自然-化学》杂志上。

了解配体的结构动力学及其在反应条件下与催化中心的相互作用仍然是一个基本的挑战，但它对催化剂设计至关重要。

研究组揭示了Ni-Fe氢氧化物向稳定的超氧氢氧化物相的原位转变，这伴随着晶格O-O （Olatt-Olatt）配体的形成，正如原位¹⁸O标记光谱电化学和机器学习辅助全局优化所证明的那样。通过将铁的固有活性与一系列铁结合的过渡金属氢氧化物和氧化物的Olatt-Olatt浓度相关联，研究组证明Olatt-Olatt触发铁的析氧电催化活化，该发现进一步得到第一性原理计算的支持。产氧过程通过吸附质演化机制进行，反应动力学的增强源于新形成的超氧氢氧结构中表面Fe位点活化能的降低。这项工作为设计高性能铁掺杂电催化剂提供了一个战略框架，并强调了配体动力学在激活催化中心中的关键作用。

附：英文原文

Title: Lattice O–O ligands in Fe-incorporated hydroxides enhance water oxidation electrocatalysis

Author: Shi, Guoshuai, Li, Jili, Lu, Tingyu, Yang, Chunlei, Xu, Qinshang, Gu, Huoliang, Tong, Haonan, Zhao, Siwen, Zhu, Chenyuan, Shen, Yuluo, Wu, Jing, Lao, Xianzhuo, Chen, Peng-Cheng, Li, Jiong, Zhang, Shuo, Shi, Jueli, Zhang, Kelvin H. L., Li, Ye-Fei, Liu, Zhi-Pan, Zhang, Liming

Issue&Volume: 2025-08-18

Abstract: Understanding the structural dynamics of ligands and their interaction with catalytic centres under reaction conditions remains a fundamental challenge, yet it is essential for catalyst design. Here we reveal an in situ transformation of Ni–Fe hydroxide into a stable superoxo-hydroxide phase, which is accompanied by the formation of lattice O–O (Olatt–Olatt) ligands, as demonstrated using operando 18O-labelling spectroelectrochemistry and machine-learning-assisted global optimization. By correlating the intrinsic activity of Fe with the Olatt–Olatt concentration across a series of Fe-incorporated transition-metal hydroxides and oxides, we demonstrate that Olatt–Olatt triggers Fe activation for oxygen evolution electrocatalysis—a finding further supported by first-principles calculations. Oxygen production proceeds via an adsorbate evolution mechanism, and the enhanced reaction kinetics stem from the lowered activation energy at surface Fe sites in the newly formed superoxo-hydroxide structure. This work offers a strategic framework for designing high-performance Fe-incorporated electrocatalysts and underscores the pivotal role of ligand dynamics in activating catalytic centres.

DOI: 10.1038/s41557-025-01898-6

Source: https://www.nature.com/articles/s41557-025-01898-6