近日，北京理工大学王鲁团队报道了调节铱配位控制析氧反应途径。这一研究成果发表在2025年10月22日出版的《美国化学会志》上。

调控活性位点的配位数有望将析氧反应路径从传统的吸附演化机制转向高活性的晶格氧机制，但目前缺乏有效的合成策略。

研究组提出一种相变策略，可精准调控负载于沸石咪唑酯框架中铱的配位模式，通过空气煅烧将其转化为两种具有不同铱配位数的Ir掺杂Co₃O₄材料（Ir₁O_x–Co₃O₄，x = 4, 6）。系统研究表明，具有较高Ir-O配位数的Ir₁O₆–Co₃O₄能增强Ir-O共价性，激活晶格氧参与反应，并遵循双金属位点晶格氧机制降低反应能垒；而Ir₁O₄–Co₃O₄仍遵循吸附演化机制。

因此，Ir₁O₆–Co₃O₄在10 mA cm^-2电流密度下仅需253 mV过电位，且能稳定运行200小时以上，其质量活性分别达到Ir₁O₄–Co₃O₄和商用IrO₂的3.4倍和17.3倍。该工作不仅为精准调控活性位点配位数提供了合成策略，更建立了配位环境与反应路径之间的直接关联，为高性能析氧反应催化剂的理性设计提供了新视角。

附：英文原文

Title: Modulating Iridium Coordination to Control the Oxygen Evolution Reaction Pathway

Author: Wenrui Li, Jiajia Zhang, Chenyu Yang, Zhide Geng, Xianchun Chen, Qinghua Liu, Bo Wang, Lu Wang

Issue&Volume: October 22, 2025

Abstract: Tailoring the coordination number of active sites can potentially shift the oxygen evolution reaction (OER) pathway from the traditional adsorbate evolution mechanism (AEM) to the highly active lattice oxygen mechanism (LOM), but effective synthesis approaches are lacking. Herein, we demonstrate a phase transformation strategy to precisely engineer the coordination modes of Ir loaded in zeolitic imidazolate frameworks (ZIFs), which are subsequently converted into two Ir-doped Co3O4 with distinct coordination numbers of Ir (Ir1Ox–Co3O4, x = 4, 6) via air calcination. Comprehensive studies reveal that Ir1O6–Co3O4, featuring a higher Ir–O coordination number, intensifies the Ir–O covalency, activates the lattice oxygen participation, and reduces the thermodynamic barrier following a dual-metal-site lattice oxygen mechanism (DMSM-LOM), while Ir1O4–Co3O4 adheres to the AEM pathway. Consequently, Ir1O6–Co3O4 exhibits a low overpotential of 253 mV at 10 mA cm–2 and superior stability over 200 h, with mass activity approximately 3.4 and 17.3 times greater than those of Ir1O4–Co3O4 and commercial IrO2, respectively. This work not only provides a synthetic strategy for precise coordination number engineering of active sites but also establishes a direct correlation between the coordination environment and the reaction pathway, offering new insights into the rational design of high-performance OER catalysts.

DOI: 10.1021/jacs.5c13365

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c13365