具有主导酸性析氧晶相的支撑调谐铱重构

Support-tuned iridium reconstruction with crystalline phase dominating acidic oxygen evolution.

作者信息

Zhang Kexin, Liang Xiao, Wang Yucheng, Zou Yongcun, Zhao Xiao, Chen Hui, Zou Xiaoxin

机构信息

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, China.

State Key Laboratory of Physical Chemistry of Solids, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China.

出版信息

Nat Commun. 2025 Sep 1;16(1):8164. doi: 10.1038/s41467-025-63541-9.

DOI:10.1038/s41467-025-63541-9

PMID:40890137

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12402471/

Abstract

The dynamic reconstruction of oxygen evolution electrocatalysts dictates their performance, yet conventional Ir-based materials face an inherent activity-stability trade-off due to surface amorphization into hydrous IrO phases accompanied by lattice oxygen mechanisms. Here, we uncover a distinct reconstruction pathway for supported Ir nanoparticles, where a TiO@Ti substrate drives a bulk phase transition from metallic Ir to crystalline rutile IrO during electrocatalysis. Unlike surface-limited amorphization, this support-guided crystallization shifts the reaction mechanism from involving lattice oxygen mechanism to the complete adsorbate evolution mechanism, as confirmed by mechanistic and structural analyses. Consequently, the Ir/TiO@Ti catalyst achieves both high activity and durability in acidic media, demonstrated in three-electrode systems and proton exchange membrane water electrolyzers. This work redefines support roles in electrocatalyst reconstruction, demonstrating that bulk phase engineering-rather than surface modification-resolves the long-standing efficiency-durability conflict in acidic oxygen evolution.

摘要

析氧电催化剂的动态重构决定了其性能，然而传统的铱基材料由于表面非晶化形成含水氧化铱相并伴随着晶格氧机制，面临着固有的活性-稳定性权衡。在此，我们发现了负载型铱纳米颗粒的一种独特重构途径，即在电催化过程中，TiO@Ti基底驱动金属铱向结晶金红石型氧化铱发生体相转变。与表面受限的非晶化不同，这种载体引导的结晶将反应机制从涉及晶格氧机制转变为完全的吸附质析出机制，这已通过机理和结构分析得到证实。因此，Ir/TiO@Ti催化剂在酸性介质中实现了高活性和耐久性，这在三电极系统和质子交换膜水电解槽中得到了证明。这项工作重新定义了载体在电催化剂重构中的作用，表明体相工程而非表面修饰解决了酸性析氧中长期存在的效率-耐久性冲突。