质子交换膜电解槽中铱基催化剂的活性-稳定性协同提升

doi:10.1016/S1872-2067(26)64962-5

摘要/Abstract

摘要： 质子交换膜电解槽(PEMWEs)制氢技术具备快速响应、高电流密度与高纯度产气等优势, 是极具前景的绿氢制取方式. 然而, 其广泛应用受限于缓慢的阳极析氧反应(酸性OER)动力学及苛刻的反应环境, 因此亟需开发高效稳定的催化剂. 铱(Ir)基催化剂仍是当前应用于酸性OER最具有前景的催化材料, 但其面临着活性低、稳定性差及成本高等问题. 当前, 对于Ir基催化剂的设计面临着平衡活性-稳定性的问题, 单一的改性方法通常无法打破该限制. 因此, 本文旨在通过钴(Co)掺杂与钨(W)载体引入的双重改性策略, 在低Ir载量的情况下实现催化剂活性与稳定性的综合提升.
基于Co掺杂可实现Ir位点的化学环境调控以及变价金属W具有“电子缓冲剂”作用的设计思路, 本文通过磁控溅射和单极脉冲电沉积成功制备了W负载的Co掺杂氧化铱(Co-IrO_x/W)催化剂. 该催化剂在三电极体系, 0.5 mol L^‒1 H₂SO₄的模拟测试环境下, 其酸性OER过程达到10 mA cm^‒2的电流密度仅需209 mV, 并且在400 mA cm^‒2的极高电流密度下可实现50 h以上的稳定性测试. 在Ir负载量为0.262 mg cm^‒2的条件下, 使用Co-IrO_x/W||Pt/C膜电极(MEA)用于PEMWEs测试时, 达到1 A cm^‒2的电流密度所需的槽压为1.86 V. 此外, 该MEA装配的PEMWEs可实现1000 h的长期稳定测试, 并表现出6.8 µV h^‒1的极低衰减率, 展现出了优异的工业化应用潜力. 电化学测试分析发现, Co-IrO_x/W在降低活化能、加速去质子化及电荷快速转移方面表现出更强的能力, 进而实现优异的酸性OER活性. 物理表征分析及密度泛函理论计算表明, Co-IrO_x/W的活性提升归因于Co掺杂改善了Ir位点的化学环境, 引起Ir位点的d带中心上移, 强化了反应过程中催化活性中心与含氧中间体的吸附能力, 进而加速了OER动力学. 此外, 在稳定性方面, 对电化学测试后的Co-IrO_x/W结构分析发现, W载体构建的W-O-Ir界面配位可实现电子重分布动态抑制Ir位点的过度氧化, 保证催化剂的结构完整性, 从而增强Co-IrO_x/W的抗衰减能力.
综上, 本研究采用一种双重改性策略, 以打破单一方法制备Ir基催化剂在平衡活性与稳定性方面的固有局限. 这种原子掺杂-载体工程的协同作用, 在Ru基及非贵金属Co基酸性析氧催化剂体系中有望展现出巨大的拓展潜力, 有望实现Ru基及Co基催化剂在PEMWEs中实现高效持久运行.

关键词: 质子交换膜电解槽, 析氧反应, 铱基催化剂, 掺杂, 载体

Abstract: Achieving both high activity and stability remains a key bottleneck for Ir-based catalysts in the acidic oxygen evolution reaction (OER) for proton exchange membrane water electrolyzers (PEMWEs). Herein, we present a cobalt-doped iridium oxide catalyst coated on tungsten substrate (Co-IrO_x/W) fabricated via a synergistic magnetron sputtering and unipolar pulse electrodeposition strategy. The optimized catalyst demonstrates exceptional acidic OER activity with an ultralow overpotential of 209 mV at 10 mA cm^‒2 in 0.5 mol L^‒1 H₂SO₄, and a Ir loading only of 0.262 mg cm^‒2 in PEMWEs to achieve over 1000 h of stable operation at 1 A cm^‒2 with a degradation rate only of 6.8 µV h^‒1. Integrated characterization reveals enhanced catalytic capacity of Co-IrO_x/W in activation energy, deprotonation, and charge transfer stemmed from Co doping induced Ir d-band upward, strengthening oxygen-intermediate adsorption and accelerates OER kinetics. Moreover, the W substrate creates a W-O-Ir interfacial coordination that dynamically suppresses over-oxidation of Ir sites via electronic redistribution, thereby enhancing the stability of iridium oxide catalyst. This work offers design insights for OER catalysts to simultaneously overcome activity-stability limitations through rational electronic-structure engineering and support interactions dual design principles, opening avenues for industrial hydrogen production.

Key words: Proton exchange membrane water electrolyzers, Oxygen evolution reaction, Ir-based catalysts, Doping, Support

张凯杨, 李惠惠, 王叔豪, 姚瑞, 李晋平, 赵川, 刘光. 质子交换膜电解槽中铱基催化剂的活性-稳定性协同提升[J]. 催化学报, DOI: 10.1016/S1872-2067(26)64962-5.

Kaiyang Zhang, Huihui Li, Shuhao Wang, Rui Yao, Jinping Li, Chuan Zhao, Guang Liu. Breaking the activity-stability trade-off of iridium-based catalysts for proton exchange membrane water electrolyzers[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)64962-5.

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