用具有亲水性结构域的多孔碳载体负载镍基催化剂以提高阴离子交换膜燃料电池性能

doi:10.1016/S1872-2067(26)65010-3

催化学报

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用具有亲水性结构域的多孔碳载体负载镍基催化剂以提高阴离子交换膜燃料电池性能

孟品¹, 汪沛辰¹, 杨佳和¹, 张云龙, 石宏达, 陈兴艳, 樊丁阁, 陈思燕, 林曦, 汪冬冬, 杨阳^*, 陈乾旺^*

中国科学技术大学, 合肥微尺度物质科学国家研究中心和材料科学与工程系, 安徽合肥 230026

收稿日期:2025-09-06 接受日期:2025-10-30
通讯作者: *电子信箱: cqw@ustc.edu.cn (陈乾旺).
作者简介:¹共同第一作者.
基金资助:
国家重点研发项目(2021YFA1600202); 国家自然科学基金(22272155, 22479135); 中央高校基本研究经费(WK9990000168).

Nickel-based catalyst supported on porous carbon carrier with hydrophilic domains enables high-performance anion exchange membrane fuel cells

Pin Meng, Peichen Wang, Jiahe Yang, Yunlong Zhang, Hongda Shi, Xingyan Chen, Dingge Fan, Siyan Chen, Xi Lin, Dongdong Wang, Yang Yang^*, Qianwang Chen^*

Hefei National Research Center for Physical Sciences at the Microscale, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2025-09-06 Accepted:2025-10-30
Contact: *E-mail: yangyang1991@ustc.edu.cn (Y. Yang), cqw@ustc.edu.cn (Q. Chen).
Supported by:
National Key R&D Program of China (2021YFA1600202), the National Natural Science Foundation (22272155, 22479135) and the Fundamental Research Funds for the Central Universities (WK9990000168).

摘要/Abstract

摘要： 阴离子交换膜燃料电池(AEMFC)因其具有环境友好、高能量转换效率等优点, 显示了广阔的应用前景. 鉴于碱性介质导致氢氧化反应(HOR)动力学比酸性介质大幅降低2‒3个数量级, 使得AEMFC阳极中所需的铂族金属(PGM)负载量远高于质子交换膜燃料电池高很得. 因此, 利用可再生氢能源进行氢发电的关键障碍在于降低贵金属用量以及开发低成本、高性能的非贵金属HOR催化剂.
镍(Ni)基催化剂是AEMFC中最有前景的无PGM阳极催化剂. 然而, 它们组装燃料电池后的功率密度距美国能源部(DOE)2025年后的目标还较远. 一方面, Ni因其很强的氢结合能(HBE)极大地限制了Volmer步骤(H_ad + OH^- → H₂O + e^-), 这可以依靠活性位点电子结构调控的热力学策略实现对中间吸附优化来改变. 另一方面, 最近的一些研究也强调了电催化界面环境在控制碱性氢电催化动力学方面的关键作用. 由于界面水与催化剂之间的相互作用是非共价的, 不受催化剂电子结构的调控. 因此这将导致热力学和动力学策略难以协同促进HOR的活性.
本文提供了一种合理的设计策略, 采用经亲水性锌(Zn)原子修饰的多孔碳材料作为载体来负载Ni纳米颗粒(Ni/Zn₁-NC), 通过碳载体的结构优化来实现对HOR热力学和动力学的双重促进作用. 高角度环形暗场扫描透射电子显微镜分析揭示了Ni纳米颗粒和Zn单原子(Zn-SAs)之间的结构活性关系. 采用X-射线近边结构和扩展X-射线吸收精细结构分析了Zn原子的局部结构. 通过衰减全反射表面增强红外吸收光谱分析检测界面水结构. 通过Gouy-Chapman电容最小值法测量材料的零电荷电势(E_PEC), 以分析氢氧物种的扩散行为. 在燃料电池中采用电化学阻抗谱结合弛豫时间分布分析, 分离并量化极化电阻的贡献. 理论计算和实验测量表明, Zn-N物种掺杂能够提高碳载体的工作函数, 促进Ni向载体转移电子, 降低Ni的HBE. 原位光谱分析表明, 位于Ni纳米颗粒附近的Zn位点通过改善双电层内氢键网络的结构, 加速了氢氧化物中间体的转移过程. 优化的HBE和氢氧化物加速转移的协同作用, 使得采用Ni/Zn₁-NC为阳极的AEMFC实现了678 mW cm^‒2的峰值功率密度, 超过了低负载量下的商业铂碳催化剂.
综上, 本工作通过在碳载体中局部引入亲水性金属单原子结构, 实现了对与热力学相关的HBE和与动力学相关的氢氧化物中间体转移的同步调控, 提高了Ni基催化剂在AEMFC应用的性能表现, 为设计和合成高效催化剂提供了新思路.

关键词: 氢氧根转移, 氢结合能, 阴离子交换膜燃料电池, 氢气氧化反应

Abstract: Nickel (Ni)-based catalysts are the most promising platinum (Pt)-free anode hydrogen oxidation reaction (HOR) catalysts in anion exchange membrane fuel cells (AEMFCs). However, the limited reactivity of Ni in alkaline HOR presents a significant barrier to the commercialization of AEMFCs, due to both thermodynamic and kinetic constraints. Here, we employ zinc single atoms (Zn-SAs) modified porous carbon support to create microscopic hydrophilic domains aimed at optimizing electrode kinetics. We found that the doping of Zn-N species could manipulate the electron transfer between Ni and carbon support, which causes a drastically diminished adsorption of hydrogen on Ni, thus boosting the alkaline HOR activity from a thermodynamic perspective. Spectral and electrochemical data reveal that Zn sites facilitate hydroxide transfer at the Ni/Zn₁-NC interface by improving hydrogen bond network connectivity. These enhancement enables the Ni/Zn₁-NC AEMFC to deliver a peak power density of 678 mW cm^‒2, surpassing even a low loading of commercial Pt/C. This work illustrates the potential for high efficiency in platinum-group metal-free AEMFCs.

Key words: Hydroxide transfer, Hydrogen binding energy, Anion exchange membrane fuel cells, Hydrogen oxidation reaction

孟品, 汪沛辰, 杨佳和, 张云龙, 石宏达, 陈兴艳, 樊丁阁, 陈思燕, 林曦, 汪冬冬, 杨阳, 陈乾旺. 用具有亲水性结构域的多孔碳载体负载镍基催化剂以提高阴离子交换膜燃料电池性能[J]. 催化学报, DOI: 10.1016/S1872-2067(26)65010-3.

Pin Meng, Peichen Wang, Jiahe Yang, Yunlong Zhang, Hongda Shi, Xingyan Chen, Dingge Fan, Siyan Chen, Xi Lin, Dongdong Wang, Yang Yang, Qianwang Chen. Nickel-based catalyst supported on porous carbon carrier with hydrophilic domains enables high-performance anion exchange membrane fuel cells[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)65010-3.

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用具有亲水性结构域的多孔碳载体负载镍基催化剂以提高阴离子交换膜燃料电池性能

Nickel-based catalyst supported on porous carbon carrier with hydrophilic domains enables high-performance anion exchange membrane fuel cells

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