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 ›› 2026, Vol. 85: 182-192.DOI: 10.1016/S1872-2067(26)65010-3

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 出版日期:2026-06-18 发布日期:2026-05-18
通讯作者: *电子信箱: cqw@ustc.edu.cn (陈乾旺),
yangyang1991@ustc.edu.cn (杨阳).
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);国家自然科学基金(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^,¹, Peichen Wang^,¹, Jiahe Yang^,¹, 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 Online:2026-06-18 Published:2026-05-18
Contact: *E-mail: cqw@ustc.edu.cn (Q. Chen),
yangyang1991@ustc.edu.cn (Y. Yang).
About author:
¹Contributed equally to this work.
Supported by:
National Key R&D Program of China(2021YFA1600202);National Natural Science Foundation(22272155);National Natural Science Foundation(22479135);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. 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. 然而其组装燃料电池后的功率密度仍远未达到美国能源部(DOE)的相关指标. 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^-), 该问题可通过调控活性位点电子结构的热力学策略优化中间体吸附来改善. 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, 难以通过催化剂电子结构直接调控. 因此这将导致单一的热力学或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), 以解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中的应用性能, 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, 2026, 85: 182-192.

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, 2026, 85: 182-192.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65010-3

https://www.cjcatal.com/CN/Y2026/V85/I6/182

图/表 5

Fig. 1. Schematic diagram of a proposed catalyst design strategy for high activity HOR.

Fig. 2. (a) Schematic illustrating the synthesis of Ni/Zn1-NC. The black, blue, green and pink small balls represent C, N, Ni and Zn atoms respectively. (b) XRD images of Ni/Zn1-NC and Ni/rGO. (c) TEM images of Ni/Zn1-NC. (d) The particle size distribution of nanoparticles in (c). (e) HAADF-STEM images of Zn1-NC in Ni/Zn1-NC. Some Zn-SAs were delineated with yellow circles. (f) HAADF-STEM images of Ni/Zn1-NC. Some Zn-SAs were delineated with yellow circles. (g) HAADF-STEM and EDS mapping of Ni/Zn1-NC.

Fig. 3. (a) HOR polarization curves for Ni/Zn1-NC, Ni/rGO and 20? wt% commercial Pt/C for an electrode rotating speed of 1600?rpm. The loading of all Ni-based catalysts was 0.612 mgcatalyst cm-2. The loading of commercial Pt/C was 20.4 µgPGM cm-2. The scan rate of Ni-based catalysts was 0.5 mV s-1. The scan rate of commercial Pt/C was 1 mV s-1. (b) Butler-Volmer plots of the HOR current densities (jk) for Ni/Zn1-NC, Ni/rGO and commercial Pt/C. (c) Comparison of normalized mass activity (jk,m) at an overpotential of 50?mV and specific activity (j0,s). (d) Polarization and power density curves of AEMFCs fed with H2-O2 and equipped with with Ni/Zn1-NC, Ni/rGO and Pt/C (0.1 mgPGM cm-2) as anodes and 40 wt% commercial Pt/C (0.22 mgPGM cm-2) as cathodes. Test conditions: the cell temperature was 95 °C, the anode dew point temperature was 86 °C, and the cathode dew point temperature was 89 °C, respectively. Back pressure of 250 kPag was applied to the gases at both the anode and cathode, and the supply flow rates of H2 and O2 were both 1.2 L?min-1. (e) Comparison of the reported PPD of PGM-free anode AEMFCs. (f) Comparison of the total PGM utilization (H2/O2 as the feeding gas) of AEMFCs. (g) Polarization and power density curves of AEMFCs fed with H2/CO2-free air and equipped with Ni/Zn1-NC and Pt/C (0.1 mgPGM cm-2) as the anode and 40 wt% commercial Pt/C (0.22 mgPGM cm-2) as the cathode. Test conditions: the cell temperature was 95 °C, the anode dew point temperature was 86 °C, and the cathode dew point temperature was 89 °C, respectively. Back pressure of 250 kPag was applied to the gases at both the anode and cathode, and the supply flow rates of H2 and CO2-free air were 0.2 and 1 L min-1, respectively. (h) H2/CO2-free air AEMFC stability test curves of Ni/Zn1-NC at 200 mA cm-2. The test conditions were as follows: the cell temperature was 80 °C; the optimized dew points for the anode and cathode were 80 and 80 °C, respectively. The back pressure was 250 kPag, and the flow rates of H2 and CO2-free air were 0.8 and 0.6 L min-1, respectively.

Fig. 4. XANES (a) and EXAFS (b) spectra at the Zn K-edge of Zn1-NC, indicating the formation of the Zn-SA structure. (c) XPS spectra of Ni 2p3/2. (d) Work functions of Ni, rGO and Zn1-NC. (e) Work function difference between rGO, Zn1-NC and Ni. (f) Schematic diagram of the Mott-Schottky junction in Ni/Zn1-NC and Ni/rGO. (g) DFT calculations of the optimized structures of Ni/rGO and Ni/Zn1-NC (brown, blue, pink, and gray balls represent C, N, Zn, and Ni atoms, respectively). (h) Positive charge density on the Ni sites of Ni/Zn1-NC and Ni/rGO. (i) Binding energies of Ni nanoparticles on Zn1-NC and rGO.

Fig. 5. (a) In-situ SEIRAS spectra of Ni/Zn1-NC were recorded in 0.1 mol L-1 KOH saturated with H2 at 0 to 0.2 V versus RHE, and the OH stretching vibration peaks in the range of approximately 3000 to 3600 cm-1 were deconvolution. (b) Stark tuning rate of Ni/rGO and Ni/Zn1-NC according to in-situ SEIRAS. (c) Deconvolution of the OH stretching vibration peaks (approximately 3000 to 3600 cm-1) at 0.1 V versus RHE was performed for Ni/Zn1-NC and Ni/rGO. (d) The relative fraction of the peak at ~3240 cm-1 of Ni/Zn1-NC and Ni/rGO with the ratio of applied potential (from 0 to 0.2 V versus RHE). (e) EPZC values measured for Ni/Zn1-NC and Ni/rGO. (f) Nyquist plots with Ni/Zn1-NC at different current densities. (g) Nyquist plots with Ni/Zn1-NC and Ni/rGO at 50 mA cm-2. (h) Corresponding DRT results of Ni/Zn1-NC and Ni/rGO. (i) Schematic of fast OH- transfer kinetics.

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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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