PrNi共掺杂Co3O4通过界面水优化和钴预氧化增强质子交换膜水电解中的析氧反应性能

doi:10.1016/S1872-2067(26)65109-1

摘要/Abstract

摘要：

质子交换膜水电解(PEMWE)凭借高电流密度、快速动态响应和高纯氢输出等优势, 被视为未来大规模可再生能源制氢的关键技术. 然而, 受限于PEMWE阳极强酸性环境和高氧化电位, 目前仅有Ir基贵金属氧化物能够实现稳定的析氧反应(OER), 显著提高了PEMWE系统成本. 因此, 开发低成本、储量丰富且耐酸的替代催化剂迫在眉睫. 基于Sabatier原理和中间体结合能标度关系, Co₃O₄被预测位于OER活性火山图的顶点, 对含氧中间体表现出近乎理想的吸附平衡. 同时, Pourbaix图也证实其在酸性高电位下能以固体氧化物形式稳定存在. 基于这些优越的热力学特性及显著的成本优势, Co₃O₄有望替代贵金属催化剂实现经济型大规模绿色产氢. 然而, Co₃O₄在OER过程中不可避免地出现表面重构现象, 严重限制了其长期的活性与稳定性.

本研究成功制备了具有空间选择性分布的PrNi共掺杂Co₃O₄(PrNi-Co₃O₄)催化剂, 通过表面与界面双重调控显著提升了其在酸性OER条件下的活性与稳定性. 拉曼光谱、球差校正扫描透射电镜元素面分布及X-射线光电子能谱深度刻蚀显示, Pr和Ni均占据八面体Co位点, 其中Ni在体相均匀掺杂, 而大离子半径的Pr受晶格应力驱动自发偏析并富集于表面. 密度泛函理论计算与电化学分析表明, 体相掺杂的Ni优化了电子结构, 诱导表面预氧化并加速高价活性Co^Ⅳ物种的生成, 从而提升本征活性. 同时Ni掺杂提高了Co的空位形成能, 有效抑制OER过程中金属的溶解. 原位表面增强红外光吸收谱表明, 表面富集的Pr有效调控了界面水结构, 提高了自由水比例并削弱了界面氢键网络, 从而降低了水解离能垒. 此外, 所构建的弱氢键界面有效缓解了氢键对金属-氧键的极化, 结合Pr-O-Co桥接位点生成的含氧中间体对晶格的稳定作用, 协同抑制了金属溶解, 进一步增强了结构稳定性. 得益于这种表面工程与界面化学的双重作用, PrNi-Co₃O₄在1.7 V下的质量活性高达23.3 A g_Co⁻¹, 分别是Ni-Co₃O₄和纯Co₃O₄的3.7倍和10.5倍, 在370 mV过电位下的TOF达到0.226 s⁻¹, 是Co₃O₄的6.8倍. 以PrNi-Co₃O₄为阳极组装的PEMWE单池在1 A cm⁻²大电流密度下运行电压仅为2.02 V, 并实现了长达490 h的稳定运行, 展现出优异的实际应用潜力.

综上, 本研究通过精确调控PrNi元素在Co₃O₄晶格中的空间分布, 构建了功能特异性的理想模型, 实现了表面-界面双重调控, 增强了非贵金属材料在酸性OER中的活性与稳定性, 为开发低成本、高性能的酸性析氧催化剂提供了新的设计思路.

关键词: 界面水, 预氧化, 尖晶石氧化钴, 非贵金属, 质子交换膜水电解

Abstract:

Spinel Co₃O₄ is theoretically predicted as a promising cost-effective anodic electrocatalyst for proton exchange membrane water electrolysis (PEMWE) owing to favorable adsorption energetics. However, the inevitable surface reconstruction under operating conditions severely compromises its long-term activity and stability. Here we report a praseodymium (Pr) and nickel (Ni) co-doped cobalt spinel (PrNi-Co₃O₄) catalyst featuring a spatially selective distribution of uniform bulk Ni doping and spontaneous surface Pr segregation, which realizes a surface-interface synergistic optimization strategy to effectively overcome this bottleneck. Density functional theory calculations and voltammetric investigations reveal that the nickel dopants induce surface pre-oxidation, boosting intrinsic activity while simultaneously increasing the energy for lattice cobalt leaching. Besides, in-situ surface-enhanced infrared absorption spectroscopy demonstrates that surface praseodymium species lowers the water dissociation barrier by decreasing the hydrogen bonding degree, while simultaneously reinforcing stability through the mitigation of metal-oxygen bond polarization and the anchoring of oxygenated intermediates. The assembled PEMWE cell employing the PrNi-Co₃O₄ anode operates at only 2.02 V at 1 A cm⁻² and sustains stable operation for 490 h, placing it at the forefront of reported non-noble metal catalysts. This study helps advance the commercial viability and scalability of green hydrogen production by circumventing the reliance on precious iridium.

Key words: Interfacial water, Pre-oxidation, Spinel oxide, Non-noble metal, Proton exchange membrane water electrolysis

吉凌仝, 邱沛萌, 马清君, 李朋, 陈胜利. PrNi共掺杂Co₃O₄通过界面水优化和钴预氧化增强质子交换膜水电解中的析氧反应性能[J]. 催化学报, 2026, 90: 253-263.

Lingtong Ji, Peimeng Qiu, Qingjun Ma, Peng Li, Shengli Chen. Praseodymium and nickel co-doped Co₃O₄ enhances oxygen evolution reaction performance via interfacial water optimization and cobalt pre-oxidation for proton exchange membrane water electrolysis[J]. Chinese Journal of Catalysis, 2026, 90: 253-263.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65109-1

https://www.cjcatal.com/CN/Y2026/V90/I11/253

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Fig. 1. Characterizations of structure for PrNi-Co3O4 catalyst. (a) Synthesis illustration of the PrNi-Co3O4 catalysts. (b,c) XRD patterns of Co3O4, Ni-Co3O4 and PrNi-Co3O4 catalysts. TEM images of the PrNi-Co3O4 catalyst (d) with the corresponding particle size distribution (e) and the marked lattice spacing (f). (g) EDS elemental mapping images of the PrNi-Co3O4. (h) Co, Ni and Pr atomic ratio depth profiles determined by XPS with Ar+ beam etching. Quantification was performed using only the Pr 3d3/2 and Ni 2p3/2 peaks to avoid spectral interference from Co 2s and Auger signals. (i) Variation of the Co/Pr atomic ratio with etching time.

Fig. 2. Chemical and structural characterizations. High-resolution XPS spectra of the Co3O4, Ni-Co3O4, and PrNi-Co3O4 catalysts in the O 1s (a), Co 2p (b), Ni 2p (c), and Pr 3d (d) regions. Raman spectra (e) of the Co3O4, Ni-Co3O4, and PrNi-Co3O4 catalysts, along with the calculated peak intensity ratios (f) of the A1g and F2g(1) modes.

Fig. 3. Electrocatalytic performance in a three-electrode system. Geometric area-normalized CV curves (a), corresponding Tafel plots (b), EIS plots (c), Cdl plots (d), and chronopotentiometric curves (e) of Co3O4, Ni-Co3O4, and PrNi-Co3O4.

Fig. 4. OER mechanism and stability analysis. (a) iR-corrected CV curves of Co3O4, Ni-Co3O4, and PrNi-Co3O4 catalysts. (b) Percentage evolution of different types of interfacial water structures on Co3O4, Ni-Co3O4, and PrNi-Co3O4 as a function of applied potential. In-situ SEIRAS spectroscopy analysis of Co3O4 (c), Ni-Co3O4 (d) and PrNi-Co3O4 (e) in 0.5 mol L−1 H2SO4 at different applied potentials. (f) Atomistic structures showing the demetallation of Co from PrNi-Co3O4 surface. Pink, green, blue, and red spheres represent Co, Ni, Pr and O atoms, respectively. (g) Calculated Co demetallation energies on Co3O4 (311), Ni-Co3O4 (311), and PrNi-Co3O4 (311) surfaces.

Fig. 5. Electrochemical performance in a PEMWE cell. (a) Schematic illustration of the PEMWE cell system. (b) Current-voltage polarizations of the PEMWE cell with Co3O4, Ni-Co3O4 and PrNi-Co3O4 anodic catalyst. (c) Evolution of PEMWE polarization curves recorded after selected cycle numbers during the voltage-cycling AST. The inset illustrates the square-wave voltage protocol alternating between 1.8 and 2.0 V. (d) Variations in PEMWE cell voltage measured at different current densities every 1000 cycles during the AST. (e) Chronoamperometric stability measurement of the PrNi-Co3O4 anode at 0.1 and 1 A cm−2.

参考文献

[1]	W. Shi, T. Shen, C. Xing, K. Sun, Q. Yan, W. Niu, X. Yang, J. Li, C. Wei, R. Wang, S. Fu, Y. Yang, L. Xue, J. Chen, S. Cui, X. Hu, K. Xie, X. Xu, S. Duan, Y. Xu, B. Zhang, Science, 2025, 387, 791-796.
[2]	C. R. Wang, J. M. Stansberry, R. Mukundan, H. J. Chang, D. Kulkarni, A. M. Park, A. B. Plymill, N. M. Firas, C. P. Liu, J. T. Lang, J. K. Lee, N. E. Tolouei, Y. Morimoto, C. H. Wang, G. Zhu, J. Brouwer, P. Atanassov, C. B. Capuano, C. Mittelsteadt, X. Peng, I. V. Zenyuk, Chem. Rev., 2025, 125, 1257-1302.
[3]	C. Wei, C. Liu, Z. Zhang, K. Sun, C. Xing, W. Shi, Y. Li, J.-F. Li, B. Zhang, Joule, 2025, 9, 102058.
[4]	A. Li, S. Kong, K. Adachi, H. Ooka, K. Fushimi, Q. Jiang, H. Ofuchi, S. Hamamoto, M. Oura, K. Higashi, T. Kaneko, T. Uruga, N. Kawamura, D. Hashizume, R. Nakamura, Science, 2024, 384, 666-670.
[5]	K. Ayers, N. Danilovic, R. Ouimet, M. Carmo, B. Pivovar, M. Bornstein, Annu. Rev. Chem. Biomol. Eng., 2019, 10, 219-239.
[6]	R. Wan, T. Yuan, L. Wang, B. Li, M. Liu, B. Zhao, Nat. Catal., 2024, 7, 1288-1304.
[7]	I. C. Man, H.-Y. Su, F. Calle-Vallejo, H. A. Hansen, J. I. Martínez, N. G. Inoglu, J. Kitchin, T. F. Jaramillo, J. K. Nørskov, J. Rossmeisl, ChemCatChem, 2011, 3, 1159-1165.
[8]	X. Zhang, C. Feng, B. Dong, C. Liu, Y. Chai, Adv. Mater., 2023, 35, 2207066.
[9]	M. Huynh, C. Shi, S. J. L. Billinge, D. G. Nocera, J. Am. Chem. Soc., 2015, 137, 14887-14904.
[10]	Y. Wang, P. Guo, J. Zhou, B. Bai, Y. Li, M. Li, P. Das, X. Wu, L. Zhang, Y. Cui, J. Xiao, Z.-S. Wu, Energy Environ. Sci., 2024, 17, 8820-8828.
[11]	J. Huang, C. N. Borca, T. Huthwelker, N. S. Yüzbasi, D. Baster, M. El Kazzi, C. W. Schneider, T. J. Schmidt, E. Fabbri, Nat. Commun., 2024, 15, 3067.
[12]	H.-Y. Wang, S.-F. Hung, H.-Y. Chen, T.-S. Chan, H.-M. Chen, B. Liu, J. Am. Chem. Soc., 2016, 138, 36-39.
[13]	J. Huang, Z. Zhang, C. Spezzati, A. H. Clark, N. Hales, N. S. Genz, N. Daffé, R. Skoupy, L. Gubler, I. E. Castelli, T. J. Schmidt, E. Fabbri, Nat. Commun., 2025, 16, 7518.
[14]	A. Bergmann, T. E. Jones, E. Martinez Moreno, D. Teschner, P. Chernev, M. Gliech, T. Reier, H. Dau, P. Strasser, Nat. Catal., 2018, 1, 711-719.
[15]	N. Yao, G. Wang, H. Jia, J. Yin, H. Cong, S. Chen, W. Luo, Angew. Chem. Int. Ed., 2022, 61, e202117178.
[16]	M. Zhang, M. de Respinis, H. Frei, Nat. Chem., 2014, 6, 362-367.
[17]	A. Moysiadou, S. Lee, C.-S. Hsu, H.-M. Chen, X. Hu, J. Am. Chem. Soc., 2020, 142, 11901-11914.
[18]	J. Huang, H. Sheng, R. D. Ross, J. Han, X. Wang, B. Song, S. Jin, Nat. Commun., 2021, 12, 3036.
[19]	Q. Yan, J. Feng, W. Shi, W. Niu, Z. Lu, K. Sun, X. Yang, L. Xue, Y. Liu, Y. Li, B. Zhang, Adv. Sci., 2024, 11, 2402356.
[20]	S. Zhu, R. Yang, H. J. W. Li, S. Huang, H. Wang, Y. Liu, H. Li, T. Zhai, Angew. Chem. Int. Ed., 2024, 63, e202319462.
[21]	K. Natarajan, E. Munirathinam, T. C. K. Yang, ACS Appl. Mater. Interfaces, 2021, 13, 27140-27148.
[22]	Y. Ping, R. J. Nielsen, W. A. Goddard III, J. Am. Chem. Soc., 2017, 139, 149-155.
[23]	L. Deng, H. Chen, S.-F. Hung, Y. Zhang, H. Yu, H.-Y. Chen, L. Li, S. Peng, J. Am. Chem. Soc., 2024, 146, 35438-35448.
[24]	C. Liang, Y. Katayama, Y. Tao, A. Morinaga, B. Moss, V. Celorrio, M. Ryan, I. E. L. Stephens, J. R. Durrant, R. R. Rao, J. Am. Chem. Soc., 2024, 146, 8928-8938.
[25]	R. Ram, L. Xia, H. Benzidi, A. Guha, V. Golovanova, A. Garzón Manjón, D. Llorens Rauret, P. Sanz Berman, M. Dimitropoulos, B. Mundet, E. Pastor, V. Celorrio, C. A. Mesa, A. M. Das, A. Pinilla-Sánchez, S. Giménez, J. Arbiol, N. López, F. P. García de Arquer, Science, 2024, 384, 1373-1380.
[26]	Z. Wang, M. Wang, X. Li, H. Huang, X. Sun, J. Feng, S. Liu, H. Luo, L. Li, X. Zou, X. Zhao, Nano Lett., 2025, 25, 13267-13275.
[27]	L. Wang, Y. Hao, J. Pan, S. Bi, S.-F. Hung, K.-S. Peng, A.-Y. Wang, T.-Y. Chen, S. Li, C. Ling, Y. Zhang, L. Li, F. Hu, X. Zhou, H.-Y. Chen, K. Wu, J. Wang, Y. Wu, S. Peng, Nat. Catal., 2026, 9, 123-133.
[28]	Z.-Y. Wu, F.-Y. Chen, B. Li, S.-W. Yu, Y. Z. Finfrock, D. M. Meira, Q.-Q. Yan, P. Zhu, M.-X. Chen, T.-W. Song, Z. Yin, H.-W. Liang, S. Zhang, G. Wang, H. Wang, Nat. Mater., 2023, 22, 100-108.
[29]	M. Li, J. Yang, S. Li, L. Deng, S. Zhao, L. Li, S.-F. Hung, G. Xing, T. Wang, Y. Liang, J. Ren, S. Peng, J. Am. Chem. Soc., 2025, 147, 45680-45690.
[30]	C. W. Lee, C. Cazorla, S. Zhou, D. Zhang, H. Xu, W. Zhong, M. Zhang, D. Chu, Z. Han, R. Amal, Adv. Energy Mater., 2025, 15, 2402786.
[31]	M. C. Biesinger, B. P. Payne, A. P. Grosvenor, L. W. M. Lau, A. R. Gerson, R. St. C. Smart, Appl. Surf. Sci., 2011, 257, 2717-2730.
[32]	P. Mountapmbeme Kouotou, M. Waqas, A. El Kasmi, Z. Atour, Z.-Y. Tian, Appl. Catal. A, 2021, 612, 117990.
[33]	K. Arjunan, R. R. Babu, Appl. Phys. A, 2024, 130, 378.
[34]	Y. Suchorski, R. Wrobel, S. Becker, A. Opalińska, U. Narkiewicz, M. Podsiadly, H. Weiss, Acta Phys. Pol. A, 2008, 114, S-125-S-134.
[35]	S. Lütkehoff, M. Neumann, A. Ślebarski, Phys. Rev. B, 1995, 52, 13808-13811.
[36]	Y. Qin, L. Guo, C. Liu, J. Zhang, Q. Wang, J. Colloid Interface Sci., 2025, 695, 137828.
[37]	J. Shan, C. Ye, S. Chen, T. Sun, Y. Jiao, L. Liu, C. Zhu, L. Song, Y. Han, M. Jaroniec, Y. Zhu, Y. Zheng, S.-Z. Qiao, J. Am. Chem. Soc., 2021, 143, 5201-5211.
[38]	L. Sun, M. Feng, Y. Peng, X. Zhao, Y. Shao, X. Yue, S. Huang, J. Mater. Chem. A, 2024, 12, 8796-8804.
[39]	R. R. Rao, B. Huang, Y. Katayama, J. Hwang, T. Kawaguchi, J. R. Lunger, J. Peng, Y. Zhang, A. Morinaga, H. Zhou, H. You, Y. Shao-Horn, J. Phys. Chem. C, 2021, 125, 8195-8207.
[40]	L. Wu, W. Huang, D. Li, B. Zhao, H. Zhou, W. Luo, Angew. Chem. Int. Ed., 2025, 64, e202420848.
[41]	L.-F. Shen, B.-A. Lu, Y.-Y. Li, J. Liu, Z.-C. Huang-fu, H. Peng, J.-Y. Ye, X.-M. Qu, J.-M. Zhang, G. Li, W.-B. Cai, Y.-X. Jiang, S.-G. Sun, Angew. Chem. Int. Ed., 2020, 59, 22397-22402.
[42]	L. Chong, G. Gao, J. Wen, H. Li, H. Xu, Z. Green, J. D. Sugar, A. J. Kropf, W. Xu, X.-M. Lin, H. Xu, L.-W. Wang, D.-J. Liu, Science, 2023, 380, 609-616.

PrNi共掺杂Co₃O₄通过界面水优化和钴预氧化增强质子交换膜水电解中的析氧反应性能

Praseodymium and nickel co-doped Co₃O₄ enhances oxygen evolution reaction performance via interfacial water optimization and cobalt pre-oxidation for proton exchange membrane water electrolysis

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