桥接氧诱导氢键网络重构提升磷掺杂碳包覆镍催化剂的碱性氢氧化电催化活性

doi:10.1016/S1872-2067(25)64917-5

催化学报 ›› 2026, Vol. 82: 144-152.DOI: 10.1016/S1872-2067(25)64917-5

桥接氧诱导氢键网络重构提升磷掺杂碳包覆镍催化剂的碱性氢氧化电催化活性

岳健超¹, 张昱¹, 熊茜茜, 罗威^*()

武汉大学化学与分子科学学院, 湖北武汉 430072

收稿日期:2025-07-05 接受日期:2025-09-30 出版日期:2026-03-18 发布日期:2026-03-05
通讯作者: * 电子信箱: wluo@whu.edu.cn (罗威).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2021YFB4001200);国家自然科学基金(22272121);国家自然科学基金(21972107)

Bridging oxygen-induced hydrogen-bond network reconstruction in phosphorus-doped carbon-coated Ni catalyst enhances alkaline hydrogen oxidation electrocatalysis

Jianchao Yue¹, Yu Zhang¹, Qianqian Xiong, Wei Luo^*()

College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China

Received:2025-07-05 Accepted:2025-09-30 Online:2026-03-18 Published:2026-03-05
Contact: * E-mail: wluo@whu.edu.cn (W. Luo).
About author:¹ Contributed equally to this work.
Supported by:
National Key Research and Development program of China(2021YFB4001200);National Natural Science Foundation of China(22272121);National Natural Science Foundation of China(21972107)

摘要/Abstract

摘要：

与铂族金属催化剂相比, 非贵金属镍基催化剂因其兼具成本优势与可观的氢电催化活性而广受关注, 但其在碱性氢氧化反应的实际应用中仍面临活性不足与长期稳定性欠佳的双重挑战. 在镍纳米颗粒表面构建碳保护层的策略不仅有效抑制了镍纳米颗粒在催化过程中的溶解和聚集, 还可调控镍活性位点的电子结构, 进而影响其对关键反应中间体的吸附强度. 然而, 当前关于碳层调控效应的研究多聚焦于上述电子结构与吸附能等描述, 而对其在重构电极/电解液界面微环境中的关键作用关注较少. 因此, 深入揭示碳层如何诱导双电层内氢键网络重构, 是进一步提升镍基催化剂性能的关键所在, 也为理性设计高效非贵金属电催化剂提供了新的方向.

本文通过在氮气/氢气的气氛中退火处理含有Ni-O-C和Ni-O-P结构的镍配合物前体, 制备了具有桥接氧结构(Ni-O-C/P)的碳层包覆镍纳米颗粒(Ni@PC)催化剂, 透射电子显微镜及高角环形暗场-扫描透射显微镜表征显示了镍纳米颗粒外部厚度约为2 nm的碳层结构. X射线光电子能谱及吸收谱表征表明桥接氧结构(Ni-O-C/P)的存在, 且电子可通过该桥接氧结构从Ni核向碳层中的C或P转移, 实现对活性位点的电子结构调节. 电化学测试表明, 与Ni和Ni@C相比, Ni@PC表现出最佳的碱性氢氧化催化活性, 甚至优于近期报道的大多数Ni基催化剂. 在碱性氢氧化反应中, 界面水分子所构成的氢键网络作为质子传递的“高速公路”, 其重构行为直接决定了质子的转移效率与反应动力学速率. 通过表面增强原位红外光谱进一步探究了催化剂表面的界面水结构. 结果表明, 在氢氧化电势范围内Ni@PC具有占比最高的强氢键水, 且能实现弱氢键水向强氢键水构型的快速转变, 表明Ni@PC的氢键网络连通性最优, 为质子快速传递提供了高效通道. 密度泛函理论计算结果发现, Ni-O-P结构调控了Ni的d带中心位置, 使Ni@PC具有最优的氢结合能; 另外, 桥接氧通过构建局部氢键将催化剂附近较弱的氢键水分子转化为强氢键水分子, 增强界面内氢键网络的连通性.

综上, 本文揭示了磷掺杂碳层与镍纳米颗粒之间的Ni-O-P配位环境不仅可以调节活性位点的电子结构, 还能重建双电层中的氢键网络, 促进质子高效转移, 展示了提高催化性能的新策略.

关键词: 氢氧化反应, 镍, 界面水, 氢键网络, 传质过程

Abstract:

The rational design of high-performance electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is significant to the widespread commercialization of alkaline exchange membrane fuel cells. However, precise regulation of proton adsorption states and interfacial transfer kinetics at the catalytic interface remains a significant challenge in advancing HOR under alkaline conditions. Herein, we demonstrate that construction of phosphorus-doped carbon-coated nickel (Ni) catalyst (Ni@PC) featuring the bridging oxygen structures (Ni-O-C/P) enables rapid desorption of adsorbed hydrogen species and dynamic reconstruction of interfacial hydrogen-bond network. Density functional theory calculations reveal that the Ni-O-P configuration induces a downward shift in the d-band center of Ni, thereby weakening hydrogen binding energy (HBE). Furthermore, the bridging oxygen atoms facilitate the formation of hydrogen bonds with interfacial water molecules, optimizing the proton transfer pathway. In-situ surface-enhanced infrared absorption spectroscopy confirms that the Ni-O-P structure effectively converts weakly hydrogen-bonded water into strongly hydrogen-bonded water, enhancing the connectivity of hydrogen-bond network and facilitating efficient proton transfer. This work successfully achieves optimization of proton dynamics during the alkaline HOR progress, while also providing a strategic framework for the rational design of advanced carbon-coated electrocatalysts.

Key words: Hydrogen oxidation reaction, Nickel, Interfacial water, Hydrogen-bond network, Mass transfer process

岳健超, 张昱, 熊茜茜, 罗威. 桥接氧诱导氢键网络重构提升磷掺杂碳包覆镍催化剂的碱性氢氧化电催化活性[J]. 催化学报, 2026, 82: 144-152.

Jianchao Yue, Yu Zhang, Qianqian Xiong, Wei Luo. Bridging oxygen-induced hydrogen-bond network reconstruction in phosphorus-doped carbon-coated Ni catalyst enhances alkaline hydrogen oxidation electrocatalysis[J]. Chinese Journal of Catalysis, 2026, 82: 144-152.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64917-5

https://www.cjcatal.com/CN/Y2026/V82/I3/144

图/表 5

Fig. 1. (a) The structural schematic diagram of Ni@PC. Ni, P, O, and C atoms are denoted by blue, pink, red, and gray spheres, respectively. (b) XRD patterns of the Ni@PC and Ni@C. (c-f) HRTEM images of the Ni@PC. (g) Elemental mappings of Ni, O, C, P and mix image.

Fig. 2. XPS Ni 2p3/2 (a), O 1s (b) and C 1s (c) spectra of Ni@PC and Ni@C. (d) XPS P 2p spectra in Ni@PC. (e) XANES spectra at the Ni K-edge of the Ni foil, NiO, Ni@C and Ni@PC. (f) Fourier transformed EXAFS spectra of the Ni foil, NiO, Ni@C and Ni@PC. (g)-(j) Corresponding wavelet transformation of Ni for Ni foil, Ni@C, Ni@PC and NiO.

Fig. 3. (a) HOR polarization curves with a scan rate of 5 mV s-1 in H2-saturated 0.1 mol L-1 KOH. (b) Tafel plots with the Butler-Volmer fitting lines. (c) Linear fitting curves in the micro-polarization region (-5 to 5 mV). (d) Comparison ECSA-normalized exchange current densities (j0,s) and exchange current densities normalized by metal mass (jk,m) of Ni, Ni@C and Ni@PC. (e) Comparisons of jk,m and j0,s of the Ni@PC with those of recently reported Ni-based HOR catalysts. (f) HOR polarization curves for Ni@PC in H2-saturated 0.1 mol L-1 KOH before and after 1000 CVs.

Fig. 4. Deconvolution of the O-H stretching vibration peaks (around 3000 to 3800 cm-1) of Ni@PC (a) and Ni (b). (c) Comparison of the O-H stretching vibration frequencies of all the samples. (d) Potential-dependent proportion of interfacial water with different structures from 0 to 0.25 V.

Fig. 5. The electron density difference after the existence of Ni-O-C/P structure for (a) Ni@PC and (b) Ni@C. (c) The relationship between j0,s (pink dots) and HBE (blue rhombus). ELF evaluation for H2O adsorption on Ni (d) and Ni@PC (e). (f) Schematic of the reaction mechanism on Ni (left) and Ni@PC (right). Ni, P, O, C, and K+ atoms are denoted by blue, pink, red, gray, and yellow spheres, respectively.

参考文献

[1]	V. R. Stamenkovic, D. Strmcnik, P. P. Lopes, N. M. Markovic, Nat. Mater., 2017, 16, 57-69.
[2]	N. Ramaswamy, S. Mukerjee, Chem. Rev., 2019, 119, 11945-11979.
[3]	Y. Zhou, W. Yuan, M. Li, Z. Xie, X. Song, Y. Yang, J. Wang, L. Li, W. Ding, W.-F. Lin, Z. Wei, Nat. Energy, 2024, 9, 1297-1309.
[4]	L. Schlapbach, A. Züttel, Nature, 2001, 414, 353-358.
[5]	Y. Yang, L. Shi, Q. Liang, Y. Liu, J. Dong, T. T. Isimjan, B. Wang, X. Yang, Chin. J. Catal., 2024, 56, 176-187.
[6]	M. Kamal, J. Jaafar, A. A. Khan, Z. Khan, A. F. Ismail, M. H. D. Othman, M. A. Rahman, F. Aziz, G. U. Rehman, Energy Fuels, 2024, 38, 12337-12386.
[7]	Y. Qiu, X. Xie, W. Li, Y. Shao, Chin. J. Catal., 2021, 42, 2094-2104.
[8]	T. Cheng, L. Wang, B. V. Merinov, W. A. Goddard III, J. Am. Chem. Soc., 2018, 140, 7787-7790.
[9]	W. Jiang, C. Ge, G. Wang, J. Lu, L. Xiao, L. Zhuang, Chin. J. Catal., 2024, 57, 51-58.
[10]	L. An, X. Zhao, T. Zhao, D. Wang, Energy Environ. Sci., 2021, 14, 2620-2638.
[11]	S.-Q. Wang, Z.-C. Yao, Z.-Q. Shi, X. Liu, T. Tang, H.-R. Pan, L. Zheng, Q. Zhang, D. Su, Z. Zhuang, L. Zhao, Q. An, J.-S. Hu, J. Am. Chem. Soc., 2025, 147, 5398-5407.
[12]	Y. Yang, X. Sun, G. Han, X. Liu, X. Zhang, Y. Sun, M. Zhang, Z. Cao, Y. Sun, Angew. Chem. Int. Ed., 2019, 58, 10644-10649.
[13]	J. He, L. Luo, J. Li, S. Chen, S. Yu, L. Zeng, Y. Wang, Y. Chen, Angew. Chem. Int. Ed., 2025, 64, e202423647.
[14]	P. Han, N. Yao, W. Zuo, W. Luo, Chin. J. Catal., 2022, 43, 1527-1534.
[15]	C. Xu, Q. Chen, R. Ding, S. Huang, Y. Zhang, G. Fan, Chin. J. Catal., 2021, 42, 251-258.
[16]	Z. Zhuang, S. A. Giles, J. Zheng, G. R. Jenness, S. Caratzoulas, D. G. Vlachos, Y. Yan, Nat. Commun., 2016, 7, 10141.
[17]	L. An, S. Deng, X. Guo, X. Liu, T. Zhao, K. Chen, Y. Zhu, Y. Fu, X. Zhao, D. Wang, Chin. J. Catal., 2022, 43, 3154-3160.
[18]	X. Zhao, X. Li, L. An, L. Zheng, J. Yang, D. Wang, Angew. Chem., Int. Ed., 2022, 61, e202206588.
[19]	F. Yang, S. Lu, Y. Feng, L. Fu, L. Feng, ACS Catal., 2024, 14, 2324-2332.
[20]	W. Ni, T. Wang, F. Héroguel, A. Krammer, S. Lee, L. Yao, A. Schüler, J. S. Luterbacher, Y. Yan, X. Hu, Nat. Mater., 2022, 21, 804-810.
[21]	J. Deng, D. Deng, X. Bao, Adv. Mater., 2017, 29, 1606967.
[22]	J. Deng, P. Ren, D. Deng, X. Bao, Angew. Chem. Int. Ed., 2015, 54, 2100-2104.
[23]	Y. Hu, X. Guo, T. Shen, Y. Zhu, D. Wang, ACS Catal., 2022, 12, 5380-5387.
[24]	Y. Hu, J. O. Jensen, W. Zhang, L. N. Cleemann, W. Xing, N. J. Bjerrum, Q. Li, Angew. Chem. Int. Ed., 2014, 53, 3675-3679.
[25]	T. Wang, Y. Zhang, B. Huang, B. Cai, R. R. Rao, L. Giordano, S.-G. Sun, Y. Shao-Horn, Nat. Catal., 2021, 4, 753-762.
[26]	N. Berg, S. Bergwinkl, P. Nuernberger, D. Horinek, R. M. Gschwind, J. Am. Chem. Soc., 2021, 143, 724-735.
[27]	B. Huang, R. R. Rao, S. You, K. Hpone Myint, Y. Song, Y. Wang, W. Ding, L. Giordano, Y. Zhang, T. Wang, S. Muy, Y. Katayama, J. C. Grossman, A. P. Willard, K. Xu, Y. Jiang, Y. Shao-Horn, JACS Au, 2021, 1, 1674-1687.
[28]	K. Zhao, H. Yu, H. Xiong, Q. Lu, Y.-Q. Gao, B. Xu, Chem. Sci., 2023, 14, 11076-11087.
[29]	P. Li, Y. Jiang, Y. Hu, Y. Men, Y. Liu, W. Cai, S. Chen, Nat. Catal., 2022, 5, 900-911.
[30]	X. Zhang, Z. Li, X. Sun, L. Wei, H. Niu, S. Chen, Q. Chen, C. Wang, F. Zheng, ACS Mater. Lett., 2022, 4, 2097-2105.
[31]	Y. Zhu, J. Zhang, Q. Qian, Y. Li, Z. Li, Y. Liu, C. Xiao, G. Zhang, Y. Xie, Angew. Chem., Int. Ed., 2022, 61, e202113082.
[32]	Y. Gao, H. Peng, Y. Wang, G. Wang, L. Xiao, J. Lu, L. Zhuang, ACS Appl. Mater. Interfaces, 2020, 12, 31575-31581.
[33]	J. Li, W. Zhou, S. Yu, C. Qing, J. He, L. Zeng, Y. Wang, Y. Chen, Chin. J. Catal., 2024, 67, 186-193.
[34]	P. Ge, S. Li, L. Xu, K. Zou, X. Gao, X. Cao, G. Zou, H. Hou, X. Ji, Adv. Energy Mater., 2019, 9, 1803035.
[35]	Y. Yang, J. Liu, S. Guo, Y. Liu, Z. Kang, J. Mater. Chem. A, 2015, 3, 18598-18604.
[36]	J. Yu, Y. He, J. Li, C. Dong, Y. Dai, T. Gao, X. Wang, K. Yue, G. Zhou, Chem. Eng. J., 2023, 477, 146996.
[37]	J. Yu, Y. Guo, S. She, S. Miao, M. Ni, W. Zhou, M. Liu, Z. Shao, Adv. Mater., 2018, 30, 1800047.
[38]	Q. Wang, Z. Zhang, C. Cai, M. Wang, Z.-L. Zhao, M. Li, X. Huang, S. Han, H. Zhou, Z. Feng, L. Li, J. Li, H. Xu, J. S. Francisco, M. Gu, J. Am. Chem. Soc., 2021, 143, 13605-13615.
[39]	W. Ji, C. Zhan, D. Li, Y. Xu, Y. Zhang, L. Wang, L. Liu, Y. Wang, W. Chen, H. Geng, X. Huang, J. Mater. Chem. A, 2021, 9, 26323-26329.
[40]	Y. Duan, Z.-Y. Yu, L. Yang, L.-R. Zheng, C.-T. Zhang, X.-T. Yang, F.-Y. Gao, X.-L. Zhang, X. Yu, R. Liu, H.-H. Ding, C. Gu, X.-S. Zheng, L. Shi, J. Jiang, J.-F. Zhu, M.-R. Gao, S.-H. Yu, Nat. Commun., 2020, 11, 4789.
[41]	F.-Y. Gao, S.-N. Liu, J.-C. Ge, X.-L. Zhang, L. Zhu, Y.-R. Zheng, Y. Duan, S. Qin, W. Dong, X. Yu, R.-C. Bao, P.-P. Yang, Z.-Z. Niu, Z.-G. Ding, W. Liu, S. Lan, M.-R. Gao, Y. Yan, S.-H. Yu, Nat. Catal., 2022, 5, 993-1005.
[42]	J. Zheng, S. Zhou, S. Gu, B. Xu, Y. Yan, J. Electrochem. Soc., 2016, 163, F499-F506.
[43]	Y. Zhou, Z. Xie, J. Jiang, J. Wang, X. Song, Q. He, W. Ding, Z. Wei, Nat. Catal., 2020, 3, 454-462.
[44]	T. Wang, L.-Y. Li, L.-N. Chen, T. Sheng, L. Chen, Y.-C. Wang, P. Zhang, Y.-H. Hong, J. Ye, W.-F. Lin, Q. Zhang, P. Zhang, G. Fu, N. Tian, S.-G. Sun, Z.-Y. Zhou, J. Am. Chem. Soc., 2022, 144, 9292-9301.
[45]	Y.-H. Wang, S. Zheng, W.-M. Yang, R.-Y. Zhou, Q.-F. He, P. Radjenovic, J.-C. Dong, S. Li, J. Zheng, Z.-L. Yang, G. Attard, F. Pan, Z.-Q. Tian, J.-F. Li, Nature, 2021, 600, 81-85.
[46]	L. F. Scatena, M. G. Brown, G. L. Richmond, Science, 2001, 292, 908-912.
[47]	Y. Jin, W. Cheng, W. Luo, Chin. J. Catal., 2025, 74, 240-249.
[48]	M. Osawa, M. Tsushima, H. Mogami, G. Samjeské, A. Yamakata, J. Phys. Chem. C, 2008, 112, 4248-4256.
[49]	X. Zhao, X. Li, L. An, K. Iputera, J. Zhu, P. Gao, R.-S. Liu, Z. Peng, J. Yang, D. Wang, Energy Environ. Sci., 2022, 15, 1234-1242.
[50]	X. Wang, Y. Tong, W. Feng, P. Liu, X. Li, Y. Cui, T. Cai, L. Zhao, Q. Xue, Z. Yan, X. Yuan, W. Xing, Nat. Commun., 2023, 14, 3767.
[51]	Z. Deng, X. Zheng, M. Deng, L. Li, L. Jing, Z. Wei, Chin. J. Catal., 2021, 42, 1659-1666.
[52]	Y. Yang, F.-Y. Gao, X.-L. Zhang, S. Qin, L.-R. Zheng, Y.-H. Wang, J. Liao, Q. Yang, M.-R. Gao, Angew. Chem. Int. Ed., 2022, 61, e202208040.
[53]	N. Yao, J. Zhu, H. Jia, H. Cong, W. Luo, Chin. J. Chem., 2024, 42, 343-350.
[54]	S. A. S. Farias, J. B. L. Martins, Chem. Phys. Lett., 2012, 533, 78-81.

桥接氧诱导氢键网络重构提升磷掺杂碳包覆镍催化剂的碱性氢氧化电催化活性

Bridging oxygen-induced hydrogen-bond network reconstruction in phosphorus-doped carbon-coated Ni catalyst enhances alkaline hydrogen oxidation electrocatalysis

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