羟基物种在过渡金属表面碱性析氢反应中的作用

引用本文: 段睿智, 王小梅, 周潘旺, 刘扬, 李灿. 羟基物种在过渡金属表面碱性析氢反应中的作用[J]. 物理化学学报, 2025, 41(9): 100111. doi: 10.1016/j.actphy.2025.100111 shu

Citation: Ruizhi Duan, Xiaomei Wang, Panwang Zhou, Yang Liu, Can Li. The role of hydroxyl species in the alkaline hydrogen evolution reaction over transition metal surfaces[J]. Acta Physico-Chimica Sinica, 2025, 41(9): 100111. doi: 10.1016/j.actphy.2025.100111 shu

羟基物种在过渡金属表面碱性析氢反应中的作用

段睿智 ^{1, 2,} ,
王小梅 ^{1, 3,} ,
周潘旺 ^2, ,
刘扬 ^2, ,
李灿 ^{1, 2,
,}

1.
甘肃省先进催化重点实验室, 兰州大学化学化工学院, 甘肃兰州 730000
2.
中国科学院大连化学物理研究所催化基础国家重点实验室, 大连清洁能源国家实验室, 辽宁大连 116023
3.
兰州交通大学材料科学与工程学院, 甘肃兰州 730000

通讯作者: 李灿, canli@dicp.ac.cn

基金项目:
人工光合作用基础研究中心 FReCAP

国家重点研发计划 2021YFB4000300

国家自然科学基金 22102065

国家自然科学基金 22088102

国家自然科学基金 22372162

甘肃省自然科学青年基金 24JRRA281

摘要: 理解过渡金属催化剂上碱性析氢反应(HER)的活性决定因素对于利用可再生能源进行水电解至关重要。然而，这一问题仍然存在重大挑战。尽管已有研究提出羟基吸附会影响碱性HER性能，但其具体的作用机制和定量关系仍不明确。在此，我们利用密度泛函理论(DFT)计算系统地研究了十种过渡金属表面上的碱性HER过程，揭示了羟基吸附在路径选择和调控反应能垒中的关键作用。然而，仅凭羟基吸附能无法完全解释某些催化剂(尤其是Pt)的异常活性。为了解决这一问题，我们引入了一个多参数耦合描述符(ECS)，该描述符整合了电子占据情况(E)、羟基吸附构型(C)和催化剂表面晶体学特征(S)，从而实现对碱性氢析出催化活性的定性评估。该描述符成功解释了过渡金属催化剂表面的活性趋势，并与包括单原子合金(SAA)催化剂在内的超过10种实验数据对比中表现出良好的关联性，表明其普适性和应用于更广泛的催化体系的潜力。我们的研究突破传统单参数描述符的局限性，构建了一种基于羟基关键物种的碱性氢析出反应活性描述符，并为推动高性能碱性HER催化剂的开发提供了基础框架。

关键词:

English

The role of hydroxyl species in the alkaline hydrogen evolution reaction over transition metal surfaces

1.
Key Laboratory of Advanced Catalysis, Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu Province, China
2.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, Dalian 116023, Liaoning Province, China
3.
School of Materials Science and Engineering, Lanzhou Jiaotong University, Lanzhou 730000, Gansu Province, China

Corresponding author: Email: canli@dicp.ac.cn (C.L.); Tel.: +86-411-84379070

Received Date: 26 March 2025
Accepted Date: 02 June 2025
Revised Date: 16 May 2025
Available Online: 15 September 2025
Fund Project:
the Fundamental Research Centre of Artificial Photosynthesis

the National Key Research and Development Program of China

the National Natural Science Foundation of China

the National Natural Science Foundation of China

the National Natural Science Foundation of China

the Natural Science Foundation of Gansu Province for Youth project, China

Abstract: Understanding the activity-determining factors governing the alkaline hydrogen evolution reaction (HER) on transition metal catalysts is indispensable for water electrolysis with renewable energy. However, it remains a critical challenge. Although hydroxyl adsorption has been proposed to influence alkaline HER performance, its exact mechanistic role and quantitative correlations remain elusive. Here, we systematically investigate the alkaline HER on ten transition metal surfaces using density functional theory (DFT), revealing that hydroxyl adsorption critically modulates both pathway selection and reaction energy barrier. However, hydroxyl adsorption energy alone cannot fully explain the anomalous activity of certain catalysts, especially Pt. To address this, we introduce a multi-parameter coupled descriptor (ECS) that integrates electron occupancy (E), adsorption configuration (C), and surface crystallographic (S), enabling a qualitative evaluation of catalytic activity. This descriptor successfully elucidates previously unexplained activity trends and demonstrates a good correlation with over 10 experimental datasets, including those involving single-atom alloy (SAA) catalysts, indicating its robustness beyond pure metals. Our findings provide a descriptor based on the key species of hydroxyl for rational catalyst design and screening, and offer a fundamental framework for advancing the development of high-performance alkaline HER catalysts.

Key words:

1. [1]
  S. E. Hosseini, M. A. Wahid, Renew. Sustain. Energy Rev. 57 (2016) 850, https://doi.org/10.1016/j.rser.2015.12.112. doi: 10.1016/j.rser.2015.12.112
2. [2]
  M. Chatenet, B. G. Pollet, D. R. Dekel, F. Dionigi, J. Deseure, P. Millet, R. D. Braatz, M. Z. Bazant, M. Eikerling, I. Staffell, P. Balcombe, Y. Shao-Horn, H. Sch fer, Chem. Soc. Rev. 51 (2022) 4583, https://doi.org/10.1039/D0CS01079K. doi: 10.1039/D0CS01079K
3. [3]
  R. T. Liu, Z. L. Xu, F. M. Li, F. Y. Chen, J. Y. Yu, Y. Yan, Y. Chen, B. Y. Xia, Chem. Soc. Rev. 52 (2023) 5652, https://doi.org/10.1039/D2CS00681B. doi: 10.1039/D2CS00681B
4. [4]
  J. K. N rskov, T. Bligaard, A. Logadottir, J. R. Kitchin, J. G. Chen, S. Pandelov, U. J. Stimming, Electrochem. Soc. 152 (2005) J23, https://doi.org/10.1149/1.1856988. doi: 10.1149/1.1856988
5. [5]
  I. T. McCrum, Nat. Catal. 5 (2022) 846, https://doi.org/10.1038/s41929-022-00858-4. doi: 10.1038/s41929-022-00858-4
6. [6]
  A. H. Shah, Z. Zhang, Z. Huang, S. Wang, G. Zhong, C. Wan, A. N. Alexandrova, Y. Huang, X. Duan, Nat. Catal. 5 (2022) 923, https://doi.org/10.1038/s41929-022-00851-x. doi: 10.1038/s41929-022-00851-x
7. [7]
  M. C. O. Monteiro, A. Goyal, P. Moerland, M. T. M. Koper, ACS Catal. 11(2021) 14328, https://doi.org/10.1021/acscatal.1c04268. doi: 10.1021/acscatal.1c04268
8. [8]
  Y. Yang, P. Li, X. Zheng, W. Sun, S. X. Dou, T. Ma, H. Pan, Chem. Soc. Rev. 51 (2022) 9620, https://doi.org/10.1039/D2CS00038E. doi: 10.1039/D2CS00038E
9. [9]
  A. Lasia, A. J. Rami, Electroanal. Chem. Interfacial Electrochem. 294 (1990) 123, https://doi.org/10.1016/0022-0728(90)87140-F. doi: 10.1016/0022-0728(90)87140-F
10. [10]
  S. A. S. Machado, L. A. Avaca, Electrochim. Acta 39 (1994) 1385, https://doi.org/10.1016/0013-4686(94)E0003-I. doi: 10.1016/0013-4686(94)E0003-I
11. [11]
  W. G. Cui, F. Gao, G. Na, X. Wang, Z. Li, Y. Yang, Z. Niu, Y. Qu, D. Wang, H. Pan, Chem. Soc. Rev. 53 (2024) 10253, https://doi.org/10.1039/D4CS00370E. doi: 10.1039/D4CS00370E
12. [12]
  N. Govindarajan, A. Xu, K. Chan, Science. 375 (2022) 379, https://doi.org/10.1126/science.abj2421. doi: 10.1126/science.abj2421
13. [13]
  C. Chen, H. Jin, P. Wang, X. Sun, M. Jaroniec, Y. Zheng, S. Z. Qiao, Chem. Soc. Rev. 53 (2024) 2022, https://doi.org/10.1039/D3CS00669G. doi: 10.1039/D3CS00669G
14. [14]
  V. J. Ovalle, M. M. J. Waegele, Phys. Chem. C 125 (2021) 18567, https://doi.org/10.1021/acs.jpcc.1c05921. doi: 10.1021/acs.jpcc.1c05921
15. [15]
  R. Subbaraman, D. Tripkovic, D. Strmcnik, K. C. Chang, M. Uchimura, A. P. Paulikas, V. Stamenkovic, N. M. Markovic, Science 334 (2011) 1256, https://doi.org/10.1126/science.1211934. doi: 10.1126/science.1211934
16. [16]
  N. Danilovic, R. Subbaraman, D. Strmcnik, K. Chang, A. P. Paulikas, V. R. Stamenkovic, N. M. Markovic, Angew. Chem. Int. Ed. 51 (2012) 12495, https://doi.org/10.1002/anie.201204842. doi: 10.1002/anie.201204842
17. [17]
  Z. Zeng, K. C. Chang, J. Kubal, N. M. Markovic, J. Greeley, Nat. Energy 2 (2017) 17070, https://doi.org/10.1038/nenergy.2017.70. doi: 10.1038/nenergy.2017.70
18. [18]
  R. Subbaraman, D. Tripkovic, K. C. Chang, D. Strmcnik, A. P. Paulikas, P. Hirunsit, M. Chan, J. Greeley, V. Stamenkovic, N. M. Markovic, Nat. Mater. 11 (2012) 550, https://doi.org/10.1038/nmat3313. doi: 10.1038/nmat3313
19. [19]
  J. Staszak-Jirkovsk , C. D. Malliakas, P. P. Lopes, N. Danilovic, S. S. Kota, K. C. Chang, B. Genorio, D. Strmcnik, V. R. Stamenkovic, M. G. Kanatzidis, N. M. Markovic, Nat. Mater. 15 (2016) 197, https://doi.org/10.1038/nmat4481. doi: 10.1038/nmat4481
20. [20]
  I. T. McCrum, M. T. M. Koper, Nat. Energy 5 (2020) 891, https://doi.org/10.1038/s41560-020-00710-8. doi: 10.1038/s41560-020-00710-8
21. [21]
  X. Chen, I. T. McCrum, K. A. Schwarz, M. J. Janik, M. T. M. Koper, Angew. Chem. Int. Ed. 56 (2017) 15025, https://doi.org/10.1002/anie.201709455. doi: 10.1002/anie.201709455
22. [22]
  M. J. Janik, I. T. McCrum, M. T. M. Koper, J. Catal. 367 (2018) 332, https://doi.org/10.1016/j.jcat.2018.09.031. doi: 10.1016/j.jcat.2018.09.031
23. [23]
  I. Ledezma-Yanez, W. D. Z. Wallace, P. Sebastián-Pascual, V. Climent, J. M. Feliu, M. T. M. Koper, Nat. Energy 2 (2017) 17031, https://doi.org/10.1038/nenergy.2017.31. doi: 10.1038/nenergy.2017.31
24. [24]
  C. Wan, Z. Zhang, J. Dong, M. Xu, H. Pu, D. Baumann, Z. Lin, S. Wang, J. Huang, A. H. Shah, X. Pan, T. Hu, A. N. Alexandrova, Y. Huang, X. Duan, Nat. Mater. 22 (2023) 1022, https://doi.org/10.1038/s41563-023-01584-3. doi: 10.1038/s41563-023-01584-3
25. [25]
  A. H. Shah, Z. Zhang, C. Wan, S. Wang, A. Zhang, L. Wang, A. N. Alexandrova, Y. Huang, X. Duan, J. Am. Chem. Soc. 146 (2024) 9623, https://doi.org/10.1021/jacs.3c12934. doi: 10.1021/jacs.3c12934
26. [26]
  X. Wang, G. Long, B. Liu, Z. Li, W. Gao, P. Zhang, H. Zhang, X. Zhou, R. Duan, W. Hu, C. Li, Angew. Chem. Int. Ed. 135 (2023) e202301562, https://doi.org/10.1002/ange.202301562. doi: 10.1002/ange.202301562
27. [27]
  G. Kresse, J. Furthmüller, Phys. Rev. B. 54 (1996) 11169, https://doi.org/10.1103/PhysRevB.54.11169. doi: 10.1103/PhysRevB.54.11169
28. [28]
  G. Kresse, J. Furthmüller, Comput. Mater. Sci. 6 (1996) 15, https://doi.org/10.1016/0927-0256(96)00008-0. doi: 10.1016/0927-0256(96)00008-0
29. [29]
  P. E. Bl chl, Phys. Rev. B. 50 (1994) 17953, https://doi.org/10.1103/physrevb.50.17953. doi: 10.1103/PhysRevB.50.17953
30. [30]
  G. Kresse, D. Joubert, Phys. Rev. B 59 (1999) 1758, https://doi.org/10.1103/PhysRevB.59.1758.
31. [31]
  S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys. 132 (2010) 154104, https://doi.org/10.1063/1.3382344. doi: 10.1063/1.3382344
32. [32]
  G. Henkelman, B. P. Uberuaga, H. Jónsson, J. Chem. Phys. 113 (2000) 9901, https://doi.org/10.1063/1.1329672. doi: 10.1063/1.1329672
33. [33]
  K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T. A. Arias, R. G. Hennig, J. Chem. Phys. 140 (2014) 084106, https://doi.org/10.1063/1.4865107. doi: 10.1063/1.4865107
34. [34]
  R. Dronskowski, P. E. Bloechl, J. Phys. Chem. 97 (1993) 8617, https://doi.org/10.1021/j100135a014. doi: 10.1021/j100135a014
35. [35]
  S. Maintz, V. L. Deringer, A. L. Tchougréeff, R. Dronskowski, J. Comput. Chem. 37 (2016) 1030, https://doi.org/10.1002/jcc.24300. doi: 10.1002/jcc.24300
36. [36]
  W. Sheng, M. Myint, J. G. Chen, Y. Yan, Energy Environ. Sci. 6 (2013) 1509, https://doi.org/10.1039/c3ee00045a. doi: 10.1039/c3ee00045a
37. [37]
  J. K. N rskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T. Bligaard, H. Jónsson, J. Phys. Chem. B 108 (2004) 17886, https://doi.org/10.1021/jp047349j. doi: 10.1021/jp047349j
38. [38]
  X. An, T. Yao, Y. Liu, G. Long, A. Wang, Z. Feng, M. Dupuis, C. Li, J. Phys. Chem. Lett. 14 (2023) 8121, https://doi.org/10.1021/acs.jpclett.3c02142. doi: 10.1021/acs.jpclett.3c02142
39. [39]
  S. Ghoshal, A. Ghosh, P. Roy, B. Ball, A. Pramanik, P. Sarkar, ACS Catal. 12 (2022) 15541, https://doi.org/10.1021/acscatal.2c04527.
40. [40]
  J. Wang, S. Xin, Y. Xiao, Z. Zhang, Z. Li, W. Zhang, C. Li, R. Bao, J. Peng, J. Yi, S. Chou, Angew. Chem. Int. Ed. 61 (2022) e202202518, https://doi.org/10.1002/anie.202202518. doi: 10.1002/anie.202202518
41. [41]
  M. T. M. Koper, R. A. Van Santen, J. Electroanal. Chem. 472 (1999) 126, https://doi.org/10.1016/S0022-0728(99)00291-0. doi: 10.1016/S0022-0728(99)00291-0
42. [42]
  I. C. Man, H. Su, F. Calle-Vallejo, H. A. Hansen, J. I. Martínez, N. G. Inoglu, J. Kitchin, T. F. Jaramillo, J. K. N rskov, J. Rossmeisl, ChemCatChem. 3 (2011) 1159, https://doi.org/10.1002/cctc.201000397. doi: 10.1002/cctc.201000397
43. [43]
  A. Michaelides, Z. P. Liu, C. J. Zhang, A. Alavi, D A. King, P. Hu, J. Am. Chem. Soc. 125 (2003) 3704, https://doi.org/10.1021/ja027366r. doi: 10.1021/ja027366r
44. [44]
  S. Wang, V. Petzold, V. Tripkovic, J. Kleis, J. G. Howalt, E. Skúlason, E. M. Fernández, B. Hvolb k, G. Jones, A. Toftelund, H. Falsig, M. Bj rketun, F. Studt, F. Abild-Pedersen, J. Rossmeisl, J. K. N rskov, T. Bligaard, Phys. Chem. Chem. Phys. 13 (2011) 20760, https://doi.org/10.1039/c1cp20547a. doi: 10.1039/c1cp20547a
45. [45]
  S. Wang, V. Vorotnikov, J. E. Sutton, D G. Vlachos, ACS Catal. 4 (2014) 604, https://doi.org/10.1021/cs400942u. doi: 10.1021/cs400942u
46. [46]
  S. J. Kurdziel, J. L. Lansford, D. G. Vlachos, J. Phys. Chem. C 125 (2021) 19780, https://doi.org/10.1021/acs.jpcc.1c05425. doi: 10.1021/acs.jpcc.1c05425
47. [47]
  S. A. Akhade, R. M. Nidzyn, G. Rostamikia, M. J. Janik, Catal. Today 312 (2018) 82, https://doi.org/10.1016/j.cattod.2018.03.048. doi: 10.1016/j.cattod.2018.03.048
48. [48]
  Z. Han, S. Zhao, J. Xiao, X. Zhong, J. Sheng, W. Lv, Q. Zhang, G. Zhou, H. Cheng, Adv. Mater. 33 (2021) 2105947, https://doi.org/10.1002/adma.202105947. doi: 10.1002/adma.202105947
49. [49]
  X. Lin, X. Du, S. Wu, S. Zhen, W. Liu, C. Pei, P. Zhang, Z. J. Zhao, J. Gong, Nat. Commun. 15 (2024) 8169, https://doi.org/10.1038/s41467-024-52519-8. doi: 10.1038/s41467-024-52519-8
50. [50]
  C. H. Chen, D. Wu, Z. Li, R. Zhang, C. G. Kuai, X. R. Zhao, C. K. Dong, S. Z. Qiao, H. Liu, X. W. Du, Adv. Energy Mater. 9 (2019) 1803913, https://doi.org/10.1002/aenm.201803913. doi: 10.1002/aenm.201803913
51. [51]
  J. Mao, C. T. He, J. Pei, W. Chen, D. He, Y. He, Z. Zhuang, C. Chen, Q. Peng, D. Wang, Y. Li, Nat. Commun. 9 (2018) 4958, https://doi.org/10.1038/s41467-018-07288-6. doi: 10.1038/s41467-018-07288-6
52. [52]
  R. Wan, M. Luo, J. Wen, S. Liu, X. Kang, Y. Tian, J. Energy Chem. 69 (2022) 44, https://doi.org/10.1016/j.jechem.2021.12.045. doi: 10.1016/j.jechem.2021.12.045

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

羟基物种在过渡金属表面碱性析氢反应中的作用

通讯作者: 李灿, canli@dicp.ac.cn

English

The role of hydroxyl species in the alkaline hydrogen evolution reaction over transition metal surfaces

Corresponding author: Email: canli@dicp.ac.cn (C.L.); Tel.: +86-411-84379070

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

羟基物种在过渡金属表面碱性析氢反应中的作用

通讯作者: 李灿, canli@dicp.ac.cn

English

The role of hydroxyl species in the alkaline hydrogen evolution reaction over transition metal surfaces

Corresponding author: Email: canli@dicp.ac.cn (C.L.); Tel.: +86-411-84379070

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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