Decoupling the HOR enhancement on PtRu: Dynamically matching interfacial water to reaction coordinates

doi:10.1016/S1872-2067(25)64785-1

Abstract

Abstract:

Platinum-ruthenium alloys (PtRu) represent state-of-the-art alkaline hydrogen oxidation reaction (HOR) catalysts, yet the atomic-scale origin of their superiority over pure Pt remains incompletely understood. Here, we employ density functional theory calculations, ab initio molecular dynamics simulations, and microkinetic modeling on Pt(111) and PtRu(111) surfaces to systematically investigate the key factors, including active sites distribution, species adsorption, and solvent reorganization, that affect the HOR activity and decouple their contributions. The results reveal that while the moderate hydrogen binding energy and improved hydroxyl (OH) species adsorption both contribute to the enhanced activity, the dominant factor is the substantial reduction in solvent reorganization energy on the PtRu(111). This is facilitated by the spatial separation of active sites: Pt atoms preferentially stabilize adsorbed hydrogen, while Ru atoms strongly bind OH and interfacial water molecules. This configuration increases the probability of hydrogen interacting with OH/water and enhances the fraction of "H-up" water molecules, forming a well-organized hydrogen bond network within the electric double layer. The dynamically compatible interfacial water structure and HOR coordination promote H desorption and proton transfer in the Volmer step, thereby accelerating the HOR kinetics.

Key words: Hydrogen oxidation reaction, PtRu alloys, Catalyst/electrolyte interface, Electric double layer, Hydrogen bond network

Jin Liu, Zhuoyang Xie, Qiong Xiang, Xia Chen, Mengting Li, Jiawei Liu, Li Li, Zidong Wei. Decoupling the HOR enhancement on PtRu: Dynamically matching interfacial water to reaction coordinates[J]. Chinese Journal of Catalysis, 2025, 78: 303-312.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64785-1

https://www.cjcatal.com/EN/Y2025/V78/I11/303

Figures/Tables 5

Fig. 1. Electronic properties and adsorption characteristics of Pt(111) and PtRu(111) surfaces. (a) Partial density of states (PDOS) of Pt(111), PtRu(111), and PtRu(111)-OH surfaces. (b) Average Bader charges of Pt and Ru atoms (left) and spatial distributions of surface atomic Bader charges (right). (c) Adsorption energies of OH and H2O on Pt(111) and PtRu(111) surfaces. (d) Adsorption energies of Had on Pt(111), PtRu(111), and PtRu(111)-OH surfaces; solid circles denote Pt sites, hollow circles denote Ru sites, and grey dashed circles indicate unstable sites.

Fig. 2. Surface characterization and electron distribution on Pt(111)-alkali and PtRu(111)-alkali. (a) Models used for explicit solvation calculations. (b) Bader charges and differential charge density maps (yellow indicates electron accumulation, cyan for depletion, isosurface at 0.003 e·??3). (c) Electrostatic potential and work-function profiles. (d) Radial distribution functions (RDFs) of interactions between metal atoms and O, H, K. (e) Water number-density distribution (histograms represent the percentage of different regions of water molecules relative to the total number of water molecules).

Fig. 3. Depiction of HOR mechanisms on Pt(111)-alkali and PtRu(111)-alkali. (a) Schematic representation of HOR mechanism. (b) Tafel step. (c) Volmer1 step. (d) Volmer2 step.

Fig. 4. Analysis of factors influencing HOR dynamics. (a) Steady-state polarization curves for the HOR. (b) Contributions of various factors to HOR activation barriers.

Fig. 5. Analysis of water molecule orientations and hydrogen bond (H-bond) at the Pt(111)-alkali and PtRu(111)-alkali interfaces. (a) Two-dimensional density profiles of cosθ for H2O at the Pt(111)-alkali and PtRu(111)-alkali interfaces. (b) Number density distribution of H2O with different orientations (bar chart represents the percentage of H2O with various orientations in the electric double layer (EDL) relative to the total number of H2O in the EDL). (c) Two-dimensional density distribution profiles of H-bond lengths at the Pt(111)-alkali and PtRu(111)-alkali interfaces. (d) Statistical analysis of H-bond lengths in the EDL.

References

[1]	Y. Chen, J. Cai, P. Li, G. Zhao, G. Wang, Y. Jiang, J. Chen, S.-X. Dou, H. Pan, W. Sun, Nano Lett., 2020, 20, 6807-6814.
[2]	F. Xiao, Y.-C. Wang, Z.-P. Wu, G. Chen, F. Yang, S. Zhu, K. Siddharth, Z. Kong, A. Lu, J.-C. Li, C.-J. Zhong, Z.-Y. Zhou, M. Shao, Adv. Mater., 2021, 33, 2006292.
[3]	E. S. Davydova, S. Mukerjee, F. Jaouen, D. R. Dekel, ACS Catal., 2018, 8, 6665-6690.
[4]	Y. Xue, X. Wang, X. Zhang, J. Fang, Z. Xu, Y. Zhang, X. Liu, M. Liu, W. Zhu, Z. Zhuang, Acta Phys.-Chim. Sin., 2021, 37, 2009103.
[5]	S. Sahoo, D. R. Dekel, R. Maric, S. P. Alpay, ACS Catal., 2021, 11, 2561-2571.
[6]	J. Durst, A. Siebel, C. Simon, F. Hasché, J. Herranz, H. A. Gasteiger, Energy Environ. Sci., 2014, 7, 2255-2260.
[7]	X. Zhang, Y. Xie, L. Wang, Nano Res., 2024, 17, 960-981.
[8]	E. R. Hamo, R. K. Singh, J. C. Douglin, S. Chen, M. Ben Hassine, E. Carbo-Argibay, S. Lu, H. Wang, P. J. Ferreira, B. A. Rosen, D. R. Dekel, ACS Catal., 2021, 11, 932-947.
[9]	M. Li, X. Zheng, L. Li, Z. Wei, Acta Phys.-Chim. Sin. 2021, 37, 2007054.
[10]	Y. Cong, C. Chai, X. Zhao, B. Yi, Y. Song, Adv. Mater. Interfaces, 2020, 7, 2000310.
[11]	W. Ni, J. L. Meibom, N. U. Hassan, M. Chang, Y.-C. Chu, A. Krammer, S. Sun, Y. Zheng, L. Bai, W. Ma, S. Lee, S. Jin, J. S. Luterbacher, A. Schüler, H.-M. Chen, W. E. Mustain, X. Hu, Nat. Catal., 2023, 6, 773-783.
[12]	J. Yue, Y. Li, C. Yang, W. Luo, Angew. Chem. Int. Ed. 2025, 64, DOI:10.1002/anie.202415447.
[13]	X. Liu, G. Wu, Q. Li, eScience, 2025, 5, 100270.
[14]	B. Pang, X. Liu, T. Liu, T. Chen, X. Shen, W. Zhang, S. Wang, T. Liu, D. Liu, T. Ding, Z. Liao, Y. Li, C. Liang, T. Yao, Energy Environ. Sci., 2022, 15, 102-108.
[15]	J. Ohyama, T. Sato, Y. Yamamoto, S. Arai, A. Satsuma, J. Am. Chem. Soc., 2013, 135, 8016-8021.
[16]	K. Ishikawa, J. Ohyama, K. Okubo, K. Murata, A. Satsuma, ACS Appl. Mater. Interfaces, 2020, 12, 22771-22777.
[17]	L. An, X. Zhao, T. Zhao, D. Wang, Energy Environ. Sci., 2021, 14, 2620-2638.
[18]	G. Wang, W. Li, N. Wu, B. Huang, L. Xiao, J. Lu, L. Zhuang, J. Power Sources, 2019, 412, 282-286.
[19]	X. Yang, B. Ouyang, P. Shen, Y. Sun, Y. Yang, Y. Gao, E. Kan, C. Li, K. Xu, Y. Xie, J. Am. Chem. Soc., 2022, 144, 11138-11147.
[20]	K. Elbert, J. Hu, Z. Ma, Y. Zhang, G. Chen, W. An, P. Liu, H. S. Isaacs, R. R. Adzic, J. X. Wang, ACS Catal., 2015, 5, 6764-6772.
[21]	F. Yang, Y. Wang, Y. Cui, X. Yang, Y. Zhu, C. M. Weiss, M. Li, G. Chen, Y. Yan, M. D. Gu, M. Shao, J. Am. Chem. Soc., 2023, 145, 27500-27511.
[22]	P. Zhang, S. Hong, N. Song, Z. Han, F. Ge, G. Dai, H. Dong, C. Li, Chin. Chem. Lett., 2024, 35, 109073.
[23]	Y. Wang, G. Wang, G. Li, B. Huang, J. Pan, Q. Liu, J. Han, L. Xiao, J. Lu, L. Zhuang, Energy Environ. Sci., 2015, 8, 177-181.
[24]	M. E. Scofield, Y. Zhou, S. Yue, L. Wang, D. Su, X. Tong, M. B. Vukmirovic, R. R. Adzic, S. S. Wong, ACS Catal., 2016, 6, 3895-3908.
[25]	Q. Li, H. Peng, Y. Wang, L. Xiao, J. Lu, L. Zhuang, Angew. Chem. Int. Ed., 2019, 58, 1442-1446.
[26]	W. Sheng, Z. Zhuang, M. Gao, J. Zheng, J. G. Chen, Y. Yan, Nat. Commun., 2015, 6, 5848.
[27]	J. Zheng, J. Nash, B. Xu, Y. Yan, J. Electrochem. Soc., 2018, 165, H27-H29.
[28]	D. Strmcnik, M. Uchimura, C. Wang, R. Subbaraman, N. Danilovic, D. van der Vliet, A. P. Paulikas, V. R. Stamenkovic, N. M. Markovic, Nat. Chem., 2013, 5, 300-306.
[29]	J. Li, S. Ghoshal, M. K. Bates, T. E. Miller, V. Davies, E. Stavitski, K. Attenkofer, S. Mukerjee, Z.-F. Ma, Q. Jia, Angew. Chem. Int. Ed. 2017, 56, 15594-15598.
[30]	Y.-F. Xing, Y. Zhou, Y.-B. Sun, C. Chi, Y. Shi, F.-B. Wang, X.-H. Xia, J. Electroanal. Chem., 2020, 872, 114348.
[31]	X.-M. Lin, X.-T. Wang, Y.-L. Deng, X. Chen, H.-N. Chen, P. M. Radjenovic, X.-G. Zhang, Y.-H. Wang, J.-C. Dong, Z.-Q. Tian, J.-F. Li, Nano Lett., 2022, 22, 5544-5552.
[32]	X.-Y. Li, Z.-M. Zhang, X.-X. Zhuang, Z.-T. Jia, T. Wang, Chin. J. Chem., 2024, 42, 3533-3552.
[33]	P. Li, Y. Jiao, J. Huang, S. Chen, JACS Au, 2023, 3, 2640-2659.
[34]	Y. Men, Y. Tan, P. Li, Y. Jiang, L. Li, X. Su, X. Men, X. Sun, S. Chen, W. Luo, Angew. Chem. Int. Ed., 2024, 63, e202411341.
[35]	W. Wang, Y. Liu, S. Chen, Acta Phys.-Chim. Sin. 2024, 40, 2303059.
[36]	P. Li, Y. Jiang, Y. Hu, Y. Men, Y. Liu, W. Cai, S. Chen, Nat. Catal., 2022, 5, 900-911.
[37]	M. Li, L. Li, X. Huang, X. Qi, M. Deng, S. Jiang, Z. Wei, J. Phys. Chem. Lett., 2022, 13, 10550-10557.
[38]	C. Cai, K. Liu, L. Zhang, F. Li, Y. Tan, P. Li, Y. Wang, M. Wang, Z. Feng, D. Motta Meira, W. Qu, A. Stefancu, W. Li, H. Li, J. Fu, H. Wang, D. Zhang, E. Cortés, M. Liu, Angew. Chem. Int. Ed., 2023, 62, e202300873.
[39]	M. Deng, H. Yang, L. Peng, L. Zhang, L. Tan, G. He, M. Shao, L. Li, Z. Wei, J. Energy Chem., 2022, 74, 111-120.
[40]	I. Ledezma-Yanez, W. D. Z. Wallace, P. Sebastián-Pascual, V. Climent, J. M. Feliu, M. T. M. Koper, Nat. Energy, 2017, 2, 17031.
[41]	D. Strmcnik, K. Kodama, D. van der Vliet, J. Greeley, V. R. Stamenkovic, N. M. Marković, Nat. Chem., 2009, 1, 466-472.
[42]	T. Cheng, L. Wang, B. V. Merinov, W. A. Goddard III, J. Am. Chem. Soc., 2018, 140, 7787-7790.
[43]	Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Nørskov, T. F. Jaramillo, Science, 2017, 355, eaad4998.
[44]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[45]	J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865-3868.
[46]	B. Hammer, L. B. Hansen, J. K. Nørskov, Phys. Rev. B, 1999, 59, 7413-7421.
[47]	M. T. M. Koper, T. E. Shubina, R. A. van Santen, J. Phys. Chem. B, 2002, 106, 686-692.
[48]	S. Zhu, X. Qin, F. Xiao, S. Yang, Y. Xu, Z. Tan, J. Li, J. Yan, Q. Chen, M. Chen, M. Shao, Nat. Catal., 2021, 4, 711-718.