Revealing the roles of oxidation states and constituents of the alloy in alkaline hydrogen evolution reaction

Cao, X; Sun, L; Pan, F; Wu, Z; Li, D; Nie, X; Li, X; Huang, P; Gao, L; Gong, C; Zhao, Y; Cai, Q; Zhang, J; Wang, G; Liu, H

Revealing the roles of oxidation states and constituents of the alloy in alkaline hydrogen evolution reaction

Cao, X Sun, L Pan, F Wu, Z Li, D Nie, X Li, X Huang, P Gao, L Gong, C Zhao, Y

Cai, Q Zhang, J

Wang, G

Liu, H

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Publisher:: ELSEVIER
Publication Type:: Journal Article
Citation:: Applied Catalysis B Environmental, 2025, 375
Issue Date:: 2025-10-15

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Field	Value	Language
dc.contributor.author	Cao, X
dc.contributor.author	Sun, L
dc.contributor.author	Pan, F
dc.contributor.author	Wu, Z
dc.contributor.author	Li, D
dc.contributor.author	Nie, X
dc.contributor.author	Li, X
dc.contributor.author	Huang, P
dc.contributor.author	Gao, L
dc.contributor.author	Gong, C
dc.contributor.author	Zhao, Y https://orcid.org/0000-0002-8653-8666
dc.contributor.author	Cai, Q
dc.contributor.author	Zhang, J https://orcid.org/0000-0001-5476-0134
dc.contributor.author	Wang, G https://orcid.org/0000-0003-4295-8578
dc.contributor.author	Liu, H https://orcid.org/0000-0003-0266-9472
dc.date.accessioned	2025-10-15T03:52:28Z
dc.date.available	2025-10-15T03:52:28Z
dc.date.issued	2025-10-15
dc.identifier.citation	Applied Catalysis B Environmental, 2025, 375
dc.identifier.issn	0926-3373
dc.identifier.issn	1873-3883
dc.identifier.uri	http://hdl.handle.net/10453/190413
dc.description.abstract	Precious metal Pt has exhibited excellent catalytic performance in numerous electrocatalytic applications. However, the slow water dissociation kinetics hinder its alkaline hydrogen evolution reaction (HER) activity. Herein, we design the partially oxidized PtRu alloys with fine-tuned structure which can significantly enhance the alkaline HER. Theoretical calculations reveal that the alteration of Pt/Ru ratio and surface oxidation state of PtRu materials can effectively tune the water and hydrogen adsorption capability, thus impacting the alkaline HER performance. We dentify Pt<inf>70</inf>Ru<inf>30</inf> with 3 O surface coverage with optimized adsorption energy to be the most suitable candidate for alkaline HER. Inspired by theoretical predictions, we prepare partially oxidized PtRu with tunable composition and structure via a facile urea-assisted method, with a “capture and release” reaction mechanism by generating complexing agents and pH gradients. The as-synthesized partially oxidized Pt<inf>70</inf>Ru<inf>30</inf> electrode exhibits excellent HER catalytic activity and stability in the alkaline electrolyte, achieving an overpotential of only 11 mV at 10 mA cm<sup>−2</sup> and a Tafel slope of 28 mV dec<sup>−1</sup>, outperforming that of Pt/C (η<inf>10</inf> = 29 mV, Tafel slope = 52 mV dec<sup>−1</sup>). In-situ spectral measurements show that the partially oxidized Pt and Ru species in Pt<inf>7</inf><inf>0</inf>Ru<inf>3</inf><inf>0</inf> can facilitate breaking the O-H bonds and improve the alkaline HER kinetics. This work unravels the influence of Pt/Ru ratio and surface partial oxidation on water dissociation and hydrogen adsorption, which provide guidelines for the rational design of highly efficient electrocatalysts.
dc.language	English
dc.publisher	ELSEVIER
dc.relation	http://purl.org/au-research/grants/arc/DE240100868
dc.relation.ispartof	Applied Catalysis B Environmental
dc.relation.isbasedon	10.1016/j.apcatb.2025.125415
dc.rights	info:eu-repo/semantics/openAccess
dc.subject	0306 Physical Chemistry (incl. Structural), 0904 Chemical Engineering, 0907 Environmental Engineering
dc.subject.classification	Physical Chemistry
dc.subject.classification	3406 Physical chemistry
dc.subject.classification	4004 Chemical engineering
dc.subject.classification	4011 Environmental engineering
dc.title	Revealing the roles of oxidation states and constituents of the alloy in alkaline hydrogen evolution reaction
dc.type	Journal Article
utslib.citation.volume	375
utslib.for	0306 Physical Chemistry (incl. Structural)
utslib.for	0904 Chemical Engineering
utslib.for	0907 Environmental Engineering
pubs.organisational-group	University of Technology Sydney
pubs.organisational-group	University of Technology Sydney/Faculty of Science
pubs.organisational-group	University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
pubs.organisational-group	University of Technology Sydney/UTS Groups
pubs.organisational-group	University of Technology Sydney/UTS Groups/Centre for Clean Energy Technology (CCET)
pubs.organisational-group	University of Technology Sydney/UTS Groups/Chancellor's Research Fellows
utslib.copyright.status	open_access	*
dc.rights.license	This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0). To view a copy of this license, visit https://creativecommons.org/licenses/by/4.0/
dc.date.updated	2025-10-15T03:52:21Z
pubs.publication-status	Accepted
pubs.volume	375

Abstract:

Precious metal Pt has exhibited excellent catalytic performance in numerous electrocatalytic applications. However, the slow water dissociation kinetics hinder its alkaline hydrogen evolution reaction (HER) activity. Herein, we design the partially oxidized PtRu alloys with fine-tuned structure which can significantly enhance the alkaline HER. Theoretical calculations reveal that the alteration of Pt/Ru ratio and surface oxidation state of PtRu materials can effectively tune the water and hydrogen adsorption capability, thus impacting the alkaline HER performance. We dentify Pt70Ru30 with 3 O surface coverage with optimized adsorption energy to be the most suitable candidate for alkaline HER. Inspired by theoretical predictions, we prepare partially oxidized PtRu with tunable composition and structure via a facile urea-assisted method, with a “capture and release” reaction mechanism by generating complexing agents and pH gradients. The as-synthesized partially oxidized Pt70Ru30 electrode exhibits excellent HER catalytic activity and stability in the alkaline electrolyte, achieving an overpotential of only 11 mV at 10 mA cm⁻² and a Tafel slope of 28 mV dec⁻¹, outperforming that of Pt/C (η10 = 29 mV, Tafel slope = 52 mV dec⁻¹). In-situ spectral measurements show that the partially oxidized Pt and Ru species in Pt70Ru30 can facilitate breaking the O-H bonds and improve the alkaline HER kinetics. This work unravels the influence of Pt/Ru ratio and surface partial oxidation on water dissociation and hydrogen adsorption, which provide guidelines for the rational design of highly efficient electrocatalysts.

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http://hdl.handle.net/10453/190413