Surface Single Atom Alloys for Alkaline Hydrogen Evolution Reaction

Li Xu; Yanping Xu; Bin Xia; Bingrong Guo; Khaja Mohaideen Kamal; Blaž Likozar; Xiumin Li; Feifei Dong; Siwei Li; Yufei Ma

doi:10.1002/adma.202502989

Surface Single Atom Alloys for Alkaline Hydrogen Evolution Reaction

Li Xu (Co-first Author)
, Yanping Xu (Co-first Author)
, Bin Xia
, Bingrong Guo
, Khaja Mohaideen Kamal
, Blaž Likozar
, Xiumin Li^*
, Feifei Dong^*
, Siwei Li^*
, Yufei Ma^*

^*Corresponding author for this work

Department of Chemistry

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

30 Citations (Scopus)

Abstract

Single atom catalysts (SACs) achieve 100% utilization of metal atoms and have versatile support effects, whereas single atom alloys (SAAs) with metallic bonds own the free-atom-like electronic structure. Herein, surface single atom alloys (SSAAs) are developed that integrate the advantages of SACs and SAAs via incorporating an ultrathin metallic layer during the synthetic process of SACs. It is shown that the Pt single atom preferentially coordinates with metallic Mo nanolayer, thereby forming a Pt₁-Mo_L surface atom alloy on Mo₂C (marked as Pt₁-Mo_L-Mo₂C SSAAs). Comprehensive spectroscopic and theoretical calculations reveal that the Mo nanolayer in SSAAs not only functions as an electron buffer between Pt₁ and Mo₂C, leading to a free-atom-like d state at Pt₁ sites and thereby balancing the adsorption and desorption of H, but also enhances the aggregation, adsorption, and activation of H₂O. Consequently, the Pt₁-Mo_L-Mo₂C SSAAs exhibit superior alkaline hydrogen evolution reaction (HER) performance compared to Pt₁/Mo₂C SACs, achieving a low overpotential of 12 mV at 10 mA cm⁻² and a low Tafel slope of 17 mV dec⁻¹. This work provides novel insights into the design of advanced single-site catalysts. © 2025 Wiley-VCH GmbH.

Original language	English
Article number	2502989
Number of pages	14
Journal	Advanced Materials
Volume	37
Issue number	41
Online published	21 Apr 2025
DOIs	https://doi.org/10.1002/adma.202502989
Publication status	Published - 16 Oct 2025

Funding

The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (Grant No. 51701046, 222091029), the Special Foundation for Key Fields of Colleges and Universities in Guangdong Province (2023ZDZX3091 and 2024ZDZX4083) and Science and Technology Research and Development Plan Joint Fund Project in Henan (advantage discipline cultivation class, Grant No. 242301420030), Innovation Capability Support Program of Shaanxi (NO. 2023-CX-TD-26). B.X. extends gratitude to the China Scholarship Council for the support provided through the State Scholarship Fund (202208330020). Y.M. sincerely thanks Dr. Meng Chen (College of Chemistry and Chemical Engineering, Xi'an University of Science and Technology) and Dr. Aiping Wang (Department of Materials Chemistry, National Institute of Chemistry, Slovenia) for their valuable collaboration and insightful discussions. Bla\u017E Likozar and Khaja Mohaideen Kamal are grateful for funding from the European climate, infrastructure and environment executive agency (CINEA) under grant agreement No. 101118129, Project: PHOTOSINT and the European innovation council and SMES executive agency (EISMEA) under grant agreement No. 101046836, Project: CATART.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Research Keywords

free-atom-like d state
hydrogen evolution reaction
molybdenum carbide
single atom catalyst
surface single-atom alloys

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title = "Surface Single Atom Alloys for Alkaline Hydrogen Evolution Reaction",

abstract = "Single atom catalysts (SACs) achieve 100\% utilization of metal atoms and have versatile support effects, whereas single atom alloys (SAAs) with metallic bonds own the free-atom-like electronic structure. Herein, surface single atom alloys (SSAAs) are developed that integrate the advantages of SACs and SAAs via incorporating an ultrathin metallic layer during the synthetic process of SACs. It is shown that the Pt single atom preferentially coordinates with metallic Mo nanolayer, thereby forming a Pt1-MoL surface atom alloy on Mo2C (marked as Pt1-MoL-Mo2C SSAAs). Comprehensive spectroscopic and theoretical calculations reveal that the Mo nanolayer in SSAAs not only functions as an electron buffer between Pt1 and Mo2C, leading to a free-atom-like d state at Pt1 sites and thereby balancing the adsorption and desorption of H, but also enhances the aggregation, adsorption, and activation of H2O. Consequently, the Pt1-MoL-Mo2C SSAAs exhibit superior alkaline hydrogen evolution reaction (HER) performance compared to Pt1/Mo2C SACs, achieving a low overpotential of 12 mV at 10 mA cm−2 and a low Tafel slope of 17 mV dec−1. This work provides novel insights into the design of advanced single-site catalysts. {\textcopyright} 2025 Wiley-VCH GmbH.",

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AU - Xu, Li

AU - Xu, Yanping

AU - Xia, Bin

AU - Guo, Bingrong

AU - Kamal, Khaja Mohaideen

AU - Likozar, Blaž

AU - Li, Xiumin

AU - Dong, Feifei

AU - Li, Siwei

AU - Ma, Yufei

PY - 2025/10/16

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N2 - Single atom catalysts (SACs) achieve 100% utilization of metal atoms and have versatile support effects, whereas single atom alloys (SAAs) with metallic bonds own the free-atom-like electronic structure. Herein, surface single atom alloys (SSAAs) are developed that integrate the advantages of SACs and SAAs via incorporating an ultrathin metallic layer during the synthetic process of SACs. It is shown that the Pt single atom preferentially coordinates with metallic Mo nanolayer, thereby forming a Pt1-MoL surface atom alloy on Mo2C (marked as Pt1-MoL-Mo2C SSAAs). Comprehensive spectroscopic and theoretical calculations reveal that the Mo nanolayer in SSAAs not only functions as an electron buffer between Pt1 and Mo2C, leading to a free-atom-like d state at Pt1 sites and thereby balancing the adsorption and desorption of H, but also enhances the aggregation, adsorption, and activation of H2O. Consequently, the Pt1-MoL-Mo2C SSAAs exhibit superior alkaline hydrogen evolution reaction (HER) performance compared to Pt1/Mo2C SACs, achieving a low overpotential of 12 mV at 10 mA cm−2 and a low Tafel slope of 17 mV dec−1. This work provides novel insights into the design of advanced single-site catalysts. © 2025 Wiley-VCH GmbH.

AB - Single atom catalysts (SACs) achieve 100% utilization of metal atoms and have versatile support effects, whereas single atom alloys (SAAs) with metallic bonds own the free-atom-like electronic structure. Herein, surface single atom alloys (SSAAs) are developed that integrate the advantages of SACs and SAAs via incorporating an ultrathin metallic layer during the synthetic process of SACs. It is shown that the Pt single atom preferentially coordinates with metallic Mo nanolayer, thereby forming a Pt1-MoL surface atom alloy on Mo2C (marked as Pt1-MoL-Mo2C SSAAs). Comprehensive spectroscopic and theoretical calculations reveal that the Mo nanolayer in SSAAs not only functions as an electron buffer between Pt1 and Mo2C, leading to a free-atom-like d state at Pt1 sites and thereby balancing the adsorption and desorption of H, but also enhances the aggregation, adsorption, and activation of H2O. Consequently, the Pt1-MoL-Mo2C SSAAs exhibit superior alkaline hydrogen evolution reaction (HER) performance compared to Pt1/Mo2C SACs, achieving a low overpotential of 12 mV at 10 mA cm−2 and a low Tafel slope of 17 mV dec−1. This work provides novel insights into the design of advanced single-site catalysts. © 2025 Wiley-VCH GmbH.

KW - free-atom-like d state

KW - hydrogen evolution reaction

KW - molybdenum carbide

KW - single atom catalyst

KW - surface single-atom alloys

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U2 - 10.1002/adma.202502989

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M3 - RGC 21 - Publication in refereed journal

SN - 0935-9648

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JO - Advanced Materials

JF - Advanced Materials

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ER -

Surface Single Atom Alloys for Alkaline Hydrogen Evolution Reaction

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