Unconventional Hexagonal Close‐Packed High‐Entropy Alloy Surfaces Synergistically Accelerate Alkaline Hydrogen Evolution
Abstract Accelerating the alkaline hydrogen evolution reaction (HER), which involves the slow cleavage of HO‐H bonds and the adsorption/desorption of hydrogen (H*) and hydroxyl (OH*) intermediates, requires developing catalysts with optimal binding strengths for these intermediates. Here, the unconv...
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Wiley
2025-01-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202409023 |
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| author | Ting‐Hsin Hu Cheng‐Yu Wu Zong Ying He Yi Chen Liang‐Ching Hsu Chih‐Wen Pao Jui‐Tai Lin Chun‐Wei Chang Shang‐Cheng Lin Rachel Osmundsen Lee Casalena Kun Han Lin Shan Zhou Tung‐Han Yang |
| author_facet | Ting‐Hsin Hu Cheng‐Yu Wu Zong Ying He Yi Chen Liang‐Ching Hsu Chih‐Wen Pao Jui‐Tai Lin Chun‐Wei Chang Shang‐Cheng Lin Rachel Osmundsen Lee Casalena Kun Han Lin Shan Zhou Tung‐Han Yang |
| author_sort | Ting‐Hsin Hu |
| collection | DOAJ |
| description | Abstract Accelerating the alkaline hydrogen evolution reaction (HER), which involves the slow cleavage of HO‐H bonds and the adsorption/desorption of hydrogen (H*) and hydroxyl (OH*) intermediates, requires developing catalysts with optimal binding strengths for these intermediates. Here, the unconventional hexagonal close‐packed (HCP) high‐entropy alloy (HEA) atomic layers are prepared composed of five platinum‐group metals to enhance the alkaline HER synergistically. The breakthrough is made by layer‐by‐layer heteroepitaxial deposition of subnanometer RuRhPdPtIr HEA layers on the HCP Ru seeds, despite the thermodynamic stability of Rh, Pd, Pt, and Ir in a face‐centered cubic (FCC) structure except for Ru. The synchrotron X‐ray absorption spectroscopy (XAS) confirms the atomic mixing and coordination environment of HCP RuRhPdPtIr HEA. Most importantly, they exhibit notable improvements in both electrocatalytic activity and durability for the HER in an alkaline environment, as compared to their FCC RuRhPdPtIr counterparts. Electrochemical measurements, operando XAS analysis, and density functional theory unveil that the binding strengths of H* and OH* intermediates on the active Pt and Ir sites can be weakened and strengthened to a moderate level, respectively, by mixing non‐active Ru, Rh, and Pd atoms with Pt and Ir atoms within the HCP HEA with strong synergistic electronic effects. |
| format | Article |
| id | doaj-art-073a6fcf7aaa4fd391189ce23f936066 |
| institution | OA Journals |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Wiley |
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| series | Advanced Science |
| spelling | doaj-art-073a6fcf7aaa4fd391189ce23f9360662025-08-20T02:27:24ZengWileyAdvanced Science2198-38442025-01-01121n/an/a10.1002/advs.202409023Unconventional Hexagonal Close‐Packed High‐Entropy Alloy Surfaces Synergistically Accelerate Alkaline Hydrogen EvolutionTing‐Hsin Hu0Cheng‐Yu Wu1Zong Ying He2Yi Chen3Liang‐Ching Hsu4Chih‐Wen Pao5Jui‐Tai Lin6Chun‐Wei Chang7Shang‐Cheng Lin8Rachel Osmundsen9Lee Casalena10Kun Han Lin11Shan Zhou12Tung‐Han Yang13Department of Chemical Engineering National Tsing Hua University Hsinchu 300044 TaiwanDepartment of Chemical Engineering National Tsing Hua University Hsinchu 300044 TaiwanCollege of Semiconductor Research National Tsing Hua University Hsinchu 300044 TaiwanDepartment of Chemical Engineering National Tsing Hua University Hsinchu 300044 TaiwanDepartment of Soil and Environmental Sciences National Chung Hsing University Taichung 40227 TaiwanNational Synchrotron Radiation Research Center Hsinchu 300092 TaiwanDepartment of Chemical Engineering National Tsing Hua University Hsinchu 300044 TaiwanDepartment of Chemical Engineering National Tsing Hua University Hsinchu 300044 TaiwanDepartment of Chemical Engineering National Tsing Hua University Hsinchu 300044 TaiwanThermo Fisher Scientific Hillsboro OR 97124 USAThermo Fisher Scientific Hillsboro OR 97124 USADepartment of Chemical Engineering National Tsing Hua University Hsinchu 300044 TaiwanDepartment of Nanoscience and Biomedical Engineering South Dakota School of Mines and Technology Rapid City SD 57701 USADepartment of Chemical Engineering National Tsing Hua University Hsinchu 300044 TaiwanAbstract Accelerating the alkaline hydrogen evolution reaction (HER), which involves the slow cleavage of HO‐H bonds and the adsorption/desorption of hydrogen (H*) and hydroxyl (OH*) intermediates, requires developing catalysts with optimal binding strengths for these intermediates. Here, the unconventional hexagonal close‐packed (HCP) high‐entropy alloy (HEA) atomic layers are prepared composed of five platinum‐group metals to enhance the alkaline HER synergistically. The breakthrough is made by layer‐by‐layer heteroepitaxial deposition of subnanometer RuRhPdPtIr HEA layers on the HCP Ru seeds, despite the thermodynamic stability of Rh, Pd, Pt, and Ir in a face‐centered cubic (FCC) structure except for Ru. The synchrotron X‐ray absorption spectroscopy (XAS) confirms the atomic mixing and coordination environment of HCP RuRhPdPtIr HEA. Most importantly, they exhibit notable improvements in both electrocatalytic activity and durability for the HER in an alkaline environment, as compared to their FCC RuRhPdPtIr counterparts. Electrochemical measurements, operando XAS analysis, and density functional theory unveil that the binding strengths of H* and OH* intermediates on the active Pt and Ir sites can be weakened and strengthened to a moderate level, respectively, by mixing non‐active Ru, Rh, and Pd atoms with Pt and Ir atoms within the HCP HEA with strong synergistic electronic effects.https://doi.org/10.1002/advs.202409023alkaline hydrogen evolutionatomic mixinghexagonal close‐packed structurehigh‐entropy alloyoperando X‐ray absorption spectroscopy |
| spellingShingle | Ting‐Hsin Hu Cheng‐Yu Wu Zong Ying He Yi Chen Liang‐Ching Hsu Chih‐Wen Pao Jui‐Tai Lin Chun‐Wei Chang Shang‐Cheng Lin Rachel Osmundsen Lee Casalena Kun Han Lin Shan Zhou Tung‐Han Yang Unconventional Hexagonal Close‐Packed High‐Entropy Alloy Surfaces Synergistically Accelerate Alkaline Hydrogen Evolution Advanced Science alkaline hydrogen evolution atomic mixing hexagonal close‐packed structure high‐entropy alloy operando X‐ray absorption spectroscopy |
| title | Unconventional Hexagonal Close‐Packed High‐Entropy Alloy Surfaces Synergistically Accelerate Alkaline Hydrogen Evolution |
| title_full | Unconventional Hexagonal Close‐Packed High‐Entropy Alloy Surfaces Synergistically Accelerate Alkaline Hydrogen Evolution |
| title_fullStr | Unconventional Hexagonal Close‐Packed High‐Entropy Alloy Surfaces Synergistically Accelerate Alkaline Hydrogen Evolution |
| title_full_unstemmed | Unconventional Hexagonal Close‐Packed High‐Entropy Alloy Surfaces Synergistically Accelerate Alkaline Hydrogen Evolution |
| title_short | Unconventional Hexagonal Close‐Packed High‐Entropy Alloy Surfaces Synergistically Accelerate Alkaline Hydrogen Evolution |
| title_sort | unconventional hexagonal close packed high entropy alloy surfaces synergistically accelerate alkaline hydrogen evolution |
| topic | alkaline hydrogen evolution atomic mixing hexagonal close‐packed structure high‐entropy alloy operando X‐ray absorption spectroscopy |
| url | https://doi.org/10.1002/advs.202409023 |
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