{"title":"用于氢气进化反应的高效稳定的高熵合金电催化剂","authors":"","doi":"10.1016/S1872-2067(24)60067-7","DOIUrl":null,"url":null,"abstract":"<div><p>High-entropy alloy (HEA) catalysts exhibit enhanced hydrogen evolution reaction (HER) activity in water electrolysis, yet the understanding of their structure and active sites in reaction environments remains unclear. Here, we systematically investigated the HER activity and stability of PtPdRhRuCu/C through a combination of electrochemical measurements, <em>in situ</em> synchrotron radiation X-ray absorption spectroscopy (XAS) at the Cu <em>K</em>-edge and Pt <em>L</em><sub>3</sub>-edge, and density functional theory (DFT) calculations. Uniformly sized PtPdRhRuCu HEA nanoparticles were prepared <em>via</em> a facile one-step solvothermal method. <em>In situ</em> XAS results revealed that the HEA nanoparticles maintained metallic states and a disordered arrangement of the overall structure at hydrogen evolution potential, implying the absence of the separated phases. Relying on multi-metal active sites, PtPdRhRuCu/C demonstrated a remarkably low overpotential of 23.3 mV at 10 mA cm<sup>–2</sup> in alkaline HER, which is significantly lower than the overpotential observed in commercial Pt/C (50.3 mV), and achieving a mass activity 7.9 times that of Pt/C. DFT calculations show that the synergy of each metal site optimizes the dissociation energy barrier of water molecules. This study not only demonstrates the advancement of high-entropy alloys in electrocatalysis but also provides a comprehensive understanding of the structure-activity relationship of these unique catalysts through detailed characterizations. Our findings further contribute to the rational design and application of high-entropy alloy catalysts, specifically in HER.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":15.7000,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"An efficient and stable high-entropy alloy electrocatalyst for hydrogen evolution reaction\",\"authors\":\"\",\"doi\":\"10.1016/S1872-2067(24)60067-7\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>High-entropy alloy (HEA) catalysts exhibit enhanced hydrogen evolution reaction (HER) activity in water electrolysis, yet the understanding of their structure and active sites in reaction environments remains unclear. Here, we systematically investigated the HER activity and stability of PtPdRhRuCu/C through a combination of electrochemical measurements, <em>in situ</em> synchrotron radiation X-ray absorption spectroscopy (XAS) at the Cu <em>K</em>-edge and Pt <em>L</em><sub>3</sub>-edge, and density functional theory (DFT) calculations. Uniformly sized PtPdRhRuCu HEA nanoparticles were prepared <em>via</em> a facile one-step solvothermal method. <em>In situ</em> XAS results revealed that the HEA nanoparticles maintained metallic states and a disordered arrangement of the overall structure at hydrogen evolution potential, implying the absence of the separated phases. Relying on multi-metal active sites, PtPdRhRuCu/C demonstrated a remarkably low overpotential of 23.3 mV at 10 mA cm<sup>–2</sup> in alkaline HER, which is significantly lower than the overpotential observed in commercial Pt/C (50.3 mV), and achieving a mass activity 7.9 times that of Pt/C. DFT calculations show that the synergy of each metal site optimizes the dissociation energy barrier of water molecules. This study not only demonstrates the advancement of high-entropy alloys in electrocatalysis but also provides a comprehensive understanding of the structure-activity relationship of these unique catalysts through detailed characterizations. Our findings further contribute to the rational design and application of high-entropy alloy catalysts, specifically in HER.</p></div>\",\"PeriodicalId\":9832,\"journal\":{\"name\":\"Chinese Journal of Catalysis\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":15.7000,\"publicationDate\":\"2024-07-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chinese Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1872206724600677\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chinese Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1872206724600677","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0
摘要
高熵合金(HEA)催化剂在电解水过程中表现出更强的氢进化反应(HER)活性,但人们对其结构和反应环境中的活性位点的了解仍不清楚。在此,我们结合电化学测量、铜 K 边和铂 L3 边的原位同步辐射 X 射线吸收光谱 (XAS) 以及密度泛函理论 (DFT) 计算,系统地研究了 PtPdRhRuCu/C 的氢进化反应活性和稳定性。通过简单的一步溶热法制备了大小均匀的 PtPdRhRuCu HEA 纳米粒子。原位 XAS 结果表明,在氢进化电位下,HEA 纳米粒子保持金属态,整体结构排列无序,这意味着不存在分离相。依靠多金属活性位点,PtPdRhRuCu/C 在碱性 HER 中的过电位非常低,在 10 mA cm-2 的条件下仅为 23.3 mV,大大低于在商用 Pt/C 中观察到的过电位(50.3 mV),其质量活性是 Pt/C 的 7.9 倍。DFT 计算表明,每个金属位点的协同作用优化了水分子的解离能垒。这项研究不仅证明了高熵合金在电催化领域的先进性,还通过详细的表征全面了解了这些独特催化剂的结构-活性关系。我们的发现进一步促进了高熵合金催化剂的合理设计和应用,特别是在 HER 中的应用。
An efficient and stable high-entropy alloy electrocatalyst for hydrogen evolution reaction
High-entropy alloy (HEA) catalysts exhibit enhanced hydrogen evolution reaction (HER) activity in water electrolysis, yet the understanding of their structure and active sites in reaction environments remains unclear. Here, we systematically investigated the HER activity and stability of PtPdRhRuCu/C through a combination of electrochemical measurements, in situ synchrotron radiation X-ray absorption spectroscopy (XAS) at the Cu K-edge and Pt L3-edge, and density functional theory (DFT) calculations. Uniformly sized PtPdRhRuCu HEA nanoparticles were prepared via a facile one-step solvothermal method. In situ XAS results revealed that the HEA nanoparticles maintained metallic states and a disordered arrangement of the overall structure at hydrogen evolution potential, implying the absence of the separated phases. Relying on multi-metal active sites, PtPdRhRuCu/C demonstrated a remarkably low overpotential of 23.3 mV at 10 mA cm–2 in alkaline HER, which is significantly lower than the overpotential observed in commercial Pt/C (50.3 mV), and achieving a mass activity 7.9 times that of Pt/C. DFT calculations show that the synergy of each metal site optimizes the dissociation energy barrier of water molecules. This study not only demonstrates the advancement of high-entropy alloys in electrocatalysis but also provides a comprehensive understanding of the structure-activity relationship of these unique catalysts through detailed characterizations. Our findings further contribute to the rational design and application of high-entropy alloy catalysts, specifically in HER.
期刊介绍:
The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.