Zhang Jiachen, Liu Guocong, Li Huiting, Chang Ruixuan, Jia Shuyu, Zhang Yechuan, Huang Kai, Tang Yawen, Sun Hanjun
School of Chemistry and Chemical Engineering, Southeast University, Nanjing, Jiangsu, 211189, China.
School of Chemistry and Materials Science, Jiangsu Key Laboratory of New Power Batteries, Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Nanjing Normal University, Nanjing, 210023, China.
Small. 2024 Dec;20(50):e2407881. doi: 10.1002/smll.202407881. Epub 2024 Sep 27.
Platinum-group metals catalysts (such as Rh, Pd, Ir, Pt) have been the most efficient hydrogen evolution reaction (HER) electrocatalysts due to their moderate H adsorption strength, while the high HO-dissociation barrier in alkaline media restrains the catalytic performance of PGM catalysts. However, the optimization of the HO-dissociation barrier and *H/*OH binding energy toward their individual optima is limited due to the constraints of their scaling relationship on a single active site. Here, a coordinatively unsaturated "M─O─W" (M = Rh, Pd, Ir, Pt) active area is constructed, where H and OH species are anchored on Pt-group metal sites and inactive W sites for individual regulation. By combining experiments and density functional theory calculations, the introduction of extra OH-adsorption sites (coordinatively unsaturated WO) avoids the competitive adsorption of H and OH on the single site, while the enhanced OH-adsorption capacity on the coordinatively unsaturated WO effectively facilitates the adsorption/dissociation of interfacial HO. As a result, the representative Rh-WO catalyst exhibits outstanding catalytic activity and durability for HER. The findings of this work not only provide valuable insights for the design of efficient PGM catalysts for HER but also shed light on the development of electrocatalysts for other catalytic reactions.
铂族金属催化剂（如铑、钯、铱、铂）因其适中的氢吸附强度，一直是最有效的析氢反应（HER）电催化剂，然而，碱性介质中较高的氢氧根解离能垒限制了铂族金属催化剂的催化性能。然而，由于单个活性位点上的比例关系限制，将氢氧根解离能垒和*H/*OH结合能优化到各自的最优值是有限的。在此，构建了一个配位不饱和的“M─O─W”（M = 铑、钯、铱、铂）活性区域，其中氢和氢氧根物种分别锚定在铂族金属位点和惰性钨位点上进行单独调控。通过结合实验和密度泛函理论计算，引入额外的氢氧根吸附位点（配位不饱和的WO）避免了氢和氢氧根在单个位点上的竞争吸附，同时配位不饱和的WO上增强的氢氧根吸附能力有效地促进了界面氢氧根的吸附/解离。结果，具有代表性的铑-氧化钨催化剂在析氢反应中表现出出色的催化活性和耐久性。这项工作的发现不仅为设计高效的析氢铂族金属催化剂提供了有价值的见解，也为其他催化反应的电催化剂开发提供了思路。
