Shi Yi, Ma Zhi-Rui, Xiao Yi-Ying, Yin Yun-Chao, Huang Wen-Mao, Huang Zhi-Chao, Zheng Yun-Zhe, Mu Fang-Ya, Huang Rong, Shi Guo-Yue, Sun Yi-Yang, Xia Xing-Hua, Chen Wei
Department of Chemistry, National University of Singapore, Singapore, Singapore.
State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China.
Nat Commun. 2021 May 21;12(1):3021. doi: 10.1038/s41467-021-23306-6.
Tuning metal-support interaction has been considered as an effective approach to modulate the electronic structure and catalytic activity of supported metal catalysts. At the atomic level, the understanding of the structure-activity relationship still remains obscure in heterogeneous catalysis, such as the conversion of water (alkaline) or hydronium ions (acid) to hydrogen (hydrogen evolution reaction, HER). Here, we reveal that the fine control over the oxidation states of single-atom Pt catalysts through electronic metal-support interaction significantly modulates the catalytic activities in either acidic or alkaline HER. Combined with detailed spectroscopic and electrochemical characterizations, the structure-activity relationship is established by correlating the acidic/alkaline HER activity with the average oxidation state of single-atom Pt and the Pt-H/Pt-OH interaction. This study sheds light on the atomic-level mechanistic understanding of acidic and alkaline HER, and further provides guidelines for the rational design of high-performance single-atom catalysts.
调节金属-载体相互作用被认为是调节负载型金属催化剂电子结构和催化活性的有效方法。在原子水平上，在多相催化中，如将水（碱性）或水合氢离子（酸性）转化为氢气（析氢反应，HER），对结构-活性关系的理解仍然模糊不清。在这里，我们揭示了通过电子金属-载体相互作用对单原子铂催化剂氧化态的精细控制，显著调节了酸性或碱性HER中的催化活性。结合详细的光谱和电化学表征，通过将酸性/碱性HER活性与单原子铂的平均氧化态以及Pt-H/Pt-OH相互作用相关联，建立了结构-活性关系。这项研究为酸性和碱性HER的原子水平机理理解提供了启示，并进一步为高性能单原子催化剂的合理设计提供了指导。
