Meng Xiangyu, Ma Chao, Jiang Luozhen, Si Rui, Meng Xianguang, Tu Yunchuan, Yu Liang, Bao Xinhe, Deng Dehui
State Key Laboratory of Catalysis,iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023, China.
University of Chinese Academy of Sciences, Beijing, 100039, China.
Angew Chem Int Ed Engl. 2020 Jun 22;59(26):10502-10507. doi: 10.1002/anie.202003484. Epub 2020 Apr 30.
Perturbing the electronic structure of the MoS basal plane by confining heteroatoms offers the opportunity to trigger in-plane activity for the hydrogen evolution reaction (HER). The key challenge consists of inducing the optimum HER activity by controlling the type and distribution of confined atoms. A distance synergy of MoS -confined single-atom rhodium is presented, leading to an ultra-high HER activity at the in-plane S sites adjacent to the rhodium. By optimizing the distance between the confined Rh atoms, an ultra-low overpotential of 67 mV is achieved at a current density of 10 mA cm in acidic solution. Experiments and first-principles calculations demonstrate a unique distance synergy between the confined rhodium atoms in tuning the reactivity of neighboring in-plane S atoms, which presents a volcanic trend with the inter-rhodium distance. This study provides a new strategy to tailor the activity of MoS surface via modulating the distance between confined single atoms.
通过限制杂原子来扰动MoS基面的电子结构，为引发析氢反应（HER）的面内活性提供了机会。关键挑战在于通过控制受限原子的类型和分布来诱导最佳的HER活性。本文提出了MoS限制的单原子铑的距离协同效应，导致在与铑相邻的面内S位点具有超高的HER活性。通过优化受限Rh原子之间的距离，在酸性溶液中电流密度为10 mA cm时实现了67 mV的超低过电位。实验和第一性原理计算表明，受限铑原子之间在调节相邻面内S原子的反应性方面存在独特的距离协同效应，其随铑间距离呈现火山趋势。本研究提供了一种通过调节受限单原子之间的距离来定制MoS表面活性的新策略。
