Dynamic CoRu Bond Shrinkage at Atomically Dispersed Ru Sites for Alkaline Hydrogen Evolution Reaction.
Dynamic CoRu Bond Shrinkage at Atomically Dispersed Ru Sites for Alkaline Hydrogen Evolution Reaction.
复制标题
DOI：
10.1002/smll.202105231
复制
发表时间：
2021-10
期刊：
影响因子：
13.3
通讯作者：
Hui Zhang;Hui Su;M. Soldatov;Yuanli Li;Xu Zhao;Meihuan Liu;Wanlin Zhou;Xiu-Tang Zhang;Xuan Sun;Yanzhi Xu;Peng Yao;Shiqiang Wei;Qinghua Liu
中科院分区：
文献类型：
--
作者：
Hui Zhang;Hui Su;M. Soldatov;Yuanli Li;Xu Zhao;Meihuan Liu;Wanlin Zhou;Xiu-Tang Zhang;Xuan Sun;Yanzhi Xu;Peng Yao;Shiqiang Wei;Qinghua Liu
在工业水碱电解槽中，准确控制金属活性中心的电子结构是开发高效、稳定电催化剂的关键。然而，缺乏一种直观的手段来捕捉反应状态下金属位置的演变，阻碍了对其电子结构的操纵。在这里，我们构建了原子分散在钴纳米粒子上的Ru单位，该纳米粒子被限制在具有可调电子耦合效应的大-微孔骨架(M-Co NPs@Ru SAS/NC)上，用于高效催化碱性析氢反应。用OPANDO X-射线吸收光谱和红外光谱确定了在工作条件下具有强电子耦合效应的动态CoRu键收缩，它显著促进了水分子的吸附，进而加速了水分子的解离，形成了Ru位上的关键H*，从而获得了高的Her活性。经过精心设计的M-Co NPs@Ru SAS/NC具有高效的HER性能，在10 mA cm-2时的小过电位为34 mV，在-0.05V时的高转换频率为≈4284H2 h-1，是基准铂/C的40倍。这项工作为操纵高效电催化过程中金属活性中心的电子结构提供了新的观点。
Accurately manipulating the electronic structure of metal active sites under working conditions is central to developing efficient and stable electrocatalysts in industrial water-alkali electrolyzers. However, the lack of an intuitive means to capture the evolution of metal sites during the reaction state inhibits the manipulation of its electronic structure. Here, atomically dispersed Ru single-sites on cobalt nanoparticles confined onto macro-microporous frameworks (M-Co NPs@Ru SAs/NC) with tunable electron coupling effect for efficient catalysis of alkaline hydrogen evolution reaction (HER) are constructed. Using operando X-ray absorption and infrared spectroscopies, a dynamic CoRu bond shrinkage with strong electron coupling effect under working conditions is identified, which significantly promotes the adsorption of water molecules and then accelerates its dissociation to form the key H* over Ru sites for high HER activity. The well-designed M-Co NPs@Ru SAs/NC delivers efficient HER performance with a small overpotential of 34 mV at 10 mA cm-2 and a high turnover frequency of ≈4284 H2 h-1 at -0.05 V, 40 times higher than that of the benchmark Pt/C. This work provides a new point of view to manipulate the electronic structure of the metal active sites for highly effective electrocatalysis processes.