Unveiling Long-Range Wavelike Alternately Competitive and Cooperative Bond Coupling Modes in Single-Atom Catalysis

作者：Jun Zhou, Jiani Jiang, Yangyang Li, Yuefeng Wu, Wenyu Jia, Yuqing Ling, Xiaoyang Wang, Shengqi Chu, Lei Zheng, Xin Liang, Weixin Huang, Dingsheng Wang, Guolei Xiang · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c08955 · 被引用次数：6 · 研究领域：Catalytic Processes in Materials Science、Electrocatalysts for Energy Conversion、Catalysis and Oxidation Reactions

Supports can critically influence or even dominate the chemical state, adsorption property, and catalytic performance of single-atom catalysts (SACs), but the fundamental physicochemical principles driving adsorbate–M 1 –ligand–support bond interactions have not been fully understood yet. Here, we reveal the orbital–level interaction modes underlying the long-range bond couplings in SACs by using single-atom Ru (Ru 1 ) supported on rutile-type oxides (TiO 2, SnO 2, and MnO 2 ) in CO adsorption and oxidation as a model system. Our results show that Ru 1 –support binding strength and catalytic activity for CO oxidation increase in the following order: Ru 1 /TiO 2 < Ru 1 /SnO 2 < Ru 1 /MnO 2, while CO–Ru 1 adsorption strength oppositely decreases as Ru 1 /TiO 2 > Ru 1 /SnO 2 > Ru 1 /MnO 2 . These interaction trends are overall controlled by the reactivity of surface lattice oxygen atoms (O sl ) on supports. We further discover an alternating competitive and cooperative bond coupling mode in the heteroatomic chains of adsorbate–M 1 –ligand–support systems, in which the strengths of adjacent bonds competitively suppress, while alternating bonds cooperatively enhance. This wavelike bond coupling mode provides a new point to understand support effects on SAC–support interactions and structure–function relationships in SACs.