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