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Published on: August 6, 2018
Dynamic distance modulation and active site separation in the Ru1-Ru3@MoS2 catalyst for C-O bond activation
Shouqin Mu1, Jiehang Wei1, Tao Ma1
1School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China. wangxin@nxu.edu.cn.
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Current strategies for C-O bond activation primarily rely on static single-site catalysts, which often suffer from steric congestion and limited catalytic efficiency. In this work, we report a dynamic synergistic catalyst, Ru1-Ru3@MoS2, consisting of a coplanar-separated Ru1 single atom and Ru3 cluster anchored on a defective MoS2 substrate. For phenol hydrodeoxygenation, this dual-site system achieves a very low C-O bond cleavage barrier of 0.67 eV, which is substantially superior to the catalytic performance of the Ru1-only and Ru3-only reference systems. Mechanistic investigations reveal a dynamic wave-like evolution of the inter-site distance (4.94 → 4.14 → 4.84 Å), which drives the phenyl group to migrate toward the Ru3 cluster while the hydroxyl group remains anchored at the Ru1 site. This arrangement enables spatially separated active sites and sequential tandem catalysis. The activation process is further governed by Ru-dxz/O-pz orbital hybridization and electron transfer mediated by bridging sulfur atoms. This dynamic structure-activity relationship offers a new design paradigm for developing high-performance catalysts for biomass conversion.
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