Asymmetric Ru–Co Dual Sites in Metal–Organic Frameworks for Heterogeneous Ethylene Methoxycarbonylation

Ethylene methoxycarbonylation (EMC) reaction, a key carbonylation process for methyl propionate production, typically relies on acid promoters and phosphine ligands in conventional homogeneous systems. Although heterogeneous Ru cluster catalysts can eliminate these additives, they still suffer from a low noble-metal utilization efficiency. Herein, we report an atomically dispersed dual-site catalyst Ru1Co1/MIL-101-EDTA for the EMC reaction, where the Ru1 and Co1 atoms are anchored on the EDTA-modified MIL-101(Cr) framework. The catalyst achieved a turnover frequency (TOF) of 125.6 h–1, which was 4.8-fold higher than that of the monometallic Ru1/MIL-101-EDTA counterpart, while maintaining 99.9% selectivity for methyl propionate without any decay over 5 recycles, being the most active Ru-based heterogeneous EMC catalyst reported to date. Experimental and theoretical studies revealed that the Cr(III) Lewis acid sites in the MIL-101(Cr) framework play a vital role in methanol dissociation, thus avoiding the addition of acid additives. The Co1 sites act as the primary *H adsorption centers and optimize the *CO adsorption path, thereby lowering the CO insertion barrier. Meanwhile, the electronic interaction between the Ru1 and Co1 species lowers the energy barrier for the rate-determining nucleophilic of the methoxyl group.