Understanding size-dependent hydrogenation of dimethyl oxalate to methyl glycolate over Ag catalysts

• Size-dependent activity of DMO hydrogenation over Ag catalysts. • A volcano-shape trend between hydrogenation activity and the Ag particle size. • Step-likes active sites are identified as the dominant active sites. • Electronic properties dominate the performances of <5.3 nm sized Ag catalysts. Ag catalysts are promising for the selective hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG), where the size of Ag nanoparticles strongly dominates their catalytic performances. Fundamental understandings on the size dependence, especially at the level of active sites, are still lacking but of great importance for the rational design of Ag-based catalysts for this reaction. Herein, a series of catalysts consisting of Ag nanoparticles sized from 2.9 to 8.8 nm anchored on amine-derivatized mesoporous silica nanospheres (Ag/AS) were synthesized and employed to understand the size-dependent DMO hydrogenation to MG. A volcano-shape trend between the hydrogenation activity and the increasing Ag particle size is observed for the differently sized Ag/AS catalysts, indicating a remarkable size dependence. The origin of the size dependence is further understood based on the cuboctahedron model of Ag nanoparticle, and the step-likes active sites are identified as the dominant ones. Results combining with the X-ray photoelectron spectroscopy, in situ Fourier transform infrared spectroscopy and temperature programmed desorption studies, indicate that the hydrogenation of DMO to MG on Ag/AS catalysts is mainly dominated by the number of active sites when the Ag particle size ≥ 5.3 nm, but by the electronic properties when the Ag particle size < 5.3 nm. The balance between the number of active sites and electronic structure gives rise to a maximal reaction rate in term of apparent TOF on the Ag/AS catalyst with Ag particle size of 5.3 nm. These understandings may guide the design of highly efficient Ag catalysts for the coal-based MG production.