Regulating mesopore structures of support toward enhanced selective hydrogenation of dimethyl oxalate to methyl glycolate on Ag catalysts.

[Display omitted] • MSNS with center-radial mesopores shows shorter pore length than SBA-15. • Shorter pore length enhances performance of Ag/MSNS catalyst for DMO hydrogenation. • Differently sized MSNS with distinct pore lengths are fabricated for Ag catalyst. • Relationship between performance and diffusion is established for Ag/MSNS catalyst. Precisely regulating mesopore structures toward enhanced diffusion of reactants and targeted product is of great significance for achieving simultaneously improved activity and selectivity, which is exemplified by this work employing mesoporous silica with distinct structured mesopores as support for Ag catalysts to selectively hydrogenate dimethyl oxalate (DMO) into methyl glycolate (MG). Mesoporous silica nanosphere (MSNS) with center-radial pores shows shorter pore length than SBA-15 with parallel mesopores, which is beneficial for the diffusion process and thus gives rise to enhanced hydrogenation activity. Inspired by these insights, MSNSs sized in 50, 90, 120 and 160 nm are further synthesized to regulate pore length and systematically explore their effects on the reaction. The diffusion process is enhanced with decreasing the size of MSNS from 160 to 50 nm, as elucidated by the effective diffusion time constant (D e /R2) determined by zero-length column (ZLC) method. Accordingly, DMO can facilely diffuse into the mesopores with shorter length to access the active sites while the formed MG product can easily diffuse out to avoid the over-hydrogenation process, which is corroborated by the comparison for performances of these Ag/MSNSs catalysts. Notably, a moderately short pore length, balancing well the diffusion and hydrogenation process, is more preferable for achieving both higher activity and better selectivity to MG, and MSNS sized in 90 nm supported Ag catalyst thus exhibits the greatest performances, with MG selectivity up to 96.6 % at 99.7 % of DMO conversion. [ABSTRACT FROM AUTHOR]