Pt-modulated Cu/SiO_(2) catalysts for efficient hydrogenation of CO_(2)-derived ethylene carbonate to methanol and ethylene glycol

Copper-based catalysts were widely used in the heterogeneous selective hydrogenation of ethylene carbonate(EC),a key step in the indirect conversion of CO_(2) to methanol.However,a high H_(2)/EC molar ratio in feed is required to achieve favorable activity and the methanol selectivity still needs to be improved.Herein,we fabricated a series of Pt-modulated Cu/SiO_(2) catalysts and investigated their catalytic performance for hydrogenation of EC in a fixed bed reactor.By modulating the Pt amount,the optimal 0.2Pt-Cu/SiO_(2) catalyst exhibited the highest catalytic performance with99%EC conversion,over 98%selectivity to ethylene glycol and 95.8%selectivity to methanol at the H_(2)/EC ratio as low as 60 in feed.In addition,0.2Pt-Cu/SiO_(2) catalyst showed excellent stability for 150 h on stream over different H_(2)/EC ratios of 180-40.It is demonstrated a proper amount of Pt could significantly lower the H_(2)/EC molar ratio,promote the reducibility and dispersion of copper,and also enhance surface density of Cu+species.This could be due to the strong interaction of Cu and Pt induced by formation of alloyed Pt single atoms on the Cu lattice.Meanwhile,a relatively higher amount of Pt would deteriorate the catalytic activity,which could be due to the surface coverage and aggregation of active species.These findings may enlighten some fundamental insights for further design of Cu-based catalysts for the hydrogenation of carbon–oxygen bonds.

Highly dispersed nickel boosts catalysis by Cu/SiO_(2) in the hydrogenation of CO_(2)-derived ethylene carbonate to methanol and ethylene glycol

The efficient hydrogenation of CO_(2)-derived ethylene carbonate(EC)to yield methanol(MeOH)and ethylene glycol(EG)is a key process for indirect conversion of CO_(2)to MeOH.However,a high H_(2)/EC molar ratio during the hydrogenation process(usually as 180-300)is generally required to achieve good catalytic performance,resulting in high cost and energy consumption for H_(2)circulation in the promising industrial application.Here,we prepared a series of Ni-modified Cu/SiO_(2)catalysts and explored the effects of synthesis methods and Ni contents on catalytic performance under different H_(2)/EC molar ratios.The Cu/SiO_(2)catalyst with 0.2%(mass)Ni loading prepared by co-ammonia evaporation method exhibited above 99%conversion of EC,91%and 98%selectivity to MeOH and EG respectively at H_(2)/EC ratio of 60.And no significant deactivation was observed within 140 h at a lower H_(2)/EC of 40.It is demonstrated that a few of Ni addition could not only promote Cu dispersion and increase surface Cu^(+) species due to the strong interaction between Cu and Ni species,but also form uniformly-dispersed CuNi alloy species and thus enhance the adsorption and dissociation of H_(2).But the excess Ni species would aggregate and segregate to cover partial surface of Cu nanoparticles,leading to a significantly drop of catalytic performance in EC hydrogenation.These insights may provide guidance for further design of catalysts for the ester hydrogenation reactions.