Lewis acidic supports promote the selective hydrogenation of carbon dioxide to methyl formate in the presence of methanol over Ag catalysts

Silica-supported silver nanoparticles exhibit outstanding efficiency in the CO2 hydrogenation to methyl formate in the presence of methanol under high pressure. Here, we show that ZrO2 and Al2O3 supports significantly increase the catalyst activity, in line with their higher Lewis acidity. The weight time yield of methyl formate over Ag/ZrO2 is up to 16.2 gMF gAg h−1 without detectable side-products, 25 times higher compared to Ag/SiO2 at the same temperature. Transient in situ and operando DRIFTS studies uncover spillover processes of formate species from Ag onto the acidic support materials and show that the surface formates can further react with adsorbed methanol at the sites near the perimeter between Ag and the support to yield methyl formate.