Realizing and Revealing Complex Isobutyl Alcohol Production over a Simple Cu-ZrO₂ Catalyst

CO hydrogenation to isobutyl alcohol is a promising route for CO transformation to high value-added products. However, the formation mechanism of isobutyl alcohol is complex, and its synthesis requires complex catalysts and harsh reaction conditions, which hinders the identification of active sites. Herein, we efficiently synthesized isobutyl alcohol under mild conditions over a simple Cu-ZrO2 catalyst by decreasing the Cu loading. The space-time yield (STY) of isobutyl alcohol using an optimal CZ-0.11 catalyst was as high as 61.3 g.L-cat(-1).h(-1) with a CO conversion of 19.2%, far surpassing the STY of the state-of-the-art isobutyl alcohol synthesis (44.6 g.L-cat(-1).h(-1)) under harsh conditions. Decreasing the Cu loading increased the distribution of smaller Cu particles and clarified the structure-activity relationship of Cu-Zr interactions for isobutyl alcohol synthesis. The enhanced Cu-Zr interaction led to the formation of more electron-deficient Cu species on the CZ-0.11 catalyst, which enriched the linearly adsorbed CO on Cu, as demonstrated by in situ diffuse reflectance infrared Fourier-transform spectroscopy. Experimental and theoretical results revealed that coupling of the bicarbonate species on ZrO2 with the linearly adsorbed CO species on electron-deficient Cu clusters promoted the formation of C-2 intermediates and finally produced isobutyl alcohol through rapid beta-addition. These insights into the active sites for CO hydrogenation to isobutyl alcohol may guide further catalyst designs.