Controlling CO2 Hydrogenation Selectivity by Metal-Supported Electron Transfer

Abstract

Tuning CO2 hydrogenation selectivity to obtain targeted value-added chemicals and fuels has attracted great yet everincreasing attention. How ever, a fundamental understanding of the nature to control the selectivity is still lacking, posing a challenge in catalyst design and development. Here, w e report our new discovery in ambient pressure CO2 hydrogenation reaction where selectivity canbe completely reversed by simply changing the crystal phases of TiO2 support (anatase- or rutile-TiO2) or changing metal loadings on anatase-TiO2. Operando spectroscopy and NAP-XPS studies reveal the determining factor is dif ferent electron transfer from metal to support under reaction conditions most probably as a result of the different extents of hydrogen spillover, which changes the adsorption and activation of the intermediate of CO. Based on this new finding, we can not only regulate CO2 hydrogenation selectivity but also tune catalytic performance in other important reactions, thus opening up a door for efficient catalyst development by rational design.