Controlling CO2 Hydrogenation Selectivity by Metal‐Supported Electron Transfer

Abstract Tuning CO 2 hydrogenation selectivity to obtain targeted value‐added chemicals and fuels has attracted increasing attention. However, a fundamental understanding of the way to control the selectivity is still lacking, posing a challenge in catalyst design and development. Herein, we report our new discovery in ambient pressure CO 2 hydrogenation reaction where selectivity can be completely reversed by simply changing the crystal phases of TiO 2 support (anatase‐ or rutile‐TiO 2 ) or changing metal loadings on anatase‐TiO 2 . Operando spectroscopy and NAP‐XPS studies reveal that the determining factor is a different electron transfer from metal to the support, 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 CO 2 hydrogenation selectivity but also tune catalytic performance in other important reactions, thus opening up a door for efficient catalyst development by rational design.