Mechanistic study of CO2 hydrogenation to C1 products on molybdenum step site

Abstract

The catalytic conversion of CO2 into fuel is an ideal solution to the energy and environment crisis in the context of carbon neutrality, while the design of high-performance catalysts is the key. Unfortunately, the complicated reaction mechanism makes the rational catalyst design with simulations challenging. Herein, we employed density functional theory (DFT) calculations to systematically analyze the complex reaction mechanism of CO2 hydrogenation to C1 products on the stepped metal active sites using molybdenum as the model catalyst, while the established mean-field microkinetic model (MKM) identified the more favorable production of carbon monoxide (CO) than formic acid (HCOOH), methanol (CH3OH) and methane (CH4). Our results not only provide the energetics of all elementary steps during CO2 hydrogenation to C1 products on metallic Mo but also propose the directions to steering the activity and selectivity of Mo in CO2 conversion.