Theoretical Insights and the Corresponding Construction of Supported Metal Catalysts for Highly Selective CO₂ to CO Conversion

Abstract

Exploration of highly selective catalysts for the reverse water-gas shift reaction, which can serve as a pivotal stage of transitioning abundant CO2 resources into chemicals or fuels, still remains a great challenge. Here, we offer a guideline about this matter on the basis of exploration of the evolution of the main intermediates during CO2 hydrogenation over a library of supported metal catalysts with density functional calculations. We identified that a high selectivity toward this reaction was correlated with the energy difference between the dissociation barrier and the desorption energy of metal carbonyls over supported metal catalysts. Generally, decreasing the coordination number of metal sites to single-atom or moving supported metals to the lower right corner in the transition-metal series hindered the carbonyl dissociation but improved CO desorption, giving rise to increased CO selectivity. Furthermore, the above strategies were truly confirmed by measuring the catalytic performance that occurred on the real synthetic catalysts.