Density functional theory study of CO₂ and H₂O adsorption on a monoclinic WO₃(001) surface

Abstract

Understanding the interaction of WO₃ with CO₂ and H₂O is vital for clarifying its role in the photocatalytic reduction of CO₂. In this study, we employed density functional theory to investigate the interaction of CO₂ and H₂O with both perfect and defective monoclinic WO₃(001) surfaces. The interactions of co-adsorbed CO₂ and H₂O were also studied. The major finding is that the presence of oxygen vacancies and co-adsorbed CO₂ or H₂O can significantly increase the stability of CO₂ and H₂O on the WO₃(001) surface. A defective WO₃(001) surface is more capable of adsorbing a single CO₂ or H₂O molecule than a perfect WO₃(001) surface, and H₂O adsorbed onto a defective WO₃(001) surface spontaneously dissociates into a hydrogen atom and a hydroxy group. The presence of co-adsorbed H₂O can increase the stability of CO₂ on the WO₃(001) surface, while the presence of the co-adsorbed CO₂ can increase the stability of H₂O on WO₃(001) surface. The analysis of the bonding mechanisms shows that the charge redistribution between the adsorbate and the WO₃(001) surface containing oxygen vacancies and co-adsorbed CO₂ or H₂O is stronger than that between the adsorbate and the perfect WO₃(001) surface; thus, adsorption energy is higher in the former case. The results will be useful for designing WO₃ photocatalysts, as well as for an atomistic-level understanding of the photocatalytic reduction of CO₂.

Keywords

Density functional theory / Carbon dioxide / Water / Adsorption / Tungsten trioxide / Photocatalysis

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