Effective Coactivation of CO₂ and CH₄ Gases into HCOOH and CH₃COOH Realized by Synergistic Effect in Double-atom Catalyst Based on 2D BC₃N₂

Abstract

We herein designed a double-atom catalyst based on 2D BC₃N₂ and calculated the properties of CO₂/CH₄ coactivation via density functional theory. PtM@2D-BC₃N₂ catalysts (M denotes Cr, Mo, Ti, V, and W) are first screened based on high binding strength of metal atoms and CH₄ caputre ability. In these candidates, the systems with M in IVB and VB subgroups have unfavorable adsorption oritation of *CH₃COO (*HCOO) for *CO₂-*CH₃ (*CO₂-*H) combination. In comparison, the systems with M in VIB subgroup are favourable and the reactivity of *CO₂-*CH₃ (*CO₂-*H) combination is decreased with increasing period. Finally, the PtCr@2D-BC₃N₂ is screened as the optimal catalyst. There exists a synergistic effect between Pt and Cr sites in PtCr@2D-BC₃N₂: the CH₄ can be effectively adsorbed on Cr site and will further be dissociated on Pt site with high reactivity. HCOOH can be produced in the temperature region of 34.84–66.85 °C. While at temperatures higher than 66.85 °C, the selectivity of CH₃COOH production is significantly higher than that of HCOOH due to the larger rate constant and ratio of atom utilization. Our study has not only clarified the potential mechanism of CO₂/CH₄ coactivation for theoretical works but also provided promising candidates for experimental works.

Keywords

CO₂/CH₄ coactivation / Double-atom catalyst / 2D BC₃N₂ substrate / CH₃COOH production

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