Catalytic reduction of carbon dioxide is potentially beneficial for both remediation of the climate change and synthesis of valuable chemicals. It was recently discovered that bismuth electrodes yield high selectivity and efficiency toward synthesis of formic acid (HCOOH) when used as a catalyst for electroreduction of CO2 [1]. However, little is known about chemical aspects of adsorption on Bi surfaces, and thus there exists limitation on analysis and application of Bi as a heterogeneous catalyst. In this study, density functional theory (DFT) calculations including corrections for spin-orbit coupling and dispersion interactions are performed to elucidate fundamental adsorption phenomena on the Bi(111) surface, focusing on the chemical species related to reduction of CO2. It is found that either molecular or dissociative adsorption on Bi(111) is unfavorable for most considered species due to small binding energies. Catalytic formation of HCOOH on Bi is suggested to proceed via bidentate formate (HCO2), analogous to recent reports on CO2 reduction using Pb [2,3]. The formate pathway on Bi is also more favorable compared to formation of CO in terms of reaction free energy, agreeing with experimental observations.

Catalytic reduction of CO2 on Bi surface: A DFT study

253rd National Meeting (2017)

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