Unveiling a Two-Electron Reaction Pathway for Electrocatalytic CO 2 Reduction on Boron-Doped Diamonds - A First-Principles Calculation
At a Glance
Section titled āAt a Glanceā| Metadata | Details |
|---|---|
| Publication Date | 2025-10-14 |
| Journal | Langmuir |
| Authors | Chuyan Zhang, Bin Chen, Zhaofeng Zhai, Chengcheng Lv, Lusheng Liu |
| Institutions | Jilin University, State Key Laboratory of Superhard Materials |
Abstract
Section titled āAbstractāConverting excessive CO<sub>2</sub> molecules into formic acid (HCOOH) as a liquid fuel and hydrogen storage carrier using a sustainable electrochemical method has received enormous attentions. However, the reaction mechanism during this two-electron reaction pathway is still controversial. Inspired by the high selectivity toward HCOOH on the boron-doped diamond (BDD) electrode, this work calculates the adsorption of the CO<sub>2</sub> molecule and first two-electron reaction pathway on BDD with different B doping configurations by the density functional theory method. The results show that CO<sub>2</sub> molecules are more readily adsorbed on the surface B doping sites with charge transfer between B-O bonding. And the total overpotential of the first two-electron reaction pathway displays a Volcano relationship with the Gibbs energy of the *CO<sub>2</sub>-*COOH step. The partially sp<sup>2</sup>-C hybridized (111) (2 Ć 1) configuration exhibits the lowest overpotential of 0.81 eV and the best CO<sub>2</sub> reduction performance toward the HCOOH product. Furthermore, the dynamic kinetics of the *CO<sub>2</sub>-*COOH step is investigated by the climbing image-nudged elastic band method under the external electric field. The negative electric field of -0.4 eV/Ć promotes the adsorption of CO<sub>2</sub> and *H but inhibits the migration of *H with an energy barrier of 4.34 eV. This work elucidates the decision factor of high selectivity toward the HCOOH product on the BDD electrode and provides a comprehensive understanding of two-electron reaction pathway mechanisms.