Theoretical insights into CO2 electroreduction on single and dual heteroatom-doped diamonds.

Investigating CO2RR on diamond and doped diamond surfaces: Highlighting initial protonation's key role and the remarkable catalytic efficiency of BN surfaces. [Display omitted] • B, N co-doped diamonds boost CO2RR performance. • Key intermediates, OCHO* and COOH* critically influences C1 products. • The OCHO* key intermediates gives HCOOH whereas COOH* favors CH 2 O, CH 3 OH, and CH 4. • BN surfaces efficiently produce HCOOH production without applied overpotentials. • BN diamonds exhibited pronounced selectivity favor CO2RR over hydrogen evolution. We employed Periodic Density Functional Theory (DFT) to investigate the catalytic activity of single and double dopant of boron (B), nitrogen (N), and phosphorous (P) anchored on diamond surfaces for the CO 2 reduction reaction (CO2RR) by analyzing reaction energy profiles. Our findings show that the double-doped catalyst exhibits lower energy barriers in CO2RR compared to the single dopants. Specifically, when considering BB and NN configurations, there is a thermodynamic preference towards the formation of formic acid (HCOOH) with overpotentials of 0.40 and 0.09 V, respectively. The co-doped catalyst comprising B and N (BN) demonstrates a tendency towards the formation of HCOOH without requiring any applied overpotentials. Notably, BN outperforms other catalysts, occupying the top position on the volcano plot, indicating the lowest limiting potential (U L), remarkable thermal stability, and the ability to suppress the competing hydrogen evolution reaction (HER). This research provides valuable insights into the product differentiation in the electroreduction of CO 2. [ABSTRACT FROM AUTHOR]