TY - JOUR

T1 - The Missing Link for Electrochemical CO2 Reduction

T2 - Classification of CO vs HCOOH Selectivity via PCA, Reaction Pathways, and Coverage Analysis

AU - Christensen, Oliver

AU - Bagger, Alexander

AU - Rossmeisl, Jan

N1 - Funding Information: O.C. and J.R. acknowledge the Danish National Research Foundation Centers of Excellence, the Center for High Entropy Alloy Catalysis (Project DNRF149). A.B. acknowledges financial support from the Pioneer Center for Accelerating P2X Materials Discovery (CAPeX), DNRF grant number P3. Publisher Copyright: © 2024 American Chemical Society.

PY - 2024

Y1 - 2024

N2 - For the electrochemical CO2 reduction reaction, different metal catalysts preferentially produce different products. However, the differences between the metals’ reaction pathways that lead to these different products are still not fully understood. In this work, we analyze CO vs HCOOH formation from CO2 using statistical analysis and density functional theory calculations. This is carried out by considering multiple descriptors, along with competing reaction pathways, reaction barriers, and high coverage of mixed adsorbates on the surface. This method is capable of explaining the discrepancy between simulations and experiments regarding Ag and Au selectivity and of properly classifying elements according to their product distribution. We find that, when considering water-assisted protonation for the disproportionation to CO, Ag and Au have a lower barrier for CO production in agreement with experimental results. We also find that, when considering the high coverage of mixed adsorbates on the Ag and Au surfaces, the most stable adsorbate configuration contains adsorbates capable of forming CO preferentially. These findings help to bridge the gap between simulations and experiments and provide a missing link for our understanding of the CO2 reduction reaction.

AB - For the electrochemical CO2 reduction reaction, different metal catalysts preferentially produce different products. However, the differences between the metals’ reaction pathways that lead to these different products are still not fully understood. In this work, we analyze CO vs HCOOH formation from CO2 using statistical analysis and density functional theory calculations. This is carried out by considering multiple descriptors, along with competing reaction pathways, reaction barriers, and high coverage of mixed adsorbates on the surface. This method is capable of explaining the discrepancy between simulations and experiments regarding Ag and Au selectivity and of properly classifying elements according to their product distribution. We find that, when considering water-assisted protonation for the disproportionation to CO, Ag and Au have a lower barrier for CO production in agreement with experimental results. We also find that, when considering the high coverage of mixed adsorbates on the Ag and Au surfaces, the most stable adsorbate configuration contains adsorbates capable of forming CO preferentially. These findings help to bridge the gap between simulations and experiments and provide a missing link for our understanding of the CO2 reduction reaction.

KW - activation energies

KW - catalysis

KW - catalysis descriptors

KW - CO reduction

KW - coverage

KW - DFT simulations

KW - electrocatalysis

KW - electrochemistry

U2 - 10.1021/acscatal.3c04851

DO - 10.1021/acscatal.3c04851

M3 - Journal article

AN - SCOPUS:85184597985

VL - 14

SP - 2151

EP - 2161

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

IS - 4

ER -