Stay Hydrated! Impact of Solvation Phenomena on the CO2 Reduction Reaction at Pb(100) and Ag(100) surfaces

ChemSusChem, vol. 16, pp. e202300885

Abstract

Abstract Herein, a comprehensive computational study of the impact of solvation on the reduction reaction of CO2 to formic acid (HCOOH) and carbon monoxide on Pb(100) and Ag(100) surfaces is presented. Results further the understanding of how solvation phenomena influence the adsorption energies of reaction intermediates. We applied an explicit solvation scheme harnessing a combined density functional theory (DFT)/microkinetic modeling approach for the CO2 reduction reaction. This approach reveals high selectivities for CO formation at Ag and HCOOH formation on Pb, resolving the prior disparity between ab initio calculations and experimental observations. Furthermore, the detailed analysis of adsorption energies of relevant reaction intermediates shows that the total number of hydrogen bonds formed by HCOO plays a primary role for the adsorption strength of intermediates and the electrocatalytic activity. Results emphasize the importance of explicit solvation for adsorption and electrochemical reaction phenomena on metal surfaces.

Authors 4

1. Oskar Cheong Aachen Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Enginering

   RWTH Aachen University · Forschungszentrum Jülich · Jülich Aachen Research Alliance

   Affiliation as printed

   Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Enginering RWTH Aachen University Intzestrasse 5 52072 Aachen Germany

   Institute of Energy and Climate Research (IEK-13) Forschungszentrum Jülich Wilhelm-Johnen-Straße 52425 Jülich Germany

   JARA Energy & Center for Simulation and Data Science (CSD) 52425 Jülich Germany

2. Thomas Bornhake

   Forschungszentrum Jülich · Jülich Aachen Research Alliance

   Affiliation as printed

   Institute of Energy and Climate Research (IEK-13) Forschungszentrum Jülich Wilhelm-Johnen-Straße 52425 Jülich Germany

   JARA Energy & Center for Simulation and Data Science (CSD) 52425 Jülich Germany

3. Xinwei Zhu Aachen Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Enginering

   RWTH Aachen University · Forschungszentrum Jülich · Jülich Aachen Research Alliance

   Affiliation as printed

   Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Enginering RWTH Aachen University Intzestrasse 5 52072 Aachen Germany

   Institute of Energy and Climate Research (IEK-13) Forschungszentrum Jülich Wilhelm-Johnen-Straße 52425 Jülich Germany

   JARA Energy & Center for Simulation and Data Science (CSD) 52425 Jülich Germany

4. Michael Hermann Eikerling corresponding Aachen Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Enginering

   RWTH Aachen University · Forschungszentrum Jülich · Jülich Aachen Research Alliance

   Affiliation as printed

   Chair of Theory and Computation of Energy Materials Faculty of Georesources and Materials Enginering RWTH Aachen University Intzestrasse 5 52072 Aachen Germany

   Institute of Energy and Climate Research (IEK-13) Forschungszentrum Jülich Wilhelm-Johnen-Straße 52425 Jülich Germany

   JARA Energy & Center for Simulation and Data Science (CSD) 52425 Jülich Germany