TY - JOUR
T1 - Surface charging activated mechanism change
T2 - A computational study of O, CO, and CO2 interactions on Ag electrodes
AU - Tezsevin, Ilker
AU - van de Sanden, Mauritius C.M.
AU - Er, Süleyman
PY - 2020/11
Y1 - 2020/11
N2 - Electrocatalytic and plasma-activated processes receive increasing attention in catalysis. Density functional theory (DFT) calculations are state-of-the-art tools for the fundamental study of reaction mechanisms and predicting the performance of catalytic materials. Proper application of DFT-based methods is crucial when investigating charge-doped electrode surfaces during electrocatalytic and plasma-activated reactions. Here, as a model electrode for plasma-activated CO2 splitting, we studied the interactions of O, CO, and CO2 with the neutral and progressively charged Ag(111) metal surfaces. We show that the application of correction procedures is necessary to obtain accurate adsorption energy profiles of O atoms, CO and CO2 molecules on Ag surfaces that are under the influence of additional electrons. Interestingly, the oxidation of CO is found to shift from a Langmuir–Hinshelwood mechanism on a neutral electrode to an Eley–Rideal mechanism on charged electrodes. Furthermore, we show that the surface charging of Ag(111) electrodes increase their CO2 reduction performance by enhancing the adsorption of O atoms and desorption of CO molecules. A further increase in the absolute charge-state of the electrode surface is expected to waive the thermodynamic barriers for the CO2 splitting reaction.
AB - Electrocatalytic and plasma-activated processes receive increasing attention in catalysis. Density functional theory (DFT) calculations are state-of-the-art tools for the fundamental study of reaction mechanisms and predicting the performance of catalytic materials. Proper application of DFT-based methods is crucial when investigating charge-doped electrode surfaces during electrocatalytic and plasma-activated reactions. Here, as a model electrode for plasma-activated CO2 splitting, we studied the interactions of O, CO, and CO2 with the neutral and progressively charged Ag(111) metal surfaces. We show that the application of correction procedures is necessary to obtain accurate adsorption energy profiles of O atoms, CO and CO2 molecules on Ag surfaces that are under the influence of additional electrons. Interestingly, the oxidation of CO is found to shift from a Langmuir–Hinshelwood mechanism on a neutral electrode to an Eley–Rideal mechanism on charged electrodes. Furthermore, we show that the surface charging of Ag(111) electrodes increase their CO2 reduction performance by enhancing the adsorption of O atoms and desorption of CO molecules. A further increase in the absolute charge-state of the electrode surface is expected to waive the thermodynamic barriers for the CO2 splitting reaction.
KW - CO reduction
KW - Density functional theory
KW - Silver electrode
KW - Surface charge
UR - http://www.scopus.com/inward/record.url?scp=85083342344&partnerID=8YFLogxK
U2 - 10.1016/j.jechem.2020.03.080
DO - 10.1016/j.jechem.2020.03.080
M3 - Article
AN - SCOPUS:85083342344
VL - 50
SP - 307
EP - 313
JO - Journal of Energy Chemistry
JF - Journal of Energy Chemistry
SN - 2095-4956
ER -