TY - JOUR
T1 - Surface phases of Cu2O(111) under CO2 electrochemical reduction conditions
AU - Nie, Xiaowa
AU - Griffin, Gregory L.
AU - Janik, Michael J.
AU - Asthagiri, Aravind
N1 - Funding Information:
We acknowledge the Ohio Supercomputing Center for computational resources. This work was supported by the Center for Atomic Level Catalyst Design , an Energy Frontier Research Center funded by the U.S. Department of Energy under Award Number DE-SC0001058 .
PY - 2014/7/5
Y1 - 2014/7/5
N2 - Density functional theory (DFT) calculations were performed to examine the relative stability of Cu- and O-terminated Cu2O(111) surfaces as well as possible surface phases of Cu2O(111) under applied potentials relevant for carbon dioxide (CO2) electrochemical reduction. The Cu-terminated surface is found to be more favored than the O-terminated surface at potentials less than - 0.52 V-SHE at a pH = 7. Adsorption stabilities of H*, OH*, O*, and H2O* were examined by calculating the formation free energy of the adsorbate as a function of electrode potential. A H* covered surface is the most favored surface under reduction conditions. At pH values of 7 and 13, formation of an O-vacancy requires potentials of 0.61 and 0.25 V-SHE, respectively. At more negative potentials relevant to reduction of CO2, formation of an O-vacancy is thermodynamically favored, indicating a facile reduction of the Cu2O surface as observed experimentally.
AB - Density functional theory (DFT) calculations were performed to examine the relative stability of Cu- and O-terminated Cu2O(111) surfaces as well as possible surface phases of Cu2O(111) under applied potentials relevant for carbon dioxide (CO2) electrochemical reduction. The Cu-terminated surface is found to be more favored than the O-terminated surface at potentials less than - 0.52 V-SHE at a pH = 7. Adsorption stabilities of H*, OH*, O*, and H2O* were examined by calculating the formation free energy of the adsorbate as a function of electrode potential. A H* covered surface is the most favored surface under reduction conditions. At pH values of 7 and 13, formation of an O-vacancy requires potentials of 0.61 and 0.25 V-SHE, respectively. At more negative potentials relevant to reduction of CO2, formation of an O-vacancy is thermodynamically favored, indicating a facile reduction of the Cu2O surface as observed experimentally.
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U2 - 10.1016/j.catcom.2014.02.022
DO - 10.1016/j.catcom.2014.02.022
M3 - Article
AN - SCOPUS:84901634923
SN - 1566-7367
VL - 52
SP - 88
EP - 91
JO - Catalysis Communications
JF - Catalysis Communications
ER -