title: Reaction Mechanisms for the Electrochemical Reduction of CO2to CO and Formate on the Cu(100) Surface at 298 K from Quantum Mechanics Free Energy Calculations with Explicit Water.
abstract: Copper is the only elemental metal that reduces a significant fraction of CO2to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions is not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or to carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). Here, we carry out QM calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO2reduction reaction conditions) to examine the initial reaction pathways to form CO and formate (HCOO-) from CO2through free energy calculations at 298 K and pH 7. We find that CO formation proceeds from physisorbed CO2to chemisorbed CO2(*CO2δ-), with a free energy barrier of ΔG⧧= 0.43 eV, the rate-determining step (RDS). The subsequent barriers of protonating *CO2δ-to form COOH* and then dissociating COOH* to form *CO are 0.37 and 0.30 eV, respectively. HCOO-formation proceeds through a very different pathway in which physisorbed CO2reacts directly with a surface H* (along with electron transfer), leading to ΔG⧧= 0.80 eV. Thus, the competition between CO formation and HCOO-formation occurs in the first electron-transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Thus, to alter the product distribution, we need to control this first step of CO2binding, which might involve controlling pH, alloying, or changing the structure at the nanoscale.
authors.affiliation: Joint Center for Artificial Photosynthesis (JCAP) and Materials and Process Simulation Center (MSC) (MC139-74), California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Tao
authors.initials: T
authors.lastname: Cheng
authors.affiliation: Joint Center for Artificial Photosynthesis (JCAP) and Materials and Process Simulation Center (MSC) (MC139-74), California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: Hai
authors.initials: H
authors.lastname: Xiao
authors.affiliation: Joint Center for Artificial Photosynthesis (JCAP) and Materials and Process Simulation Center (MSC) (MC139-74), California Institute of Technology , Pasadena, California 91125, United States.
authors.forename: William A
authors.initials: WA
authors.lastname: Goddard