(726h) Mechanistic Insights into Electrochemical CO(2) Reduction on Copper and Copper-Based Bimetallic Catalysts

Peng, H., SLAC National Accelerator Laboratory
Tang, M., Stanford
Nishimura, Y. F., Stanford University
Wang, L., Stanford University
Nitopi, S., Stanford University
Schlexer, P., SLAC National Accelerator Laboratory
Bajdich, M., SLAC National Accelerator Laboratory
Morales Guio, C., Stanford University
Hahn, C., Stanford University
Abild-Pedersen, F., SLAC National Accelerator Laboratory
Jaramillo, T. F., Stanford University
Electrochemical carbon dioxide/monoxide (CO2/CO) reduction is a potential candidate for sustainable energy conversion and storage. Copper (Cu)-based materials are the only catalysts capable of producing more reduced hydrocarbons and alcohols, yet the high overpotential and poor selectivity still remain a huge challenge, which require mechanistic insights into the reaction mechanism and active site identification. Here we present microkinetic studies for CO(2) reduction on different coppers facets with different terrace/step site ensembles based on energetics estimated from density functional theory (DFT) based models. Our microkinetic models unveils the key reaction steps and site identities that dictate the C1/C2/C3 and hydrocarbon/oxygenate selectivity. The simulation gives reasonable agreement with the experimental observation and provides some theoretical insights into the design principles of practical Cu and Cu-based catalysts under reaction conditions.