Proceedings of nanoGe Fall Meeting 2021 (NFM21)
DOI: https://doi.org/10.29363/nanoge.nfm.2021.209
Publication date: 23rd September 2021
Electrochemical CO2 reduction (eCO2R) is a promising process to store renewable energy into chemical bonds and close the carbon cycle. However, to date the industrial exploitation of this technology is limited to CO and HCOO–, whilst production of desirable C2+ chemicals is possible only at laboratory scale and on copper-based catalysts. Dynamic phenomena, such as surface reconstruction during operation [1] or specific electrolyte effects,[2] can promote selectivity toward multi-carbon compounds and long-term stability of the device, thus calling for computational modeling to unveil this complexity.
Here, by means of ab initio molecular dynamics (AIMD) simulations, we modeled surface reconstruction on an oxide-derived copper material,[3] and we confirmed experimental observations on the crucial role of metal cations in electrochemical CO2 reduction.[4]
In the first study, we identified the main ensembles which control the catalytic performance of seven oxygen-depleted oxide-derived copper models. Generally, copper differentiates in three classes: metallic Cu0, polarized Cuð+, and oxidic Cu+, respectively coordinated to 0, 1, and 2 oxygens. These three species form 14 ensembles. Low coordinated Cu adatoms and polarized sites are responsible for binding CO2 and thus improving eCO2R activity. Metastable oxygens and metallic fcc-(111) or (100)-like Cu facets promote CO-CO dimerization step via a deprotonated glyoxylate species. In the second study, we rationalized sound experimental evidences on the absence of eCO2R on gold, silver, and copper without a metal cation in solution. By applying AIMD on a large Au supercell with 72 explicit water molecules and 1 cation, we demonstrated that cations steadily coordinate with adsorbed CO2, with a coordination rate which increases with the ionic cation radius. Overall, such coordination accounts for a short-range electrostatic interaction which enables eCO2R by stabilizing CO2 activation by 0.5 eV and enhancing the first electron transfer from the surface. Specific eCO2R activity trends are solely due to larger accumulation at the Outer Helmholtz layer for weakly solvated cations. Both studies provide new sets of concepts for modeling dynamic processes driven by high surface polarization and electrolyte species characteristic of CO2 reduction conditions.
The authors thank the financial support from the Spanish Ministry of Science and Innovation (Grant RTI2018-101394-B-I00) and the European Union (projects FlowPhotoChem 862453-FLOWPHOTOCHEM, ELCoREL 722614-ELCOREL). The Barcelona Supercomputing Center (BSC-RES) and the ioChem-BD database are further acknowledged for having provided generous computational resources and continuous access to generated datasets.
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