CO-CO coupling on Cu facets: Coverage, strain and field effects

Authors
Robert B. Sandberg,
Joseph H. Montoya,
Karen Chan,
Jens K. Nørskov
Year of publication
2016
Journal
Surface Science
Volume
654
Starting page
56
Ending page
62
We present a DFT study on the effect of coverage, strain, and electric field on CO-CO coupling energetics on Cu (100), (111), and (211). Our calculations indicate that CO-CO coupling is facile on all three facets in the presence of a cation-induced electric field in the Helmholtz plane, with the lowest barrier on Cu(100). The CO dimerization pathway is therefore expected to play a role in C2 formation at potentials negative of the Cu potential of zero charge, corresponding to CO2/CO reduction conditions at high pH. Both increased *CO coverage and tensile strain further improve C-C coupling energetics on Cu (111) and (211). Since CO dimerization is facile on all 3 Cu facets, subsequent surface hydrogenation steps may also play an important role in determining the overall activity towards C2 products. Adsorption of *CO, *H, and *OH on the 3 facets were investigated with a Pourbaix analysis. The (211) facet has the largest propensity to co-adsorb *CO and *H, which would favor surface hydrogenation following CO dimerization.
Funding sources