Rationally Tailoring Catalysts for the CO Oxidation Reaction by Using DFT Calculations

18 October 2021, Version 3
This content is a preprint and has not undergone peer review at the time of posting.


Rational design of catalysts by tailoring specific surface sites with different elements could result in catalysts with high activity, selectivity and stability. In this work, we show that *CO on-top and O* on-top adsorption energies are good descriptors for catalysis of the CO oxidation reaction (COOR) on pure metals and binary alloys. The observed Brønsted-Evans-Polanyi (BEP) and scaling relations for COOR on different surfaces are incorporated into a predictive model that uses the binding strength of the four adjacent metal atoms making up the active site for COOR catalysis to estimate reaction and activation energies. The model is used to screen 161 multi-metallic catalyst candidates made by combining Ru, Pt, Pd, Cu and Au at these four sites. The screening and subsequent calculations suggest that Ru-Pt-Cu alloys are good catalysts for COOR. Our study shows that it is possible to use information from pure metals and binary alloys to predict the catalytic behavior of more complex alloys, and hereby reduce the computational cost of identifying new catalyst candidates for COOR.


Alloy surfaces
Adsorption energies
Scaling relations
BEP relations
Catalyst Screening

Supplementary materials

Supporting Information
Configurations and adsorption energies of O* adsorbed on-top, bridge and hollow sites on binary alloys; energy cutoff and k-points convergence test; linear scaling relations with unfixed slopes; linear scaling relation between *CO on-top and O* on-top adsorption energies; NEB pathways going through *CO-top and O*-bridge TS, and *CO-top and O*-top TS; BEP relations between ETS with *CO-top and O*-bridge and descriptors utilizing O*-top, O*-bridge and O*-hollow adsorption energies; parity plot between the predicted T and the calculated ones; linear scaling relation between *COOH on-top and *CO on-top adsorption energies; BEP relations between the two kinds of ETS and the *COOH on-top adsorption energy plus half of the average adsorption energy for O* at two neighboring top sites; illustration of additional active sites when the A,B,C,D surface is repeated; NEB pathways for ternary alloys; catalysts candidates plotted with ETS versus ∆E.


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