Supporting Information
Recent progress in syngas production via catalytic CO
2hydrogenation reaction
Ali M Bahmanpour1, Matteo Signorile2, Oliver Kröcher1,3*
1 Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL) 1015 Lausanne, Switzerland
2 Department of Chemistry, NIS Centre and INSTM Reference Center, University of Turin, via P. Giuria 7, 10125 Turin, Italy
3 Paul Scherrer Institut (PSI) 5232 Villigen, Switzerland
1. Computational Details
The calculation of CO adsorption on the (1 1 1) metal surfaces were performed by means of the CRYSTAL17 code, [1] by adopting the PBE functional [2] for both correlation-exchange and the triple-ζ basis set by Jorge and coworkers [3] (functions with angular momentum higher than 4 were pruned, since not yet implemented in the code). The contribution from dispersive forces was described through the empirical Grimme D3 scheme. [4] Smearing of the Fermi surface with a fictitious temperature of 3000 K was adopted for a correct description of the metallic systems. The k-space was sampled with 145 k points.
The structure of bulk fcc metals was initially optimized, thus three layers thick (1 1 1) surfaces were derived and re-optimized (only atomic positions were optimized, while keeping constant lattice parameters in the 2D models). Finally, CO molecules were manually positioned at 2.5 Å from the surface, occupying on-top position over atoms. A monolayer surface coverage (one CO molecule per metal atom) was considered. Upon structural relaxation, adsorption energies were computed using the following equation:
Eads = Esurface+CO – Esurface – ECO,gas
2. References
[1] A. Erba, J. Baima, I. Bush, R. Orlando, R. Dovesi, Large-Scale Condensed Matter DFT Simulations: Performance and Capabilities of the CRYSTAL Code, J. Chem. Theory Comput. 13 (2017) 5019–5027. https://doi.org/10.1021/acs.jctc.7b00687.
[2] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Physical Review Letters. 77 (1996) 3865–3868. https://doi.org/10.1103/PhysRevLett.77.3865.
[3] C.T. Campos, F.E. Jorge, Triple zeta quality basis sets for atoms Rb through Xe: Application in CCSD(T) atomic and molecular property calculations, Molecular Physics. 111 (2013) 167–173.
https://doi.org/10.1080/00268976.2012.709282.
[4] S. Grimme, J. Antony, S. Ehrlich, H. Krieg, A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu, Journal of Chemical Physics.
132 (2010). https://doi.org/10.1063/1.3382344.
