Abstract
Novel research avenues have been explored over the last decade on the use of transition metal carbides (TMCs) as catalytically active supports for metal nanoclusters, which display high catalytic activity despite the poor reactivity (or even inertness) of the bulk metal. It has been postulated that TMCs polarise the electron density of adsorbed metal particles in such a way that their catalytic activity ends up being superior to those dispersed on more traditional metal oxide supports. Herein, we investigate the structural and electronic properties of small clusters of precious metals (Rh, Pd, Pt and Au) and more affordable metals (Co, Ni and Cu) supported on TMCs with 1:1 stoichiometry (TiC, ZrC, HfC, VC, NbC, TaC, MoC and WC) by means of periodic Density Functional Theory calculations. Our high-throughput screening studies indicate that it is possible not only to have strongly bonded and stably dispersed metal nanoparticles on TMC surfaces, but also to manipulate their charge by carefully selecting elements with desired electronegativity for the host TMC and the metal cluster. By doing so, it is possible to tune the amount of charge density on the cluster hollow sites, which can facilitate the bonding of certain molecules. Moreover, we identify Pt, Pd and Rh clusters supported on hexagonal TMC (001) facets as the candidates with the highest potential catalytic activity -as estimated by the significant polarisation of the cluster electron density- and stability -as quantified by the strongly negative values of adsorption energy per atom and formation energy-.
Supplementary materials
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Electronic Supplementary Information
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Electronic Supplementary Information for the article entitled "Atomistic and electronic structure of metal clusters supported on transition metal carbides: implications for catalysis", which includes comparison between calculated and experimental lattice parameters, additional details on the convergence with respect to k-points and vacuum length, additional figures on the binding strength of the supported clusters, a discussion on the vertical displacement of surface C atoms upon cluster adsorption, Bader charges on surface C atoms, and charge density difference plots.
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This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant Agreement No. 891756. A description of this project can be found in this link
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Database
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A dataset containing all relevant VASP input files (INCAR, POSCAR and KPOINTS) and output files (vasprun.xml, CONTCAR, CHGCAR, ACF.dat, ACF.dat and BFC.dat) has been made available in the NOMAD repository.
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