Understanding the Reactivity of Supported Late Transition Metals on a Bare Anatase (101) Surface: A Periodic Conceptual DFT Investigation

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The rapidly growing interest for new heterogeneous catalytic systems providing high atomic efficiency along with high stability and reactivity triggered an impressive progress in the field of single-atom catalysis. Nevertheless, unravelling the factors governing the interaction strength between the support and the adsorbed metal atoms remains a major challenge. Based on periodic Density Functional Theory (DFT) calculations, this paper provides insight into the adsorption of single late transition metals on a defect-free anatase surface. The obtained adsorption energies fluctuate, with the exception of Pd, between -3.11 and -3.80 eV and are indicative of a strong interaction. Depending on the considered transition metal, we could attribute the strength of this interaction with the support to: i) an electron transfer towards anatase (Ru, Rh, Ni), ii) s-d orbital hybridisation effects (Pt), or iii) a synergistic effect between both factors (Fe, Co, Os, Ir). The driving forces behind the adsorption were also found to be strongly related to Klechkowsky's rule for orbital filling. In contrast, the deviating behaviour of Pd is most likely associated with the lower dissociation enthalpy of the Pd-O bond. Additionally, the reactivity of these systems was evaluated using the Fermi weighted density of states approach. The resulting softness values can be clearly related to the electron configuration of the catalytic systems as well as with the net charge on the transition metal. Finally, these indices were used to construct a model that predicts the adsorption strength of CO on these anatase-supported d-metal atoms. The values obtained from this regression model show, within a 95% probability interval, a correlation of 84% with the explicitly calculated CO adsorption energies.
Originele taal-2English
Pagina's (van-tot)1-13
Aantal pagina's13
Nummer van het tijdschrift6
StatusPublished - 14 mrt 2023

Bibliografische nota

Funding Information:
The authors wish to thank the Vrije Universiteit Brussel (VUB) for the continuous support and in particular the funding through a Strategic Research Program. M. A. and J. T. would like to acknowledge the financial support of the Research Foundation‐Flanders (Project No. 12F4416 N and 12Y7718 N). The computational resources and services used in this work were provided by the VSC (Flemish Supercomputer Center), funded by the Research Foundation Flanders (FWO) and the Flemish Government – department EWI.

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