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Adsorption and Dimerization of Late Transition Metal Atoms on the Regular and Defective Quartz (001) Surface

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Abstract

Using a density functional theory approach with dispersion corrections, we have studied the adsorption properties of Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au monomers and dimers on the hydroxylated surface of α-quartz. We also considered the interaction with ≡Si–O• paramagnetic centers (NBO centers) or with silanols (≡Si–O–H) to form a ≡Si–O–TMx (x = 1, 2) group and a 1/2 H2 molecule. On the hydroxylated surface, the TM atoms bind relatively weakly, while strong adsorption energies of 4–5 eV are found on the NBO center where due to the coupling of the unpaired electron of the ≡Si–O• unit and the valence states of the metal atom. The TM atoms can react with the silanol groups releasing H2 and forming a stable ≡Si–O–TM complex with exothermic reactions. Dimers arriving from the gas-phase interact with the hydroxylated quartz surface with energies between 0.5 and 1.4 eV. If two TM atoms diffusing on the surface form a dimer, they release a large amount of energy which largely exceeds the dimer adsorption energy, leading to possible dimer desorption (with the exception of Pd). Also dimers bind strongly to NBO centers. Here the dimerization energies are considerably smaller than the desorption energy showing that the NBO sites act as effective nucleation centers. Differently from TM atoms, only some of the dimers react with ≡Si–O–H groups.

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Adsorption and nucleation of late transition metal atoms on quartz (001) surface.

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Acknowledgments

Financial support from the European Marie Curie Project CATSENSE (Grant Agreement Number: 607417) and from the Italian MIUR (FIRB Project RBAP115AYN “Oxides at the nanoscale: multifunctionality and applications”) is gratefully acknowledged. We also thank the COST Action CM1104 “reducible oxide chemistry, structure and functions”.

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  1. Dipartimento di Scienza dei Materiali, Università di Milano-Bicocca, via Cozzi 55, 20125, Milan, Italy

    Philomena Schlexer & Gianfranco Pacchioni

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  1. Philomena Schlexer
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  2. Gianfranco Pacchioni
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Correspondence to Gianfranco Pacchioni.

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Schlexer, P., Pacchioni, G. Adsorption and Dimerization of Late Transition Metal Atoms on the Regular and Defective Quartz (001) Surface. Top Catal 60, 459–470 (2017). https://doi.org/10.1007/s11244-016-0712-x

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