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Trinuclear tantalum clusters grafted to hydroxylated silica surfaces: A density-functional embedded-cluster study

  • 2ND Russian Congress on Catalysis—Russcatalysis (Samara, (October 2–5, 2014)
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Abstract

To identify the coordination modes of bare and hydrogenated trinuclear tantalum species on hydroxylated silica, we computationally examined models of Ta3H n (n = 0, 3, 5–9) species grafted to a β-cris-tobalite surface. Ta3H n clusters are bound to the surface by substitution of hydrogen atoms of vicinal (…O-)3SiOH and geminal (…O-)2Si(OH)2 groups via three and six, respectively, Ta–O bonds of ~193 pm on average, in both types of models. The maximum Ta–O coordination number of non-hydrogenated Ta3 species to a silica surface is seven for the second type model surface; the additional Ta–O bond is due to an oxygen atom located in a bridging position to Ta–Ta bond. In the latter case, the mean Ta–O bond distance to one of =Si(O–)2 group is increased by 15 pm. For the complexes bound via vicinal silanol groups, each additional unit of hydrogen loading on the metal elongated the average Ta–Ta distance by ~2 pm, covering a range of 258–277 pm. For the most stable hydrogenated trimers, Ta3H9, the desorption energies of hydrogen atoms are relatively high, above 70 kJ/mol. The average Ta–Ta distances increase by ~19 pm on going from the complex (=SiO–)3Ta3H9 to complex (=SiO–)3Ta3 and by ~5 pm when the hydrogen loading is increased by one unit for (=Si(O–)2)3Ta3H n complexes, reaching the maximum value 319 pm when n = 9. The desorption energies of hydrogen atoms for the most stable tantalum trimer species grafted to the surface by geminal silanol groups, (=Si(O–)2)3Ta3H7, are rather low, less than 40 kJ/mol.

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Authors and Affiliations

  1. Institute of Chemistry and Chemical Technology, Siberian Branch of Russian Academy of Sciences, Krasnoyarsk, 660049, Russia

    V. A. Nasluzov, A. M. Shor & E. A. Ivanova-Shor

  2. Department Chemie and Catalysis Research Center, Technische Universitát München, Garching, 85747, Germany

    Shane M. Parker, A. Genest & Notker Rösch

Authors
  1. V. A. Nasluzov
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  2. Shane M. Parker
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  4. A. M. Shor
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  5. E. A. Ivanova-Shor
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  6. Notker Rösch
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Correspondence to E. A. Ivanova-Shor.

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Original Russian Text © V.A. Nasluzov, Shane M. Parker, A. Genest, A.M. Shor, E.A. Ivanova-Shor, Notker Rösch, 2015, published in Kinetika i Kataliz, 2015, Vol. 56, No. 5, pp. 640–648.

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Nasluzov, V.A., Parker, S.M., Genest, A. et al. Trinuclear tantalum clusters grafted to hydroxylated silica surfaces: A density-functional embedded-cluster study. Kinet Catal 56, 631–639 (2015). https://doi.org/10.1134/S0023158415050134

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