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DFT quantum-chemical calculations of nitrogen oxide chemisorption and reactivity on the Cu(100) surface

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Abstract

A DFT quantum-chemical study of NO adsorption and reactivity on the Cu20 and Cu16 metal clusters showed that only the molecular form of NO is stabilized on the copper surface. The heat of monomolecular adsorption was calculated to be ΔH m = −49.9 kJ/mol, while dissociative adsorption of NO is energetically unfavorable, ΔH d = + 15.7 kJ/mol, and dissociation demands a very high activation energy, E a = + 125.4 kJ/mol. Because of the absence of NO dissociation on the copper surface, the formation mechanism of the reduction products, N2 and N2O, is debatable since the surface reaction ultimately leads to N-O bond cleavage. As the reaction occurs with a very low activation energy, E a = 7.3 kJ/mol, interpretation of the NO direct reduction mechanism is both an important and intriguing problem because the binding energy in the NO molecule is high (630 kJ/mol) and the experimental studies revealed only physically adsorbed forms on the copper surface. It was found that the formation mechanism of the N2 and N2O reduction products involves formation (on the copper surface) of the (OadN-NOad) dimer intermediate that is chemisorbed via the oxygen atoms and characterized by a stable N-N bond (r N-N ∼1.3 Å). The N-N binding between the adsorbed NO molecules occurs through electron-accepting interaction between the oxygen atoms in NO and the metal atoms on the “defective” copper surface. The electronic structure of the (OadN-NOad) surface dimer is characterized by excess electron density (ON-NO)δ− and high reactivity in N-Oad bond dissociation. The calculated activation energy of the destruction of the chemisorbed intermediate (OadN-NOad) is very low (E a = 5–10 kJ/mol), which shows that it is kinetically unstable against the instantaneous release of the N2 and N2O reduction products into the gas phase and cannot be identified by modern experimental methods of metal surface studies. At the same time, on the MgO surface and in the individual (Ph3P)2Pt(O2N2) complex, a stable (OadN-NOad) dimer was revealed experimentally.

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Authors and Affiliations

  1. G. K. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk

    I. I. Zakharov

  2. Technological Institute, East Ukrainian National University, Severodonetsk

    I. I. Zakharov, A. V. Suvorin, A. I. Kolbasin & O. I. Zakharova

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  1. I. I. Zakharov
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  2. A. V. Suvorin
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  3. A. I. Kolbasin
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  4. O. I. Zakharova
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Correspondence to I. I. Zakharov.

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Translated from Zhurnal Strukturnoi Khimii, Vol. 48, Supplement, pp. S155–S168, 2007.

Original Russian Text Copyright © 2007 by I. I. Zakharov, A. V. Suvorin, A. I. K lbasin, and O. I. Zakharova

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Zakharov, I.I., Suvorin, A.V., Kolbasin, A.I. et al. DFT quantum-chemical calculations of nitrogen oxide chemisorption and reactivity on the Cu(100) surface. J Struct Chem 48 (Suppl 1), S147–S159 (2007). https://doi.org/10.1007/s10947-007-0158-x

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  • DOI: https://doi.org/10.1007/s10947-007-0158-x

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