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Reactivity of transition metal atoms supported or not on TiO2(110) toward CO and H adsorption

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Abstract

Following our strategy to analyze the metal–support interaction, we present periodic DFT calculations for adsorption of metal atoms on a perfect rutile TiO2(110) surface (at low coverage, θ = 1/3) to investigate the interaction of an individual metal atom, M, with TiO2 and its consequence on the coadsorption of H and CO over M/TiO2. M under investigation varies in a systematic way from K to Zn. It is found that the presence of the support decreases or increases the strength of M–H or M–CO interaction according to the nature of M. The site of the adsorption for H and the formation of HCO/M also depend on M. From the left- to the right-hand side of the period, C and O both interact while O progressively detaches from M. On the contrary, for M = Fe–Cu, CO dissociation is more likely to happen. For CO and H coadsorption, two extreme cases emerge: For Ni, the hydrogen adsorbed should easily move on the support and CO dissociation is more likely. For Ti or Sc, H is easily coadsorbed with CO on the metal and CO hydrogenation could be the initial step.

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Notes

  1. Note that a “minimalistic or reductionist approach,” reducing the number of variables, is not only a tool for theoretical analysis; according to Somorjai, it allows designing the right experiment (An American scientist, 2013 Archway publishing Bloomington).

  2. Note that the formal electron transfer referring to oxidation states may be hardly visible through charge analysis [14]. The site of adsorption (on O dianion) confirms the cationic feature. In cases of unpaired electrons, the reduction is often better revealed by spin analysis [1, 30]. Gold on reduced surfaces (O defective, hydrogenated surface) is the exception [1, 30].

  3. We never see Cu2+.

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Acknowledgments

We are grateful to CMCU-PHC (09G 1212) and the Institut Français de Cooperation in Tunisia (IFC) for their financial support. The authors thank GENCI and CCRE for computing facilities.

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Author notes

  1. Abdesslem Jedidi

    Present address: Modeling Group, Division of Physical Sciences and Engineering, KAUST Catalysis Center, King Abdullah University of Science and Technology (KAUST), 4700 KAUST, Thuwal, 23955-6900, Saudi Arabia

Authors and Affiliations

  1. Laboratoire de Chimie Théorique, UPMC Univ Paris 06, UMR 7616, Sorbonne Universités, 75005, Paris, France

    Zeineb Helali, Abdesslem Jedidi, Alexis Markovits & Christian Minot

  2. Laboratoire Matériaux Molécules et Applications, Université de Carthage, Boîte postale BP51, 2070, La Marsa, Tunisia

    Zeineb Helali, Abdesslem Jedidi & Manef Abderrabba

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  1. Zeineb Helali
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Correspondence to Alexis Markovits.

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Helali, Z., Jedidi, A., Markovits, A. et al. Reactivity of transition metal atoms supported or not on TiO2(110) toward CO and H adsorption. Theor Chem Acc 134, 50 (2015). https://doi.org/10.1007/s00214-015-1652-4

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