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Microkinetic simulation and fitting of the temperature programmed reaction of methanol on CeO2(111): H2 and H2O + V production

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Abstract

The kinetics and mechanism for temperature programmed reaction following adsorption of an adsorbate can be better understood by simulation and fitting with comparison to experiment. A case study is presented here for the chemistry of adsorption of methanol on a CeO2(111) surface followed by heating. The gas products observed are CH3OH, CH2O, H2, H2O, CO, CO2. At low temperatures (< 500 K), there is formation of H2 and H2O, where the H2O formation is accompanied by lattice oxygen vacancy (V) formation and is thus important in determining the selectivity towards different products. Microkinetic modeling was performed using a recently published method for fitting to gain mechanistic knowledge of the H2 and H2O + V formation at < 500 K. In the kinetic models used here, most of the H2 and H2O + V formation can be explained by a mechanism in which a metastable state of hydrogen on the surface (H*) acts as an intermediate. Two possibilities were investigated for the source of the metastable H* intermediate: H* from CH bond breaking of methoxies, or promotion of H+ to H* via electron transfer from ionic methoxies absorbed in oxygen vacancies (CH3O/V). From this study, we consider the latter to be more likely at < 500 K. For the H2O formation, it was found to be critical that H2O cannot dissociate directly on oxygen vacancies. Catalytic chemistry was observed in simulations, including catalytic formation of oxygen vacancies. Various features of the experimental results were reproduced, including methoxies being the major carbon containing species on the surface at < 500 K.

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Notes

  1. 1.

    An alternative to the electron transfer mechanism is a mechanism which involves CH3O- and H+ exchanging site positions (the mechanism for doing so would actually involve CH3* exchanging positions with H*) [28]. The site exchange idea has recently been discussed by Mullins [25]. We have not considered the site exchange mechanism, as there is no transition state or activation energy available for this mechanism in the literature, but it would play a role similar to that of our electron transfer mechanism.

  2. 2.

    To reproduce the experimental behaviour observed, the binding strength of ionic methoxies outside of vacancies was required to be stronger than the DFT values calculated by Mei et al. [33] by 20 or 30 kJ/mol, which is in line with the stronger binding strengths calculated by Beste et al. [31] and also consistent with the results of Kropp et al. [34].

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Acknowledgements

This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. A. Savara thanks David R. Mullins for providing experimentally obtained TPR data and for useful conversations. A. Savara also thanks Michael Caracotsios for aid in understanding the basic use of Athena Visual Studio modelling and estimation software.

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Correspondence to Aditya Savara.

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Savara, A. Microkinetic simulation and fitting of the temperature programmed reaction of methanol on CeO2(111): H2 and H2O + V production. Reac Kinet Mech Cat 129, 181–203 (2020). https://doi.org/10.1007/s11144-019-01710-w

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Keywords

  • Temperature programmed reaction
  • Methanol
  • Oxygen vacancy
  • Complex reaction network
  • Metastable hydrogen
  • Activated hydrogen