Understanding Methanol Coupling on SrTiO3 from First Principles

Huang, Runhong; Fung, Victor; Zhang, Yafen; Mullins, David R.; Wu, Zili; Jiang, De-en

doi:10.1021/acs.jpcc.8b00273

Title: Understanding Methanol Coupling on SrTiO₃ from First Principles

Journal Article · 19 March 2018 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.8b00273 · OSTI ID:1435220

Huang, Runhong ^[1];

^[1]; Zhang, Yafen ^[2];

^[2];

^[3];

^[1]

Univ. of California, Riverside, CA (United States). Dept. of Chemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division. Center for Nanophase Materials Sciences

Perovskites are interesting materials for catalysis due to their great tunability. However, the correlation of many reaction processes to the termination of a perovskite surface is still unclear. In this paper, we use the methanol coupling reaction on the SrTiO₃(100) surface as a probe reaction to investigate direct C–C coupling from a computational perspective. We use density functional theory to assess methanol adsorption, C–H activation, and direct C–C coupling reactions on the SrTiO₃(100) surface of different terminations. We find that, although methanol molecules dissociatively adsorb on both A and B terminations with similar strength, the dehydrogenation and C–C coupling reactions have significantly lower activation energies on the B termination than on the A termination. The predicted formation of methoxy and acetate on the SrTiO₃(100) B termination can well explain the ambient-pressure XPS data of methanol on the single-crystal SrTiO₃(100) surface at 250 °C. Finally, this work suggests that a choice of B termination of perovskites would be beneficial for the C–C coupling reaction of methanol.

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