Band Gap as a Novel Descriptor for the Reactivity of 2D Titanium Dioxide and its Supported Pt Single Atom for Methane Activation

Xianglan Xu; Xiang Wang; De-En Jiang

doi:10.1021/acs.jpclett.1c00318

Band Gap as a Novel Descriptor for the Reactivity of 2D Titanium Dioxide and its Supported Pt Single Atom for Methane Activation

J Phys Chem Lett. 2021 Mar 18;12(10):2484-2488. doi: 10.1021/acs.jpclett.1c00318. Epub 2021 Mar 5.

Authors

Xianglan Xu^{1

2}, Xiang Wang¹, De-En Jiang²

Affiliations

¹ Key Laboratory of Jiangxi Province for Environment and Energy Catalysis, College of Chemistry, Nanchang University, Nanchang, Jiangxi 330031, China.
² Department of Chemistry, University of California, Riverside, California 92521, United States.

PMID: 33666442
DOI: 10.1021/acs.jpclett.1c00318

Abstract

Ultrathin transition-metal oxides (TMOs) from nonlayered bulk structures are emerging 2D materials. Here we investigate the reactivity of a 2D TMO of varying thickness from first principles. We find that the band gap of the 2D nL-TiO₂(110) shows a strong linear correlation with its surface reactivity: the smaller the band gap, the more reactive the surface oxygen; 3L-TiO₂(110) has the smallest band gap and the highest reactivity. We further design Pt₁ single-atom catalysts (SAC) by substituting a Pt single atom for a surface Ti atom. We find that the band gap of nL-TiO₂(110) dictates both chemisorption and dissociation of CH₄ on Pt₁-nL-TiO₂(110): the smaller the band gap, the stronger the adsorption of CH₄ and the lower the barrier of heterolytic C-H activation of CH₄. We propose that band gap can be a novel and direct descriptor for the reactivity of 2D TMOs and their supported SACs.