CO Adsorbate Promotes Polaron Photoactivity on the Reduced Rutile TiO2(110) Surface

• Published in: JACS Au Vol. 2; no. 1; pp. 234 - 245
• Main Authors: Cheng, Cheng, Zhu, Yonghao, Fang, Wei-Hai, Long, Run, Prezhdo, Oleg V
• Format: Journal Article
• Language: English
• Published: American Chemical Society 24.01.2022
• Subjects: time-dependent density functional theory; adsorbate−polaron interaction; polaron; electron−hole recombination; nonadiabatic molecular dynamics; TiO2
• ISSN: 2691-3704; 2691-3704
• DOI: 10.1021/jacsau.1c00508

Polarons play a major role in determining the chemical properties of transition-metal oxides. Recent experiments show that adsorbates can attract inner polarons to surface sites. These findings require an atomistic understanding of the adsorbate influence on polaron dynamics and lifetime. We consider reduced rutile TiO2(110) with an oxygen vacancy as a prototypical surface and a CO molecule as a classic probe and perform ab initio adiabatic molecular dynamics, time-domain density functional theory, and nonadiabatic molecular dynamics simulations. The simulations show that subsurface polarons have little influence on CO adsorption and CO can desorb easily. On the contrary, surface polarons strongly enhance CO adsorption. At the same time, the adsorbed CO attracts polarons to the surface, allowing them to participate in catalytic processes with CO. The CO interaction with polarons changes their orbital origin, suppresses polaron hopping, and stabilizes them at surface sites. Partial delocalization of polarons onto CO decouples them from free holes, decreasing the nonadiabatic coupling and shortening the quantum coherence time, thereby reducing charge recombination. The calculations demonstrate that CO prefers to adsorb at the next-nearest-neighbor five-coordinated Ti3+ surface electron polaron sites. The reported results provide a fundamental understanding of the influence of electron polarons on the initial stage of reactant adsorption and the effect of the adsorbate–polaron interaction on the polaron dynamics and lifetime. The study demonstrates how charge and polaron properties can be controlled by adsorbed species, allowing one to design high-performance transition-metal oxide catalysts.