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Mechanism of photocatalytic water oxidation on small TiO2 nanoparticles

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c6sc04378j· OSTI ID:1423815
 [1];  [2];  [3];  [2];  [4];  [2]
  1. Univ. of California, Irvine, CA (United States). Dept. of Chemistry; University of California Irvine
  2. Univ. of California, Irvine, CA (United States). Dept. of Chemistry
  3. Imperial College, London (United Kingdom). Dept. of Chemistry; Univ. College London, London (United Kingdom). Dept. of Chemistry
  4. Univ. College London, London (United Kingdom). Dept. of Chemistry
+ Show Author Affiliations
Here, we present the first unconstrained nonadiabatic molecular dynamics (NAMD) simulations of photocatalytic water oxidation by small hydrated TiO2 nanoparticles using Tully surface hopping and time-dependent density functional theory. The results indicate that ultrafast electron–proton transfer from physisorbed water to the photohole initiates the photo-oxidation on the S1 potential energy surface. The new mechanism readily explains the observation of mobile hydroxyl radicals in recent experiments. Two key driving forces for the photo-oxidation reaction are identified: localization of the electron–hole pair and stabilization of the photohole by hydrogen bonding interaction. Our findings illustrate the scope of recent advances in NAMD methods and emphasize the importance of explicit simulation of electronic excitations.
Research Organization:
Univ. of California, Irvine, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0008694
OSTI ID:
1423815
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 3 Vol. 8; ISSN 2041-6520; ISSN CSHCBM
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (11)

Influence of Surface-Related Phenomena on Mechanism, Selectivity, and Conversion of TiO 2 -Induced Photocatalytic Reactions journal December 2018
Phosphorylation of Polymeric Carbon Nitride Photoanodes with Increased Surface Valence Electrons for Solar Water Splitting journal April 2019
A Review of Recent Applications of Ion Beam Techniques on Nanomaterial Surface Modification: Design of Nanostructures and Energy Harvesting journal June 2019
Self-hydrogenated shell promoting photocatalytic H2 evolution on anatase TiO2 journal July 2018
Cadmium sulfide-based nanomaterials for photocatalytic hydrogen production journal January 2018
Multistate hybrid time-dependent density functional theory with surface hopping accurately captures ultrafast thymine photodeactivation journal January 2019
Charge transfer in time-dependent density functional theory journal September 2017
Introducing catalysis in photocatalysis: What can be understood from surface science studies of alcohol photoreforming on TiO 2 journal August 2019
Enhanced photocatalytic activity in porphyrin-sensitized TiO 2 nanorods journal June 2017
The Nanosized Dye Adsorbents for Water Treatment journal February 2020
Charge-Transfer in Time-Dependent Density Functional Theory text January 2017

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