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Title: Self-hydrogenated shell promoting photocatalytic H 2 evolution on anatase TiO 2

Abstract

As one of the most important photocatalysts, TiO 2 has triggered broad interest and intensive studies for decades. Observation of the interfacial reactions between water and TiO 2 at microscopic scale can provide key insight into the mechanisms of photocatalytic processes. Currently, experimental methodologies for characterizing photocatalytic reactions of anatase TiO 2 are mostly confined to water vapor or single molecule chemistry. Here, we investigate the photocatalytic reaction of anatase TiO 2 nanoparticles in water using liquid environmental transmission electron microscopy. A self-hydrogenated shell is observed on the TiO 2 surface before the generation of hydrogen bubbles. First-principles calculations suggest that this shell is formed through subsurface diffusion of photo-reduced water protons generated at the aqueous TiO 2 interface, which promotes photocatalytic hydrogen evolution by reducing the activation barrier for H 2 (H–H bond) formation. Experiments confirm that the self-hydrogenated shell contains reduced titanium ions, and its thickness can increase to several nanometers with increasing UV illuminance.

Authors:
 [1];  [2];  [3];  [1];  [2];  [4];  [5]; ORCiD logo [6]; ORCiD logo [1]
  1. Beijing Univ. of Technology, Beijing (China)
  2. Beijing Computational Science Research Center, Beijing (China)
  3. National Tsing Hua Univ., Taiwan (China)
  4. Princeton Univ., Princeton, NJ (United States)
  5. National Tsing Hua Univ., Taiwan (China); City Univ., Hong Kong (China)
  6. Beijing Computational Science Research Center, Beijing (China); Beihang Univ., Beijing (China)
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1511483
Grant/Contract Number:  
SC0007347
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lu, Yue, Yin, Wen -Jin, Peng, Kai -Lin, Wang, Kuan, Hu, Qi, Selloni, Annabella, Chen, Fu -Rong, Liu, Li -Min, and Sui, Man -Ling. Self-hydrogenated shell promoting photocatalytic H2 evolution on anatase TiO2. United States: N. p., 2018. Web. doi:10.1038/s41467-018-05144-1.
Lu, Yue, Yin, Wen -Jin, Peng, Kai -Lin, Wang, Kuan, Hu, Qi, Selloni, Annabella, Chen, Fu -Rong, Liu, Li -Min, & Sui, Man -Ling. Self-hydrogenated shell promoting photocatalytic H2 evolution on anatase TiO2. United States. doi:10.1038/s41467-018-05144-1.
Lu, Yue, Yin, Wen -Jin, Peng, Kai -Lin, Wang, Kuan, Hu, Qi, Selloni, Annabella, Chen, Fu -Rong, Liu, Li -Min, and Sui, Man -Ling. Mon . "Self-hydrogenated shell promoting photocatalytic H2 evolution on anatase TiO2". United States. doi:10.1038/s41467-018-05144-1. https://www.osti.gov/servlets/purl/1511483.
@article{osti_1511483,
title = {Self-hydrogenated shell promoting photocatalytic H2 evolution on anatase TiO2},
author = {Lu, Yue and Yin, Wen -Jin and Peng, Kai -Lin and Wang, Kuan and Hu, Qi and Selloni, Annabella and Chen, Fu -Rong and Liu, Li -Min and Sui, Man -Ling},
abstractNote = {As one of the most important photocatalysts, TiO2 has triggered broad interest and intensive studies for decades. Observation of the interfacial reactions between water and TiO2 at microscopic scale can provide key insight into the mechanisms of photocatalytic processes. Currently, experimental methodologies for characterizing photocatalytic reactions of anatase TiO2 are mostly confined to water vapor or single molecule chemistry. Here, we investigate the photocatalytic reaction of anatase TiO2 nanoparticles in water using liquid environmental transmission electron microscopy. A self-hydrogenated shell is observed on the TiO2 surface before the generation of hydrogen bubbles. First-principles calculations suggest that this shell is formed through subsurface diffusion of photo-reduced water protons generated at the aqueous TiO2 interface, which promotes photocatalytic hydrogen evolution by reducing the activation barrier for H2 (H–H bond) formation. Experiments confirm that the self-hydrogenated shell contains reduced titanium ions, and its thickness can increase to several nanometers with increasing UV illuminance.},
doi = {10.1038/s41467-018-05144-1},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {7}
}

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