Structural evolution of titanium dioxide during reduction in high-pressure hydrogen

Selcuk, Sencer; Zhao, Xunhua; Selloni, Annabella

doi:10.1038/s41563-018-0135-0

Title: Structural evolution of titanium dioxide during reduction in high-pressure hydrogen

Journal Article · Mon Jul 16 00:00:00 EDT 2018 · Nature Materials

DOI:https://doi.org/10.1038/s41563-018-0135-0· OSTI ID:1543760

^[1]; Zhao, Xunhua ^[1]; Selloni, Annabella ^[1]

Princeton Univ., NJ (United States)

The excellent photocatalytic properties of titanium oxide (TiO₂) under ultraviolet light have long motivated the search for doping strategies capable of extending its photoactivity to the visible part of the spectrum. One approach is high-pressure and high-temperature hydrogenation, which results in reduced ‘black TiO₂’ nanoparticles with a crystalline core and a disordered shell that absorbs visible light. Here we elucidate the formation mechanism and structural features of black TiO₂ using first-principles-validated reactive force field molecular dynamics simulations of anatase TiO₂ surfaces and nanoparticles at high temperature and under high hydrogen pressures. Simulations reveal that surface oxygen vacancies created upon reaction of H₂ with surface oxygen atoms diffuse towards the bulk material but encounter a high barrier for subsurface migration on {001} facets of the nanoparticles, which initiates surface disordering. Besides confirming that the hydrogenated amorphous shell has a key role in the photoactivity of black TiO₂, our results provide insight into the properties of the disordered surface layers that are observed on regular anatase nanocrystals under photocatalytic water-splitting conditions.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0007347

OSTI ID:: 1543760

Journal Information:: Nature Materials, Vol. 17, Issue 10; ISSN 1476-1122

Publisher:: Springer Nature - Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 78 works

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