Islam, Syed; Reed, Allen; Nagpure, Suraj; Wanninayake, Namal; Browning, James ; Strzalka, Joseph; Kim, Doo Young; Rankin, Stephen
In this work, we use neutron reflectometry (NR) to investigate the roles of hydrogen in plasma treated hydrogen doped mesoporous black titania thin films in their visible light absorption and enhanced photoactivity for water oxidation. The cubic ordered mesoporous TiO2 thin films are prepared by a surfactant-templated sol-gel method and are treated with hydrogen plasma, an approach hypothesized to capitalize on the high degree of disorder in the material and the high energy of the plasma species to achieve efficient hydrogen doping. UV-vis absorbance spectra indicate that H2 plasma treatment makes TiO2 films black, with broad-spectrum enhancement of visible light absorption, and XPS analysis shows peak for Ti3+ state in treated films. The presence of hydrogen in black mesoporous titania (H-TiO2) films is confirmed by the scattering length density (SLD) profiles obtained from neutron reflectometry measurements. The H-TiO2 shows ca. 28 times and 8 times higher photocurrent for photoelectrochemical water oxidation compared to undoped TiO2 films under UV (365 nm) and blue (455 nm) LED irradiation, respectively. These findings provide the first direct evidence that the dramatic change in visible light absorbance of H-treated black TiO2 is accompanied by significant hydrogen uptake and not just Ti3+ generation or surface disordering.