Enhanced Charge Collection for Splitting of Water Enabled by an Engineered Three-Dimensional Nanospike Array

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Department of Chemistry, and Department of Electronic and Computer Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People’s Republic of China
§ i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou, Jiangsu 215123, China
*Phone: +852 2358-8027. E-mail: [email protected]
*Phone: +852 2358-7362. E-mail: [email protected]
Cite this: J. Phys. Chem. C 2014, 118, 39, 22465–22472
Publication Date (Web):September 10, 2014
Copyright © 2014 American Chemical Society
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Photoelectrochemical (PEC) water splitting is a promising method of converting solar energy to hydrogen fuel from water using photocatalysts. Despite much effort in preparing mesoporous thin films on planar substrates, relatively little attention has been paid to their deposition on three-dimensional (3D) substrates, which could improve electron collection and enhance light-trapping. Here, we report the first synthesis of hierarchically branched anatase TiO2 nanotetrapods, achieved by dissolution and nucleation processes on a ZnO nanotetrapods template. When used as a photoanode for efficient PEC water splitting, the unique branched anatase TiO2 nanotetrapods yielded a photocurrent density of 0.54 mA cm–2 at applied potential of 0.35 V vs RHE, much higher than that of commercial TiO2 nanoparticles under otherwise identical conditions. Moreover, when the nanotetrapods were deposited on an ordered, purposely engineered 3D F-doped tin oxide (FTO) nanospike array, the photocurrent density was upgraded to 0.72 mA cm–2. This large photocurrent enhancement can be attributed to the ultrahigh contact surface area with the electrolyte, which is bequeathed by the hierarchically branched TiO2 nanotetrapods with a skin layer of vertically aligned ultrathin nanospines, as well as the short charge transport distance and enhanced light-trapping due to the peculiar 3D FTO nanospike array we have engineered by design.

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Other characterizations including SEM image of the surface of an Al piece, optical microscopy and light-scattering spectroscopy of the flat Al and the spiked Al substrates, schematic drawing illustrating the growth of the branched TiO2 NTs, XRD patterns, EDS analysis and XPS spectrum, SEM images of P25 TiO2 NPs deposited on the spiked substrate, and electrochemical impedance spectra of the branched TiO2 NTs and commercial P25 TiO2 NPs. This material is available free of charge via the Internet at http://pubs.acs.org.

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