In the present study, selectively exposed (101)-crystal facet engineered TiO2 photoanode is investigated for the higher efficiency of hydrogen evolution reaction. Till date, even the photoelectrochemical performance (PEC) depending on the exposed crystal facet have been calculated and demonstrated in the semiconducting microcrystals, selectively exposed crystal facet of photocatalyst thin films has not been reported yet. Herein, we demonstrate TiO2 thin film photoanode with 100%-exclusively exposed crystal facet and suggest the methodology for metal oxide thin film photoanode with selectively exposed crystal facet. Selectively exposed crystal facet-manipulated metal oxide thin film photoanode is fabricated over the pre-synthesized microcrystals through a three-step strategy: 1) hydrothermal synthesis of microcrystals, 2) positioning of microcrystals via polymer-induced manual assembly, and 3) fabrication of selectively exposed crystal facet of TiO2 thin film through secondary growth hydrothermal reaction. Based on the synthesis of representative TiO2 microcrystals with dominantly exposed (101), (100) and (001) crystal facet, selectively exposed crystal faceted TiO2 thin film photoanode is comparatively investigated for practical PEC performance. The photocurrent density of selectively exposed (101) crystal faceted TiO2 thin film photoanode is determined as 0.13 mA cm -2 and produce 18% of incident photon-to-current conversion efficiency at 0.65 V Ag/AgCl potential under AM 1.5 G illumination. Its photoelectrochemical hydrogen production reached to 0.07 mmol cm -2 for 12 hrs, which is higher than those of (100) and (001) faceted photoelectrode.
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