Tailored Synthesis of Porous TiO2 Nanocubes and Nanoparallelepipeds with Exposed {111} Facets and Mesoscopic Void Space: A Superior Candidate for Efficient Dye-Sensitized Solar Cells.

Anatase TiO2 nanocubes and nanoparallelepipeds, with highly reactive {111} facets exposed, were developed for the first time through a modified one pot hydrothermal method, through the hydrolysis of tetrabutyltitanate in the presence of oleylamine as the morphology-controlling capping-agent and using ammonia/hydrofluoric acid for stabilizing the {111} faceted surfaces. These nanocubes/nanoparallelepipeds were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) and high angle annular dark-field scanning TEM (HAADF-STEM). Accordingly, a possible growth mechanism for the nanostructures is elucidated. The morphology, surface area and the pore size distribution of the TiO2 nanostructures can be tuned simply by altering the HF and ammonia dosage in the precursor solution. More importantly, optimization of the reaction system leads to the assembly of highly crystalline, high surface area, {111} faceted anatase TiO2 nanocubes/nanoparallelepipeds to form uniform mesoscopic void space. We report the development of a novel double layered photoanode for dye sensitized solar cells (DSSCs) made of highly crystalline, self-assembled faceted TiO2 nanocrystals as upper layer and commercial titania nanoparticles paste as under layer. The bilayered DSSC made from TiO2 nanostructures with exposed {111} facets as upper layer shows a much higher power conversion efficiency (9.60%), than DSSCs fabricated with commercial (P25) titania powder (4.67%) or with anatase TiO2 nanostructures having exposed {101} facets (7.59%) as the upper layer. The improved performance in bilayered DSSC made from TiO2 nanostructures with exposed {111} facets as the upper layer is attributed to high dye adsorption and fast electron transport dynamics owing to the unique structural features of the {111} facets in TiO2. Electrochemical impedance spectroscopy (EIS) measurements conducted on the cells supported these conclusions, which showed that the bilayered DSSC made from TiO2 nanostructures with exposed {111} facets as the upper layer possessed lower charge transfer resistance, higher electron recombination resistance, longer electron lifetime and higher collector efficiency characteristics, compared to DSSCs fabricated with commercial (P25) titania powder or with anatase TiO2 nanostructures having exposed {101} facets as the upper layer.

Green synthesis of Pt-doped TiO2 nanocrystals with exposed (001) facets and mesoscopic void space for photo-splitting of water under solar irradiation.

We report a non-trivial facile chemical approach using ionic liquid ([bmim][Cl]) as a porogen for the synthesis of (001) faceted TiO2 nanocrystals having mesoscopic void space. This faceted TiO2 nanomaterial has been doped with Pt nanoclusters through chemical impregnation. The resulting Pt-doped TiO2 nanomaterials are thoroughly characterized by powder X-ray diffraction (PXRD), Raman spectroscopy, field emission scanning electron microscopy (FE-SEM), ultra high resolution transmission electron microscopy (UHR-TEM), energy dispersive X-ray spectrometry (EDX), UV-vis diffuse reflection spectroscopy (DRS) and N2 sorption studies. These Pt/TiO2 nanocrystals with (001) exposed facets are employed as efficient and benign catalysts for hydrogen production from pure water and methanol-water systems under one AM 1.5G sunlight illumination. The effect of platinum loading and methanol-water ratio on the photocatalytic activity of the faceted TiO2 nanocrystals are investigated and it is found that hydrogen evolution rates have been enhanced significantly upon Pt loading. Under optimized reaction conditions the highest photocatalytic activity of 11.2 mmol h(-1) g(-1) has been achieved over ca. 1.0 wt% Pt loaded Pt/TiO2 nanocrystals with (001) exposed facets, which is one of the highest hydrogen evolution rates over the noble metal/TiO2 system reported to date in the literature.

Faceted titania nanocrystals doped with indium oxide nanoclusters as a superior candidate for sacrificial hydrogen evolution without any noble-metal cocatalyst under solar irradiation.

Development of unique nanoheterostructures consisting of indium oxide nanoclusters like species doped on the TiO2 nanocrystals surfaces with {101} and {001} exposed facets, resulted in unprecedented sacrificial hydrogen production (5.3 mmol h(-1) g(-1)) from water using methanol as a sacrificial agent, under visible light LED source and AM 1.5G solar simulator (10.3 mmol h(-1) g(-1)), which is the highest H2 production rate ever reported for titania based photocatalysts, without using any noble metal cocatalyst. X-ray photoelectron spectroscopy (XPS) analysis of the nanostructures reveals the presence of Ti-O-In and In-O-In like species on the surface of nanostructures. Electron energy-loss spectroscopy (EELS) elemental mapping and EDX spectroscopy techniques combined with transmission electron microscope evidenced the existence of nanoheterostructures. XPS, EELS, EDX, and HAADF-STEM tools collectively suggest the presence of indium oxide nanoclusters like species on the surface of TiO2 nanostructures. These indium oxide nanocluster doped TiO2 (In2O3/T{001}) single crystals with {101} and {001} exposed facets exhibited 1.3 times higher visible light photocatalytic H2 production than indium oxide nanocluster doped TiO2 nanocrystals with only {101}facets (In2O3/T{101}) exposed. The remarkable photocatalytic activity of the obtained nanoheterostructures is attributed to the combined synergetic effect of indium oxide nanoclusters interacting with the titania surface, enhanced visible light response, high crystallinity, and unique structural features.