Localized Building Titania-Graphene Charge Transfer Interfaces for Enhanced Photocatalytic Performance.

Achieving high photocatalytic activity of titania-graphene composites calls for well-controlled titania size and efficient charge transfer interfaces. However, it is rather difficult because of easy restacking of graphene sheets and random nucleation and growth of titania nanoparticles in solution. Here, we reported a facile way to control the TiO2 sizes and interfaces by localizing the nucleation and growth of titania on graphene sheets, which prohibits both restacking of graphene and random growth of TiO2. As a result, a composite with controllably less than 10-nm-sized TiO2 nanoparticles evenly distributed on thin graphene sheets was achieved. Thanks to the small size of titania and efficient charge transfer interfaces, the TiO2/graphene composite exhibits a significant enhancement of photocatalytic H2 evolution activity, reaching 1.35 mmol g-1 h-1. Furthermore, the composite also shows high photocatalytic activity on dye degradation under visible light illumination.

Particulate Oxynitride Photoanodes Assembled with Transparent Electron-Collecting Oxide Nanorod Arrays.

The collection of photogenerated electrons is commonly a bottleneck in photoelectrochemical water oxidation on a particulate photoanode. Herein, a new strategy called "array insertion" for particulate photoanode preparation is proposed to improve electron collection. ZnO nanorod arrays are inserted between LaTiO2N particles and Al-doped ZnO (AZO) substrates via epitaxial electrodeposition, which make electronic connections. Using this methodology, charge separation efficiency is improved drastically, and the photocurrent at 1.23 VRHE is enhanced by more than 1 order of magnitude, because the obstacle of electron collection in the particulate LaTiO2N photoanodes is overcome.

A facile two-step method for fabrication of plate-like WO3 photoanode under mild conditions.

Fabrication of photoelectrodes on a large-scale, with low-cost and high efficiency is a challenge for their practical application in photoelectrochemical (PEC) water splitting. In this work, a typical plate-like WO(3) photoanode was fabricated with chemical etching of the as-prepared mixed tungsten-metal oxides (W-M-O, M = Cu, Zn or Al) by a reactive magnetron co-sputtering technique, which results in a greatly enhanced PEC performance for water oxidation in comparison with that obtained from a conventional magnetron sputtering method. The current approach is applicable for the fabrication of some other semiconductor photoelectrodes and is promising for the scaling up of applications for highly efficient solar energy conversion systems.

Visible light driven overall water splitting using cocatalyst/BiVO4 photoanode with minimized bias.

BiVO4 and many other semiconductor materials are ideal visible light responsive semiconductors, but are insufficient for overall water splitting. Upon loading water oxidation cocatalyst, for example Co-borate (denoted as CoBi) used here, onto BiVO4 photoanode, it is found that not only the onset potential is negatively shifted but also the photocurrent and the stability are significantly improved. And more importantly, PEC overall water splitting to H2 and O2 is realized using CoBi/BiVO4 as photoanode with a rather low applied bias (less than 0.3 V vs. counter electrode) in a two-electrode scheme, while at least 0.6 V is needed for bare BiVO4. This work demonstrates the practical possibility of achieving overall water splitting using the PEC strategy under a bias as low as the theoretical minimum, which is the difference between the flat band and proton reduction potential for a photoanode thermodynamically insufficient for water reduction. As long as the water oxidation overpotential is overcome with an efficient cocatalyst, the applied bias of the whole system is only used for that thermodynamically required for the proton reduction.

Crucial Role of Donor Density in the Performance of Oxynitride Perovskite LaTiO2 N for Photocatalytic Water Oxidation.

LaTiO2 N photocatalysts were prepared by thermal ammonolysis of flux-synthesized La2 Ti2 O7 and La2 TiO5 , and were investigated for water oxidation. Though LaTiO2 N derived from La2 TiO5 appears defect-free by UV/Vis/near-IR and electron paramagnetic resonance (EPR) spectroscopy, its performance is much lower than that of conventional La2 Ti2 O7 -derived LaTiO2 N with defects. It is shown by Mott-Schottky analysis that La2 TiO5 -derived LaTiO2 N has significantly lower donor density; this can result in insufficient built-in electric field for the separation of photogenerated electrons and holes. The lower donor density is also consistent with the smaller difference between the Fermi level and the valence-band maximum, which accounts for a lower oxidative power of the holes. In light of this discovery, the donor density was increased substantially by introducing anion vacancies through annealing in Ar. This resulted in improved performance. The CoOx -assisted La2 TiO5 -derived LaTiO2 N annealed at 713 °C has a higher quantum efficiency (25 %) at 450 nm than high-performance conventional CoOx /LaTiO2 N (21 %).

Synthesis of BaTaO2N oxynitride from Ba-rich oxide precursor for construction of visible-light-driven Z-scheme overall water splitting.

Barium tantalum oxynitride (BaTaO2N) with an absorption edge of ca. 660 nm is one of the most promising photocatalysts for solar water splitting, and is usually synthesized by nitriding a mixture of Ba and Ta-containing compounds with a Ba/Ta molar ratio of unity under ammonia flow at high temperature, usually causing a high density of defect sites. Herein, we introduce a novel synthesis method for BaTaO2N (BTON) by employing Ba-rich LiBa4Ta3O12, prepared by a flux method, as a precursor of nitridation. As a comparison, BaTaOx was prepared by conventional solid state reaction and used as the precursor. The as-nitrided samples were correspondingly denoted as BTON-Flux and BTON-SSR. It was found that well-crystallized BTON oxynitride can be similarly obtained by both methods, but the BTON-Flux sample exhibits significantly decreased defect density and enhanced surface area relative to the BTON-SSR sample. As a result of their structural differences, the photocatalytic water splitting performance of the BTON-Flux sample, regardless of the H2-evolving half reaction in the presence of methanol or Z-scheme overall water splitting, is much better than that of BTON-SSR. This study may open up a novel strategy for preparing oxynitride photocatalyst with decreased defect density for the promotion of solar water splitting.

Controlled growth of semiconductor nanofilms within TiO2 nanotubes for nanofilm sensitized solar cells.

Anodized TiO2 nanotubes were decorated by II-VI semiconductor nanofilms via atomic layer deposition (ALD) and further employed as photoanodes of semiconductor nanofilm sensitized solar cells (NFSCs) exhibiting superior photovoltaic performance.

Low-cost and high-performance CoMoS4 and NiMoS4 counter electrodes for dye-sensitized solar cells.

Porous chalcogels CoMoS4 and NiMoS4 made by a facile solution reaction displayed good electrocatalytic activity in the redox reaction of the I(-)/I3(-) shuttle. Dye-sensitized solar cells with these ternary compounds as counter electrodes (CEs) showed photovoltaic performance similar to the devices made with noble metal platinum CE (7.46%).