Controlled Band Offsets in Ultrathin Hematite for Enhancing the Photoelectrochemical Water Splitting Performance of Heterostructured Photoanodes.

Formation of type II heterojunctions is a promising strategy to enhance the photoelectrochemical performance of water-splitting photoanodes, which has been tremendously studied. However, there have been few studies focusing on the formation of type II heterojunctions depending on the thickness of the overlayer. Here, enhanced photoelectrochemical activities of a Fe2O3 film deposited-BiVO4/WO3 heterostructure with different thicknesses of the Fe2O3 layer have been investigated. The Fe2O3 (10 nm)/BiVO4/WO3 heterojunction photoanode shows a much higher photocurrent density compared to the Fe2O3 (100 nm)/BiVO4/WO3 photoanode. The Fe2O3 (10 nm)/BiVO4/WO3 trilayer heterojunction anodes have sequential type II junctions, while a thick Fe2O3 overlayer forms an inverse type II junction between Fe2O3 and BiVO4. Furthermore, the incident-photon-to-current efficiency measured under back-illumination is higher than those measured under front-illumination, demonstrating the importance of the illumination sequence for light absorption and charge transfer and transport. This study shows that the thickness of the oxide overlayer influences the energy band alignment and can be a strategy to improve solar water splitting performance. Based on our findings, we propose a photoanode design strategy for efficient photoelectrochemical water splitting.

p-p Heterojunction of Nickel Oxide-Decorated Cobalt Oxide Nanorods for Enhanced Sensitivity and Selectivity toward Volatile Organic Compounds.

The utilization of p-p isotype heterojunctions is an effective strategy to enhance the gas sensing properties of metal-oxide semiconductors, but most previous studies focused on p-n heterojunctions owing to their simple mechanism of formation of depletion layers. However, a proper choice of isotype semiconductors with appropriate energy bands can also contribute to the enhancement of the gas sensing performance. Herein, we report nickel oxide (NiO)-decorated cobalt oxide (Co3O4) nanorods (NRs) fabricated using the multiple-step glancing angle deposition method. The effective decoration of NiO on the entire surface of Co3O4 NRs enabled the formation of numerous p-p heterojunctions, and they exhibited a 16.78 times higher gas response to 50 ppm of C6H6 at 350 °C compared to that of bare Co3O4 NRs with the calculated detection limit of approximately 13.91 ppb. Apart from the p-p heterojunctions, increased active sites owing to the changes in the orientation of the exposed lattice surface and the catalytic effects of NiO also contributed to the enhanced gas sensing properties. The advantages of p-p heterojunctions for gas sensing applications demonstrated in this work will provide a new perspective of heterostructured metal-oxide nanostructures for sensitive and selective gas sensing.