ABSTRACT
We previously reported that the hydrolysis of Ir3+ in homogeneous solution could be triggered by irradiation with light whose energy was larger than a threshold value. In this work, we demonstrated that, by introducing Fe2O3 particles into solution, the incident light energy-restriction for the photo-catalyzed hydrolysis could be broken and the hydrolysis occurred at the Fe2O3/solution interface. The photo-generated holes on the Fe2O3 surface played a key role in oxidizing Ir(iii) to Ir(iv) species and triggered the deposition of IrOx. We showed that this photo-catalyzed surface hydrolysis is a universal phenomenon that takes place on the surface of many n-type semiconductors such as Fe2O3, TiO2, and Ag3PO4. As IrOx is an efficient catalyst for oxygen evolution reaction, surface hydrolysis is a general, facile and efficient strategy to prepare semiconductor/IrOx composites, which can be used as anodic materials for photoelectrochemical water splitting.
ABSTRACT
Solar powered hydrogen evolution reaction (HER) is one of the key reactions in solar-to-chemical energy conversion. It is desirable to develop photocathodic materials that exhibit high activity toward photoelectrochemical (PEC) HER at more positive potentials because a higher potential means a lower overpotential for HER. In this work, the Cu2O/CuO bilayered composites were prepared by a facile method that involved an electrodeposition and a subsequent thermal oxidation. The resulting Cu2O/CuO bilayered composites exhibited a surprisingly high activity and good stability toward PEC HER, expecially at high potentials in alkaline solution. The photocurrent density for HER was 3.15 mA·cm-2 at the potential of 0.40 V vs. RHE, which was one of the two highest reported at the same potential on copper-oxide-based photocathode. The high photoactivity of the bilayered composite was ascribed to the following three advantages of the Cu2O/CuO heterojunction: (1) the broadened light absorption band that made more efficient use of solar energy, (2) the large space-charge-region potential that enabled a high efficiency for electron-hole separation, and (3) the high majority carrier density that ensured a faster charge transportation rate. This work reveals the potential of the Cu2O/CuO bilayered composite as a promising photocathodic material for solar water splitting.
ABSTRACT
We report the preparation of CuWO4 nanoflake (NF) array films by using a solid phase reaction method in which WO3 NFs were employed as sacrificial templates. The SEM, TEM and XRD results demonstrated that the obtained CuWO4 films possessed a network structure that was composed of single crystalline NFs intersected with each other. The CuWO4 NF films showed superior photoelectrochemical (PEC) activity to other CuWO4 photoanodes reported recently for the oxygen evolution reaction (OER). We attributed the high activity to the unique morphological and crystalline structure of the CuWO4 film, which enhanced the photoactivity by providing a large specific area, a short hole transport distance from the inside of CuWO4 to the CuWO4/solution interface, and a low grain boundary density. Hydrogen treatment by annealing the CuWO4 NF film in mixed gases of H2 and Ar could further enhance the photoactivity, as hydrogen treatment significantly increased the electron density of CuWO4 by generating oxygen vacancy in the lattice. The photocurrent density for OER obtained on the hydrogen-treated (H-treated) CuWO4 NF film is the largest ever reported on CuWO4 photoanodes in the literature. Moreover, the CuWO4 photoanodes exhibit good stability in weak alkaline solution, while the H-treated CuWO4 photoanodes exhibit acceptable stability. This work not only reveals the potential of CuWO4 as a photoanode material for solar water splitting but also shows that the construction of nanostructured CuWO4 photoanodes is a promising method to achieve high PEC activity toward OER.
ABSTRACT
Hydrous iridium oxide (IrOx) nanoparticles (NPs) with an average diameter of 1.7 ± 0.3 nm were prepared via photochemical hydrolysis of iridium chloride in alkaline medium at room temperature. The photoinduced hydrolysis was monitored by time-dependent ultraviolet-visible (UV-vis) spectroscopy, and the effects of the incident wavelength and irradiation time on the production of IrOx NPs were systematically investigated. It was found that UV-vis irradiation is crucial for the generation of IrOx NPs during the hydrolysis of IrCl3, and once the irradiation was turned off, the hydrolysis reaction stopped immediately. The production rate of IrOx NPs greatly depended on the incident wavelength. There is a critical wavelength of 500 nm for the hydrolysis reaction, and IrOx NPs can only be produced under the illumination with an incident wavelength shorter than 500 nm. Moreover, the shorter the incident wavelength, the faster the growth rate of IrOx NPs. The obtained IrOx NPs were highly stable during two months of storage at 4 °C. The Ir/IrOx nanocomposites were prepared by surface reduction of IrOx NPs with NaBH4. The microstructure of the Ir/IrOx composite was characterized by transmission electron microscopy (TEM), and the presence of zero-valence Ir was confirmed by the X-ray diffraction (XRD) result. The Ir/IrOx nanocomposite exhibited good catalytic activity and high recycling stability toward the reduction of 4-nitrophenol. The catalytic activity per unit surface area of the Ir/IrOx composite catalyst was increased by a factor of 15 compared to that of pure Ir catalyst. The presence of the Ir/IrOx interfaces in the composite catalyst is believed to be responsible for the high activity.
