Jun Kubota

Photocatalytic and photoelectrochemical water splitting under irradiation by sunlight has received much attention for production of renewable hydrogen from water on a large scale. Many challenges still remain in improving energy conversion efficiency, such as utilizing longer-wavelength photons for hydrogen production, enhancing the reaction efficiency at any given wavelength, and increasing the lifetime of the semiconductor materials. This introductory review covers the fundamental aspects of photocatalytic and photoelectrochemical water splitting. Controlling the semiconducting properties of photocatalysts and photoelectrode materials is the primary concern in developing materials for solar water splitting, because they determine how much photoexcitation occurs in a semiconductor under solar illumination and how many photoexcited carriers reach the surface where water splitting takes place. Given a specific semiconductor material, surface modifications are important not only to activate the semiconductor for water splitting but also to facilitate charge separation and to upgrade the stability of the material under photoexcitation. In addition, reducing resistance loss and forming p-n junction have a significant impact on the efficiency of photoelectrochemical water splitting. Correct evaluation of the photocatalytic and photoelectrochemical activity for water splitting is becoming more important in enabling an accurate comparison of a number of studies based on different systems. In the latter part, recent advances in the water splitting reaction under visible light will be presented with a focus on non-oxide semiconductor materials to give an overview of the various problems and solutions.

A hematite photoanode showing a stable, record-breaking performance of 4.32 mA/cm² photoelectrochemical water oxidation current at 1.23 V vs. RHE under simulated 1-sun (100 mW/cm²) irradiation is reported. This photocurrent corresponds to ca. 34% of the maximum theoretical limit expected for hematite with a band gap of 2.1 V. The photoanode produced stoichiometric hydrogen and oxygen gases in amounts close to the expected values from the photocurrent. The hematitle has a unique single-crystalline "wormlike" morphology produced by in-situ two-step annealing at 550°C and 800°C of β-FeOOH nanorods grown directly on a transparent conducting oxide glass via an all-solution method. In addition, it is modified by platinum doping to improve the charge transfer characteristics of hematite and an oxygen-evolving co-catalyst on the surface.

Highly efficient water oxidation utilizing visible photons of up to 600 nm is a crucial step in artificial photosynthesis. Here we present a highly active photocatalyst for visible-light-driven water oxidation, consisting of single-crystalline meso- and macroporous LaTiO(2)N (LTON) with a band gap of 2.1 eV, and earth-abundasnt cobalt oxide (CoO(x)) as a cocatalyst. The optimized CoO(x)/LTON had a high quantum efficiency of 27.1 ± 2.6% at 440 nm, which substantially exceeds the values reported for previous particulate photocatalysts with a 600-nm absorption edge.

A vertically aligned Ta(3)N(5) nanorod photoelectrode is fabricated by through-mask anodization and nitridation for water splitting. The Ta(3)N(5) nanorods, working as photoanodes of a photoelectrochemical cell, yield a high photocurrent density of 3.8 mA cm(-2) at 1.23 V versus a reversible hydrogen electrode under AM 1.5G simulated sunlight and an incident photon-to-current conversion efficiency of 41.3% at 440 nm, one of the highest activities reported for photoanodes so far.

Spectral sensitization of a mesoporous graphite carbon nitride (mpg-C(3)N(4)) photocatalyst was investigated by depositing magnesium phthalocyanine (MgPc) to expand the absorption to wavelengths longer than those of the principal mpg-C(3)N(4). The obtained sample, MgPc/Pt/mpg-C(3)N(4) (Pt as a cocatalyst) showed stable photocatalytic evolution of hydrogen from aqueous solution in the presence of sacrificial reagents (triethanolamine), even under irradiation at wavelengths longer than 600 nm. Increasing the amount of MgPc led to ordered MgPc aggregation on the photocatalyst surfaces. The rate of photocatalytic hydrogen evolution was highest on a sample with an amount of MgPc corresponding to a monolayer on the Pt/mpg-C(3)N(4) photocatalyst surface. The obtained action spectra of hydrogen evolution and the observation that the amount of evolved hydrogen substantially surpassed the amount of MgPc, confirm that the introduced MgPc functioned as a photocatalytic sensitizer.