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.

Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting

Solar driven catalysis on semiconductors to produce clean chemical fuels, such as hydrogen, is widely considered as a promising route to mitigate environmental issues caused by the combustion of fossil fuels and to meet increasing worldwide demands for energy. The major limiting factors affecting the efficiency of solar fuel synthesis include; (i) light absorption, (ii) charge separation and transport and (iii) surface chemical reaction; therefore substantial efforts have been put into solving these problems. In particular, the loading of co-catalysts or secondary semiconductors that can act as either electron or hole acceptors for improved charge separation is a promising strategy, leading to the adaptation of a junction architecture. Research related to semiconductor junction photocatalysts has developed very rapidly and there are a few comprehensive reviews in which the strategy is discussed (A. Kudo and Y. Miseki, Chemical Society Reviews, 2009, 38, 253–278, K. Li, D. Martin, and J. Tang, Chinese Journal of Catalysis, 2011, 32, 879–890, R. Marschall, Advanced Functional Materials, 2014, 24, 2421–2440). This critical review seeks to give an overview of the concept of heterojunction construction and more importantly, the current state-of-the art for the efficient, visible-light driven junction water splitting photo(electro)catalysts reported over the past ten years. For water splitting, these include BiVO4, Fe2O3, Cu2O and C3N4, which have attracted increasing attention. Experimental observations of the proposed charge transfer mechanism across the semiconductor/semiconductor/metal junctions and the resultant activity enhancement are discussed. In parallel, recent successes in the theoretical modelling of semiconductor electronic structures at interfaces and how these explain the functionality of the junction structures is highlighted.

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Visible-light driven heterojunction photocatalysts for water splitting – a critical review

Harnessing solar energy for the production of clean hydrogen fuels by a photoelectrochemical (PEC) cell represents a very attractive but challenging alternative This review focuses on recent developments of some promising photoelectrode materials, such as BiVO4, a-Fe2O3, TaON, and Ta3N5 for solar hydrogen production Some strategies have been developed to improve PEC performances of the photoelectrode materials, including: (i) doping for enhancing visible light absorption in the wide bandgap semiconductor or promoting charge transport in the narrow bandgap semiconductor, respectively; (ii) surface treatment for removing segregation phase or surface states; (iii) electrocatalysts for decreasing the overpotentials; (iv) morphology control for enhancing the light absorption and shortening transfer distance of minority carriers; (v) other methods, such as sensitization, passivating layer, and band structure engineering using heterojunction structures, and so on Photochemical durability of the photoelectrodes is also discussed, since any potential PEC technology must balance efficiency against cost and photochemical durability Photochemical durability may be amended by optimizing the photoelectrode, electrocatalyst, and electrolyte at the same time In addition, solar seawater splitting is briefly introduced because it has received attention recently Finally, trends in research in PEC cells for solar hydrogen production are detailed

Photoelectrochemical cells for solar hydrogen production: current state of promising photoelectrodes, methods to improve their properties, and outlook

Globally increasing energy demands and environmental concerns related to the use of fossil fuels have stimulated extensive research to identify new energy systems and economies that are sustainable, clean, low cost, and environmentally benign. Hydrogen generation from solar-driven water splitting is a promising strategy to store solar energy in chemical bonds. The subsequent combustion of hydrogen in fuel cells produces electric energy, and the only exhaust is water. These two reactions compose an ideal process to provide clean and sustainable energy. In such a process, a hydrogen evolution reaction (HER), an oxygen evolution reaction (OER) during water splitting, and an oxygen reduction reaction (ORR) as a fuel cell cathodic reaction are key steps that affect the efficiency of the overall energy conversion. Catalysts play key roles in this process by improving the kinetics of these reactions. Porphyrin-based and corrole-based systems are versatile and can efficiently catalyze the ORR, OER, and HER. Becau...

Energy-Related Small Molecule Activation Reactions: Oxygen Reduction and Hydrogen and Oxygen Evolution Reactions Catalyzed by Porphyrin- and Corrole-Based Systems

Semiconductor-based photocatalysts and photoelectrochemical cells for solar fuel generation: a review

We studied photoelectrochemical performance of the undoped, Si-doped, Ti-doped, and codoped α-Fe2O3 film prepared by ultrasonic spray pyrolysis. Since the ions radius of Si4+<Fe3+<Ti4+, Si and Ti codoping can balance the ion radius difference between Fe3+ and Si4+ (or Ti4+) and increase the donor concentration. Their donor concentrations, calculated from slopes of the Mott–Schottky plots, are 9.10×1018 cm−3, 1.89×1020 cm−3, 2.04×1020 cm−3, and 7.06×1020 cm−3, respectively. Incident photon to current efficiency of the codoped film is 34% at 365 nm and 0.6 V versus Ag/AgCl, much higher than 10%, 20%, and 22% for the undoped, Si-doped, and Ti-doped film, respectively.

Improved photoelectrochemical responses of Si and Ti codoped α-Fe2O3 photoanode films

A facile strategy to passivate surface states on the undoped hematite photoanode for water splitting

A stable, efficient, and powerful 1314 nm Nd:YLF laser inband-pumped by a wavelength-locked narrowband 880 nm laser diode is demonstrated. The influence of mode-to-pump ratio on the performance of the diode-end-pumped Nd:YLF laser has been systematically investigated by taking into account the thermal effect and the energy transfer upconversion effect. For the optimum mode-to-pump ratio of 0.84, the maximum continuous wave output power of 21.9 W was extracted under the pump power of 70 W, which corresponded to the optical power efficiency of 31.3% and the beam quality of M2 ≈ 1.6. The resultant output power stability was determined to be 0.059% (RMS) within 1 h. In addition, by increasing the mode-to-pump ratio to 1.0, the near-diffraction-limited beam (M2 ≈ 1.3) was achieved with the output power of 17.0 W and the optical power efficiency of 24.3%.

Minglong Zhang

Papers

Photoelectrochemical cells for solar hydrogen production: current state of promising photoelectrodes, methods to improve their properties, and outlook

Improved photoelectrochemical responses of Si and Ti codoped α-Fe2O3 photoanode films

A facile strategy to passivate surface states on the undoped hematite photoanode for water splitting

High-performance diode-end-pumped Nd:YLF laser operating at 1314 nm.

Surface modification of hematite photoanode films with rhodium