The behavior of semiconducting electrodes for photoelectrolysis of water is examined in terms of the physical properties of the semiconductor. The semiconductor‐electrolyte junction is treated as a simple Schottky barrier, and the photocurrent is described using this model. The approach is appropriate since large‐band‐gap semiconductors have an intrinsic oxygen overpotential which removes the electrode reaction kinetics as the rate‐limiting step. The model is successful in describing the wavelength and potential dependence of the photocurrent in WO3 and allows a determination of the band gap, optical absorption depth, minority‐carrier diffusion length, flat‐band potential, and the nature of the fundamental optical transition (direct or indirect). It is shown for WO3 that minority‐carrier diffusion plays a limited role in determining the photoresponse of the semiconductor‐electrolyte junction. There are indications that the diffusion length in this low carrier mobility material is determined by diffusion‐controlled bulk recombination processes rather than the more common trap‐limited recombination. It is also shown that the fundamental optical transition is indirect and that the band‐gap energy depends relatively strongly on applied potential and electrolyte. This effect seems to be the result of field‐induced crystallographic distortions in antiferroelectric WO3.

Photoelectrolysis and physical properties of the semiconducting electrode WO2

Photo-electrochemical hydrogen generation from water using solar energy. Materials-related aspects

Part I: Basic Principles: Introduction.- Principles of Photoelectrochemical Cells.- Photoelectrochemical Measurements.- Part II: Materials Properties and Synthesis: Nanostructured alpha-Fe2O3 Photoanodes.- Mixed Metal Oxide Photoelectrodes and Photocatalysts.- Combinatorial Identification and Optimization of New Oxide Semiconductors.- Part III: Devices and Device Characterization.- Multijunction Approaches to Photo-electrochemical Water Splitting.- Part IV: Future Perspectives.- Economic and Business Perspectives.- Emerging Trends in Water Photoelectrolysis.

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Photoelectrochemical hydrogen production

The photoelectrochemical characteristics of highly transparent nanoporous WO3 films are described. The photocurrent versus excitation wavelength spectra of these photoelectrodes exhibit a maximum close to 400 nm and a significant photoresponse to the blue part of the visible spectrum. The observed conversion efficiencies attain 75% for the photogeneration of oxygen from 1 M aq HClO4 and reach 190% in the presence of methanol in the solution, denoting in the latter case the occurrence of a perfect photocurrent doubling. Experiments conducted under simulated solar AM 1.5 illumination resulted in steady-state anodic photocurrents of the order of several mA/cm2.

M.A. Butler

Papers

Tungsten trioxide as an electrode for photoelectrolysis of water

Wavelength and temperature dependence of the Faraday effect in Cd(1 − x)Mn(x)Te