The production of hydrogen by water splitting has been a very attractive idea for several decades. However, the energy consumption that is necessary for water oxidation is too high for practical applications. On the contrary, the oxidation of organics is a much easier and less energy-demanding process. In addition, it may be used to consume organic wastes with a double environmental benefit: renewable energy production with environmental remediation. The oxidation of organics in a photoelectrochemical cell, which in that case is also referenced as a photocatalytic fuel cell, has the additional advantage of providing an alternative route for solar energy conversion. With this in mind, the present work describes a realistic choice of materials for the Pt-free photoelectrochemical production of hydrogen, by employing ethanol as a model organic fuel. The photoanode was made of a combination of titania with cadmium sulfide as the photosensitizer in order to enhance visible light absorbance. The cathode electrode was a simple carbon paper. Thus, it is shown that substantial hydrogen can be produced without electrocatalysts by simply exploiting carbon electrodes. Even though an ion transfer membrane was used in order to allow for an oxygen-free cathode environment, the electrolyte was the same in both the anode and cathode compartments. An alkaline electrolyte has been used to allow high hydroxyl concentration, thus facilitating organic fuel (photocatalytic) oxidation. Hydrogen production was then obtained by water reduction at the cathode (counter) electrode.

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Hydrogen and hydrogen peroxide have been photoelectrocatalytically produced by electrocatalytic reduction using simple carbon electrodes made by depositing a mesoporous carbon film on carbon cloth. Visible-light-absorbing photoanodes have been constructed by depositing mesoporous CdS/TiO2 or WO3 films on transparent fluorine-doped tin oxide (FTO) electrodes. Both produced substantial photocurrents of up to 50 mA in the case of CdS/TiO2 and 25 mA in the case of WO3 photoanodes, and resulting in the production of substantial quantities of H2 gas or aqueous H2O2. Maximum hydrogen production rate was 7.8 µmol/min, and maximum hydrogen peroxide production rate was equivalent, i.e., 7.5 µmol/min. The same reactor was employed for the production of both solar fuels, with the difference being that hydrogen was produced under anaerobic and hydrogen peroxide under aerated conditions. The present data promote the photoelectrochemical production of solar fuels by using simple inexpensive materials for the synthesis of catalysts and the construction of electrodes.