Photochemical hydrogen production with cadmium sulfide suspensions

Active photocatalysts for photochemical hydrogen production have been prepared by platinum deposition on microcrystals of CdS powders. Hydrogen produced by irradiating suspensions of platinized CdS in various electrolyte solutions (S/sup 2 -/, SO/sub 3//sup 2 -/, H/sub 2/PO/sup 2 -/) has been shown to be significantly improved by photoetching the CdS microcrystals. The efficiency of hydrogen formation in solutions containing S/sup 2 -/ is low due to the formation of disulfide ions. Additional of reducing agents such as sulfite or hypophosphite ions, which efficiently suppresses disulfide formation, allows hydrogen to evolve at a surprisingly high rate. In the case of a solution containing both S/sup 2/ and SO/sub 3//sup 2 -/ ions, the formation of thiosulfate is observed with a quantum yield of 0.25. In mixtures of sulfide and hypophosphite ions, phosphite and phosphate ions are the oxidation products. Hydrogen formation occurs in solutions containing SO/sub 3//sup 2 -/ ions only when the platinized CdS particles have previously been photoetched. Concomitant to the proton reduction, SO/sub 3//sup 2 -/ ions are oxidized to sulfate and dithionate. In 12 days, 9 L of H/sub 2/ was generated by irradiating 1 g of CdS/Pt suspended in an Na/sub 2/SO/sub 3/ solution. After this period, the efficiency of the photocatalyst dropped to about 60% of the initial rate. The reaction parameters and the formation of the oxidation products have been investigated in detail. 57 references, 10 figures, 4 tables.