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J . Phys. Chem. 1985,89, 1236-1238
an empty acceptor level to generate an excited state (A-*). The thermal quenching of the EL efficiency is probably caused by the thermal activation of electrons from the donor states to the conduction band. Acknowledgment. The support of this research by the US Army
Research OfficeDurham and the National Science Foundation (CHE830466) is gratefully acknowledged. We are also grateful for the assistance of Mr. Keith D. Wilkins in the single-photoncounting experiment. Registry No. ZnS, 1314-98-3; AI, 7429-90-5.
Incorporation of a Recyclable Surface-Active Electron Donor in Synthetic Vesicles: Application to Photosensitized Hydrogen Formation by Vesicle-Stabilized Rh-Coated Colloidal CdS Particles Rafael Rafaeloff,' Yves-M. Tricot, Faruk Nome: Pietro Tundo: and Janos H. Fendler* Department of Chemistry and Institute sf Colloid and Surface Science, Clarkson University, Potsdam, New York 13676 (Received: October 4 , 1984)
Colloidal rhodium-coated CdS particles were in situ generated in thiol-functionalized surfactant/dioctadecyldimethylammonium chloride (DODAC) mixed vesicles. Upon visible light irradiation, the thiol-functionalized surfactant acted as a recyclable electron donor and promoted hydrogen generation. This vesicle-integrated electron donor could be chemically regenerated to resume hydrogen production at the same rate as during its first oxidation. This is a new concept in surfactant stabilized colloidal semiconductor systems, making possible a cyclic process of hydrogen generation.
Introduction Artifical photosynthesis continues to be an area of intense interest.&' One approach involves the utilization of catalystcoated colloidal semiconductors in photosensitized relayless water r e d ~ c t i o n . ~ - Light ' ~ absorption (Le., band-gap excitation) leads to the promotion of an electron from the valence to the conduction band and, hence, to the creation of an electron-hole pair in the semiconductor. Intercepting electron-hole recombinations by appropriate electron donors results, in turn, in water reduction (1) On leave from Israel Atomic Energy Commission, Soreq Nuclear Research Center, Yavne, 70600, Israel. (2) Permanent Address: Depto. de Quimica, Universidade Federal de Santa Catarina, 88000 Florianopolis, Santa Catarina, Brazil. (3) Permanent Address: Istituto di Chimica Organica della Universita de Torino, Via Bidone 36, 10125 Torino, Italy. (4) Gritzel, M. Acc. Chem. Res. 1981, 14, 376-384. (5) Porter, G. Proc. R. SOC.London, Ser. A . 1978, 362, 281-303. (6) Calvin, M. Acc. Chem. Res. 1978, 11, 369-374. (7) Fendler, J. H. J . Phys. Chem. 1980, 84, 1485-1491. (8) Sakata, T.; Kawai, T. In "Energy Resources through Photochemistry and Catalysis"; Academic Press: New York, 1983; pp 322-358. (9) Krautler, B.;Bard, A. J. J . Am. Chem. Soc. 1978,100, 4317-4318. (10) Kiwi, J.; Borgarello, E.; Pelizetti, E.; Visca, M.; Grfitzel, M. Angew. Chem., Int. Ed. Engl. 1980, 19, 646-648. (11) Pichat, J.; Mozzanega, M. N.; Disdier, J.; Hemnann, J-M. Nouu. J . Chim. 1982,6, 559-564. (12) Lehn, J.-M.; Sauvage, J.-P.; Ziessel, R. N o w . J . Chim. 1980, 4,
623-627. (13) Sato, S.; White, J. M. Chem. Phys. Lett. 1980, 70, 83-86. (14) Sato, S.; White, J. M. J. Am. Chem. Soc. 1980, 102, 7206-7210. (15) Darwent. J. R.; Porter, G.J . Chem. Soc., Chem. Commun. 1981, 145- 146. (16) Darwent, J. R. J. Chem. SOC.,Faraday Trans. 2, 1981, 77, 1703-1 709. (17) Harbour, J. R.; Wolkow, R.; Hair, M. L. J . Phys. Chem. 1981, 85, 4026-4029. (18) Duonghong, D.; Ramsden, J.; Gritzel, M. J . Am. Chem. SOC.1982, 104, 2977-2985. (19) Magliozzo, R. S.; Krasna, A. I. Photochem. Photobid. 1983, 38, 15-21.
0022-3654/85/2089-1236$01.50/0
at the catalyst-water interface. The extremely short electron-hole lifetime (
