Journal of the Chemical Society - Faraday Transactions p. 1055 - 1062 (1992)
Update date:2022-08-11
Topics:
Shiragami, Tsutomu
Ankyu, Hirofumi
Fukami, Shinako
Pac, Chyongjin
Yanagida, Shozo
et al.
Colloidal CdS suspensions (CdS-0) prepared at 0 deg C from methanolic Cd(ClO4)2 and Na2S solutions consist of quantised CdS microcrystallites (2-5 nm) and their loose aggregates, which catalyse the effective photoreduction of aromatic ketones and electron-deficient alkenes with triethylamine as electron donor.Under visible light induced photolysis, the methanolic CdS-0 suspension becomes brown owing to the reduction of lattice Cd2+ to Cd0, leading to the effective formation of alcohols from ketones, and dihydro compounds from alkenes.With the reduction potential< -1.56 V vs. standard calomel electrode (SCE), ketones were partly photoreduced to pinacols in methanol.Compared with highly pure bulk CdS (CdS-Ald), CdS-0 is more effective for photoreduction because of the size quantisation effect.The presence of an excess of sulfide ion (S2-) in the CdS-0 system, however, suppresses the formation of lattice Cd0, inducing one-electron transfer photoreductions which result in the exclusive formation of pinacols and 1,2,3,4-tetra(methoxycarbonyl)butane from the respective ketones and dimethyl maleate.The relationship between the two-electron reductions and the photogenerated lattice Cd0 is discussed in terms of the regulation of semiconductor photocatalysis.
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