Interaction of diethyldithiocarbamate with n-type cadmium sulfide and cadmium selenide: efficient photoelectrochemical oxidation to the disulfide and flat-band potential of the semiconductor as a function of adsorbate concentration
The behavior of sodium diethyldithiocarbamate, Na(Et/sub 2/NCS/sub 2/), at n-type semiconducting CdX (X = S, Se) in CH/sub 3/CN/0.2 M NaClO/sub 4/ has been studied. The Et/sub 2/NCS/sub 2//sup -/ interacts strongly with the CdX surface and shifts the flat-band potential, E/sub FB/, up to 1.0 V more negative with increasing Et/sub 2/NCS/sub 2//sup -/ concentration. The concentration dependence of the shift in E/sub FB/ has been studied in the range 0-0.2 M, with 0.01 M Et/sub 2/NCS/sub 2//sup -/ being sufficient to shift E/sub FB/ the maximum amount. High current efficiency (at least 98%) can be maintained to large extent conversion (70%) in the photoelectrochemical oxidation of Et/sub 2/NCS/sub 2//sup -/ to (Et/sub 2/NC(S)S)/sub 2/ at either illuminated CdS or CdSe. Oxidation of Et/sub 2/NCS/sub 2//sup -/ can be effected at an electrode potential significantly more negative than E/sup 0/' of Et/sub 2/NCS/sub 2//sup -//(Et/sub 2/NC(S)S)/sub 2/, showing that visible light can be used to drive the oxidation in an uphill sense. Compared to a Pt anode, the CdX (X = S, Se) photoanodes allow a voltage savings of the order of 1.0 V. The photoanodes are durable and show constant output of at least 10 mA/cm/sup 2/ for greater than 48 h.
- Research Organization:
- Massachusetts Institute of Technology, Cambridge
- OSTI ID:
- 5532489
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:13; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400400* -- Electrochemistry
400500 -- Photochemistry
ALKALI METAL COMPLEXES
ANODES
CADMIUM COMPOUNDS
CADMIUM SELENIDES
CADMIUM SULFIDES
CARBAMATES
CARBONIC ACID DERIVATIVES
CARBOXYLIC ACID SALTS
CHALCOGENIDES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
EFFICIENCY
ELECTROCHEMISTRY
ELECTRODES
EXPERIMENTAL DATA
INFORMATION
INORGANIC PHOSPHORS
MATERIALS
N-TYPE CONDUCTORS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDATION
PHOSPHORS
PHOTOANODES
PHOTOCHEMICAL REACTIONS
QUANTUM EFFICIENCY
SELENIDES
SELENIUM COMPOUNDS
SEMICONDUCTOR MATERIALS
SODIUM COMPLEXES
SULFIDES
SULFUR COMPOUNDS