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Electrochemical characterization of surface-bound redox polymers derived from 1,1'-bis(((3-(triethoxysilyl)propyl)amino)carbonyl)cobaltocenium: charge transport, anion binding, and use in photoelectrochemical hydrogen generation

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00214a008· OSTI ID:6007400

This paper describes the behavior of electrode-bound redox material derived from the hydrolysis of the -Si(OEt)/sub 3/ groups of 1,1'-bis(((3-(triethoxysilyl)propyl)amino)carbonyl)cobaltocenium (I). Surfaces of the conventional electrodes SnO/sub 2/ and Pt derivatized with I have a reversible electrochemical response in H/sub 2/O/electrolyte; the E/sup 0/' is pH independent at -0.62 V vs. SCE. The photoelectrochemical behavior of p-type Si photocathodes derivatized with I reveals that the photoreduction of the cobaltocenium derivative can be effected at an electrode potential approx. 500 mV more positive than on metallic electrodes, consistent with the known behavior of p-type Si photocathodes. When polymer from I is deposited on p-type Si and subsequently coated with a small amount of Rh or Pd (approx. 10/sup -7/ mol/cm/sup 2/), the photoelectrochemical generation of H/sub 2/ is possible with 632.8-nm (approx. 15 mW/cm/sup 2/) radiation and efficiencies in the vicinity of 2%. The polymer derived from I is more optically transparent and more durable at negative potentials than redox polymers derived from vilogen monomers. Potential-step measurements and steady-state-current measurements for mediated redox processes show that the charge-transport rate for the polymer derived from I is about the same as for polymers from viologen monomers. 32 references, 8 figures.

Research Organization:
Massachusetts Institute of Technology, Cambridge
OSTI ID:
6007400
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:20; ISSN INOCA
Country of Publication:
United States
Language:
English