Chemically derivatized n-type silicon photoelectrodes. Stabilization to surface corrosion in aqueous electrolyte solutions and mediation of oxidation reactions by surface-attached electroactive ferrocene reagents

Bolts, Jeffrey M.; Bocarsly, Andrew Bruce; Palazzotto, M. C.; Walton, Erick G.; Lewis, Nathan S.; Wrighton, Mark S.

doi:10.1021/ja00500a004

Cited by 153 publications

(81 citation statements)

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“…1 These data correspond to curves given in Fig. 7 Electrodes and Surface Derivatization with I. Electrodes were prepared by using procedures and materials described previously (2,24). Typical photoelectrode areas ranged from 5 to 15 mm2.…”

Section: Replacement Of Br-by Ptcl02-in Surfaces Treated Withsupporting

confidence: 55%

Synthesis and characterization of a photosensitive interface for hydrogen generation: Chemically modified p-type semiconducting silicon photocathodes

Bookbinder

Bruce

Dominey

et al. 1980

Proc. Natl. Acad. Sci. U.S.A.

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results in improved kinetics for H2 evolution from the p-type semiconductor. Kinetics for H2 evolution was previously identified as a major problem at p-semiconductor aqueous electrolyte interfaces (1-3). Surface modification of electrodes has recently been an active area of research, and examples of electrocatalysts are emerging (4). To produce an efficient photosensitive interface from which to evolve H2 we take advantage of the light absorption and charge separating properties of a semiconductor (5-8). But additionally we employ surface modification to achieve good H2 evolution kinetics. A p-type semiconductor should serve as a photocathode, because the minority carrier is the electron, e-. As indicated in Fig. 1, the photoexcited electron becomes available at the interface as a reducing equivalent with reducing power no greater than the bottom of the conduction band at the interface ECB. Efficient solar-driven electrolysis requires: (i) use of a photocathode having a small Eg, 1-2 eV; (ii) optimization of the product of Ev and photocurrent; and (iii) a durable interface. Experiments show that Ev can be significant for small Eg photocathodes, but the kinetics for H2 evolution are so poor that little if any efficiency can be realized for p-type Si (Eg =

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Section: Replacement Of Br-by Ptcl02-in Surfaces Treated Withsupporting

confidence: 55%

Synthesis and characterization of a photosensitive interface for hydrogen generation: Chemically modified p-type semiconducting silicon photocathodes

Bookbinder

Bruce

Dominey

et al. 1980

Proc. Natl. Acad. Sci. U.S.A.

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“…The initial product is an oil from which a yellow solid can be extracted. A ferrocenophane cleavage reaction would be expected to proceed according to reaction [3]. The isolated product has a mass spectrum with a parent peak of mle 378 and fragmentation pattern expected for both 7 and 8.…”

Section: Resultsmentioning

confidence: 99%

“…The reaction of ferrocenophanes such as l a with an electrode surface is a useful means of attaching a ferrocenyl group (1)(2)(3)(4). In the case of l a and l b one Si-C bond is believed to be cleaved during attachment so that the final product, 2a = 3a, is as shown in reaction [I].…”

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confidence: 99%

The synthesis and structure of

Butler¹,

Cullen²,

Rettig³

1987

Can. J. Chem.

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“…48,49 To provide a solution to these problems, various groups used polymer layers with electron mediator groups and catalytic metal particles to modify the semiconductor surfaces. [50][51][52][53][54][55][56][57][58][59] Recently, we briefly demonstrated that an organic monolayer with viologen terminal group bonded on hydrogen-terminated n-and p-type Si(111) surfaces via a Si-C bond acted as electron transfer mediator and improved the electrochemical hydrogen evolution reaction rate in the dark and under illumination, respectively. 60 Nakato and colleagues also showed that the stability of the Si photoelectrode for I -oxidation was improved by Pt/alkyl monolayer modification.…”

Section: Introductionmentioning

confidence: 99%

Construction of Mono- and Multimolecular Layers with Electron Transfer Mediation Function and Catalytic Activity for Hydrogen Evolution on a Hydrogen-Terminated Si(111) Surface via Si−C Bond

2008

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Organic molecular layers with viologen moiety (i.e., electron acceptor) were constructed on a hydrogenterminated Si(111) surface via a Si-C bond. Electrochemical characteristics after each synthetic process were measured, and electron mediation capability of the viologen moiety was demonstrated. Incorporation of platinum particles on the viologen-modified Si(111) surface was proved to enhance the hydrogen evolution reaction (HER) rate. Further improvement of the HER rate was achieved by the modification with viologen/ Pt multilayers. Photoelectrochemical HER at the p-Si(111) electrode was also significantly accelerated by the modification with mono-and multiviologen/Pt layers.

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Chemically derivatized n-type silicon photoelectrodes. Stabilization to surface corrosion in aqueous electrolyte solutions and mediation of oxidation reactions by surface-attached electroactive ferrocene reagents

Cited by 153 publications

References 1 publication

Synthesis and characterization of a photosensitive interface for hydrogen generation: Chemically modified p-type semiconducting silicon photocathodes

Synthesis and characterization of a photosensitive interface for hydrogen generation: Chemically modified p-type semiconducting silicon photocathodes

The synthesis and structure of

Construction of Mono- and Multimolecular Layers with Electron Transfer Mediation Function and Catalytic Activity for Hydrogen Evolution on a Hydrogen-Terminated Si(111) Surface via Si−C Bond

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