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Title: Characterization of Photochemical Processes for H2 Production by CdS Nanorod-[FeFe] Hydrogenase Complexes

Abstract

We have developed complexes of CdS nanorods capped with 3-mercaptopropionic acid (MPA) and Clostridium acetobutylicum [FeFe]-hydrogenase I (CaI) that photocatalyze reduction of H{sup +} to H{sub 2} at a CaI turnover frequency of 380-900 s{sup -1} and photon conversion efficiencies of up to 20% under illumination at 405 nm. In this paper, we focus on the compositional and mechanistic aspects of CdS:CaI complexes that control the photochemical conversion of solar energy into H{sub 2}. Self-assembly of CdS with CaI was driven by electrostatics, demonstrated as the inhibition of ferredoxin-mediated H{sub 2} evolution by CaI. Production of H{sub 2} by CdS:CaI was observed only under illumination and only in the presence of a sacrificial donor. We explored the effects of the CdS:CaI molar ratio, sacrificial donor concentration, and light intensity on photocatalytic H{sub 2} production, which were interpreted on the basis of contributions to electron transfer, hole transfer, or rate of photon absorption, respectively. Each parameter was found to have pronounced effects on the CdS:CaI photocatalytic activity. Specifically, we found that under 405 nm light at an intensity equivalent to total AM 1.5 solar flux, H{sub 2} production was limited by the rate of photon absorption ({approx}1 ms{sup -1}) and notmore » by the turnover of CaI. Complexes were capable of H{sub 2} production for up to 4 h with a total turnover number of 106 before photocatalytic activity was lost. This loss correlated with inactivation of CaI, resulting from the photo-oxidation of the CdS capping ligand MPA.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Division of Chemical Sciences, Geosciences, and Biosciences and Biological and Environmental Research Program
OSTI Identifier:
1043784
Report Number(s):
NREL/JA-2700-53672
Journal ID: ISSN 0002-7863; JACSAT; TRN: US201213%%462
DOE Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 134; Journal Issue: 12; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES; 77 NANOSCIENCE AND NANOTECHNOLOGY; ABSORPTION; CLOSTRIDIUM ACETOBUTYLICUM; ELECTRON TRANSFER; ELECTROSTATICS; HYDROGENASES; ILLUMINANCE; INACTIVATION; PHOTONS; PRODUCTION; SOLAR ENERGY; SOLAR FLUX; characterization; photochemical; hydrogenase; water oxidation; renewable fuel technologies

Citation Formats

Brown, Katherine A., Wilker, Molly B., Boehm, Marko, Dukovic, Gordana, and King, Paul W. Characterization of Photochemical Processes for H2 Production by CdS Nanorod-[FeFe] Hydrogenase Complexes. United States: N. p., 2012. Web. doi:10.1021/ja2116348.
Brown, Katherine A., Wilker, Molly B., Boehm, Marko, Dukovic, Gordana, & King, Paul W. Characterization of Photochemical Processes for H2 Production by CdS Nanorod-[FeFe] Hydrogenase Complexes. United States. https://doi.org/10.1021/ja2116348
Brown, Katherine A., Wilker, Molly B., Boehm, Marko, Dukovic, Gordana, and King, Paul W. 2012. "Characterization of Photochemical Processes for H2 Production by CdS Nanorod-[FeFe] Hydrogenase Complexes". United States. https://doi.org/10.1021/ja2116348.
@article{osti_1043784,
title = {Characterization of Photochemical Processes for H2 Production by CdS Nanorod-[FeFe] Hydrogenase Complexes},
author = {Brown, Katherine A. and Wilker, Molly B. and Boehm, Marko and Dukovic, Gordana and King, Paul W.},
abstractNote = {We have developed complexes of CdS nanorods capped with 3-mercaptopropionic acid (MPA) and Clostridium acetobutylicum [FeFe]-hydrogenase I (CaI) that photocatalyze reduction of H{sup +} to H{sub 2} at a CaI turnover frequency of 380-900 s{sup -1} and photon conversion efficiencies of up to 20% under illumination at 405 nm. In this paper, we focus on the compositional and mechanistic aspects of CdS:CaI complexes that control the photochemical conversion of solar energy into H{sub 2}. Self-assembly of CdS with CaI was driven by electrostatics, demonstrated as the inhibition of ferredoxin-mediated H{sub 2} evolution by CaI. Production of H{sub 2} by CdS:CaI was observed only under illumination and only in the presence of a sacrificial donor. We explored the effects of the CdS:CaI molar ratio, sacrificial donor concentration, and light intensity on photocatalytic H{sub 2} production, which were interpreted on the basis of contributions to electron transfer, hole transfer, or rate of photon absorption, respectively. Each parameter was found to have pronounced effects on the CdS:CaI photocatalytic activity. Specifically, we found that under 405 nm light at an intensity equivalent to total AM 1.5 solar flux, H{sub 2} production was limited by the rate of photon absorption ({approx}1 ms{sup -1}) and not by the turnover of CaI. Complexes were capable of H{sub 2} production for up to 4 h with a total turnover number of 106 before photocatalytic activity was lost. This loss correlated with inactivation of CaI, resulting from the photo-oxidation of the CdS capping ligand MPA.},
doi = {10.1021/ja2116348},
url = {https://www.osti.gov/biblio/1043784}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 12,
volume = 134,
place = {United States},
year = {2012},
month = {3}
}