Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 122, Issue 1, Pages 741-750Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.7b07229
Keywords
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Funding
- U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering [DE-SC0010334]
- National Science Foundation Graduate Research Fellowships [DGE 1144083]
- Kolenkow-Reitz Fellowship from Carleton College
- U.S. Department of Energy [DE-AC36-08-GO28308]
- U.S. Department of Energy (DOE) [DE-SC0010334] Funding Source: U.S. Department of Energy (DOE)
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Complexes of CdS nanorods and [FeFe] hydrogenase I from Clostridium acetobutylicum have been shown to photochemically produce H-2. This study examines the role of the ligands that passivate the nanocrystal surfaces in the electron transfer from photoexcited CdS to hydrogenase and the H-2 generation that follows. We functionalized CdS nanorods with a series of mercaptocarboxylate surface-capping ligands of varying lengths and measured their photoexcited electron relaxation by transient absorption (TA) spectroscopy before and after hydrogenase adsorption. Rate constants for electron transfer from the nanocrystals to the enzyme, extracted by modeling of TA kinetics, decrease exponentially with ligand length, suggesting that the ligand layer acts as a barrier to charge transfer and controls the degree of electronic coupling. Relative light-driven H-2 production efficiencies follow the relative quantum efficiencies of electron transfer, revealing the critical role of surface-capping ligands in determining the photochemical activity of these nanocrystal enzyme complexes. Our results suggest that the H-2 production in this system could be maximized with a choice of a surface-capping ligand that decreases the distance between the nanocrystal surface and the electron injection site of the enzyme.
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