title: Electron transfer kinetics in CdS nanorod-[FeFe]-hydrogenase complexes and implications for photochemical H₂ generation.
abstract: This Article describes the electron transfer (ET) kinetics in complexes of CdS nanorods (CdS NRs) and [FeFe]-hydrogenase I from Clostridium acetobutylicum (CaI). In the presence of an electron donor, these complexes produce H2 photochemically with quantum yields of up to 20%. Kinetics of ET from CdS NRs to CaI play a critical role in the overall photochemical reactivity, as the quantum efficiency of ET defines the upper limit on the quantum yield of H2 generation. We investigated the competitiveness of ET with the electron relaxation pathways in CdS NRs by directly measuring the rate and quantum efficiency of ET from photoexcited CdS NRs to CaI using transient absorption spectroscopy. This technique is uniquely suited to decouple CdS→CaI ET from the processes occurring in the enzyme during H2 production. We found that the ET rate constant (k(ET)) and the electron relaxation rate constant in CdS NRs (k(CdS)) were comparable, with values of 10(7) s(-1), resulting in a quantum efficiency of ET of 42% for complexes with the average CaI:CdS NR molar ratio of 1:1. Given the direct competition between the two processes that occur with similar rates, we propose that gains in efficiencies of H2 production could be achieved by increasing k(ET) and/or decreasing k(CdS) through structural modifications of the nanocrystals. When catalytically inactive forms of CaI were used in CdS-CaI complexes, ET behavior was akin to that observed with active CaI, demonstrating that electron injection occurs at a distal iron-sulfur cluster and is followed by transport through a series of accessory iron-sulfur clusters to the active site of CaI. Using insights from this time-resolved spectroscopic study, we discuss the intricate kinetic pathways involved in photochemical H2 generation in CdS-CaI complexes, and we examine how the relationship between the electron injection rate and the other kinetic processes relates to the overall H2 production efficiency.
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado Boulder , Boulder, Colorado 80309, United States.
authors.forename: Molly B
authors.initials: MB
authors.lastname: Wilker
authors.forename: Katherine E
authors.initials: KE
authors.lastname: Shinopoulos
authors.forename: Katherine A
authors.initials: KA
authors.lastname: Brown
authors.forename: David W
authors.initials: DW
authors.lastname: Mulder
authors.forename: Paul W
authors.initials: PW
authors.lastname: King
authors.forename: Gordana
authors.initials: G
authors.lastname: Dukovic
mesh_terms: D019187:Cadmium Compounds / Q000737:chemistry* / Q000378:metabolism; D046969:Clostridium acetobutylicum / Q000201:enzymology; D004579:Electron Transport; D006859:Hydrogen / Q000737:chemistry* / Q000378:metabolism; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism; D007700:Kinetics; D043942:Nanotubes / Q000737:chemistry*; D055668:Photochemical Processes; D013440:Sulfides / Q000737:chemistry* / Q000378:metabolism
chemical_list: D019187:Cadmium Compounds; D007506:Iron-Sulfur Proteins; D013440:Sulfides; C034939:cadmium sulfide; D006859:Hydrogen; C118830:iron hydrogenase; D006864:Hydrogenase