title: Diameter dependent electron transfer kinetics in semiconductor-enzyme complexes.
abstract: Excited state electron transfer (ET) is a fundamental step for the catalytic conversion of solar energy into chemical energy. To understand the properties controlling ET between photoexcited nanoparticles and catalysts, the ET kinetics were measured for solution-phase complexes of CdTe quantum dots and Clostridium acetobutylicum [FeFe]-hydrogenase I (CaI) using time-resolved photoluminescence spectroscopy. Over a 2.0-3.5 nm diameter range of CdTe nanoparticles, the observed ET rate (kET) was sensitive to CaI concentration. To account for diameter effects on CaI binding, a Langmuir isotherm and two geometric binding models were created to estimate maximal CaI affinities and coverages at saturating concentrations. Normalizing the ET kinetics to CaI surface coverage for each CdTe diameter led to k(ET) values that were insensitive to diameter, despite a decrease in the free energy for photoexcited ET (ΔGET) with increasing diameter. The turnover frequency (TOF) of CaI in CdTe-CaI complexes was measured at several molar ratios. Normalization for diameter-dependent changes in CaI coverage showed an increase in TOF with diameter. These results suggest that k(ET) and H2 production for CdTe-CaI complexes are not strictly controlled by ΔG(ET) and that other factors must be considered.
authors.affiliation: Biosciences Center, National Renewable Energy Laboratory , Golden, Colorado 80401, United States.
authors.forename: Katherine A
authors.initials: KA
authors.lastname: Brown
authors.forename: Qing
authors.initials: Q
authors.lastname: Song
authors.forename: David W
authors.initials: DW
authors.lastname: Mulder
authors.forename: Paul W
authors.initials: PW
authors.lastname: King
mesh_terms: D004579:Electron Transport; D004798:Enzymes / Q000737:chemistry*; D007700:Kinetics; D012666:Semiconductors
chemical_list: D004798:Enzymes
keywords: binding complex; biohybrid; hydrogen; interfacial electron-transfer; nanoparticle; photochemical