Diameter Dependent Electron Transfer Kinetics in Semiconductor–Enzyme Complexes Katherine A. Brown Qing Song David W. Mulder Paul W. King 10.1021/nn504561v.s001 https://acs.figshare.com/articles/journal_contribution/Diameter_Dependent_Electron_Transfer_Kinetics_in_Semiconductor_Enzyme_Complexes/2241412 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 (<i>k</i><sub>ET</sub>) 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 <i>k</i><sub>ET</sub> values that were insensitive to diameter, despite a decrease in the free energy for photoexcited ET (Δ<i>G</i><sub>ET</sub>) 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 <i>k</i><sub>ET</sub> and H<sub>2</sub> production for CdTe–CaI complexes are not strictly controlled by Δ<i>G</i><sub>ET</sub> and that other factors must be considered. 2014-10-28 00:00:00 kET CaI surface coverage H 2 production Diameter Dependent Electron Transfer Kinetics diameter TOF complex CdTe quantum dots ET kinetics