TY - JOUR
T1 - Interplay between Light Flux, Quantum Efficiency, and Turnover Frequency in Molecular-Modified Photoelectrosynthetic Assemblies
AU - Wadsworth, Brian L.
AU - Beiler, Anna M.
AU - Khusnutdinova, Diana
AU - Reyes Cruz, Edgar A.
AU - Moore, Gary F.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/10/9
Y1 - 2019/10/9
N2 - We report on the interplay between light absorption, charge transfer, and catalytic activity at molecular-catalyst-modified semiconductor liquid junctions. Factors limiting the overall photoelectrosynthetic transformations are presented in terms of distinct regions of experimental polarization curves, where each region is related to the fraction of surface-immobilized catalysts present in their activated form under varying intensities of simulated solar illumination. The kinetics associated with these regions are described using steady-state or pre-equilibrium approximations yielding rate laws similar in form to those applied in studies involving classic enzymatic reactions and Michaelis-Menten-type kinetic analysis. However, in the case of photoelectrosynthetic constructs, both photons and electrons serve as reagents for producing activated catalysts. This work forges a link between kinetic models describing biological assemblies and emerging molecular-based technologies for solar energy conversion, providing a conceptual framework for extracting kinetic benchmarking parameters currently not possible to establish.
AB - We report on the interplay between light absorption, charge transfer, and catalytic activity at molecular-catalyst-modified semiconductor liquid junctions. Factors limiting the overall photoelectrosynthetic transformations are presented in terms of distinct regions of experimental polarization curves, where each region is related to the fraction of surface-immobilized catalysts present in their activated form under varying intensities of simulated solar illumination. The kinetics associated with these regions are described using steady-state or pre-equilibrium approximations yielding rate laws similar in form to those applied in studies involving classic enzymatic reactions and Michaelis-Menten-type kinetic analysis. However, in the case of photoelectrosynthetic constructs, both photons and electrons serve as reagents for producing activated catalysts. This work forges a link between kinetic models describing biological assemblies and emerging molecular-based technologies for solar energy conversion, providing a conceptual framework for extracting kinetic benchmarking parameters currently not possible to establish.
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U2 - 10.1021/jacs.9b07295
DO - 10.1021/jacs.9b07295
M3 - Article
C2 - 31461276
AN - SCOPUS:85073086035
SN - 0002-7863
VL - 141
SP - 15932
EP - 15941
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 40
ER -