nz0c00714_si_001.pdf (1.14 MB)
Decoupling Kinetics and Thermodynamics of Interfacial Catalysis at a Chemically Modified Black Silicon Semiconductor Photoelectrode
journal contribution
posted on 2020-05-19, 17:04 authored by Caitlin
M. Hanna, Ryan T. Pekarek, Elisa M. Miller, Jenny Y. Yang, Nathan R. NealeUnderstanding
the interplay between the kinetics of interfacial
catalytic reactions and the thermodynamics of an underlying semiconductor
electrode is imperative for rational construction of efficient photoelectrocatalytic
systems. Current understanding of the thermodynamic effects of molecular
catalyst attachment to semiconductor electrodes is limited. We report
the immobilization of a molecular cobalt bis(benzenedithiolate) proton
reduction catalyst onto nanoporous black silicon (b-Si) electrodes
through π–π interactions with a series of aromatic
molecules covalently attached to the surface. Intensity-modulated
high-frequency resistivity and linear sweep voltammetry measurements
are used to show that the kinetics of proton reduction are decoupled
from the thermodynamic properties of the underlying b-Si photoelectrode.
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proton reductionkineticcatalyst attachmentphotoelectrocatalytic systemssweep voltammetry measurementsb-Si photoelectrodeCurrent understandingmolecules covalentlyChemically Modified Black Silicon Semiconductor Photoelectrodesemiconductor electrodesInterfacial CatalysisDecoupling Kineticssemiconductor electrode
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