Decoupling Kinetics and Thermodynamics of Interfacial Catalysis at a Chemically Modified Black Silicon Semiconductor Photoelectrode

Hanna, Caitlin M.; Pekarek, Ryan T.; Miller, Elisa M.; Yang, Jenny Y.; Neale, Nathan R.

doi:10.1021/acsenergylett.0c00714

Title: Decoupling Kinetics and Thermodynamics of Interfacial Catalysis at a Chemically Modified Black Silicon Semiconductor Photoelectrode

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Abstract

Understanding 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 p–p interactions with a series of aromatic molecules covalently attached to the surface. Furthermore, 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.

Authors:

^[1]; Pekarek, Ryan T. ^[2];

^[2];

^[1];

^[2]

Univ. of California, Irvine, CA (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemistry and Nanosciences Center

Publication Date:: Mon May 11 00:00:00 EDT 2020

Research Org.:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Division of Chemical Sciences, Geosciences, and Biosciences, Solar Photochemistry Program

OSTI Identifier:: 1660098

Report Number(s):: NREL/JA-5900-77356
Journal ID: ISSN 2380-8195; MainId:26302;UUID:28fb0e98-ad38-433f-87f4-8a283cf3cd94;MainAdminID:14088

Grant/Contract Number:: AC36-08GO28308; SC0014664; SC0012150; 0000243266

Resource Type:: Accepted Manuscript

Journal Name:: ACS Energy Letters

Additional Journal Information:: Journal Volume: 5; Journal Issue: 6; Journal ID: ISSN 2380-8195

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis; catalysts; electrodes; kinetics; solar-photochemistry; thermodynamic properties

Citation Formats


                    Hanna, Caitlin M., Pekarek, Ryan T., Miller, Elisa M., Yang, Jenny Y., and Neale, Nathan R. Decoupling Kinetics and Thermodynamics of Interfacial Catalysis at a Chemically Modified Black Silicon Semiconductor Photoelectrode.  United States: N. p., 2020. 
Web.  doi:10.1021/acsenergylett.0c00714.

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                    Hanna, Caitlin M., Pekarek, Ryan T., Miller, Elisa M., Yang, Jenny Y., & Neale, Nathan R. Decoupling Kinetics and Thermodynamics of Interfacial Catalysis at a Chemically Modified Black Silicon Semiconductor Photoelectrode.  United States.  https://doi.org/10.1021/acsenergylett.0c00714

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                    Hanna, Caitlin M., Pekarek, Ryan T., Miller, Elisa M., Yang, Jenny Y., and Neale, Nathan R. Mon .  
"Decoupling Kinetics and Thermodynamics of Interfacial Catalysis at a Chemically Modified Black Silicon Semiconductor Photoelectrode".  United States.  https://doi.org/10.1021/acsenergylett.0c00714.  https://www.osti.gov/servlets/purl/1660098.

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@article{osti_1660098,

  title        = {Decoupling Kinetics and Thermodynamics of Interfacial Catalysis at a Chemically Modified Black Silicon Semiconductor Photoelectrode},

  author       = {Hanna, Caitlin M. and Pekarek, Ryan T. and Miller, Elisa M. and Yang, Jenny Y. and Neale, Nathan R.},

  abstractNote = {Understanding 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 p–p interactions with a series of aromatic molecules covalently attached to the surface. Furthermore, 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.},

  doi          = {10.1021/acsenergylett.0c00714},

  journal      = {ACS Energy Letters},

  number       = 6,

  volume       = 5,

  place        = {United States},

  year         = {Mon May 11 00:00:00 EDT 2020},

  month        = {Mon May 11 00:00:00 EDT 2020}

}

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