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Title: Photoelectrochemical NADH Regeneration using Pt-Modified p -GaAs Semiconductor Electrodes

Cofactor regeneration in enzymatic reductions is crucial for the application of enzymes to both biological and energy-related catalysis. Specifically, regenerating NADH from NAD + is of great interest, and using electrochemistry to achieve this end is considered a promising option. Here in this paper, we report the first example of photoelectrochemical NADH regeneration at the illuminated (λ >600 nm), metal-modified p-type semiconductor electrode Pt/p-GaAs. Although bare p-GaAs electrodes produce only enzymatically inactive NAD 2, NADH was produced at the illuminated Pt-modified p-GaAs surface. At low overpotential (–0.75 V vs. Ag/AgCl), Pt/p-GaAs exhibited a seven-fold greater Faradaic efficiency for the formation of NADH than Pt alone, with reduced competition from the hydrogen evolution reaction. Improved Faradaic efficiency and low overpotential suggest the possible utility of Pt/p-GaAs in energy-related NADH-dependent enzymatic processes.
Authors:
 [1] ;  [1] ; ORCiD logo [1]
  1. Princeton Univ., NJ (United States). Frick Lab., Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0002133; DGE-1148900
Type:
Accepted Manuscript
Journal Name:
ChemElectroChem
Additional Journal Information:
Journal Volume: 4; Journal Issue: 5; Journal ID: ISSN 2196-0216
Publisher:
ChemPubSoc Europe
Research Org:
Princeton Univ., NJ (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES; photoelectrochemistry; p-GaAs photocathode; NAD/NADH; CO2 utilization; Cofactor Regeneration; GaAs; Semiconductor
OSTI Identifier:
1418016
Alternate Identifier(s):
OSTI ID: 1401746

Stufano, Paolo, Paris, Aubrey R., and Bocarsly, Andrew. Photoelectrochemical NADH Regeneration using Pt-Modified p -GaAs Semiconductor Electrodes. United States: N. p., Web. doi:10.1002/celc.201600488.
Stufano, Paolo, Paris, Aubrey R., & Bocarsly, Andrew. Photoelectrochemical NADH Regeneration using Pt-Modified p -GaAs Semiconductor Electrodes. United States. doi:10.1002/celc.201600488.
Stufano, Paolo, Paris, Aubrey R., and Bocarsly, Andrew. 2017. "Photoelectrochemical NADH Regeneration using Pt-Modified p -GaAs Semiconductor Electrodes". United States. doi:10.1002/celc.201600488. https://www.osti.gov/servlets/purl/1418016.
@article{osti_1418016,
title = {Photoelectrochemical NADH Regeneration using Pt-Modified p -GaAs Semiconductor Electrodes},
author = {Stufano, Paolo and Paris, Aubrey R. and Bocarsly, Andrew},
abstractNote = {Cofactor regeneration in enzymatic reductions is crucial for the application of enzymes to both biological and energy-related catalysis. Specifically, regenerating NADH from NAD+ is of great interest, and using electrochemistry to achieve this end is considered a promising option. Here in this paper, we report the first example of photoelectrochemical NADH regeneration at the illuminated (λ >600 nm), metal-modified p-type semiconductor electrode Pt/p-GaAs. Although bare p-GaAs electrodes produce only enzymatically inactive NAD2, NADH was produced at the illuminated Pt-modified p-GaAs surface. At low overpotential (–0.75 V vs. Ag/AgCl), Pt/p-GaAs exhibited a seven-fold greater Faradaic efficiency for the formation of NADH than Pt alone, with reduced competition from the hydrogen evolution reaction. Improved Faradaic efficiency and low overpotential suggest the possible utility of Pt/p-GaAs in energy-related NADH-dependent enzymatic processes.},
doi = {10.1002/celc.201600488},
journal = {ChemElectroChem},
number = 5,
volume = 4,
place = {United States},
year = {2017},
month = {2}
}

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