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Title: Correlated Single-Molecule Reaction Imaging and Photocurrent Measurements Reveal Underlying Rate Processes in Photoelectrochemical Water Splitting

Abstract

Understanding reaction processes at the semiconductor/electrolyte interface is critical to developing (photo)electrochemical energy conversion systems. For the water oxidation reaction at a photoanode in a solar water splitting cell, there are multiple reaction steps that produce surface adsorbed reaction intermediates, such as OH• and H2O2. Little is known about how the reaction intermediate surface concentrations evolve during the water oxidation reaction. Here we use single-molecule fluorescence microscopy to track the time-dependent surface concentration of Ti-OH• species on TiO2 photoanodes under chopped light illumination. We correlate the reaction intermediate surface concentration with the net rate of photoelectrochemical water oxidation (i.e., the photocurrent). The reaction intermediate dynamics follow different time scales in its temporal evolution from the photocurrent dynamics. By fitting the temporal evolutions of Ti-OH• species and photocurrent over a range of light on/off conditions and applied potentials, we observed that the rate constants for interfacial hole transfer and O-O bond formation depend on the applied potential under illumination. The variation in the rate constants could be attributed to the presence of surface states and/or a change in the chemical nature of Ti-OH• species on the photoanode surface. Our findings provide insight into water oxidation kinetics under intermittent solar irradiation conditions.

Authors:
ORCiD logo; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Cornell Univ., Ithaca, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1503942
Alternate Identifier(s):
OSTI ID: 1610770; OSTI ID: 1658607
Grant/Contract Number:  
SC0004911
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society Journal Volume: 166 Journal Issue: 5; Journal ID: ISSN 0013-4651
Publisher:
IOP Publishing - The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Electrochemistry; Materials Science

Citation Formats

Sambur, Justin B., Shepherd, Douglas P., Hesari, Mahdi, Van Erdewyk, Michael, Choudhary, Eric, and Chen, Peng. Correlated Single-Molecule Reaction Imaging and Photocurrent Measurements Reveal Underlying Rate Processes in Photoelectrochemical Water Splitting. United States: N. p., 2019. Web. doi:10.1149/2.040195jes.
Sambur, Justin B., Shepherd, Douglas P., Hesari, Mahdi, Van Erdewyk, Michael, Choudhary, Eric, & Chen, Peng. Correlated Single-Molecule Reaction Imaging and Photocurrent Measurements Reveal Underlying Rate Processes in Photoelectrochemical Water Splitting. United States. doi:10.1149/2.040195jes.
Sambur, Justin B., Shepherd, Douglas P., Hesari, Mahdi, Van Erdewyk, Michael, Choudhary, Eric, and Chen, Peng. Fri . "Correlated Single-Molecule Reaction Imaging and Photocurrent Measurements Reveal Underlying Rate Processes in Photoelectrochemical Water Splitting". United States. doi:10.1149/2.040195jes.
@article{osti_1503942,
title = {Correlated Single-Molecule Reaction Imaging and Photocurrent Measurements Reveal Underlying Rate Processes in Photoelectrochemical Water Splitting},
author = {Sambur, Justin B. and Shepherd, Douglas P. and Hesari, Mahdi and Van Erdewyk, Michael and Choudhary, Eric and Chen, Peng},
abstractNote = {Understanding reaction processes at the semiconductor/electrolyte interface is critical to developing (photo)electrochemical energy conversion systems. For the water oxidation reaction at a photoanode in a solar water splitting cell, there are multiple reaction steps that produce surface adsorbed reaction intermediates, such as OH• and H2O2. Little is known about how the reaction intermediate surface concentrations evolve during the water oxidation reaction. Here we use single-molecule fluorescence microscopy to track the time-dependent surface concentration of Ti-OH• species on TiO2 photoanodes under chopped light illumination. We correlate the reaction intermediate surface concentration with the net rate of photoelectrochemical water oxidation (i.e., the photocurrent). The reaction intermediate dynamics follow different time scales in its temporal evolution from the photocurrent dynamics. By fitting the temporal evolutions of Ti-OH• species and photocurrent over a range of light on/off conditions and applied potentials, we observed that the rate constants for interfacial hole transfer and O-O bond formation depend on the applied potential under illumination. The variation in the rate constants could be attributed to the presence of surface states and/or a change in the chemical nature of Ti-OH• species on the photoanode surface. Our findings provide insight into water oxidation kinetics under intermittent solar irradiation conditions.},
doi = {10.1149/2.040195jes},
journal = {Journal of the Electrochemical Society},
number = 5,
volume = 166,
place = {United States},
year = {2019},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1149/2.040195jes

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