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Title: Single Nanoflake Photoelectrochemistry Reveals Intrananoflake Doping Heterogeneity That Explains Ensemble-Level Photoelectrochemical Behavior

Abstract

Transition metal dichalcogenide (TMD) nanoflake thin films are attractive electrode materials for photoelectrochemical (PEC) solar energy conversion and sensing applications, but their photocurrent quantum yields are generally lower than those of bulk TMD electrodes. The poor PEC performance has been primarily attributed to enhanced charge carrier recombination at exposed defect and edge sites introduced by the exfoliation process. In this work, a single nanoflake PEC approach reveals how an alternative effect, doping heterogeneity, limits ensemble-level PEC performance. Photocurrent mapping and local photocurrent–potential (i–E) measurements of MoS2 nanoflakes exfoliated from naturally occurring bulk crystals revealed the presence of n- and ptype domains within the same nanoflake. Interestingly, the n- and p-type domains in the natural MoS2 nanoflakes were equally efficient for iodide oxidation and tri-iodide reduction (IQE values exceed 80%). At the single domain-level, the natural MoS2 nanoflakes were nearly as efficient as nanoflakes exfoliated from synthetic n-type MoS2 crystals. Single domain-level i–E measurements explain why natural MoS2 nanoflakes exhibit an n-type to p-type photocurrent switching effect in ensemble-level measurements: the n- and p-type diode currents from individual domains oppose each other upon illuminating the entire nanoflake, resulting in zero photocurrent at the switching potential. The doping heterogeneity effect is likelymore » due to nonideal stoichiometry, where p-type domains are S-rich according to XPS measurements. Although this doping heterogeneity effect limits photoanode or photocathode performance, these findings open the possibility to synthesize efficient TMD nanoflake photocatalysts with well-defined lateral p- and n-type domains for enhanced charge separation.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]
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  1. Colorado State Univ., Fort Collins, CO (United States)
Publication Date:
Research Org.:
Colorado State Univ., Fort Collins, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1830754
Grant/Contract Number:  
SC0021189
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 14; Journal Issue: 20; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 2D materials; single nanoflake; photocurrent mapping; n-type MoS2; p-type MoS2

Citation Formats

Erdewyk, Michael Van, and Sambur, Justin B. Single Nanoflake Photoelectrochemistry Reveals Intrananoflake Doping Heterogeneity That Explains Ensemble-Level Photoelectrochemical Behavior. United States: N. p., 2021. Web. doi:10.1021/acsami.1c14928.
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Erdewyk, Michael Van, & Sambur, Justin B. Single Nanoflake Photoelectrochemistry Reveals Intrananoflake Doping Heterogeneity That Explains Ensemble-Level Photoelectrochemical Behavior. United States. https://doi.org/10.1021/acsami.1c14928
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Erdewyk, Michael Van, and Sambur, Justin B. Mon . "Single Nanoflake Photoelectrochemistry Reveals Intrananoflake Doping Heterogeneity That Explains Ensemble-Level Photoelectrochemical Behavior". United States. https://doi.org/10.1021/acsami.1c14928. https://www.osti.gov/servlets/purl/1830754.
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@article{osti_1830754,
title = {Single Nanoflake Photoelectrochemistry Reveals Intrananoflake Doping Heterogeneity That Explains Ensemble-Level Photoelectrochemical Behavior},
author = {Erdewyk, Michael Van and Sambur, Justin B.},
abstractNote = {Transition metal dichalcogenide (TMD) nanoflake thin films are attractive electrode materials for photoelectrochemical (PEC) solar energy conversion and sensing applications, but their photocurrent quantum yields are generally lower than those of bulk TMD electrodes. The poor PEC performance has been primarily attributed to enhanced charge carrier recombination at exposed defect and edge sites introduced by the exfoliation process. In this work, a single nanoflake PEC approach reveals how an alternative effect, doping heterogeneity, limits ensemble-level PEC performance. Photocurrent mapping and local photocurrent–potential (i–E) measurements of MoS2 nanoflakes exfoliated from naturally occurring bulk crystals revealed the presence of n- and ptype domains within the same nanoflake. Interestingly, the n- and p-type domains in the natural MoS2 nanoflakes were equally efficient for iodide oxidation and tri-iodide reduction (IQE values exceed 80%). At the single domain-level, the natural MoS2 nanoflakes were nearly as efficient as nanoflakes exfoliated from synthetic n-type MoS2 crystals. Single domain-level i–E measurements explain why natural MoS2 nanoflakes exhibit an n-type to p-type photocurrent switching effect in ensemble-level measurements: the n- and p-type diode currents from individual domains oppose each other upon illuminating the entire nanoflake, resulting in zero photocurrent at the switching potential. The doping heterogeneity effect is likely due to nonideal stoichiometry, where p-type domains are S-rich according to XPS measurements. Although this doping heterogeneity effect limits photoanode or photocathode performance, these findings open the possibility to synthesize efficient TMD nanoflake photocatalysts with well-defined lateral p- and n-type domains for enhanced charge separation.},
doi = {10.1021/acsami.1c14928},
journal = {ACS Applied Materials and Interfaces},
number = 20,
volume = 14,
place = {United States},
year = {Mon Nov 01 00:00:00 EDT 2021},
month = {Mon Nov 01 00:00:00 EDT 2021}
}
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https://doi.org/10.1021/acsami.1c14928
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