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Oxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors

Electrochemical reactions represent essential processes in fundamental chemistry that foster a wide range of applications. Although most electrochemical reactions in bulk substances can be well described by the classical Marcus-Gerischer charge transfer theory, the realistic reaction character and m...

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Autores principales: Xu, Ning, Shi, Li, Pei, Xudong, Zhang, Weiyang, Chen, Jian, Han, Zheng, Samorì, Paolo, Wang, Jinlan, Wang, Peng, Shi, Yi, Li, Songlin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10333350/
https://www.ncbi.nlm.nih.gov/pubmed/37429836
http://dx.doi.org/10.1038/s41467-023-39781-y
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author Xu, Ning
Shi, Li
Pei, Xudong
Zhang, Weiyang
Chen, Jian
Han, Zheng
Samorì, Paolo
Wang, Jinlan
Wang, Peng
Shi, Yi
Li, Songlin
author_facet Xu, Ning
Shi, Li
Pei, Xudong
Zhang, Weiyang
Chen, Jian
Han, Zheng
Samorì, Paolo
Wang, Jinlan
Wang, Peng
Shi, Yi
Li, Songlin
author_sort Xu, Ning
collection PubMed
description Electrochemical reactions represent essential processes in fundamental chemistry that foster a wide range of applications. Although most electrochemical reactions in bulk substances can be well described by the classical Marcus-Gerischer charge transfer theory, the realistic reaction character and mechanism in dimensionally confined systems remain unknown. Here, we report the multiparametric survey on the kinetics of lateral photooxidation in structurally identical WS(2) and MoS(2) monolayers, where electrochemical oxidation occurs at the atomically thin monolayer edges. The oxidation rate is correlated quantitatively with various crystallographic and environmental parameters, including the density of reactive sites, humidity, temperature, and illumination fluence. In particular, we observe distinctive reaction barriers of 1.4 and 0.9 eV for the two structurally identical semiconductors and uncover an unusual non-Marcusian charge transfer mechanism in these dimensionally confined monolayers due to the limit in reactant supplies. A scenario of band bending is proposed to explain the discrepancy in reaction barriers. These results add important knowledge into the fundamental electrochemical reaction theory in low-dimensional systems.
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spelling pubmed-103333502023-07-12 Oxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors Xu, Ning Shi, Li Pei, Xudong Zhang, Weiyang Chen, Jian Han, Zheng Samorì, Paolo Wang, Jinlan Wang, Peng Shi, Yi Li, Songlin Nat Commun Article Electrochemical reactions represent essential processes in fundamental chemistry that foster a wide range of applications. Although most electrochemical reactions in bulk substances can be well described by the classical Marcus-Gerischer charge transfer theory, the realistic reaction character and mechanism in dimensionally confined systems remain unknown. Here, we report the multiparametric survey on the kinetics of lateral photooxidation in structurally identical WS(2) and MoS(2) monolayers, where electrochemical oxidation occurs at the atomically thin monolayer edges. The oxidation rate is correlated quantitatively with various crystallographic and environmental parameters, including the density of reactive sites, humidity, temperature, and illumination fluence. In particular, we observe distinctive reaction barriers of 1.4 and 0.9 eV for the two structurally identical semiconductors and uncover an unusual non-Marcusian charge transfer mechanism in these dimensionally confined monolayers due to the limit in reactant supplies. A scenario of band bending is proposed to explain the discrepancy in reaction barriers. These results add important knowledge into the fundamental electrochemical reaction theory in low-dimensional systems. Nature Publishing Group UK 2023-07-10 /pmc/articles/PMC10333350/ /pubmed/37429836 http://dx.doi.org/10.1038/s41467-023-39781-y Text en © Crown 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Xu, Ning
Shi, Li
Pei, Xudong
Zhang, Weiyang
Chen, Jian
Han, Zheng
Samorì, Paolo
Wang, Jinlan
Wang, Peng
Shi, Yi
Li, Songlin
Oxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors
title Oxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors
title_full Oxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors
title_fullStr Oxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors
title_full_unstemmed Oxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors
title_short Oxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors
title_sort oxidation kinetics and non-marcusian charge transfer in dimensionally confined semiconductors
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10333350/
https://www.ncbi.nlm.nih.gov/pubmed/37429836
http://dx.doi.org/10.1038/s41467-023-39781-y
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