Covalently Linked Polyoxometalate-Polypyrrole Hybrids: Electropolymer Materials with Dual-Mode Enhanced Capacitive Energy Storage

Sarah A. Alshehri; Ahmed Al-Yasari; Frank Marken; John Fielden

doi:10.1021/acs.macromol.0c02354

Covalently Linked Polyoxometalate-Polypyrrole Hybrids: Electropolymer Materials with Dual-Mode Enhanced Capacitive Energy Storage

Sarah A. Alshehri, Ahmed Al-Yasari, Frank Marken, John Fielden

Research output: Contribution to journal › Article › peer-review

14 Citations (SciVal)

Abstract

Lindqvist-type polyoxometalates (POMs) derivatized with pyrrole (Py) via an aryl-imido linkage [Mo6O18NPhPy]2- (1) and [Mo6O18NPhCCPhPy]2- (2) undergo coelectropolymerization with pyrrole, producing the first electropolymer films with covalently attached POM "molecular metal oxides". X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray (EDX) elemental analyses indicate that the loadings of POM achieved are far higher than in conventional, noncovalent inclusion films, and covalent attachment prevents loss of POM on initial reduction cycles. Cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge measurements together indicate that the POMs enhance the specific capacitance (up to 5×) and decrease the charge-transfer resistance of the films by both modifying the behavior of the polypyrrole (PPy) film and introducing a substantial additional faradaic contribution through the POM redox processes. Increasing the length of the POM-PPy linker improves both capacitance and stability, with PPy-2 retaining 95% of its initial capacitance over 1200 cycles.

Original language	English
Pages (from-to)	11120-11129
Number of pages	10
Journal	Macromolecules
Volume	53
Issue number	24
Early online date	10 Dec 2020
DOIs	https://doi.org/10.1021/acs.macromol.0c02354
Publication status	Published - 22 Dec 2020

Bibliographical note

Funding Information:
We thank Professor Chris Pickett and Dr. Saad Ibrahim of the University of East Anglia for helpful discussions on electropolymerization; Dr. Michael Ward, Dr. Benjamin Johnson, and Dr. Kellye Curtis of LENNF (University of Leeds) for electron microscopy and XPS measurements; and Mr. Bertrand Leze of the University of East Anglia for electron microscopy measurements. A.A.Y. thanks the Iraqi Government for financial support via the Ministry of Higher Education and Scientific Research (MOHER), University of Kerbala, for a postdoctoral fellowship; and S.A.A. thanks Princess Nourah bint Abdulrahman University for a Ph.D. scholarship. This work was also supported by EU FP7 (Marie Curie IOF POMHYDCAT contract 254339 to J.F.), EPSRC (EP/M00452X/1), and the University of East Anglia.

Publisher Copyright:
©

Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/acs.macromol.0c02354Licence: CC BY

Cite this

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title = "Covalently Linked Polyoxometalate-Polypyrrole Hybrids: Electropolymer Materials with Dual-Mode Enhanced Capacitive Energy Storage",

abstract = "Lindqvist-type polyoxometalates (POMs) derivatized with pyrrole (Py) via an aryl-imido linkage [Mo6O18NPhPy]2- (1) and [Mo6O18NPhCCPhPy]2- (2) undergo coelectropolymerization with pyrrole, producing the first electropolymer films with covalently attached POM {"}molecular metal oxides{"}. X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray (EDX) elemental analyses indicate that the loadings of POM achieved are far higher than in conventional, noncovalent inclusion films, and covalent attachment prevents loss of POM on initial reduction cycles. Cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge measurements together indicate that the POMs enhance the specific capacitance (up to 5×) and decrease the charge-transfer resistance of the films by both modifying the behavior of the polypyrrole (PPy) film and introducing a substantial additional faradaic contribution through the POM redox processes. Increasing the length of the POM-PPy linker improves both capacitance and stability, with PPy-2 retaining 95% of its initial capacitance over 1200 cycles. ",

author = "Alshehri, {Sarah A.} and Ahmed Al-Yasari and Frank Marken and John Fielden",

note = "Funding Information: We thank Professor Chris Pickett and Dr. Saad Ibrahim of the University of East Anglia for helpful discussions on electropolymerization; Dr. Michael Ward, Dr. Benjamin Johnson, and Dr. Kellye Curtis of LENNF (University of Leeds) for electron microscopy and XPS measurements; and Mr. Bertrand Leze of the University of East Anglia for electron microscopy measurements. A.A.Y. thanks the Iraqi Government for financial support via the Ministry of Higher Education and Scientific Research (MOHER), University of Kerbala, for a postdoctoral fellowship; and S.A.A. thanks Princess Nourah bint Abdulrahman University for a Ph.D. scholarship. This work was also supported by EU FP7 (Marie Curie IOF POMHYDCAT contract 254339 to J.F.), EPSRC (EP/M00452X/1), and the University of East Anglia. Publisher Copyright: {\textcopyright} Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

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doi = "10.1021/acs.macromol.0c02354",

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AU - Al-Yasari, Ahmed

AU - Marken, Frank

AU - Fielden, John

N1 - Funding Information: We thank Professor Chris Pickett and Dr. Saad Ibrahim of the University of East Anglia for helpful discussions on electropolymerization; Dr. Michael Ward, Dr. Benjamin Johnson, and Dr. Kellye Curtis of LENNF (University of Leeds) for electron microscopy and XPS measurements; and Mr. Bertrand Leze of the University of East Anglia for electron microscopy measurements. A.A.Y. thanks the Iraqi Government for financial support via the Ministry of Higher Education and Scientific Research (MOHER), University of Kerbala, for a postdoctoral fellowship; and S.A.A. thanks Princess Nourah bint Abdulrahman University for a Ph.D. scholarship. This work was also supported by EU FP7 (Marie Curie IOF POMHYDCAT contract 254339 to J.F.), EPSRC (EP/M00452X/1), and the University of East Anglia. Publisher Copyright: © Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2020/12/22

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N2 - Lindqvist-type polyoxometalates (POMs) derivatized with pyrrole (Py) via an aryl-imido linkage [Mo6O18NPhPy]2- (1) and [Mo6O18NPhCCPhPy]2- (2) undergo coelectropolymerization with pyrrole, producing the first electropolymer films with covalently attached POM "molecular metal oxides". X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray (EDX) elemental analyses indicate that the loadings of POM achieved are far higher than in conventional, noncovalent inclusion films, and covalent attachment prevents loss of POM on initial reduction cycles. Cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge measurements together indicate that the POMs enhance the specific capacitance (up to 5×) and decrease the charge-transfer resistance of the films by both modifying the behavior of the polypyrrole (PPy) film and introducing a substantial additional faradaic contribution through the POM redox processes. Increasing the length of the POM-PPy linker improves both capacitance and stability, with PPy-2 retaining 95% of its initial capacitance over 1200 cycles.

AB - Lindqvist-type polyoxometalates (POMs) derivatized with pyrrole (Py) via an aryl-imido linkage [Mo6O18NPhPy]2- (1) and [Mo6O18NPhCCPhPy]2- (2) undergo coelectropolymerization with pyrrole, producing the first electropolymer films with covalently attached POM "molecular metal oxides". X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray (EDX) elemental analyses indicate that the loadings of POM achieved are far higher than in conventional, noncovalent inclusion films, and covalent attachment prevents loss of POM on initial reduction cycles. Cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge measurements together indicate that the POMs enhance the specific capacitance (up to 5×) and decrease the charge-transfer resistance of the films by both modifying the behavior of the polypyrrole (PPy) film and introducing a substantial additional faradaic contribution through the POM redox processes. Increasing the length of the POM-PPy linker improves both capacitance and stability, with PPy-2 retaining 95% of its initial capacitance over 1200 cycles.

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IS - 24

ER -

Covalently Linked Polyoxometalate-Polypyrrole Hybrids: Electropolymer Materials with Dual-Mode Enhanced Capacitive Energy Storage

Abstract

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Covalently Linked Polyoxometalate-Polypyrrole Hybrids: Electropolymer Materials with Dual-Mode Enhanced Capacitive Energy Storage

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

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Autolab Potentiostat & FRA32M module

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