Insights into the electric double-layer capacitance of two-dimensional electrically conductive metal-organic frameworks

Jamie W. Gittins; Chloe J. Balhatchet; Yuan Chen; Cheng Liu; David G. Madden; Sylvia Britto; Matthias J. Golomb; Aron Walsh; David Fairen-Jimenez; Siân E. Dutton; Alexander C. Forse

doi:10.1039/d1ta04026j

Insights into the electric double-layer capacitance of two-dimensional electrically conductive metal-organic frameworks

Jamie W. Gittins, Chloe J. Balhatchet, Yuan Chen, Cheng Liu, David G. Madden, Sylvia Britto, Matthias J. Golomb, Aron Walsh, David Fairen-Jimenez, Siân E. Dutton, Alexander C. Forse

Department of Materials Science and Engineering

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

17 Citations (Scopus)

Abstract

Two-dimensional electrically conductive metal-organic frameworks (MOFs) have emerged as promising model electrodes for use in electric double-layer capacitors (EDLCs). However, a number of fundamental questions about the behaviour of this class of materials in EDLCs remain unanswered, including the effect of the identity of the metal node and organic linker molecule on capacitive performance, and the limitations of current conductive MOFs in these devices relative to traditional activated carbon electrode materials. Herein, we address both these questionsviaa detailed study of the capacitive performance of the framework Cu₃(HHTP)₂(HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) with an acetonitrile-based electrolyte, finding a specific capacitance of 110-114 F g⁻¹at current densities of 0.04-0.05 A g⁻¹and a modest rate capability. By directly comparing its performance with the previously reported analogue, Ni₃(HITP)₂(HITP = 2,3,6,7,10,11-hexaiminotriphenylene), we illustrate that capacitive performance is largely independent of the identity of the metal node and organic linker molecule in these nearly isostructural MOFs. Importantly, this result suggests that EDLC performance in general is uniquely defined by the 3D structure of the electrodes and the electrolyte, a significant finding not demonstrated using traditional electrode materials. Finally, we probe the limitations of Cu₃(HHTP)₂in EDLCs, finding a limited stable double-layer voltage window of 1 V and only a modest capacitance retention of 81% over 30 000 cycles, both significantly lower than state-of-the-art porous carbons. These important insights will aid the design of future conductive MOFs with greater EDLC performances.

Original language	English
Pages (from-to)	16006-16015
Number of pages	10
Journal	Journal of Materials Chemistry A
Volume	9
Issue number	29
DOIs	https://doi.org/10.1039/d1ta04026j
Publication status	Published - 2021 Aug 7

Bibliographical note

Funding Information:
J. W. G. acknowledges the School of the Physical Sciences (Cambridge) for the award of an Oppenheimer Studentship. This work was supported by the Faraday Institution (FIRG017),viaa Faraday Undergraduate Summer Experience (FUSE) internship to Y. C. The work at Imperial (A. W.) was supported by a Royal Society University Research Fellowship (UF100278) and benefited from the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). M. J. G. thanks the Royal Society for PhD funding. D. F.-J. thanks the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (NanoMOFdeli), ERC-2016-COG 726380, and Innovate UK (104384). S. E. D. acknowledges funding from the Winton Programme for the Physics of Sustainability (Cambridge). A. C. F. thanks the Isaac Newton Trust of Trinity College (Cambridge) for a Research Grant (G101121), and the Yusuf Hamied Department of Chemistry (Cambridge) for the award of a BP Next Generation Fellowship. This work was also supported by a UKRI Future Leaders Fellowship to A. C. F. (MR/T043024/1). We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. We thank Dr Phillip Milner and Dr Lewis Owen for collaboration and stimulating discussion over the course of the project. We thank Dr Chris Truscott and Dr Nigel Howard for collaboration and technical expertise.

Funding Information:
J. W. G. acknowledges the School of the Physical Sciences (Cambridge) for the award of an Oppenheimer Studentship. This work was supported by the Faraday Institution (FIRG017), via a Faraday Undergraduate Summer Experience (FUSE) internship to Y. C. The work at Imperial (A. W.) was supported by a Royal Society University Research Fellowship (UF100278) and beneted from the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). M. J. G. thanks the Royal Society for PhD funding. D. F.-J. thanks the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (NanoMOFdeli), ERC-2016-COG 726380, and Innovate UK (104384). S. E. D. acknowledges funding from the Winton Programme for the Physics of Sustainability (Cambridge). A. C. F. thanks the Isaac Newton Trust of Trinity College (Cambridge) for a Research Grant (G101121), and the Yusuf Hamied Department of Chemistry (Cambridge) for the award of a BP Next Generation Fellowship. This work was also supported by a UKRI Future Leaders Fellowship to A. C. F. (MR/T043024/1). We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. We thank Dr Phillip Milner and Dr Lewis Owen for collaboration and stimulating discussion over the course of the project. We thank Dr Chris Truscott and Dr Nigel Howard for collaboration and technical expertise.

Publisher Copyright:
© The Royal Society of Chemistry 2021.

All Science Journal Classification (ASJC) codes

Chemistry(all)
Renewable Energy, Sustainability and the Environment
Materials Science(all)

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1039/d1ta04026j

Cite this

Gittins, J. W., Balhatchet, C. J., Chen, Y., Liu, C., Madden, D. G., Britto, S., Golomb, M. J., Walsh, A., Fairen-Jimenez, D., Dutton, S. E., & Forse, A. C. (2021). Insights into the electric double-layer capacitance of two-dimensional electrically conductive metal-organic frameworks. Journal of Materials Chemistry A, 9(29), 16006-16015. https://doi.org/10.1039/d1ta04026j

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title = "Insights into the electric double-layer capacitance of two-dimensional electrically conductive metal-organic frameworks",

abstract = "Two-dimensional electrically conductive metal-organic frameworks (MOFs) have emerged as promising model electrodes for use in electric double-layer capacitors (EDLCs). However, a number of fundamental questions about the behaviour of this class of materials in EDLCs remain unanswered, including the effect of the identity of the metal node and organic linker molecule on capacitive performance, and the limitations of current conductive MOFs in these devices relative to traditional activated carbon electrode materials. Herein, we address both these questionsviaa detailed study of the capacitive performance of the framework Cu3(HHTP)2(HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) with an acetonitrile-based electrolyte, finding a specific capacitance of 110-114 F g−1at current densities of 0.04-0.05 A g−1and a modest rate capability. By directly comparing its performance with the previously reported analogue, Ni3(HITP)2(HITP = 2,3,6,7,10,11-hexaiminotriphenylene), we illustrate that capacitive performance is largely independent of the identity of the metal node and organic linker molecule in these nearly isostructural MOFs. Importantly, this result suggests that EDLC performance in general is uniquely defined by the 3D structure of the electrodes and the electrolyte, a significant finding not demonstrated using traditional electrode materials. Finally, we probe the limitations of Cu3(HHTP)2in EDLCs, finding a limited stable double-layer voltage window of 1 V and only a modest capacitance retention of 81% over 30 000 cycles, both significantly lower than state-of-the-art porous carbons. These important insights will aid the design of future conductive MOFs with greater EDLC performances.",

author = "Gittins, {Jamie W.} and Balhatchet, {Chloe J.} and Yuan Chen and Cheng Liu and Madden, {David G.} and Sylvia Britto and Golomb, {Matthias J.} and Aron Walsh and David Fairen-Jimenez and Dutton, {Si{\^a}n E.} and Forse, {Alexander C.}",

note = "Funding Information: J. W. G. acknowledges the School of the Physical Sciences (Cambridge) for the award of an Oppenheimer Studentship. This work was supported by the Faraday Institution (FIRG017),viaa Faraday Undergraduate Summer Experience (FUSE) internship to Y. C. The work at Imperial (A. W.) was supported by a Royal Society University Research Fellowship (UF100278) and benefited from the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). M. J. G. thanks the Royal Society for PhD funding. D. F.-J. thanks the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (NanoMOFdeli), ERC-2016-COG 726380, and Innovate UK (104384). S. E. D. acknowledges funding from the Winton Programme for the Physics of Sustainability (Cambridge). A. C. F. thanks the Isaac Newton Trust of Trinity College (Cambridge) for a Research Grant (G101121), and the Yusuf Hamied Department of Chemistry (Cambridge) for the award of a BP Next Generation Fellowship. This work was also supported by a UKRI Future Leaders Fellowship to A. C. F. (MR/T043024/1). We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. We thank Dr Phillip Milner and Dr Lewis Owen for collaboration and stimulating discussion over the course of the project. We thank Dr Chris Truscott and Dr Nigel Howard for collaboration and technical expertise. Funding Information: J. W. G. acknowledges the School of the Physical Sciences (Cambridge) for the award of an Oppenheimer Studentship. This work was supported by the Faraday Institution (FIRG017), via a Faraday Undergraduate Summer Experience (FUSE) internship to Y. C. The work at Imperial (A. W.) was supported by a Royal Society University Research Fellowship (UF100278) and beneted from the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). M. J. G. thanks the Royal Society for PhD funding. D. F.-J. thanks the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (NanoMOFdeli), ERC-2016-COG 726380, and Innovate UK (104384). S. E. D. acknowledges funding from the Winton Programme for the Physics of Sustainability (Cambridge). A. C. F. thanks the Isaac Newton Trust of Trinity College (Cambridge) for a Research Grant (G101121), and the Yusuf Hamied Department of Chemistry (Cambridge) for the award of a BP Next Generation Fellowship. This work was also supported by a UKRI Future Leaders Fellowship to A. C. F. (MR/T043024/1). We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. We thank Dr Phillip Milner and Dr Lewis Owen for collaboration and stimulating discussion over the course of the project. We thank Dr Chris Truscott and Dr Nigel Howard for collaboration and technical expertise. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2021.",

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doi = "10.1039/d1ta04026j",

language = "English",

volume = "9",

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T1 - Insights into the electric double-layer capacitance of two-dimensional electrically conductive metal-organic frameworks

AU - Gittins, Jamie W.

AU - Balhatchet, Chloe J.

AU - Chen, Yuan

AU - Liu, Cheng

AU - Madden, David G.

AU - Britto, Sylvia

AU - Golomb, Matthias J.

AU - Walsh, Aron

AU - Fairen-Jimenez, David

AU - Dutton, Siân E.

AU - Forse, Alexander C.

N1 - Funding Information: J. W. G. acknowledges the School of the Physical Sciences (Cambridge) for the award of an Oppenheimer Studentship. This work was supported by the Faraday Institution (FIRG017),viaa Faraday Undergraduate Summer Experience (FUSE) internship to Y. C. The work at Imperial (A. W.) was supported by a Royal Society University Research Fellowship (UF100278) and benefited from the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). M. J. G. thanks the Royal Society for PhD funding. D. F.-J. thanks the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (NanoMOFdeli), ERC-2016-COG 726380, and Innovate UK (104384). S. E. D. acknowledges funding from the Winton Programme for the Physics of Sustainability (Cambridge). A. C. F. thanks the Isaac Newton Trust of Trinity College (Cambridge) for a Research Grant (G101121), and the Yusuf Hamied Department of Chemistry (Cambridge) for the award of a BP Next Generation Fellowship. This work was also supported by a UKRI Future Leaders Fellowship to A. C. F. (MR/T043024/1). We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. We thank Dr Phillip Milner and Dr Lewis Owen for collaboration and stimulating discussion over the course of the project. We thank Dr Chris Truscott and Dr Nigel Howard for collaboration and technical expertise. Funding Information: J. W. G. acknowledges the School of the Physical Sciences (Cambridge) for the award of an Oppenheimer Studentship. This work was supported by the Faraday Institution (FIRG017), via a Faraday Undergraduate Summer Experience (FUSE) internship to Y. C. The work at Imperial (A. W.) was supported by a Royal Society University Research Fellowship (UF100278) and beneted from the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). M. J. G. thanks the Royal Society for PhD funding. D. F.-J. thanks the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (NanoMOFdeli), ERC-2016-COG 726380, and Innovate UK (104384). S. E. D. acknowledges funding from the Winton Programme for the Physics of Sustainability (Cambridge). A. C. F. thanks the Isaac Newton Trust of Trinity College (Cambridge) for a Research Grant (G101121), and the Yusuf Hamied Department of Chemistry (Cambridge) for the award of a BP Next Generation Fellowship. This work was also supported by a UKRI Future Leaders Fellowship to A. C. F. (MR/T043024/1). We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. We thank Dr Phillip Milner and Dr Lewis Owen for collaboration and stimulating discussion over the course of the project. We thank Dr Chris Truscott and Dr Nigel Howard for collaboration and technical expertise. Publisher Copyright: © The Royal Society of Chemistry 2021.

PY - 2021/8/7

Y1 - 2021/8/7

N2 - Two-dimensional electrically conductive metal-organic frameworks (MOFs) have emerged as promising model electrodes for use in electric double-layer capacitors (EDLCs). However, a number of fundamental questions about the behaviour of this class of materials in EDLCs remain unanswered, including the effect of the identity of the metal node and organic linker molecule on capacitive performance, and the limitations of current conductive MOFs in these devices relative to traditional activated carbon electrode materials. Herein, we address both these questionsviaa detailed study of the capacitive performance of the framework Cu3(HHTP)2(HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) with an acetonitrile-based electrolyte, finding a specific capacitance of 110-114 F g−1at current densities of 0.04-0.05 A g−1and a modest rate capability. By directly comparing its performance with the previously reported analogue, Ni3(HITP)2(HITP = 2,3,6,7,10,11-hexaiminotriphenylene), we illustrate that capacitive performance is largely independent of the identity of the metal node and organic linker molecule in these nearly isostructural MOFs. Importantly, this result suggests that EDLC performance in general is uniquely defined by the 3D structure of the electrodes and the electrolyte, a significant finding not demonstrated using traditional electrode materials. Finally, we probe the limitations of Cu3(HHTP)2in EDLCs, finding a limited stable double-layer voltage window of 1 V and only a modest capacitance retention of 81% over 30 000 cycles, both significantly lower than state-of-the-art porous carbons. These important insights will aid the design of future conductive MOFs with greater EDLC performances.

AB - Two-dimensional electrically conductive metal-organic frameworks (MOFs) have emerged as promising model electrodes for use in electric double-layer capacitors (EDLCs). However, a number of fundamental questions about the behaviour of this class of materials in EDLCs remain unanswered, including the effect of the identity of the metal node and organic linker molecule on capacitive performance, and the limitations of current conductive MOFs in these devices relative to traditional activated carbon electrode materials. Herein, we address both these questionsviaa detailed study of the capacitive performance of the framework Cu3(HHTP)2(HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) with an acetonitrile-based electrolyte, finding a specific capacitance of 110-114 F g−1at current densities of 0.04-0.05 A g−1and a modest rate capability. By directly comparing its performance with the previously reported analogue, Ni3(HITP)2(HITP = 2,3,6,7,10,11-hexaiminotriphenylene), we illustrate that capacitive performance is largely independent of the identity of the metal node and organic linker molecule in these nearly isostructural MOFs. Importantly, this result suggests that EDLC performance in general is uniquely defined by the 3D structure of the electrodes and the electrolyte, a significant finding not demonstrated using traditional electrode materials. Finally, we probe the limitations of Cu3(HHTP)2in EDLCs, finding a limited stable double-layer voltage window of 1 V and only a modest capacitance retention of 81% over 30 000 cycles, both significantly lower than state-of-the-art porous carbons. These important insights will aid the design of future conductive MOFs with greater EDLC performances.

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Insights into the electric double-layer capacitance of two-dimensional electrically conductive metal-organic frameworks

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