Molecular Level Control of the Capacitance of Two-Dimensional Covalent Organic Frameworks: Role of Hydrogen Bonding in Energy Storage Materials

Suman Chandra; Debarati Roy Chowdhury; Matthew Addicoat; Thomas Heine; Amit Paul; Rahul Banerjee

doi:10.1021/acs.chemmater.6b04178

Molecular Level Control of the Capacitance of Two-Dimensional Covalent Organic Frameworks: Role of Hydrogen Bonding in Energy Storage Materials

Suman Chandra, Debarati Roy Chowdhury, Matthew Addicoat, Thomas Heine, Amit Paul, Rahul Banerjee

Department of Chemistry

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

236 Citations (Scopus)

Abstract

Two-dimensional redox-active covalent organic frameworks (COFs) are ideal materials for energy storage applications due to their high surface area, extended π conjugated structure, tunable pore size, and adjustable functionalities. Herein, we report the synthesis and supercapacitor application of two redox active COFs [TpPa-(OH)₂ and TpBD-(OH)₂] along with the role of their redox active functional groups for the enrichment of specific capacitance. Of these COFs, TpPa-(OH)₂ exhibited the highest specific capacitance of 416 F g^-1 at 0.5 A g^-1 current density in three electrode configuration while the highest specific capacitance was 214 F g^-1 at 0.2 A g^-1 current density in two electrode configuration. Superior specific capacitance was due to emergence of excellent pseudocapacitance by virtue of precise molecular level control over redox functionalities present in the COF backbone. This COF also demonstrated 66% capacitance retention after 10000 cycles along with 43% accessibility of the redox-active hydroquinone (H₂Q) moieties in three electrode configuration while the capacitance retention was 88% after 10000 cycles in two electrode configuration. Exceptionally high specific capacitance of TpPa-(OH)₂ was due to the reversible proton-coupled electron transfer (2H⁺/2e^-) of hydroquinone/benzoquinone (H₂Q/Q) moieties wherein H₂Q and Q had comparable chemical stabilities during redox cycling that originated from H-bonding, which was supported by calculated structures.

Original language	English
Pages (from-to)	2074-2080
Number of pages	7
Journal	Chemistry of Materials
Volume	29
Issue number	5
DOIs	https://doi.org/10.1021/acs.chemmater.6b04178
Publication status	Published - 2017 Mar 14

Bibliographical note

Funding Information:
S.C. and D.R.C. acknowledge UGC (New Delhi, India) and IISER Bhopal for SRF. R.B. acknowledges CSIR [CSC0122 and CSC0102] and DST (SR/S1/IC-22/2009, INT/SIN/P-05, and SR/NM/NS-1179/2012G) for funding. A.P. acknowledges financial support from the Department of Atomic Energy (DAE), India (Grant No. 2012/20/34/9/BRNS) and IISER Bhopal. We sincerely thank Chanderpratap Singh and Arunkumar M. for their assistance in performing electrochemical experiments and data analysis.

Publisher Copyright:
© 2017 American Chemical Society.

All Science Journal Classification (ASJC) codes

Chemistry(all)
Chemical Engineering(all)
Materials Chemistry

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10.1021/acs.chemmater.6b04178

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title = "Molecular Level Control of the Capacitance of Two-Dimensional Covalent Organic Frameworks: Role of Hydrogen Bonding in Energy Storage Materials",

abstract = "Two-dimensional redox-active covalent organic frameworks (COFs) are ideal materials for energy storage applications due to their high surface area, extended π conjugated structure, tunable pore size, and adjustable functionalities. Herein, we report the synthesis and supercapacitor application of two redox active COFs [TpPa-(OH)2 and TpBD-(OH)2] along with the role of their redox active functional groups for the enrichment of specific capacitance. Of these COFs, TpPa-(OH)2 exhibited the highest specific capacitance of 416 F g-1 at 0.5 A g-1 current density in three electrode configuration while the highest specific capacitance was 214 F g-1 at 0.2 A g-1 current density in two electrode configuration. Superior specific capacitance was due to emergence of excellent pseudocapacitance by virtue of precise molecular level control over redox functionalities present in the COF backbone. This COF also demonstrated 66% capacitance retention after 10000 cycles along with 43% accessibility of the redox-active hydroquinone (H2Q) moieties in three electrode configuration while the capacitance retention was 88% after 10000 cycles in two electrode configuration. Exceptionally high specific capacitance of TpPa-(OH)2 was due to the reversible proton-coupled electron transfer (2H+/2e-) of hydroquinone/benzoquinone (H2Q/Q) moieties wherein H2Q and Q had comparable chemical stabilities during redox cycling that originated from H-bonding, which was supported by calculated structures.",

author = "Suman Chandra and {Roy Chowdhury}, Debarati and Matthew Addicoat and Thomas Heine and Amit Paul and Rahul Banerjee",

note = "Funding Information: S.C. and D.R.C. acknowledge UGC (New Delhi, India) and IISER Bhopal for SRF. R.B. acknowledges CSIR [CSC0122 and CSC0102] and DST (SR/S1/IC-22/2009, INT/SIN/P-05, and SR/NM/NS-1179/2012G) for funding. A.P. acknowledges financial support from the Department of Atomic Energy (DAE), India (Grant No. 2012/20/34/9/BRNS) and IISER Bhopal. We sincerely thank Chanderpratap Singh and Arunkumar M. for their assistance in performing electrochemical experiments and data analysis. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

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doi = "10.1021/acs.chemmater.6b04178",

language = "English",

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AU - Addicoat, Matthew

AU - Heine, Thomas

AU - Paul, Amit

AU - Banerjee, Rahul

N1 - Funding Information: S.C. and D.R.C. acknowledge UGC (New Delhi, India) and IISER Bhopal for SRF. R.B. acknowledges CSIR [CSC0122 and CSC0102] and DST (SR/S1/IC-22/2009, INT/SIN/P-05, and SR/NM/NS-1179/2012G) for funding. A.P. acknowledges financial support from the Department of Atomic Energy (DAE), India (Grant No. 2012/20/34/9/BRNS) and IISER Bhopal. We sincerely thank Chanderpratap Singh and Arunkumar M. for their assistance in performing electrochemical experiments and data analysis. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/3/14

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N2 - Two-dimensional redox-active covalent organic frameworks (COFs) are ideal materials for energy storage applications due to their high surface area, extended π conjugated structure, tunable pore size, and adjustable functionalities. Herein, we report the synthesis and supercapacitor application of two redox active COFs [TpPa-(OH)2 and TpBD-(OH)2] along with the role of their redox active functional groups for the enrichment of specific capacitance. Of these COFs, TpPa-(OH)2 exhibited the highest specific capacitance of 416 F g-1 at 0.5 A g-1 current density in three electrode configuration while the highest specific capacitance was 214 F g-1 at 0.2 A g-1 current density in two electrode configuration. Superior specific capacitance was due to emergence of excellent pseudocapacitance by virtue of precise molecular level control over redox functionalities present in the COF backbone. This COF also demonstrated 66% capacitance retention after 10000 cycles along with 43% accessibility of the redox-active hydroquinone (H2Q) moieties in three electrode configuration while the capacitance retention was 88% after 10000 cycles in two electrode configuration. Exceptionally high specific capacitance of TpPa-(OH)2 was due to the reversible proton-coupled electron transfer (2H+/2e-) of hydroquinone/benzoquinone (H2Q/Q) moieties wherein H2Q and Q had comparable chemical stabilities during redox cycling that originated from H-bonding, which was supported by calculated structures.

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Molecular Level Control of the Capacitance of Two-Dimensional Covalent Organic Frameworks: Role of Hydrogen Bonding in Energy Storage Materials

Abstract

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