Observation of Ion Electrosorption in Metal–Organic Framework Micropores with In Operando Small-Angle Neutron Scattering
Abstract
A molecular-level understanding of transport and adsorption mechanisms of electrolyte ions in nanoporous electrodes under applied potentials is essential to control the performance of double-layer capacitors. In this paper, in operando small-angle neutron scattering (SANS) is used to directly detect ion movements into the nanopores of a conductive metal–organic framework (MOF) electrode under operating conditions. Neutron-scattering data reveals that most of the void space within the MOF is accessible to the solvent. Upon the addition of the electrolyte sodium triflate (NaOTf), the ions are adsorbed on the outer surface of the protrusions to form a 30 Å layer instead of entering the ionophobic pores in the absence of an applied charging potential. The changes in scattering intensity when potentials are applied suggests the ion rearrangement in the micropores following different mechanisms depending on the electrode polarization. These observations shed insights on ion electrosorption in electrode materials.
- Authors:
-
[1];
[1]
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Pennsylvania State Univ., University Park, PA (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1649585
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Volume: 132; Journal Issue: 24; Journal ID: ISSN 0044-8249
- Publisher:
- German Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; electrosorption; metal–organic frameworks; microporous materials; small-angle neutron scattering; supercapacitors
Citation Formats
He, Lilin, Yang, Luming, Dinca, Mircea, Zhang, Rui, and Li, Jianlin. Observation of Ion Electrosorption in Metal–Organic Framework Micropores with In Operando Small-Angle Neutron Scattering. United States: N. p., 2020.
Web. doi:10.1002/ange.201916201.
He, Lilin, Yang, Luming, Dinca, Mircea, Zhang, Rui, & Li, Jianlin. Observation of Ion Electrosorption in Metal–Organic Framework Micropores with In Operando Small-Angle Neutron Scattering. United States. https://doi.org/10.1002/ange.201916201
He, Lilin, Yang, Luming, Dinca, Mircea, Zhang, Rui, and Li, Jianlin. Wed .
"Observation of Ion Electrosorption in Metal–Organic Framework Micropores with In Operando Small-Angle Neutron Scattering". United States. https://doi.org/10.1002/ange.201916201. https://www.osti.gov/servlets/purl/1649585.
@article{osti_1649585,
title = {Observation of Ion Electrosorption in Metal–Organic Framework Micropores with In Operando Small-Angle Neutron Scattering},
author = {He, Lilin and Yang, Luming and Dinca, Mircea and Zhang, Rui and Li, Jianlin},
abstractNote = {A molecular-level understanding of transport and adsorption mechanisms of electrolyte ions in nanoporous electrodes under applied potentials is essential to control the performance of double-layer capacitors. In this paper, in operando small-angle neutron scattering (SANS) is used to directly detect ion movements into the nanopores of a conductive metal–organic framework (MOF) electrode under operating conditions. Neutron-scattering data reveals that most of the void space within the MOF is accessible to the solvent. Upon the addition of the electrolyte sodium triflate (NaOTf), the ions are adsorbed on the outer surface of the protrusions to form a 30 Å layer instead of entering the ionophobic pores in the absence of an applied charging potential. The changes in scattering intensity when potentials are applied suggests the ion rearrangement in the micropores following different mechanisms depending on the electrode polarization. These observations shed insights on ion electrosorption in electrode materials.},
doi = {10.1002/ange.201916201},
journal = {Angewandte Chemie},
number = 24,
volume = 132,
place = {United States},
year = {2020},
month = {3}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Computational Insights into Materials and Interfaces for Capacitive Energy Storage
journal, April 2017
- Zhan, Cheng; Lian, Cheng; Zhang, Yu
- Advanced Science, Vol. 4, Issue 7
Conductive MOF electrodes for stable supercapacitors with high areal capacitance
journal, October 2016
- Sheberla, Dennis; Bachman, John C.; Elias, Joseph S.
- Nature Materials, Vol. 16, Issue 2
Anomalous Increase in Carbon Capacitance at Pore Sizes Less Than 1 Nanometer
journal, September 2006
- Chmiola, J.
- Science, Vol. 313, Issue 5794
Accelerating charging dynamics in subnanometre pores
journal, March 2014
- Kondrat, Svyatoslav; Wu, Peng; Qiao, Rui
- Nature Materials, Vol. 13, Issue 4
Ion Dynamics in Porous Carbon Electrodes in Supercapacitors Using in Situ Infrared Spectroelectrochemistry
journal, August 2013
- Richey, Francis W.; Dyatkin, Boris; Gogotsi, Yury
- Journal of the American Chemical Society, Vol. 135, Issue 34
Tracking the structural arrangement of ions in carbon supercapacitor nanopores using in situ small-angle X-ray scattering
journal, January 2015
- Prehal, C.; Weingarth, D.; Perre, E.
- Energy & Environmental Science, Vol. 8, Issue 6
Investigation of morphology and hydrogen adsorption capacity of disordered carbons
journal, December 2014
- He, Lilin; Melnichenko, Yuri B.; Gallego, Nidia C.
- Carbon, Vol. 80
Real-Time NMR Studies of Electrochemical Double-Layer Capacitors
journal, December 2011
- Wang, Hao; Köster, Thomas K. -J.; Trease, Nicole M.
- Journal of the American Chemical Society, Vol. 133, Issue 48
Small-Angle Neutron Scattering for In Situ Probing of Ion Adsorption Inside Micropores
journal, February 2013
- Boukhalfa, S.; He, L.; Melnichenko, Y. B.
- Angewandte Chemie, Vol. 125, Issue 17
Oscillation of Capacitance inside Nanopores
journal, December 2011
- Jiang, De-en; Jin, Zhehui; Wu, Jianzhong
- Nano Letters, Vol. 11, Issue 12
Theoretical Model for Nanoporous Carbon Supercapacitors
journal, January 2008
- Huang, Jingsong; Sumpter, Bobby G.; Meunier, Vincent
- Angewandte Chemie, Vol. 120, Issue 3
Carbons and Electrolytes for Advanced Supercapacitors
journal, February 2014
- Béguin, François; Presser, Volker; Balducci, Andrea
- Advanced Materials, Vol. 26, Issue 14, p. 2219-2251
Capacitance in carbon pores of 0.7 to 15 nm: a regular pattern
journal, January 2011
- Centeno, Teresa A.; Sereda, Olha; Stoeckli, Fritz
- Physical Chemistry Chemical Physics, Vol. 13, Issue 27
Small angle scattering from porous mass fractal solids
journal, August 1996
- McMahon, Phillip; Snook, Ian
- The Journal of Chemical Physics, Vol. 105, Issue 6
High Electrical Conductivity in Ni 3 (2,3,6,7,10,11-hexaiminotriphenylene) 2 , a Semiconducting Metal–Organic Graphene Analogue
journal, April 2014
- Sheberla, Dennis; Sun, Lei; Blood-Forsythe, Martin A.
- Journal of the American Chemical Society, Vol. 136, Issue 25
Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR
journal, February 2013
- Deschamps, Michaël; Gilbert, Edouard; Azais, Philippe
- Nature Materials, Vol. 12, Issue 4
Efficient storage mechanisms for building better supercapacitors
journal, May 2016
- Salanne, M.; Rotenberg, B.; Naoi, K.
- Nature Energy, Vol. 1, Issue 6
Metal-organic frameworks and their derived materials for electrochemical energy storage and conversion: Promises and challenges
journal, December 2017
- Wu, Hao Bin; Lou, Xiong Wen (David)
- Science Advances, Vol. 3, Issue 12
New Perspectives on the Charging Mechanisms of Supercapacitors
journal, April 2016
- Forse, Alexander C.; Merlet, Céline; Griffin, John M.
- Journal of the American Chemical Society, Vol. 138, Issue 18
Exploring metal organic frameworks for energy storage in batteries and supercapacitors
journal, May 2017
- Xu, Guiyin; Nie, Ping; Dou, Hui
- Materials Today, Vol. 20, Issue 4
Charge storage mechanism in nanoporous carbons and its consequence for electrical double layer capacitors
journal, June 2010
- Simon, P.; Gogotsi, Y.
- Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1923, p. 3457-3467
Application of a quartz-crystal microbalance to measure ionic fluxes in microporous carbons for energy storage
journal, October 2009
- Levi, Mikhael D.; Salitra, Grigory; Levy, Naomi
- Nature Materials, Vol. 8, Issue 11
Small-angle scattering from porous solids with fractal geometry
journal, August 1986
- Mildner, D. F. R.; Hall, P. L.
- Journal of Physics D: Applied Physics, Vol. 19, Issue 8
Characterization and Analysis of Porosity and Pore Structures
journal, January 2015
- Anovitz, Lawrence M.; Cole, David R.
- Reviews in Mineralogy and Geochemistry, Vol. 80, Issue 1
Selective Charging Behavior in an Ionic Mixture Electrolyte-Supercapacitor System for Higher Energy and Power
journal, December 2017
- Wang, Xuehang; Mehandzhiyski, Aleksandar Yordanov; Arstad, Bjørnar
- Journal of the American Chemical Society, Vol. 139, Issue 51
On the mechanism of microporous carbon supercapacitors
journal, March 2018
- Eftekhari, Ali
- Materials Today Chemistry, Vol. 7
The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013
- Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
- Science, Vol. 341, Issue 6149, p. 1230444-1230444
Supercapacitor Capacitance Exhibits Oscillatory Behavior as a Function of Nanopore Size
journal, October 2011
- Feng, Guang; Cummings, Peter T.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 22
Relation between the Ion Size and Pore Size for an Electric Double-Layer Capacitor
journal, March 2008
- Largeot, Celine; Portet, Cristelle; Chmiola, John
- Journal of the American Chemical Society, Vol. 130, Issue 9
Small-Angle Neutron Scattering for In Situ Probing of Ion Adsorption Inside Micropores
journal, January 2013
- Boukhalfa, S.; He, L.; Melnichenko, Y. B.
- Angewandte Chemie International Edition, Vol. 52, Issue 17
Theoretical Model for Nanoporous Carbon Supercapacitors
journal, January 2008
- Huang, Jingsong; Sumpter, Bobby G.; Meunier, Vincent
- Angewandte Chemie International Edition, Vol. 47, Issue 3
Effects of pore size and surface charge on Na ion storage in carbon nanopores
journal, January 2016
- Karatrantos, Argyrios; Cai, Qiong
- Physical Chemistry Chemical Physics, Vol. 18, Issue 44