Modulation of CO2 adsorption in novel pillar-layered MOFs based on carboxylate–pyrazole flexible linker
Abstract
Metal–organic frameworks (MOFs) have attracted significant attention as sorbents due to their high surface area, tunable pore volume and pore size, coordinatively unsaturated metal sites, and ability to install desired functional groups by post-synthetic modification. Herein, we report three new MOFs with pillar–paddlewheel structures that have been synthesized solvothermally from the mixture of the carboxylate–pyrazole flexible linker (H2L), 4,4-bipyridine (BPY)/triethylenediamine (DABCO), and Zn(II)/Cu(II) ions. The MOFs obtained, namely [ZnII(L)BPY], [CuII(L)BPY], and [CuII(L)DABCO], exhibit two-fold interpenetration and dinuclear paddle–wheel nodes. The Zn(II)/Cu(II) cations are coordinated by two equatorial L linkers that result in two-dimensional sheets which in turn are pillared by BPY or DABCO in the perpendicular direction to obtain a neutral three-dimensional framework that shows one-dimensional square channels. The three pillar-layered MOFs were characterized as microporous materials showing high crystalline stability after activation at 120 °C and CO2 adsorption. All MOFs contain uncoordinated Lewis basic pyrazole nitrogen atoms in the framework which have an affinity toward CO2 and hence could potentially serve as CO2 adsorption material. The CO2 uptake capacity was initially enhanced by replacing Zn with Cu and then replacing the pillar, going from BPY to DABCO. Overall, all the MOFs exhibit low isosteric heat (Qst) of adsorption whichmore »
- Authors:
-
[2];
[2];
[2];
- Pontificia Univ. Católica de Chile, Santiago (Chile); ANID -Millennium Science Initiative Program- Millennium Nuclei on Catalytic Process Towards Sustainable Chemistry (CSC) (Chile); Northwestern Univ., Evanston, IL (United States)
- Northwestern Univ., Evanston, IL (United States)
- Univ. Autónoma de Chile, Santiago (Chile)
- Pontificia Univ. Católica de Chile, Santiago (Chile); ANID -Millennium Science Initiative Program- Millennium Nuclei on Catalytic Process Towards Sustainable Chemistry (CSC) (Chile)
- Publication Date:
- Research Org.:
- Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1849841
- Alternate Identifier(s):
- OSTI ID: 1768689
- Grant/Contract Number:
- FG02-08ER15967
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 50; Journal Issue: 8; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Lancheros, Andrés, Goswami, Subhadip, Mian, Mohammad Rasel, Zhang, Xuan, Zarate, Ximena, Schott, Eduardo, Farha, Omar K., and Hupp, Joseph T. Modulation of CO2 adsorption in novel pillar-layered MOFs based on carboxylate–pyrazole flexible linker. United States: N. p., 2021.
Web. doi:10.1039/d0dt03166f.
Lancheros, Andrés, Goswami, Subhadip, Mian, Mohammad Rasel, Zhang, Xuan, Zarate, Ximena, Schott, Eduardo, Farha, Omar K., & Hupp, Joseph T. Modulation of CO2 adsorption in novel pillar-layered MOFs based on carboxylate–pyrazole flexible linker. United States. https://doi.org/10.1039/d0dt03166f
Lancheros, Andrés, Goswami, Subhadip, Mian, Mohammad Rasel, Zhang, Xuan, Zarate, Ximena, Schott, Eduardo, Farha, Omar K., and Hupp, Joseph T. Thu .
"Modulation of CO2 adsorption in novel pillar-layered MOFs based on carboxylate–pyrazole flexible linker". United States. https://doi.org/10.1039/d0dt03166f. https://www.osti.gov/servlets/purl/1849841.
@article{osti_1849841,
title = {Modulation of CO2 adsorption in novel pillar-layered MOFs based on carboxylate–pyrazole flexible linker},
author = {Lancheros, Andrés and Goswami, Subhadip and Mian, Mohammad Rasel and Zhang, Xuan and Zarate, Ximena and Schott, Eduardo and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {Metal–organic frameworks (MOFs) have attracted significant attention as sorbents due to their high surface area, tunable pore volume and pore size, coordinatively unsaturated metal sites, and ability to install desired functional groups by post-synthetic modification. Herein, we report three new MOFs with pillar–paddlewheel structures that have been synthesized solvothermally from the mixture of the carboxylate–pyrazole flexible linker (H2L), 4,4-bipyridine (BPY)/triethylenediamine (DABCO), and Zn(II)/Cu(II) ions. The MOFs obtained, namely [ZnII(L)BPY], [CuII(L)BPY], and [CuII(L)DABCO], exhibit two-fold interpenetration and dinuclear paddle–wheel nodes. The Zn(II)/Cu(II) cations are coordinated by two equatorial L linkers that result in two-dimensional sheets which in turn are pillared by BPY or DABCO in the perpendicular direction to obtain a neutral three-dimensional framework that shows one-dimensional square channels. The three pillar-layered MOFs were characterized as microporous materials showing high crystalline stability after activation at 120 °C and CO2 adsorption. All MOFs contain uncoordinated Lewis basic pyrazole nitrogen atoms in the framework which have an affinity toward CO2 and hence could potentially serve as CO2 adsorption material. The CO2 uptake capacity was initially enhanced by replacing Zn with Cu and then replacing the pillar, going from BPY to DABCO. Overall, all the MOFs exhibit low isosteric heat (Qst) of adsorption which signifies an advantage due to the energy required for the adsorption and regeneration processes.},
doi = {10.1039/d0dt03166f},
journal = {Dalton Transactions},
number = 8,
volume = 50,
place = {United States},
year = {Thu Jan 28 00:00:00 EST 2021},
month = {Thu Jan 28 00:00:00 EST 2021}
}
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