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Title: Selective Carbon Dioxide Adsorption by Two Robust Microporous Coordination Polymers

In the present work we report the design, synthesis, crystal structure determination, and adsorption properties of two new cadmium-based porous coordination polymers, [Cd(pda) 0.5(spiro-4-py) 0.5(HCOO)]•2H 2O•DMF (compound 1, pda = p-phenylenediacetate, spiro- 4-py = (2,2’,7,7’-tetra(pyridin-4-yl)-9,9’-spirobi[fluorene], DMF = N,N’-dimethylformamide) and [Cd 2(pda)(spiro-4-py)(CH 3COO) 2]•DMA (compound 2, DMA = N,N’-dimethylacetamide) with similar structures. The coordination between cadmium and two organic linkers, pda and spiro-4-py, has yielded two-dimensional frameworks with rhombic openings. Stacking of these two-dimensional networks does not block the openings but rather results in permanent porosity with one-dimensional channels in the final structures. The permanent porosity of these compounds is confirmed by gas adsorption measurements. Compounds 1 and 2 have BET (Brunauer-Emmett-Teller) surface areas of 687 and 584 m 2/g, respectively. Both compounds show favorable adsorption towards carbon dioxide over other light gases such as nitrogen, oxygen, and carbon monoxide. IAST (Ideal adsorbed solution theory) is employed to predict the adsorption selectivity of binary gas mixtures. Though compounds 1 and 2 possess similar structures, differences are observed in their gas adsorption behaviors, which can be attributed to their different terminal ligands of formate and acetate, respectively. Strikingly, both compounds show exceptionally high stability in aqueous media with a wide pH range,more » a characteristic that is highly desirable for gas separation-related applications. The robustness of these structures suggests that the use of hydrophobic spiro based multipyridine ligands can lead to water stable frameworks built on late-transition metals that are otherwise sensitive to moisture.« less
Authors:
 [1] ;  [2] ;  [3] ;  [2] ;  [2] ;  [2] ; ORCiD logo [2]
  1. Huaiyin Normal Univ.,(China). Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, College of Chemistry and Chemical Engineering; Rutgers Univ., New Brunswick, NJ (United States). Dept. of Chemistry and Chemical Biology
  2. Rutgers Univ., New Brunswick, NJ (United States). Dept. of Chemistry and Chemical Biology
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Grant/Contract Number:
FG02-08ER-46491; 12KJD150002; 15KJA150003; 21375044; 51602118
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; Journal Issue: 24; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation of Jiangsu Provincial Department of Education
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1459900

An, Litao, Wang, Hao, Teat, Simon J., Xu, Feng, Wang, Xin-Long, Wang, Fangming, and Li, Jing. Selective Carbon Dioxide Adsorption by Two Robust Microporous Coordination Polymers. United States: N. p., Web. doi:10.1021/acs.inorgchem.6b02332.
An, Litao, Wang, Hao, Teat, Simon J., Xu, Feng, Wang, Xin-Long, Wang, Fangming, & Li, Jing. Selective Carbon Dioxide Adsorption by Two Robust Microporous Coordination Polymers. United States. doi:10.1021/acs.inorgchem.6b02332.
An, Litao, Wang, Hao, Teat, Simon J., Xu, Feng, Wang, Xin-Long, Wang, Fangming, and Li, Jing. 2016. "Selective Carbon Dioxide Adsorption by Two Robust Microporous Coordination Polymers". United States. doi:10.1021/acs.inorgchem.6b02332. https://www.osti.gov/servlets/purl/1459900.
@article{osti_1459900,
title = {Selective Carbon Dioxide Adsorption by Two Robust Microporous Coordination Polymers},
author = {An, Litao and Wang, Hao and Teat, Simon J. and Xu, Feng and Wang, Xin-Long and Wang, Fangming and Li, Jing},
abstractNote = {In the present work we report the design, synthesis, crystal structure determination, and adsorption properties of two new cadmium-based porous coordination polymers, [Cd(pda)0.5(spiro-4-py)0.5(HCOO)]•2H2O•DMF (compound 1, pda = p-phenylenediacetate, spiro- 4-py = (2,2’,7,7’-tetra(pyridin-4-yl)-9,9’-spirobi[fluorene], DMF = N,N’-dimethylformamide) and [Cd2(pda)(spiro-4-py)(CH3COO)2]•DMA (compound 2, DMA = N,N’-dimethylacetamide) with similar structures. The coordination between cadmium and two organic linkers, pda and spiro-4-py, has yielded two-dimensional frameworks with rhombic openings. Stacking of these two-dimensional networks does not block the openings but rather results in permanent porosity with one-dimensional channels in the final structures. The permanent porosity of these compounds is confirmed by gas adsorption measurements. Compounds 1 and 2 have BET (Brunauer-Emmett-Teller) surface areas of 687 and 584 m2/g, respectively. Both compounds show favorable adsorption towards carbon dioxide over other light gases such as nitrogen, oxygen, and carbon monoxide. IAST (Ideal adsorbed solution theory) is employed to predict the adsorption selectivity of binary gas mixtures. Though compounds 1 and 2 possess similar structures, differences are observed in their gas adsorption behaviors, which can be attributed to their different terminal ligands of formate and acetate, respectively. Strikingly, both compounds show exceptionally high stability in aqueous media with a wide pH range, a characteristic that is highly desirable for gas separation-related applications. The robustness of these structures suggests that the use of hydrophobic spiro based multipyridine ligands can lead to water stable frameworks built on late-transition metals that are otherwise sensitive to moisture.},
doi = {10.1021/acs.inorgchem.6b02332},
journal = {Inorganic Chemistry},
number = 24,
volume = 55,
place = {United States},
year = {2016},
month = {11}
}