skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Eutectic Molten Salt Synthesis of Highly Microporous Macrocyclic Porous Organic Polymers for CO 2 Capture
Abstract The development of porous materials is of great interest for the capture of CO2from various emission sources, which is essential to mitigate its detrimental environmental impact. In this direction, porous organic polymers (POPs) have emerged as prime candidates owing to their structural tunability, physiochemical stability and high surface areas. In an effort to transfer an intrinsic property of a cyclotetrabenzoin‐derived macrocycle – its high CO2affinity – into porous networks, herein we report the synthesis of three‐dimensional (3D) macrocycle‐based POPs through the polycondensation of an octaketone macrocycle with phenazine‐2,3,7,8‐tetraamine hydrochloride. This polycondensation was performed under ionothermal conditions, using a eutectic salt mixture in the temperature range of 200 to 300 °C. The resulting polymers, named 3D‐mmPOPs, showed reaction temperature‐dependent surface areas and gas uptake properties. 3D‐mmPOP‐250 synthesized at 250 °C exhibited a surface area of 752 m2 g−1and high microporosity originating from the macrocyclic units, thus resulting in an excellent CO2binding enthalpy of 40.6 kJ mol−1and CO2uptake capacity of 3.51 mmol g−1at 273 K, 1.1 bar.  more » « less
Award ID(s):
2204236
PAR ID:
10430970
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Helvetica Chimica Acta
Volume:
106
Issue:
8
ISSN:
0018-019X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; (, Organic Materials)
    null (Ed.)
    Porous organic polymers (POPs) incorporating macrocyclic units have been investigated in recent years in an effort to transfer macrocycles' intrinsic host–guest properties onto the porous networks to achieve complex separations. In this regard, highly interesting building blocks are presented by the family of cyclotetrabenzoin macrocycles with rigid, well-defined, electron-deficient cavities. This macrocycle shows high affinity towards linear guest molecules such as carbon dioxide, thus offering an ideal building block for the synthesis of CO2-philic POPs. Herein, we report the synthesis of a POP through the condensation reaction between cyclotetrabenzil and 1,2,4,5-tetraaminobenzene under ionothermal conditions using the eutectic zinc chloride/sodium chloride/potassium chloride salt mixture at 250 °C. Notably, following the condensation reaction, the macrocycle favors three-dimensional (3D) growth rather than a two-dimensional one while retaining the cavity. The resulting polymer, named 3D-mPOP, showed a highly microporous structure with a BET surface area of 1142 m2 g−1 and a high carbon dioxide affinity with a binding enthalpy of 39 kJ mol−1. Moreover, 3D-mPOP showed very high selectivity for carbon dioxide in carbon dioxide/methane and carbon dioxide/nitrogen mixtures. 
    more » « less
  2. ; ; ; ; ; ; ; ; ; ; et al (, Angewandte Chemie)
    Abstract The recovery and separation of organic solvents is highly important for the chemical industry and environmental protection. In this context, porous organic polymers (POPs) have significant potential owing to the possibility of integrating shape‐persistent macrocyclic units with high guest selectivity. Here, we report the synthesis of a macrocyclic porous organic polymer (np‐POP) and the corresponding model compound by reacting the cyclotetrabenzil naphthalene octaketone macrocycle with 1,2,4,5‐tetraaminobenzene and 1,2‐diaminobenzene, respectively, under solvothermal conditions. Co‐crystallization of the macrocycle and the model compound with various solvent molecules revealed their size‐selective inclusion within the macrocycle. Building on this finding, thenp‐POP with a hierarchical pore structure and a surface area of 579 m2 g−1showed solvent uptake strongly correlated with their kinetic diameters. Solvents with kinetic diameters below 0.6 nm – such as acetonitrile and dichloromethane – showed high uptake capacities exceeding 7 mmol g−1. Xylene separation tests revealed a high overall uptake (~34 wt %), witho‐xylene displaying a significantly lower uptake (~10 wt % less than other isomers), demonstrating the possibility of size and shape selective separation of organic solvents. 
    more » « less
  3. ; ; ; ; ; ; ; ; ; ; et al (, Nature Communications)
    Abstract Herein, we report a strategy to construct highly efficient perfluorooctanoic acid (PFOA) adsorbents by installing synergistic electrostatic/hydrophobic sites onto porous organic polymers (POPs). The constructed model material of PAF-1-NDMB (NDMB = N,N-dimethyl-butylamine) demonstrates an exceptionally high PFOA uptake capacity over 2000 mg g−1, which is 14.8 times enhancement compared with its parent material of PAF-1. And it is 32.0 and 24.1 times higher than benchmark materials of DFB-CDP (β-cyclodextrin (β-CD)-based polymer network) and activated carbon under the same conditions. Furthermore, PAF-1-NDMB exhibits the highestk2value of 24,000 g mg−1h−1among all reported PFOA sorbents. And it can remove 99.99% PFOA from 1000 ppb to <70 ppt within 2 min, which is lower than the advisory level of Environmental Protection Agency of United States. This work thus not only provides a generic approach for constructing PFOA adsorbents, but also develops POPs as a platform for PFOA capture. 
    more » « less
  4. ; ; ; (, Advanced Materials)
    Abstract Currently, few porous vanadium metal‐organic frameworks (V‐MOFs) are known and even fewer are obtainable as single crystals, resulting in limited information on their structures and properties. Here this work demonstrates remarkable promise of V‐MOFs by presenting an extensible family of V‐MOFs with tailorable pore geometry and properties. The synthesis leverages inter‐modular synergy on a tri‐modular pore‐partitioned platform. New V‐MOFs show a broad range of structural features and sorption properties suitable for gas storage and separation applications for C2H2/CO2, C2H6/C2H4, and C3H8/C3H6. Thec/aratio of the hexagonal cell, a measure of pore shape, is tunable from 0.612 to 1.258. Other tunable properties include pore size from 5.0 to 10.9 Å and surface area from 820 to 2964 m2g−1. With C2H2/CO2selectivity from 3.3 to 11 and high uptake capacity for C2H2from 65.2 to 182 cm3g−1(298K, 1 bar), an efficient separation is confirmed by breakthrough experiments. The near‐record high uptake for C2H6(166.8 cm3g−1) contributes to the promise for C2H6‐selective separation of C2H6/C2H4. The multi‐module pore expansion enables transition from C3H6‐selective to more desirable C3H8‐selective separation with extraordinarily high C3H8uptake (254.9 cm3g−1) and high separation potential (1.25 mmol g−1) for C3H8/C3H6(50:50 v/v) mixture. 
    more » « less
  5. ; ; ; ; (, Small)
    Abstract Isoreticular chemistry is among the most powerful strategies for designing novel materials with optimizable pore geometry and properties. Of great significance to the further advance of isoreticular chemistry is the development of broadly applicable new concepts capable of guiding and systematizing the ligand‐family expansion as well as establishing correlations between dissimilar and seemingly uncorrelated ligands for better predictive synthetic design and more insightful structure and property analysis. Here ligand circuit concept is proposed and its use has been demonstrated for the synthesis of a family of highly stable, high‐performance pore‐space‐partitioned materials based on an acyclic ligand,trans,trans‐muconic acid. This work represents a key step toward developing highly porous and highly stable pore‐space‐partitioned materials from acyclic ligands. The new materials exhibit excellent sorption properties such as high uptake capacity for CO2(81.3 cm3 g−1) and C2H2(165.4 cm3 g−1) by CPM‐7.3a‐NiV. CPM‐7.3a‐CoV shows C2H6‐selective C2H6/C2H4separation properties and its high uptakes for C2H4(134.0 cm3 g−1) and C2H6(148.0 cm3 g−1) at 1 bar and 298 K contribute to the separation potential of 1.35 mmol g−1. The multi‐cycle breakthrough experiment confirms the promising separation performance for C2H2/CO2. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email