Microporous organic polymers (MOPs) are of potential significance for gas storage1, 2, 3, gas separation4 and low-dielectric applications5. Among many approaches for obtaining such materials, solution-processable MOPs derived from rigid and contorted macromolecular structures are promising because of their excellent mass transport and mass exchange capability. Here we show a class of amorphous MOP, prepared by [2+3] cycloaddition modification of a polymer containing an aromatic nitrile group with an azide compound, showing super-permeable characteristics and outstanding CO2 separation performance, even under polymer plasticization conditions such as CO2/light gas mixtures. This unprecedented result arises from the introduction of tetrazole groups into highly microporous polymeric frameworks, leading to more favourable CO2 sorption with superior affinity in gas mixtures, and selective CO2 transport by presorbed CO2 molecules that limit access by other light gas molecules. This strategy provides a direction in the design of MOP membrane materials for economic CO2 capture processes.
At a glance
- Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003). et al.
- Conjugated microporous polymers. Adv. Mater. 21, 1291–1295 (2009).
- Towards polymer-based hydrogen storage materials: Engineering ultramicroporous cavities within polymers of intrinsic microporosity. Angew. Chem. Int. Ed. 45, 1804–1807 (2006). et al.
- Polymers with cavities tuned for fast selective transport of small molecules and ions. Science 318, 254–258 (2007). et al.
- Molecular design of free volume as a route to low-k dielectric materials. J. Am. Chem. Soc. 125, 14113–14119 (2005). &
- Ordered porous materials for emerging applications. Nature 417, 817–821 (2002).
- Microporous and mesoporous materials. Adv. Mater. 14, 629–638 (2002). &
- Functional porous coordination polymers. Angew. Chem. Int. Ed. 43, 2334–2375 (2004). , &
- Poly[1-(trimethylsilyl)-1-propyne] and related polymers: Synthesis, properties and functions. Prog. Polym. Sci. 26, 721–798 (2001). , , , &
- Thermally rearranged (TR) polymer membranes for CO2 separation. J. Membr. Sci. 359, 11–24 (2010). , , , &
- Polymers of intrinsic microporosity (PIMs): High free volume polymers for membrane applications. Macromol. Sym. 245, 403–405 (2006). , &
- Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005). et al.
- Designed synthesis of 3D covalent organic frameworks. Science 316, 268–272 (2007). et al.
- Gas separation membranes from polymers of intrinsic microporosity. J. Membr. Sci. 251, 263–269 (2005). et al.
- Polymers of intrinsic microporosity derived from novel disulfone-based monomers. Macromolecules 42, 6023–6030 (2009). , &
- High-performance carboxylated polymers of intrinsic microporosity (PIMs) with tunable gas transport properties. Macromolecules 42, 6038–6043 (2009). , , &
- Polymers of intrinsic microporosity containing trifluoromethyl and phenylsulfone groups as materials for membrane gas separation. Macromolecules 41, 9656–9662 (2008). et al.
- The upper bound revisited. J. Membr. Sci. 320, 390–400 (2008).
- Materials selection guideline for membranes that remove CO2 from gas mixtures. J. Mol. Struct. 739, 57–74 (2005). &
- Gas solubility, diffusivity and permeability in poly(ethylene oxide). J. Membr. Sci. 239, 105–117 (2004). &
- Ab initio study of the interactions between CO2 and N-containing organic heterocycles. ChemPhysChem 10, 374–383 (2009). , , &
- Asymmetric 1,3-dipolar cycloaddition reactions. Chem. Rev. 98, 863–910 (1998). &
- 1,3-Dipolar cycloadditions. XXXII. Kinetics of the addition of organic azides to carbon-carbon multiple bonds. Chem. Ber. 100, 2494–2507 (1967). , &
- Click chemistry in polymer and materials science. Macromol. Rapid Commun. 28, 15–54 (2007). &
- Functionalized polysulfones: Methods for chemical modification and membrane applications. ACS Symp. Ser. 744, 137–161 (2000) Chapter 10. , , &
- & US Patent 5,475,065 (1995).
- Well-defined (co)polymers with 5-vinyltetrazole units via combination of atom transfer radical (co)polymerization of acrylonitrile and click chemistry-type postpolymerization modification. Macromolecules 37, 9308–9313 (2004). , , , &
- Hydrocarbon/hydrogen mixed gas permeation in poly(1-trimethylsilyl-1-propyne) (PTMSP), poly(1-phenyl-1-propyne) (PPP), and PTMSP/PPP blends. J. Polym. Sci. Polym. Phys. 34, 2613–2621 (1996). , , &
- Hydrocarbon/hydrogen mixed-gas permeation properties of PIM-1, an amorphous microprous spirobisindane polymer. J. Membr. Sci. 338, 1–4 (2009). , , &
- Power plant post-combustion carbon dioxide capture: An opportunity for membranes. J. Membr. Sci. 359, 126–139 (2010). , , &
- Advances in CO2 capture technology—the US Department of Energy’s Carbon Sequestration Program. Int. J. Greenhouse Gas Control 2, 9–20 (2008). , , , &
- Supplementary Information (796 KB)