Naiying Du

Polymer nanosieve membranes for CO2-capture applications

Microporous organic polymers (MOPs) are of potential significance for gas storage, gas separation and low-dielectric applications. 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 CO(2) separation performance, even under polymer plasticization conditions such as CO(2)/light gas mixtures. This unprecedented result arises from the introduction of tetrazole groups into highly microporous polymeric frameworks, leading to more favourable CO(2) sorption with superior affinity in gas mixtures, and selective CO(2) transport by presorbed CO(2) molecules that limit access by other light gas molecules. This strategy provides a direction in the design of MOP membrane materials for economic CO(2) capture processes.

Advances in high permeability polymeric membrane materials for CO2 separations

Global CO2 emissions have increased steadily in tandem with the use of fossil fuels. A paradigm shift is needed in developing new ways by which energy is supplied and utilized, together with the mitigation of climate change through CO2 reduction technologies. There is an almost universal acceptance of the link between rising anthropogenic CO2 levels due to fossil fuel combustion and global warming accompanied by unpredictable climate change. Therefore, renewable energy, non-fossil fuels and CO2 capture and storage (CCS) must be deployed on a massive scale. CCS technologies provide a means for reducing greenhouse gas emissions, in addition to the current strategies of improving energy efficiency. Coal-fired power plants are among the main large-scale CO2 emitters, and capture of the CO2 emissions can be achieved with conventional technologies such as amine absorption. However, this energy-consuming process, calculated at approximately 30% of the power plant capacity, would result in unacceptable increases in power generation costs. Membrane processes offer a potentially viable energy-saving alternative for CO2 capture because they do not involve any phase transformation. However, typical gas separation membranes that are currently available have insufficiently high permeability to be able to process the massive volumes of flue gas, which would result in a high CO2 capture. Polymer membranes highly permeable to CO2 and having good selectivity should be developed for the membrane process to be viable. This perspective review summarizes recent noteworthy advances in polymeric materials having very high CO2 permeability and good CO2/N2 selectivity that largely surpass the separation performance of conventional polymer materials. Five important classes of polymer membrane materials are highlighted: polyimides, thermally rearranged polymers (TRs), substituted polyacetylenes, polymers with intrinsic microporosity (PIM) and polyethers, which provide insights into polymer designs suitable for CO2 separation from, for example, the post-combustion flue gases in coal-fired power plants.

Azide-based Cross-Linking of Polymers of Intrinsic Microporosity (PIMs) for Condensable Gas Separation†

Cross-linked polymers of intrinsic microporosity (PIM)s for gas separation membranes, were prepared by a nitrene reaction from a representative PIM in the presence of two different diazide cross-linkers. The reaction temperature was optimized using TGA. The homogenous membranes were cast from THF solutions of different ratios of PIM to azides. The resulting cross-linked structures of the PIMs membranes were formed at 175 °C after 7.5 h and confirmed by TGA, XPS, FT-IR spectroscopy and gel content analysis. These resulting cross-linked polymeric membranes showed excellent gas separation performance and can be used for O(2) /N(2) and CO(2) /N(2) gas pairs, as well as for condensable gases, such as CO(2) /CH(4) , propylene/propane separation. Most importantly, and differently from typical gas separation membranes derived from glassy polymers, the crosslinked PIMs showed no obvious CO(2) plasticization up to 20 atm pressure of pure CO(2) and CO(2) /CH(4) mixtures.

Copolymers of Intrinsic Microporosity Based on 2,2′,3,3′-Tetrahydroxy-1,1′-dinaphthyl†

A series of new copolymers with high molecular weight and low polydispersity, prepared from tetrahydroxydinaphthyl, tetrahydroxyspirobisindane, and tetrafluoroterephthalonitrile monomers, prevent efficient space packing of the stiff polymer chains and consequently show intrinsic microporosity. One copolymer, DNPIM-33, has an excellent combination of properties with good film-forming characteristics and gas transport performance, and exhibits higher selectivity than the corresponding spirobisindane-based homopolymer PIM-1 for gas pairs, such as O(2) /N(2) , with a corresponding small decrease in permeability. This work demonstrates that significant improvements in properties may be obtained through development of copolymers with intrinsic microporosity (CoPIMs) that extends the spectrum of high-molecular-weight ladder structures of poly(dibenzodioxane)s.