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SPAEK-based binary blends and ternary composites as proton exchange membranes for DMFCs
Zhu, M.,Song, Y.,Hu, W.,Li, X.,Jiang, Z.,Guiver, M.D.,Liu, B. Elsevier Scientific Pub. Co 2012 Journal of membrane science Vol.415 No.-
Naphthalene-containing blend membranes, comprising sulfonated polyaryletherketone (SPAEK) as the primary matrix, and basic component polyazomethine (PAM), which has a chemical structure partially similar with SPAEK, were investigated as proton exchange membranes (PEMs). Further, a ternary-composite membrane was successfully prepared by introducing acid-functionalized polysilsesquioxane (POSS-SO<SUB>3</SUB>H) into SPAEK/PAM composite using a sol-gel process. The relevant properties of the PEMs, such as proton conductivity, methanol permeability, water uptake, and morphology were determined, and it was shown that the ternary-composite membrane, SPAEK/PAM/POSS-SO<SUB>3</SUB>H, showed a superior combination of properties for proton conductivity and methanol resistance. Its selectivity was 7.5 times higher than Nafion.
Du, Naiying,Dal-Cin, Mauro M.,Robertson, Gilles P.,Guiver, Michael D. American Chemical Society 2012 Macromolecules Vol.45 No.12
<P>Cross-linked membranes for gas separation have been prepared by thermal treatment of carboxylated polymers of intrinsic microporosity (C-PIMs). The optimal cross-linking temperature was investigated and possible cross-linking pathways involving aryl radical-induced thermal decarboxylation are provided, while several other possible mechanisms are ruled out. Carboxylated PIMs are accessible by controlled hydrolysis of the nitrile-containing parent polymer. The resulting cross-linked PIMs were insoluble in typical solvents and were characterized by Fourier transform infrared spectroscopy (FTIR), TGA-MS, TGA-FTIR, and gel content analysis. The decarboxylated PIM (DC-PIM) membranes showed higher selectivities for the O<SUB>2</SUB>/N<SUB>2</SUB>, CO<SUB>2</SUB>/N<SUB>2</SUB>, and CO<SUB>2</SUB>/CH<SUB>4</SUB> gas pairs, with evidence of suppression of swelling-induced densification under high CO<SUB>2</SUB> pressure.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/mamobx/2012/mamobx.2012.45.issue-12/ma300751s/production/images/medium/ma-2012-00751s_0005.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ma300751s'>ACS Electronic Supporting Info</A></P>
Advances in high permeability polymeric membrane materials for CO<sub>2</sub> separations
Du, Naiying,Park, Ho Bum,Dal-Cin, Mauro M.,Guiver, Michael D. The Royal Society of Chemistry 2012 ENERGY AND ENVIRONMENTAL SCIENCE Vol.5 No.6
<P>Global CO<SUB>2</SUB> 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 CO<SUB>2</SUB> reduction technologies. There is an almost universal acceptance of the link between rising anthropogenic CO<SUB>2</SUB> levels due to fossil fuel combustion and global warming accompanied by unpredictable climate change. Therefore, renewable energy, non-fossil fuels and CO<SUB>2</SUB> 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 CO<SUB>2</SUB> emitters, and capture of the CO<SUB>2</SUB> 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 CO<SUB>2</SUB> 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 CO<SUB>2</SUB> capture. Polymer membranes highly permeable to CO<SUB>2</SUB> 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 CO<SUB>2</SUB> permeability and good CO<SUB>2</SUB>/N<SUB>2</SUB> 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 CO<SUB>2</SUB> separation from, for example, the post-combustion flue gases in coal-fired power plants.</P> <P>Graphic Abstract</P><P>Highly permeable CO<SUB>2</SUB>-selective polymeric membranes have the potential to capture CO<SUB>2</SUB> from coal-fired power station flue gas. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c1ee02668b'> </P>
Polymer nanosieve membranes for CO<sub>2</sub>-capture?applications
Du, Naiying,Park, Ho Bum,Robertson, Gilles P.,Dal-Cin, Mauro M.,Visser, Tymen,Scoles, Ludmila,Guiver, Michael D. Nature Publishing Group 2011 Nature materials Vol.10 No.5
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<SUB>2</SUB> separation performance, even under polymer plasticization conditions such as CO<SUB>2</SUB>/light gas mixtures. This unprecedented result arises from the introduction of tetrazole groups into highly microporous polymeric frameworks, leading to more favourable CO<SUB>2</SUB> sorption with superior affinity in gas mixtures, and selective CO<SUB>2</SUB> transport by presorbed CO<SUB>2</SUB> molecules that limit access by other light gas molecules. This strategy provides a direction in the design of MOP membrane materials for economic CO<SUB>2</SUB> capture processes.