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However the permeation of CO2 through the metal-carbonate membrane requires the presence of oxygen and t he m embrane su ffers from a st ability i ssue d ue to m etal o xidation an d m etal-carbonate interaction. These problems can be addressed by replacing the metal phase with a mixed electronic-ionic conducting metal oxi de p hase [ 102]. A d ual-phase m embrane c onsisting of a m olten carbonate (Li2CO3/Na2CO3/K2CO3) entrapped i n a porous La0.6Sr0.4Co0.8Fe0.2O3-δ support i s pe rm-selective t o CO2 (with C O2/N2 selectivity w ell a bove 225) w ith C O2 permeance of ab ove 1.0x10-8 mol/ m 2·s·Pa a t temperatures a bove 500 oC. T hese m embranes ha ve pot ential f or p re-combustion C O2 capture applications, but much more work need to be done to improve the CO2 permeance. 3.3.2 Theoretical and Experimental Studies on the Mechanism of Gas Separation Development o f m embranes t hat create a step ch ange i n p erformance relative t o existing m aterials presents two complementary challenges. First, a large search space of possible materials must be considered to select a small number of materials that are expected to yield high performance membranes. If the aim is to use zeolites to make a membrane, for example, the identity and chemical composition of the zeolite(s) to be studied must be chosen from among hundreds of possible candidate materials. Second, the physical issues that affect the practical performance of membranes that are fabricated into working devices m ust be u nderstood a nd c ontrolled. To continue w ith t he e xample o f a zeolite m embrane, t he crystal o rientation a nd m icrostructure o f a z eolite f ilm i s o ften d ecisive i n m embrane p erformance. I n broad t erms, t heoretical st udies a re cu rrently making v aluable co ntributions i n t he f irst ar ea ( materials selection), w hile d evice performance i ssues a re c urrently m ost ef fectively ad dressed experimentally. Below, the current status of these issues for several different classes of membranes is briefly reviewed. Nanoporous membranes: The potential for crystalline nanoporous materials to overcome the fundamental selectivity/throughput tradeoff that e xists for po lymeric m embranes i s w idely k nown. E xtensive experience h as b een accumulated i n f abrication of z eolite membranes [105]. MO Fs represent a useful extension of the class of nanoporous materials that can be considered as membranes, but development of MOF m embranes i s a t an ear ly st age o f d evelopment. D etailed t heoretical m odels show p romise f or guiding materials selection of MOFs for membrane development [106]. The characteristics of molecular diffusion in n anoporous materials are critical to the pe rformance of m embranes g rown f rom t hese materials, a nd most i nformation a bout molecular diffusion in M OFs to da te has come f rom t heoretical studies. T he development of t heoretical models t hat combine qua ntum c hemistry a nd f orce f ield-based calculations to accurately d escribe t he s ubtle balance o f dispersion f orces a nd f ramework f lexibility effects in MOFs has progressed rapidly in recent years, although this work has been hampered in some instances by the availability of reliable, reproducible experimental data. It appears likely that in the near future it will be possible to use theoretical methods to screen large numbers of MOFs to reliably select which materials have most promise as membrane materials. When membranes are fabricated based on intergrown thin films of zeolites or MOFs, the microstructure of the resulting films can be critical in the effectiveness of the membrane. Significant progress has been made in controlling film microstructure for some zeolite films [105], but control of these issues for new materials remains a severe challenge. Theoretical models currently contribute little to this challenge. An attractive alternative to making membranes from intergrown thin films of crystalline materials is to use polymer/filler composites as membranes. These so-called mixed matrix membranes are likely to play an important role in near term technologies because they can be used to manufacture membranes at large scales using minor variations on known approaches [107]. As theoretical methods are used to screen new nanoporous m aterials, it i s be coming pos sible to consider w hich pol ymer/filler combinations w ill h ave desirable m embrane p roperties and t o f ocus experimental ef forts on t hese m aterials [108]. I ssues o f particle si ze, p article d ispersion, and the i nterface b etween f iller p articles an d the p olymer m atrix a re typically critical in the viability of mixed matrix membranes. A significant body of knowledge already Carbon Capture Factual Document 36PDF Image | 2020 Carbon Capture
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