Title: Controllable microfl uidic production of multicomponent multiple emulsionsA hierarchical and scalable microfl uidic device enables highly controlled generation of multicomponent multiple emulsions with exceptionally diverse structures. The number, ratio and size of droplets, each with distinct contents being independently co-encapsulated in the same level, can be precisely controlled.
A novel positively K+‐responsive membrane with functional gates driven by host‐guest molecular recognition is prepared by grafting poly(N‐isopropylacrylamide‐co‐acryloylamidobenzo‐15‐crown‐5) (poly(NIPAM‐co‐AAB15C5)) copolymer chains in the pores of porous nylon‐6 membranes with a two‐step method combining plasma‐induced pore‐filling grafting polymerization and chemical modification. Due to the cooperative interaction of host‐guest complexation and phase transition of the poly(NIPAM‐co‐AAB15C5), the grafted gates in the membrane pores could spontaneously switch from “closed” state to “open” state by recognizing K+ ions in the environment and vice versa; while other ions (e.g., Na+, Ca2+ or Mg2+) can not trigger such an ion‐responsive switching function. The positively K+‐responsive gating action of the membrane is rapid, reversible, and reproducible. The proposed K+‐responsive gating membrane provide a new mode of behavior for ion‐recognizable “smart” or “intelligent” membrane actuators, which is highly attractive for controlled release, chemical/biomedical separations, tissue engineering, sensors, etc.
with Nafi on/SiO 2 hybrid membrane at the current density, 10 mA cm −2 . [ 10 ] Apart from the modifi cation of Nafi on membrane, the enhanced performances of VRB were recently also achieved with several kinds of sulfonated aromatic polymers in terms of the minimized hydrophilic domains. [11][12][13] Therefore, it is understood that the control of hydrophobic nature seems to be a common way to reduce the vanadium cross-over.More recently, Zhang et al. reported a VRB with a nanofi ltration type porous membrane that achieved competitive performances, a CE up to 95% and an EE of 76%. [ 14 ] The working principle has been based on the size sieving separation owing to the quite different size of proton and vanadium ions. [ 15 ] This strategy offers not only tremendously decreased cost owing to the already commercialized product, but also an ultimate insight toward maximizing H + /V selectivity. If the pore size of the membrane only enables protons (or water) transfer, the maximized performances could be achieved through the maximized H + /V selectivity. Thus, the subnano-sieving membrane for proton permselective transport is challenging. Here we report a fundamentally new concept to realize such proton/ vanadium selectivity. The concept is unprecedented as the material is hydrophobic, does not swell in water, contains micro porosity hosting water molecules along which protons can migrate and does not allow any other (vanadium) whatsoever. The proposed working principle of such hydrophobic polymers with intrinsic microporosity is disclosed in Scheme 1 .PIM-1 is the fi rst generation polymer having an intrinsic microporosity. We hypothesize that these materials can transport protons preferentially in VRBs because of its hydrophobic molecular structure, limited swelling in aqueous solution, inherent microporous structure with a pore diameter less than 2 nm, high free volume fraction above 20%, good solution processability, and relatively slow physical ageing compared to other high free volume polymers. [16][17][18] Even though hydrophobic, its microporosity is suspected to transport water molecules at high rates: Kentish and co-workers demonstrated water vapor permeation through PIM-1 at no fewer than 30 000 Barrer (1 Barrer = 10 −10 cm 3 (STP) cm (cm 2 s cm Hg) −1 ) above a water activity of 0.7. [ 19 ] Yet, little is known about the state of water inside such microporous polymers: one may anticipate the water being preferentially partitioned in the free-volume forming the microporosity rather than being absorbed into the polymer matrix. This could imply that a certain degree of proton transfer could occur by water molecules inside PIM-1. Meanwhile, the partitioning of hydro-solvated vanadium ions is expected to be limited by both the small radius of its pores and the difference of dielectric property, as illustrated in Scheme 1 .Recent increasing interest in the integration of renewable energy sources has accelerated efforts to develop electric energy storage (EES). [ 1,2 ] Among many approaches for EES, the allvanad...
Ion (perm)selectivity and conductivity are the two most essential properties of an ion exchange membrane, yet no quantitative relation between them has been suggested. In this work, the selectivity between two different counter-ions is correlated to the membrane conductivity. We show that the counter-ion selectivity measured by conventional electrodialysis (ED) can be expressed by the product of two parameters: (a) the mobility ratio between these two different counter-ions in the membrane and (b) their partition coefficient between the solution and the membrane. This is reminiscent of the classical solution-diffusion model. Via the counter-ion mobility in the membrane, the selectivity could be simply expressed with the membrane conductivity and dimensional swelling degree at pure counter-ion forms and at mixed counter-ion form when the membrane has been equilibrated with 1:1 equivalence ratio of the two counter-ions in the solution. This correlation is validated experimentally for the ion selectivity of K + /Na + in two commercial hydrocarbon-based cation exchange membranes (CEMs). For K + /Na + in a commercial perfluorosulfonic CEM, and for Mg 2+ /Na + in all the three types of CEMs, the correlation could predict the counter-ion partition very well; but there is an underestimation of the K + /Na + and Mg 2+ /Na + mobility ratios afforded by this correlation, which might be due to simplification of the cation activity coefficients in CEMs. This work offers a convenient method to decouple experimentally the effect of partition and mobility in controlling the membrane selectivity, and also proposes a new perspective to study the selectivity as well as conductivity of ion exchange membranes.
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