Polyelectrolyte multilayer films as backflushable nanofiltration membranes with tunable hydrophilicity and surface charge

A diverse set of supported polyelectrolyte multilayer (PEM) membranes with controllable surface charge, hydrophilicity, and permeability to water and salt was designed by choosing constituent polyelectrolytes and by adjusting conditions of their deposition. The membranes were characterized in terms of their water and MgSO4 permeabilities and resistance to colloidal fouling. The commercial nanofiltration membrane (NF270) was used as a comparative basis. Highly hydrophilic and charged PEMs could be designed. For all membranes, MgSO4 permeability coefficients of NF270 and all PEM membranes exhibited a power law dependence on concentration: Ps [is proportional to] C-[tau], 0.19 < [tau] < 0.83. PEM membranes were highly selective and capable of nearly complete intrinsic rejection of MgSO4 at sufficiently high fluxes. With the deposition of colloids onto the PEM surface, the separation properties of one type of polyelectrolyte membrane showed similar rejection and superior flux properties compared to NF270 membranes. We hypothesize that a PEM-colloid nanocomposite was formed as a result of colloidal fouling of these PEM films. The feasibility of regenerating the PEM membranes fouled by colloids was also demonstrated. In summary, the PEM-based approach to membrane preparation was shown to enable the design of membranes with the unique combination of desirable ion separation characteristics and regenerability of the separation layer

Balance-of-force selective accumulation of trace ionic species in hierarchical sub-nano-/nano-/micro-porous structures

Separation of species of close electrochemical mobilities (peptides, isotopes) is of interest for a number of applications. In this presentation, we will explore selective accumulation of ionic species in current-polarized hierarchical sub-nano-/nano-/micro-porous structures. Please click Additional Files below to see the full abstract

Nanopores: synergy from DNA sequencing to industrial filtration - small holes with big impact

Nanopores in thin membranes play important roles in science and industry. Single nanopores have provided a step-change in portable DNA sequencing and understanding nanoscale transport while multipore membranes facilitate food processing and purification of water and medicine. Despite the unifying use of nanopores, the fields of single nanopores and multipore membranes differ - to varying degrees - in terms of materials, fabrication, analysis, and applications. Such a partial disconnect hinders scientific progress as important challenges are best resolved together. This Viewpoint suggests how synergistic crosstalk between the two fields can provide considerable mutual benefits in fundamental understanding and the development of advanced membranes. We first describe the main differences including the atomistic definition of single pores compared to the less defined conduits in multipore membranes. We then outline steps to improve communication between the two fields such as harmonizing measurements and modelling of transport and selectivity. The resulting insight is expected to improve the rational design of porous membranes. The Viewpoint concludes with an outlook of other developments that can be best achieved by collaboration across the two fields to advance the understanding of transport in nanopores and create next-generation porous membranes tailored for sensing, filtration, and other applications

Development of polymeric hollow fiber membranes containing catalytic metal nanoparticules.

Metal nanoparticles (MNPs) have unique physico-chemical properties advantageous for catalytic applications which differ from bulk material. However, the main drawback of MNPs is their insufficient stability due to a high trend for aggregation. To cope with this inconvenience, the stabilization of MNPs in polymeric matrices has been tested. This procedure is a promising strategy to maintain catalytic properties. The aim of this work is the synthesis of polymer-stabilized MNPs inside functionalized polymeric membranes in order to build catalytic membrane reactors. First, the polymeric support must have functional groups capable to retain nanoparticle precursors (i.e. sulfonic), then, nanoparticles can grow inside the polymeric matrix by chemical reduction of metal ions. Two different strategies have been used in this work. Firstly, polyethersulfone microfiltration hollow fibers have been modified by applying polyelectrolyte multilayers. Secondly, polysulfone ultrafiltration membranes were modified by UV-photografting using sodium p-styrene sulfonate as a vinyl monomer. The catalytic performance of developed hollow fibers has been evaluated by using the reduction of nitrophenol to aminophenol by sodium borohydride. Hollow fiber modules with Pd MNPs have been tested in dead-end and cross-flow filtration. Complete nitrophenol degradation is possible depending on operation parameters such as applied pressure and permeate flux

Catalytic hollow fiber membranes prepared using layer-by-layer adsorption of polyelectrolytes and metal nanoparticles

Immobilization of metalnanoparticles in hollowfibermembranes via alternating adsorption of polyelectrolytes and negatively charged Au nanoparticles yields catalytic reactors with high surface areas. SEM images show that this technique deposits a high density of unaggregated metalnanoparticles both on the surfaces and in the pores of the hollowfibers. Catalytic reduction of 4-nitrophenol with NaBH4, which can be easily monitored by UV–vis spectrophotometry, demonstrates that the nanoparticles in the hollowfibermembrane are highly catalytically active. In a single pass through the membrane, >99% of the 4-nitrophenol is reduced to 4-aminophenol, but this conversion decreases over time. The conversion decline may stem from catalyst fouling caused by by-products of 4-aminophenol oxidation

Wet air oxidation of formic acid using nanoparticle-modified polysulfone hollow fibers as gas-liquid contactors

Catalytic wet air oxidation (CWAO) using membrane contactors is attractive for remediation of aqueous pollutants, but previous studies of even simple reactions such as formic acid oxidation required multiple passes through tubular ceramic membrane contactors to achieve high conversion. This work aims to increase single-pass CWAO conversions by using polysulfone (PS) hollow fibers as contactors to reduce diffusion distances in the fiber lumen. Alternating adsorption of polycations and citrate-stabilized platinum colloids in fiber walls provides catalytically active PS hollow fibers. Using a single PS fiber, 50% oxidation of a 50 mM formic acid feed solution results from a single pass through the fiber lumen (15 cm length) with a solution residence time of 40 s. Increasing the number of PS fibers to five while maintaining the same volumetric flow rate leads to over 90% oxidation, suggesting that further scale up in the number of fibers will facilitate high single pass conversions at increased flow rates. The high conversion compared to prior studies with ceramic fibers stems from shorter diffusion distances in the fiber lumen. However, the activity of the Pt catalyst is 20-fold lower than in previous ceramic fibers. Focusing the Pt deposition near the fiber lumen and limiting pore wetting to this region might increase the activity of the catalyst

Fundamentals of selective ion transport through multilayer polyelectrolyte membranes

Membranes composed of multilayer poly(4-styrenesul- fonate) (PSS)/protonated poly(allylamine) (PAH) fi lms on porous alumina supports exhibit high monovalent/divalent cation selectivities. Remarkably, the di ff usion dialysis K + /Mg 2+ selectivity is >350. However, in nano fi ltration this selectivity is only 16, suggesting some convective ion transport through fi lm imperfections. Under MgCl 2 concentration gradients across either (PSS/PAH) 4 - or (PSS/ PAH) 4 PSS-coated alumina, transmembrane potentials indicate Mg 2+ transference numbers approaching 0. The low Mg 2+ transference numbers with both polycation- and polyanion-terminated fi lms likely stem from exclusion of Mg 2+ due to its large size or hydration energy. However, these high anion/cation selectivities decrease as the solution ionic strength increases. In nano fi ltration, the high asymmetry of membrane permeabilities to Mg 2+ and Cl − creates transmembrane di ff usion potentials that lead to negative rejections (the ion concentration in the permeate is larger than in the feed) as low as − 200% for trace monovalent cations such as K + and Cs + . Moreover, rejection becomes more negative as the mobility of the trace cation increases. Knowledge of single-ion permeabilities is vital for predicting the performance of polyelectrolyte fi lms in the separation and puri fi cation of mixed salts.Peer ReviewedPostprint (published version

Ion Separations Based on Spontaneously Arising Streaming Potentials in Rotating Isoporous Membranes

Highly selective ion separations are vital for producing pure salts, and membrane-based separations are promising alternatives to conventional ion-separation techniques. Our previous work demonstrated that simple pressure-driven flow through negatively charged isoporous membranes can separate Li+ and K+ with selectivities as high as 70 in dilute solutions. The separation mechanism relies on spontaneously arising streaming potentials that induce electromigration, which opposes advection and separates cations based on differences in their electrophoretic mobilities. Although the separation technique is simple, this work shows that high selectivities are possible only with careful consideration of experimental conditions including transmembrane pressure, solution ionic strength, the K+/Li+ ratio in the feed, and the extent of concentration polarization. Separations conducted with a rotating membrane show Li+/K+ selectivities as high as 150 with a 1000 rpm membrane rotation rate, but the selectivity decreases to 1.3 at 95 rpm. These results demonstrate the benefits and necessity of quantitative control of concentration polarization in highly selective separations. Increases in solution ionic strength or the K+/Li+ feed ratio can also decrease selectivities more than an order of magnitude