Guangwei He

Recent advances in the fabrication of advanced composite membranes

Composite membranes comprising a continuous polymer phase and a dispersed filler phase have revealed appealing potential in selective transport of molecules and ions. The multiphase characteristics of composite membranes provide more degrees of freedom to manipulate multiple interactions, tailor multiscale structures, and integrate multiple functionalities, compared to pristine polymer membranes. In this feature article, we have reviewed the various methods for the fabrication of composite membranes. In particular, we have thoroughly discussed two typical methods: the physical blending method and the sol–gel method. For each method, the major advances and challenges have been summarized. We have also tentatively delineated the new generation of composite membranes.

Advances in high permeability polymer-based membrane materials for CO2 separations

Membrane processes have evolved as a competitive approach in CO2 separations compared with absorption and adsorption processes, due to their inherent attributes such as energy-saving and continuous operation. High permeability membrane materials are crucial to efficient membrane processes. Among existing membrane materials for CO2 separations, polymer-based materials have some intrinsic advantages such as good processability, low price and a readily available variety of materials. In recent years, enormous research effort has been devoted to the use of membrane technology for CO2 separations from diverse sources such as flue gas (mainly N2), natural gas (mainly CH4) and syngas (mainly H2). Polymer-based membrane materials occupy the vast majority of all the membrane materials. For large-scale CO2 separations, polymer-based membrane materials with high CO2 permeability and good CO2/gas selectivity are required. In 2012, we published a Perspective review in Energy & Environmental Science on high permeability polymeric membrane materials for CO2 separations. Since then, more rapid progress has been made and the research focus has changed significantly. This review summarises the advances since 2012 on high permeability polymer-based membrane materials for CO2 separations. The major features of this review are reflected in the following three aspects: (1) we cover polymer-based membrane materials instead of purely polymeric membrane materials, which encompass both polymeric membranes and polymer–inorganic hybrid membranes. (2) CO2 facilitated transport membrane materials are presented. (3) Biomimetism and bioinspired membrane concepts are incorporated. A number of representative examples of recent advances in high permeability polymer-based membrane materials is highlighted with some critical analysis, followed by a brief perspective on future research and development directions.

Nanostructured Ion‐Exchange Membranes for Fuel Cells: Recent Advances and Perspectives

Polymer-based materials with tunable nanoscale structures and associated microenvironments hold great promise as next-generation ion-exchange membranes (IEMs) for acid or alkaline fuel cells. Understanding the relationships between nanostructure, physical and chemical microenvironment, and ion-transport properties are critical to the rational design and development of IEMs. These matters are addressed here by discussing representative and important advances since 2011, with particular emphasis on aromatic-polymer-based nanostructured IEMs, which are broadly divided into nanostructured polymer membranes and nanostructured polymer-filler composite membranes. For each category of membrane, the core factors that influence the physical and chemical microenvironments of the ion nanochannels are summarized. In addition, a brief perspective on the possible future directions of nanostructured IEMs is presented.

Enhanced Proton Conductivity of Nafion Hybrid Membrane under Different Humidities by Incorporating Metal–Organic Frameworks With High Phytic Acid Loading

In this study, phytic acid (myo-inositol hexaphosphonic acid) was first immobilized by MIL101 via vacuum-assisted impregnation method. The obtained phytic@MIL101 was then utilized as a novel filler to incorporate into Nafion to fabricate hybrid proton exchange membrane for application in PEMFC under different relative humidities (RHs), especially under low RHs. High loading and uniform dispersion of phytic acid in MIL 101(Cr) were achieved as demonstrated by ICP, FT-IR, XPS, and EDS-mapping. The phytic@MIL101 was dispersed homogeneously in the Nafion matrix when the filler content was less than 12%. Hybrid membranes were evaluated by proton conductivity, mechanical property, thermal stability, and so forth. Remarkably, the Nafion/phytic@MIL hybrid membranes showed high proton conductivity at different RHs, especially under low RHs, which was up to 0.0608 S cm(-1) and 7.63 × 10(-4) S cm(-1) at 57.4% RH and 10.5% RH (2.8 and 11.0 times higher than that of pristine membrane), respectively. Moreover, the mechanical property of Nafion/phtic@MIL hybrid membranes was substantially enhanced and the thermal stability of membranes was well preserved.

Efficient CO2 capture by humidified polymer electrolyte membranes with tunable water state

Polymer electrolyte membranes containing alkali or alkaline-earth metal salts were designed and utilized for CO2 capture. These membranes showed higher CO2 permeability than the un-doped control membrane due to the increase of water content, and CO2/gas selectivity was simultaneously enhanced due to the “salting-out” effect, which was strongly dependent on the content of bound water. More specifically, water content, water state and separation performance of polymer electrolyte membranes were strongly dependent on the salt type: (1) membranes containing alkaline-earth metal salts displayed a higher amount of bound water than those containing alkali cations, because the hydration energy of the alkaline-earth cation is relatively larger than that of the alkali cation; (2) the salts (KCl and CaCl2) that can efficiently interrupt chain packing by metal–polymer complexation facilitated the diffusion of water molecules into the polymer matrix and thus increased the total amount of absorbed water. As a consequence, CaCl2-doped membranes showed the highest CO2 permeability (2030 Barrer) and a high separation factor (108 for CO2/N2 and 31 for CO2/CH4) at 2 bar (gage pressure) and 298 K for fully humidified gas streams. The effects of annealing conditions and feed pressure were also explored to elucidate the relevant separation mechanism of the polymer electrolyte membrane.

Incorporating Zwitterionic Graphene Oxides into Sodium Alginate Membrane for Efficient Water/Alcohol Separation

For the selective water-permeation across dense membrane, constructing continuous pathways with high-density ionic groups are of critical significance for the preferential sorption and diffusion of water molecules. In this study, zwitterionic graphene oxides (PSBMA@GO) nanosheets were prepared and incorporated into sodium alginate (SA) membrane for efficient water permeation and water/alcohol separation. The two-dimensional GO provides continuous pathway, while the high-density zwitterionic groups on GO confer electrostatic interaction sites with water molecules, leading to high water affinity and ethanol repellency. The simultaneous optimization of the physical and chemical structures of water transport pathway on zwitterionic GO surface endows the membrane with high-efficiency water permeation. Using dehydration of water/alcohol mixture as the model system, the nanohybrid membranes incorporating PSBMA@GO exhibit much higher separation performance than the SA membrane and the nanohybrid membrane utilizing unmodified GO as filler (with the optimal permeation flux of 2140 g m(-2) h(-1), and separation factor of 1370). The study indicates the great application potential of zwitterionic graphene materials in dense water-permeation membranes and provides a facile approach to constructing efficient water transport pathway in membrane.

Independent control of water retention and acid–base pairing through double-shelled microcapsules to confer membranes with enhanced proton conduction under low humidity

Proton exchange membranes (PEM) with affordable and controllable proton conductivity under low humidity are crucial to the commercial application of PEM fuel cells. In this study, double-shelled polymer microcapsules bearing a carboxylic acid inner shell and imidazole outer shell (PMC-Ns) are synthesized via distillation–precipitation polymerization and then incorporated into a sulfonated poly(ether ether ketone) matrix to fabricate composite membranes. The inner shell renders the absorbed water of lower chemical potential and higher bound water content, yielding the composite membrane with enhanced water retention properties. The higher water uptake ensures composite membrane facilitated proton transfer via a vehicle mechanism and the lower water loss confers a reduced proton conductivity decline. The outer shell generates sulfonic acid–imidazole pairs within the membranes, which construct low-energy-barrier pathways to facilitate proton transfer via the Grotthuss mechanism. Under identical conditions, PMC-Ns endow much higher proton conductivity to composite membranes than the microcapsules with both carboxylic acid inner shell and outer shell, or both imidazole inner shell and outer shell. Particularly, incorporating 20 wt% PMC-Ns affords the composite membrane a 1.7 times increase in proton conductivity under 100% relative humidity (RH) and a 41.8 times increase in proton conductivity under 20% RH. Moreover, the methanol barrier property of the composite membranes is explored.

Enhanced CO2 permeability of membranes by incorporating polyzwitterion@CNT composite particles into polyimide matrix.

In this study, polyzwitterion is introduced into a CO2 separation membrane. Composite particles of polyzwitterion coated carbon nanotubes (SBMA@CNT) are prepared via a precipitation polymerization method. Hybrid membranes are fabricated by incorporating SBMA@CNT in polyimide matrix and utilized for CO2 separation. The prepared composite particles and hybrid membranes are characterized by transmission electron microscopy (TEM) with element mapping, field emission scanning electron microscopy (FESEM), Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC) and an electronic tensile machine. Water uptake and water state of membranes are measured to probe the relationship among water uptake, water state and CO2 transport behavior. Hybrid membranes show significantly enhanced CO2 permeability compared to an unfilled polyimide membrane at a humidified state. A hybrid membrane with 5 wt % SBMA@CNT exhibits the maximum CO2 permeability of 103 Barrer with a CO2/CH4 selectivity of 36. The increase of CO2 permeability is attributed to the incorporation of the SBMA@CNT composite particles. First, SBMA@CNT form interconnected channels for CO2 transport due to the facilitated transport effect of the quaternary ammonium in repeat unit of pSBMA. Second, SBMA@CNT improve water uptake and adjust water state of membrane, which further increases CO2 permeability. Meanwhile, the variation of CO2/CH4 selectivity is dependent on the bound water portion in the membrane. A gas permeation test at a dry state and a pressure test are conducted to further probe the membrane separation performance.

Zwitterionic microcapsules as water reservoirs and proton carriers within a Nafion membrane to confer high proton conductivity under low humidity.

Zwitterionic microcapsules (ZMCs) based on sulfobetaine with tunable hierarchical structures, superior water retention properties, and high proton conduction capacities are synthesized via precipitation polymerization. The incorporation of ZMCs into a Nafion matrix renders the composite membranes with significantly enhanced proton conductivity especially under low humidity. The composite membrane with 15 wt % ZMC-I displayed the highest proton conductivity of 5.8 × 10(-2) S cm(-1) at 40 °C and 20% relative humidity after 90 min of testing, about 21 times higher than that of the Nafion control membrane. The increased proton conductivity is primarily attributed to the versatile roles of ZMCs as water reservoirs and proton conductors for rendering a stable water environment and an additional proton conduction pathway within the membranes. This study may contribute to the rational design of water-retaining and proton-conducting materials.

A highly permeable graphene oxide membrane with fast and selective transport nanochannels for efficient carbon capture

Ultrathin graphene oxide membranes using borate as both crosslinker of GO nanosheets and facilitated transport carrier of CO2 are designed and fabricated. The membranes exhibited high CO2 permeance up to 650 GPU and a CO2/CH4 selectivity of 75, due to the rational manipulation of the interlayer nanochannel size, sufficient facilitated transport carriers and high water content.