Aqueous Two-Phase Interfacial Assembly of COF Membranes for Water Desalination

Aqueous two-phase system features with ultralow interfacial tension and thick interfacial region,affording unique confined space for membrane assembly.Here,for the first time,an aqueous two-phase interfacial assembly method is proposed to fabricate covalent organic framework(COF)membranes.The aqueous solution containing polyethylene glycol and dextran undergoes segregated phase separation into two water-rich phases.By respectively distributing aldehyde and amine monomers into two aqueous phases,a series of COF membranes are fabricated at water-water interface.The resultant membranes exhibit high NaCl rejection of 93.0-93.6% and water permeance reaching 1.7-3.7 L m^(−2) h^(−1) bar^(−1),superior to most water desalination membranes.Interestingly,the interfacial tension is found to have pronounced effect on membrane structures.The appropriate interfacial tension range(0.1-1.0 mN m^(−1))leads to the tight and intact COF membranes.Furthermore,the method is extended to the fabrication of other COF and metal-organic polymer membranes.This work is the first exploitation of fabricating membranes in all-aqueous system,confering a green and generic method for advanced membrane manufacturing.

Computational exploration of H_2S/CH_4 mixture separation using acid-functionalized UiO-66(Zr) membrane and composites

A computational study was firstly performed in this work to examine the applicability of an acid-functionalized metal-organic framework(MOF), Ui O-66(Zr)-(COOH)2, in membrane-based H2S/CH4 separation. The results show that this MOF could be potentially interesting when being used as the pure membrane material for the separation of the mixture with low H2 S concentration. Further, the performance of 10 different mixed matrix membranes(MMMs) on the basis of the MOF was predicted by combing the molecular simulation data and the Maxwell permeation model. The results indicate that using this MOF as filler particles in MMMs can signi ficantly enhance the permeation performance of pure polymers. The findings obtained in this work may be helpful in facilitating the application of this promising MOF for practical desulfurization process of fuel gas.

Research Progress in the Fabrication of Covalent Organic Framework Membranes for Chemical Separations

Membrane technology has become one of the most promising separation technologies for its energy saving, high separation efficiency, environmental friendliness, and economic feasibility. Covalent organic frameworks(COFs) with intrinsically high porosity, controllable pore size, uniform pore size distribution and long-range ordered channel structure, have emerged as next-generation materials to fabricate advanced separation membranes. This feature article summarizes some latest studies in the development of pure COF membranes in our lab, including their fabrication and applications in chemical separations. Finally, current challenges facing high-performance COF separation membranes are discussed.

Growth of ZnO self-converted 2D nanosheet zeolitic imidazolate framework membranes by an ammoniaassisted strategy

Shaping crystalline porous materials such as metal organic frameworks （MOFs） and zeolites into two-dimensional （2D） nanosheet forms is highly desirable for developing high-performance molecular sieving membranes. However, conventional exfoliation-deposition is complex and challenging for the large-scale fabrication of nanosheet MOF tubular membranes. Here, for the first time, we report a direct growth technique by ZnO self-conversion and ammonia assistance to fabricate zeolitic imidazolate framework （ZIF） membranes consisting of 2D nanosheets on porous hollow fiber substrates; the membranes are suitable for large-scale industrial gas separation processes. The proposed fabrication process for ZIF nanosheet membranes is based on the localized self-conversion of a pre-deposited thin layer of ZnO in a ligand solution containing ammonium hydroxide as a modulator. The resulting ZIF 2D nanosheet tubular membrane is highly oriented and only 50 nm in thickness. It exhibits excellent molecular sieving performance, with high H2 permeance and selectivity for H2/CO2 separation. This technique shows great promise in MOF nanosheet membrane fabrication for large-scale molecular sieving applications.

Recent progress of covalent organic frameworks membranes:Design,synthesis,and application in water treatment

To date,significant efforts have been devoted to eliminating hazardous components to purify wastewater through the development of various nanomaterials.Covalent organic frameworks(COFs),an important branch of the porous crystalline family,possess the peculiarity of ultrahigh surface area,adjustable pore size,and facile functionality.Exciting studies from design fabrication to potential applications in water treatment by COF-based membranes(COMs)have emerged.This review summarizes various preparation strategies and synthesis mechanisms for COMs,including layer-by-layer stacking,in situ growth,interfacial polymerization,and electrochemical synthesis,and briefly describes the advanced characterization techniques for COMs.Moreover,the application of COMs in heavy metal removal,dye separation,purification of radionuclides,pollutant detection,sea water desalination,and so on,is described and discussed.Finally,the perspectives on future opportunities for designing COMs in water purification have been proposed.

Free-standing polymer-metal-organic framework membrane with high proton conductivity and water stability

As a new class of porous material,polymer-metal-organic framework(polyMOF)has attracted tremendous interests owing to their combined advantages of polymer and crystalline MOF.However,the poor film-forming ability of polyMOF limits its widespread application,especially in membrane separation area.Herein,for the first time,we demonstrate the fabrication of freestanding polyMOF membrane.The polyMOF nanosheets are synthesized by a polymer-assisted self-inhibition crystal growth strategy.Followed by self-assembly through vacuum filtration,a 20μm-thick free-standing polyMOF membrane is constructed.Benefiting from the inclusion of polymer with hydrophobic backbone and the continuously distributed non-coordinated hydrophilic groups along polymer chain,the polyMOF membrane attains excellent structure stability against water,as well as superior proton transfer property.Proton conductivity as high as 112 and 25.6 mS·cm^(–1)is obtained by this polyMOF membrane at 100%and 20%relative humidity(RH),respectively,which are two orders of magnitude higher than those of pristine MOF.The conductivity under low humidity(20%RH)is even over 8 times higher than that of commercial Nafion membrane(3 mS·cm^(–1)).This study may provide some guidance on the development of polyMOF membranes.

Interfacially stable MOF nanosheet membrane with tailored nanochannels for ultrafast and thermo-responsive nanofiltration

Two-dimensional nanosheet membranes with responsive nanochannels are appealing for controlled mass transfer/separation,but limited by everchanging thicknesses arising from unstable interfaces.Herein,an interfacially stable,thermo-responsive nanosheet membrane is assembled from twin-chain stabilized metal-organic framework(MOF)nanosheets,which function via two cyclic amide-bearing polymers,thermo-responsive poly(N-vinyl caprolactam)(PVCL)for adjusting channel size,and non-responsive polyvinylpyrrolidone for supporting constant interlayer distance.Owing to the microporosity of MOF nanosheets and controllable interface wettability,the hybrid membrane demonstrates both superior separation performance and stable thermo-responsiveness.Scattering and correlation spectroscopic analyses further corroborate the respective roles of the two polymers and reveal the microenvironment changes of nanochannels are motivated by the dehydration of PVCL chains.

Inorganic microporous membranes for hydrogen separation:Challenges and solutions

Porous membrane separation is a competitive hydrogen purification technology due to the advantages of environmental friendliness,energy-saving,simple operation,and low cost.Benefiting from the booming development of materials science and chemical science,great progress has been made in H_(2) separation with porous membranes.This review focuses on the latest advances in the design and fabrication of H_(2) separation inorganic microporous membranes,with emphasis on the synthetic strategies to achieve structural integrity,continuity and stability.This review starts with a brief introduction to the membrane separation mechanisms,followed by an elaboration on the synthetic challenges and corresponding solutions of various high-performance inorganic microporous membranes based on zeolites,silica,carbon,and metal-organic frameworks(MOFs).At last,by highlighting the prospects of ultrathin two-dimensional(2D)porous membranes,we wish to shed some light on the further development of new materials and membranes for highly efficient hydrogen separation.