Preparation and Conducting Behavior of Amphibious Organic/Inorganic Hybrid Proton Exchange Membranes Based on Benzyltetrazole

A series of novel amphibious organic/inorganic hybrid proton exchange membranes with H3PO4 doped which could be used under both wet and dry conditions was prepared through a sol-gel process based on acrylated triethoxysilane（A-TES） and benzyltetrazole-modified triethoxysilane（BT-TES）.The dual-curing approach including UV-curing and thermal curing was used to obtain the crosslinked membranes.Polyethylene glycol（400） diacrylate（PEGDA） was used as an oligomer to form the polymeric matrix.The molecular structures of precursors were characterized by 1 H,13 C and 29 Si NMR spectra.The thermogravimetric analysis（TGA） results show that the membranes exhibit acceptable thermal stability for their application at above 200 oC.The differential scanning calorimeter（DSC） determination indicates that the crosslinked membranes with the mass ratios of below 1.6 of BT-TES to A-TES and the same mass of H3PO4 doped as that of A-TES possess the-T g s,and the lowest T g（-28.9 ℃） exists for the membrane with double mass of H3PO4 doped as well.The high proton conductivity in a range of 9.4―17.3 mS/cm with the corresponding water uptake of 19.1%―32.8% of the membranes was detected at 90 oC under wet conditions.Meanwhile,the proton conductivity in a dry environment for the membrane with a mass ratio of 2.4 of BT-TES to A-TES and double H3PO4 loading increases from 4.89×10-2 mS/cm at 30 ℃ to 25.7 mS/cm at 140 ℃.The excellent proton transport ability under both hydrous and anhydrous conditions demonstrates a potential application in the polymer electrolyte membrane fuel cells.

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.

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.

A heterogeneous double chamber electro-Fenton with high production of H_(2)O_(2) using La–CeO_(2) modified graphite felt as cathode

Hydrogen peroxide synthesis by electro-reduction of O_(2) to substitute the current anthraquinone process has attracted a great deal of attention. Low oxygen utilization rate and low hydrogen peroxide production remain obstacles to electro-Fenton application. In situ H_(2)O_(2) generated by electrochemical reaction depends on the electrochemical performance of the cathode and the structure of the reactor. Here, novel graphite felt(GF) modified by La-doped CeO_(2)(La-CeO_(2)) was developed as a cathode. A new double chamber electro-Fenton reactor was proposed, where an organic ultrafiltration membrane was used to prevent H_(2)O_(2) from spreading to the anode. The effects of hydrothermal temperature, time and urea concentration on the electrochemical properties of graphite felt were investigated. The accumulated concentration of H_(2)O_(2) on the modified cathode reached 218.4 mg·L^(-1)in 1 h when the optimal conditions of hydrothermal temperature 120 ℃ and urea concentration 0.55%(mass) in 24 h. The degradation rate of methyl orange reached 98.29%. The new electro-Fenton reactor can efficiently produce hydrogen peroxide to degrade various organic substances and has a high potential for treating wastewater in the chemical industry.

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.

Preparation,characterization and performance of poly(m-phenylene isophthalamide)/organically modified montmorillonite nanocomposite membranes in removal of perfluorooctane sulfonate

Nanocomposite membranes containing poly（m-phenylene isophthalamide）（PMIA） and organically modified montmorillonite（OMMT） were prepared by a combination of solution dispersion and wet-phase inversion methods, and the effects of OMMT addition on the properties and performance of fabricated nanofiltration membranes were investigated. The membranes were characterized by contact angle measurements, scanning electron microscopy（SEM）, atomic force microscopy（AFM）, thermogravimetric analysis, and zeta potential.The performance of the membranes was elucidated by the removal of perfluorooctane sulfonate（PFOS） at neutral p H. Increasing OMMT concentration improved the thermal stability and hydrophilicity of the membranes. The permeation and rejection of PFOS were significantly improved. The performance of fabricated nanofiltration membranes in removal of PFOS varied depending on the solute and membrane properties as well as solution conditions. Finally,a comparison between fabricated membranes and a commercial NF membrane（ESNA1-K1,Hydecanme） proved that the OMMT addition is a convenient procedure for producing nanocomposite membranes with superior properties and performance.

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.

Roles of membrane and organic fouling layers on the removal of endocrine disrupting chemicals in microfiltration

To understand the adsorption behavior of endocrine disrupting chemicals（EDCs） is important for enhancing the treatment performance and preventing potential secondary pollution caused by EDCs desorption in a microfiltration system. The dynamic adsorption of four representative EDCs, namely estriol（E3）, 17β-estradiol（E2）, 17α-ethynylestradiol（EE2）, and 4-nonylphenol（4-NP） in a microfiltration system was investigated using the Thomas＇ model.The product of the equilibrium constant and the total adsorption capacity of the membrane,Ka, for E3, E2, EE2, and 4-NP were 4.91, 9.78, 15.6, and 826, respectively, strongly correlating with the compound octanol–water partition coefficient（KOW）. Adsorption appeared to be enhanced when organic fouling formed on the surface of membrane, indicating the role of an additional adsorption column for EDCs acted by a fouling layer in microfiltration. Results of a comparison between the Ka values for clean membrane and fouled membrane illustrated that the significant contribution made by fouling layers may be attributed to the foulant layer＇s hydrophobicity（in the case of calcium humate layer） and thickness（in the case of calcium alginate layer）. This study provided a novel perspective to quantitatively analyze the dynamic adsorption behavior of trace pollutants in membrane process.

Microstructure Manipulation of Covalent Organic Frameworks(COFs)-based Membrane for Efficient Separations

Covalent organic framework(COF) membranes have exhibited great potential to become the next-generation membranes for efficient separations due to the diverse structures, ordered framework pores, tunable functionality and excellent stability. This review presents the microstructure manipulation strategies for separation performance enhancement of COF membranes in recent years. Based on the three mechanisms of molecular sieving, surface diffusion, and facilitated transport, the structural modulation methods to enhance the selectivity of COF membranes are analyzed in detail. Next, strategies of realizing ultrashort mass transfer pathways and ultralow mass transfer resistance for the permeability enhancement are elaborated. Furthermore, the framework stability in COFs, interlayer stability between COF nanosheets and interfacial stability between COF layer and substrate are discussed. Finally, we discuss the existing challenges and perspectives on the future development of COF membranes, targeting at identifying the most promising strategies and directions for the engineering of COF membranes.

Role of membrane and compound properties in affecting the rejection of pharmaceuticals by different RO/NF membranes

This study was conducted to assess the merits and limitations of various high-pressure membranes, tight nanofiltration （NF） membranes in particular, for the removal of trace organic compounds （TrOCs）. The performance of a low-pressure reverse osmosis （LPRO） membrane （ESPA1）, a tight NF membrane （NF90） and two loose NF membranes （HL and NF270） was compared for the rejection of 23 different pharmaceuticals （PhACs）. Efforts were also devoted to understand the effect of adsorption on the rejection performance of each membrane. Difference in hydrogen bond formation potential （HFP） was taken into consideration. Results showed that NF90 performed similarly to ESPA1 with mean rejection higher than 95%. NF270 outperformed HL in terms of both water permeability and PhAC rejection higher than 90%. Electrostatic effects were more significant in PhAC rejection by loose NF membranes than tight NF and LPRO membranes. The adverse effect of adsorption on rejection by HL and ESPA1 was more substantial than NF270 and NF90, which could not be simply explained by the difference in membrane surface hydrophobicity, selective layer thickness or pore size. The HL membrane had a lower rejection of PhACs of higher hydrophobicity （log D〉0） and higher HFP （〉0.02）. Nevertheless, the effects of PhAC hydrophobicity and HFP on rejection by ESPA1 could not be discerned. Poor rejection of certain PhACs could generally be explained by aspects of steric hindrance, electrostatic interactions and adsorption. High-pressure membranes like NF90 and NF270 have a high promise in TrOC removal from contaminated water.

Sealing functional ionic liquids in conjugated microporous polymer membrane by solvent-assisted micropore tightening

Porous organic polymers hold great promise for molecular sieving membrane separation.Although the inclusion of functional ionic liquid(IL)in the pores offers a facile way to manipulate their separation properties,the IL leaching during the separation process is difficult to avoid.Herein,we report a strategy to in-situ encapsulate ILs into the micropores of the conjugated microporous polymer membrane via a 6-min electropolymerization and further seal the aperture of the pores to prevent ILs leaching by solvent-assisted micropore tightening(SAMT).Upon screening the binding energy between different ILs and gas molecules,two ILs were selected to be incorporated into the membrane for CO_(2)/CH_(4) and O_(2)/N_(2) gas separations.The resultant separation performances surpass the 2008 Robeson upper bound.Notably,the ILs can be locked in the micropores by a facile high surface tension solvent treatment process to improve their separation stability,as evidenced by a 7-day continuous test.This simple and controllable process not only enables efficient and steady separation performance but also provides an effective strategy for confining and sealing functional guest molecules in the porous solids for various applications.

Identifying the major fluorescent components responsible for ultrafiltration membrane fouling in different water sources

Three-dimensional fluorescence excitation–emission matrix（EEM） coupled with parallel factor analysis（PARAFAC） was performed for a total of 18 water samples taken from three water sources（two lakes and one wastewater treatment plant（WWTP） secondary effluent）,with the purpose of identifying the major ultrafiltration（UF） membrane foulants in different water sources. Three fluorescent components（C1, C2 and C3） were identified,which represented terrestrially derived humic-like substances（C1）, microbially derived humic-like substances（C2）, and protein-like substances（C3）. The correlations between the different fluorescent components and UF membrane fouling were analyzed. It was shown that for the WWTP secondary effluent, all three components（C1, C2 and C3） made a considerable contribution to the irreversible and total fouling of the UF membrane.However, for the two lakes, only the C3 exhibited a strong correlation with membrane fouling, indicating that the protein-like substances were the major membrane foulants in the lake waters. Significant attachment of C1, C2 and C3 to the UF membrane was also confirmed by mass balance analyses for the WWTP secondary effluent; while the attachment of C1 and C2 was shown to be negligible for the two lakes. The results may provide basic formation for developing suitable fouling control strategies for sustainable UF processes.

Positively charged microporous ceramic membrane for the removal of Titan Yellow through electrostatic adsorption

To develop a depth filter based on the electrostatic adsorption principle, positively charged microporous ceramic membrane was prepared from a diatomaceous earth ceramic membrane.The internal surface of the highly porous ceramic membrane was coated with uniformly distributed electropositive nano-Y2O3 coating. The dye removal performance was evaluated through pressurized filtration tests using Titan Yellow aqueous solution. It showed that positively charged microporous ceramic membrane exhibited a flow rate of 421 L/（m^2·hr） under the trans-membrane pressure of 0.03 bar. Moreover it could effectively remove Titan Yellow with feed concentration of 10 mg/L between pH 3 to 8. The removal rate increased with the enhancement of the surface charge properties with a maximum rejection of 99.6%. This study provides a new and feasible method of removing organic dyes in wastewater. It is convinced that there will be a broad market for the application of charged ceramic membrane in the field of dye removal or recovery from industry wastewater.

Fouling distribution in forward osmosis membrane process

Fouling behavior along the length of membrane module was systematically investigated by performing simple modeling and lab-scale experiments of forward osmosis （FO） membrane process. The flux distribution model developed in this study showed a good agreement with experimental results, validating the robustness of the model. This model demonstrated, as expected, that the permeate flux decreased along the membrane channel due to decreasing osmotic pressure differential across the FO membrane. A series of fouling experiments were conducted under the draw and feed solutions at various recoveries simulated by the model. The simulated fouling experiments revealed that higher organic （alginate） fouling and thus more flux decline were observed at the last section of a membrane channel, as foulants in feed solution became more concentrated. Furthermore, the water flux in FO process declined more severely as the recovery increased due to more foulants transported to membrane surface with elevated solute concentrations at higher recovery, which created favorable solution environments for organic adsorption. The fouling reversibility also decreased at the last section of the membrane channel, suggesting that fouling distribution on FO membrane along the module should be carefully examined to improve overall cleaning efficiency. Lastly, it was found that such fouling distribution observed with co-current flow operation became less pronounced in counter- current flow operation of FO membrane process.