Thin film composite(TFC) membranes represent a highly promising platform for efficient nanofiltration(NF)processes. However, the improvement in permeance is impeded by the substrates with low permeances. Herein,highly...Thin film composite(TFC) membranes represent a highly promising platform for efficient nanofiltration(NF)processes. However, the improvement in permeance is impeded by the substrates with low permeances. Herein,highly permeable gradient phenolic membranes with tight selectivity are used as substrates to prepare TFC membranes with high permeances by the layer-by-layer assembly method. The negatively charged phenolic substrates are alternately assembled with polycation polyethylenimine(PEI) and polyanion poly(acrylic acid)(PAA)as a result of electrostatic interactions, forming thin and compact PEI/PAA layers tightly attached to the substrate surface. Benefiting from the high permeances and tight surface pores of the gradient nanoporous structures of the substrates, the produced PEI/PAA membranes exhibit a permeance up to 506 L? m-2?h-1?MPa-1, which is ~2–10 times higher than that of other membranes with similar rejections. The PEI/PAA membranes are capable of retaining N 96.1% of negatively charged dyes following the mechanism of electrostatic repulsion. We demonstrate that the membranes can also separate positively and neutrally charged dyes from water via other mechanisms.This work opens a new avenue for the design and preparation of high-flux NF membranes, which is also applicable to enhance the permeance of other TFC membranes.展开更多
The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane.In this work,a hydrophilic PDA-[PDDA/TiO2]+Cl-membrane was prepared by a one-step codeposition of poly(d...The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane.In this work,a hydrophilic PDA-[PDDA/TiO2]+Cl-membrane was prepared by a one-step codeposition of poly(diallyldimethylammonium chloride)(PDDA)polyelectrolyte solution containing positively charged TiO2@PDDA nanoparticles with the assistance of dopamine(DA).Such positively charged membrane can be transformed into a hydrophobic membrane PDA-[PDDA/TiO2]+PFO-via the counterion exchange between Cl-and PFO-(perfluorooctanoate).The transformation between hydrophilicity and hydrophobicity is reversible.For both hydrophilic and hydrophobic membranes,the nanofiltration performances were respectively investigated by the aqueous solution and ethanol solution of dyes including methyl blue(MB),Congo red(CR)and Evans blue(EB),and as well metal salt aqueous solution.The consecutive running stability and anti-fouling performance of both hydrophilic and hydrophobic membranes were explored.The results revealed that both membranes showed high nanofiltration performances for retention of dyes in(non)aqueous solution.For the hydrophilic membrane,the rejection of salts in a sequence is MgSO4>Na2SO4>MgCl2>NaCl.Moreover,both of the hydrophilic and hydrophobic membranes showed high stability and antifouling property.展开更多
The adsorption amount of poly(styrene sulfonate) and poly(dimethyldiallyl ammonium chloride) (PSS/PDDA) self-assembled multilayer membranes in designed dipping solvents were measured by UV-Vis-spectroscopy and quartz ...The adsorption amount of poly(styrene sulfonate) and poly(dimethyldiallyl ammonium chloride) (PSS/PDDA) self-assembled multilayer membranes in designed dipping solvents were measured by UV-Vis-spectroscopy and quartz crystal microbalance (QCM). Intrinsic viscosities of PSS and PDDA in corresponding dipping solvents were determined by an Ubbelohde viscometer. It is found that the adsorption amount of PSS/PDDA self-assembled multilayer membranes built up in different dipping solutions, added salt concentration, pH of solution and solvent quality, respectively changed oppositely with the corresponding intrinsic viscosity of PSS and PDDA in dipping solvents. A negative relation between the adsorption amount and intrinsic viscosity was revealed, and explained in term of the concept of excluded volume of polymer molecule in dilute solutions.展开更多
Electrolyte hydrogels are perspective materials for applications in electrochemical devices, which work at ambient temperatures. In this work, hydrogel sulpho-modified membranes were formed by radical co-polymerizatio...Electrolyte hydrogels are perspective materials for applications in electrochemical devices, which work at ambient temperatures. In this work, hydrogel sulpho-modified membranes were formed by radical co-polymerization of sodium styrensulphonate and potassium sulphopropyl acrylate with acrylamide and acrylonitrile. The hydrogel membranes were obtained in the form of thin films. Properties of the membranes were studied by thermogravimetry, mass-spectrometry and IR-spectrometry. The prepared membranes were thermally stable up to 70°C - 90°C, and showed ion exchange capacity and swelling coefficients sufficient for use as ion-exchange or proton-conducting membranes.展开更多
A series of sulfonated polybenzimidazoles(sPBI-SF)were prepared from 2,2-bis(4-carboxyphenyl)hexafluoro- propane(BIS-B-AF),3,3′-disulfonyl-4,4′-dicarboxyldiphenylsulfone(DSDCDPS)and 3,3′-diaminobenzidine(DAB)at var...A series of sulfonated polybenzimidazoles(sPBI-SF)were prepared from 2,2-bis(4-carboxyphenyl)hexafluoro- propane(BIS-B-AF),3,3′-disulfonyl-4,4′-dicarboxyldiphenylsulfone(DSDCDPS)and 3,3′-diaminobenzidine(DAB)at various stoichiometric ratio by solution copolycondensation in poly(phosphoric acid).The chemical structure of the resulting sPBI-SF was confirmed by FTIR and ~1H-NMR.The sPBI-SFs with high molecular-weights(M_n=39400-65500)were soluble in DMF,DMSO or DMAc.Therefore,they could form some transparent a...展开更多
Owing to the recent push toward efficient energy storage/conversion devices, fuel cells have become a strong candidate for energy conversion equipments. On the other hand, block copolymer polyelectrolytes are interest...Owing to the recent push toward efficient energy storage/conversion devices, fuel cells have become a strong candidate for energy conversion equipments. On the other hand, block copolymer polyelectrolytes are interesting materials for proton exchange membranes in fuel cells. Thus a considerable attention has been paid to the development of block copolymer polyelectrolyte membranes. In this study, the microdomains in block copolymer polyelectrolytes were controlled by external electric fields to develop high performance membranes with improved proton conductivity. The microdomain alignments in sulfonated polystyrene-b-hydrogenated poly butadiene-b-polystyrene block copolymer electrolyte were monitored by cross-sectional transmission electron microscopy analysis. The proton conductivities of the block copolymer electrolyte membranes were measured before and after exposure to electric field. In addition, the morphological features of the block copolymer electrolyte were observed with small angle x-ray scattering and atomic force microscopy.展开更多
Polyelectrolyte porous membranes(PPMs)belong to the most interesting classes of materials,because the synergy of tunable pore sizes and charge nature of polyelectrolyte endow them with wide-ranging practical applicati...Polyelectrolyte porous membranes(PPMs)belong to the most interesting classes of materials,because the synergy of tunable pore sizes and charge nature of polyelectrolyte endow them with wide-ranging practical applications.However,owing to the water solu-bility and ionic nature of the polyelectrolytes,traditional polyelectrolytes are difficult to use in scalable preparation of high-quality PPMs through the well-developed industrial methods.Poly(ionic liquid)s(PIL)are a subclass of functional polyelectrolytes bearing ionic liquid groups in their repeating unites,inheriting the advantages of ionic liquids(ILs)and macromolecular architecture features.In recent years,along with rapid development of PIL materials chemistry,considerable and significant developments involving the novel preparation methods,and structure-property-function relationships of PPMs have been made.In this review,we highlight the latest discovery and proceedings of PPMs,particularly the advancements in how to tailor structures and properties of PPMs by ra-tional structure design of PILs.The formation mechanisms of various PPMs were also discussed in detail from the viewpoint of PILs molecular structures.A future perspective of the challenges and promising potential of PPMs is cast on the basis of these achieve-ments.We expect that these analyses and deductions will be useful for the design of useful PPMs and serve as a source of inspira-tion for the design of future multifunctional PPMs.展开更多
Polyelectrolytes have a high hydrophilicity and can be used in pervaporation(PV) dehydration of alcohol. Chitosan(CS) used as polycation polysaccharide and carboxymethyl cellulose(CMC) used as polyanion polysaccharide...Polyelectrolytes have a high hydrophilicity and can be used in pervaporation(PV) dehydration of alcohol. Chitosan(CS) used as polycation polysaccharide and carboxymethyl cellulose(CMC) used as polyanion polysaccharide were chosen as PV membrane materials. CS membrane cross linked with oxalic acid or citric acid and CS CMC polyelectrolyte membrane were prepared. The results showed that the polyelectrolyte membranes had an excellent PV performance for alcohol dehydration. For example, when the separation factor gone up to 2 300, the total flux of CS CMC polyelectrolyte membrane was above 800 g/(m 2·h) in 95% EtOH and at 72 ℃. The nature and content of crosslinking agents affected the separation properties of cross linked CS membrane. The total flux of the cross linked CS membrane increased with operating temperature increasing and corresponded to the Arrhenius equation.展开更多
基金Supported by the National Basic Research Program of China(2015CB655301)the Natural Science Foundation of China(21825803)+2 种基金and the Natural Science Foundation of Jiangsu Province(BK20150063)the Program of Excellent Innovation Teams of Jiangsu Higher Education Institutionsthe Project of Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Thin film composite(TFC) membranes represent a highly promising platform for efficient nanofiltration(NF)processes. However, the improvement in permeance is impeded by the substrates with low permeances. Herein,highly permeable gradient phenolic membranes with tight selectivity are used as substrates to prepare TFC membranes with high permeances by the layer-by-layer assembly method. The negatively charged phenolic substrates are alternately assembled with polycation polyethylenimine(PEI) and polyanion poly(acrylic acid)(PAA)as a result of electrostatic interactions, forming thin and compact PEI/PAA layers tightly attached to the substrate surface. Benefiting from the high permeances and tight surface pores of the gradient nanoporous structures of the substrates, the produced PEI/PAA membranes exhibit a permeance up to 506 L? m-2?h-1?MPa-1, which is ~2–10 times higher than that of other membranes with similar rejections. The PEI/PAA membranes are capable of retaining N 96.1% of negatively charged dyes following the mechanism of electrostatic repulsion. We demonstrate that the membranes can also separate positively and neutrally charged dyes from water via other mechanisms.This work opens a new avenue for the design and preparation of high-flux NF membranes, which is also applicable to enhance the permeance of other TFC membranes.
基金financially supported by the National Natural Science Foundation of China(21476005,21878003)the National Natural Science Fund for Innovative Research Groups(51621003)。
文摘The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane.In this work,a hydrophilic PDA-[PDDA/TiO2]+Cl-membrane was prepared by a one-step codeposition of poly(diallyldimethylammonium chloride)(PDDA)polyelectrolyte solution containing positively charged TiO2@PDDA nanoparticles with the assistance of dopamine(DA).Such positively charged membrane can be transformed into a hydrophobic membrane PDA-[PDDA/TiO2]+PFO-via the counterion exchange between Cl-and PFO-(perfluorooctanoate).The transformation between hydrophilicity and hydrophobicity is reversible.For both hydrophilic and hydrophobic membranes,the nanofiltration performances were respectively investigated by the aqueous solution and ethanol solution of dyes including methyl blue(MB),Congo red(CR)and Evans blue(EB),and as well metal salt aqueous solution.The consecutive running stability and anti-fouling performance of both hydrophilic and hydrophobic membranes were explored.The results revealed that both membranes showed high nanofiltration performances for retention of dyes in(non)aqueous solution.For the hydrophilic membrane,the rejection of salts in a sequence is MgSO4>Na2SO4>MgCl2>NaCl.Moreover,both of the hydrophilic and hydrophobic membranes showed high stability and antifouling property.
基金supported by the NNSFC(Nos.20574059,50633030)the Major State Basic Research Program of China(No.9732003C8615700).
文摘The adsorption amount of poly(styrene sulfonate) and poly(dimethyldiallyl ammonium chloride) (PSS/PDDA) self-assembled multilayer membranes in designed dipping solvents were measured by UV-Vis-spectroscopy and quartz crystal microbalance (QCM). Intrinsic viscosities of PSS and PDDA in corresponding dipping solvents were determined by an Ubbelohde viscometer. It is found that the adsorption amount of PSS/PDDA self-assembled multilayer membranes built up in different dipping solutions, added salt concentration, pH of solution and solvent quality, respectively changed oppositely with the corresponding intrinsic viscosity of PSS and PDDA in dipping solvents. A negative relation between the adsorption amount and intrinsic viscosity was revealed, and explained in term of the concept of excluded volume of polymer molecule in dilute solutions.
文摘Electrolyte hydrogels are perspective materials for applications in electrochemical devices, which work at ambient temperatures. In this work, hydrogel sulpho-modified membranes were formed by radical co-polymerization of sodium styrensulphonate and potassium sulphopropyl acrylate with acrylamide and acrylonitrile. The hydrogel membranes were obtained in the form of thin films. Properties of the membranes were studied by thermogravimetry, mass-spectrometry and IR-spectrometry. The prepared membranes were thermally stable up to 70°C - 90°C, and showed ion exchange capacity and swelling coefficients sufficient for use as ion-exchange or proton-conducting membranes.
基金This work was financially supported by the National Basic Research Program(No.2007CB808000)the basic research foundation of Shanghai Science and Technique Committee(No.05DJ14005)the Zhejiang Provincial Natural Science Foundation of China(No.Y405500).
文摘A series of sulfonated polybenzimidazoles(sPBI-SF)were prepared from 2,2-bis(4-carboxyphenyl)hexafluoro- propane(BIS-B-AF),3,3′-disulfonyl-4,4′-dicarboxyldiphenylsulfone(DSDCDPS)and 3,3′-diaminobenzidine(DAB)at various stoichiometric ratio by solution copolycondensation in poly(phosphoric acid).The chemical structure of the resulting sPBI-SF was confirmed by FTIR and ~1H-NMR.The sPBI-SFs with high molecular-weights(M_n=39400-65500)were soluble in DMF,DMSO or DMAc.Therefore,they could form some transparent a...
文摘Owing to the recent push toward efficient energy storage/conversion devices, fuel cells have become a strong candidate for energy conversion equipments. On the other hand, block copolymer polyelectrolytes are interesting materials for proton exchange membranes in fuel cells. Thus a considerable attention has been paid to the development of block copolymer polyelectrolyte membranes. In this study, the microdomains in block copolymer polyelectrolytes were controlled by external electric fields to develop high performance membranes with improved proton conductivity. The microdomain alignments in sulfonated polystyrene-b-hydrogenated poly butadiene-b-polystyrene block copolymer electrolyte were monitored by cross-sectional transmission electron microscopy analysis. The proton conductivities of the block copolymer electrolyte membranes were measured before and after exposure to electric field. In addition, the morphological features of the block copolymer electrolyte were observed with small angle x-ray scattering and atomic force microscopy.
基金We greatly acknowledge the financial supports by the National Natural Science Foundation of China(Grant No.21875119)the Natural Science Foundation of Tianjin City(Grant Nos.19JCYBJC17500,21JCZDJC00250)the National Programfor Support of Top-notch Young Professionals。
文摘Polyelectrolyte porous membranes(PPMs)belong to the most interesting classes of materials,because the synergy of tunable pore sizes and charge nature of polyelectrolyte endow them with wide-ranging practical applications.However,owing to the water solu-bility and ionic nature of the polyelectrolytes,traditional polyelectrolytes are difficult to use in scalable preparation of high-quality PPMs through the well-developed industrial methods.Poly(ionic liquid)s(PIL)are a subclass of functional polyelectrolytes bearing ionic liquid groups in their repeating unites,inheriting the advantages of ionic liquids(ILs)and macromolecular architecture features.In recent years,along with rapid development of PIL materials chemistry,considerable and significant developments involving the novel preparation methods,and structure-property-function relationships of PPMs have been made.In this review,we highlight the latest discovery and proceedings of PPMs,particularly the advancements in how to tailor structures and properties of PPMs by ra-tional structure design of PILs.The formation mechanisms of various PPMs were also discussed in detail from the viewpoint of PILs molecular structures.A future perspective of the challenges and promising potential of PPMs is cast on the basis of these achieve-ments.We expect that these analyses and deductions will be useful for the design of useful PPMs and serve as a source of inspira-tion for the design of future multifunctional PPMs.
文摘Polyelectrolytes have a high hydrophilicity and can be used in pervaporation(PV) dehydration of alcohol. Chitosan(CS) used as polycation polysaccharide and carboxymethyl cellulose(CMC) used as polyanion polysaccharide were chosen as PV membrane materials. CS membrane cross linked with oxalic acid or citric acid and CS CMC polyelectrolyte membrane were prepared. The results showed that the polyelectrolyte membranes had an excellent PV performance for alcohol dehydration. For example, when the separation factor gone up to 2 300, the total flux of CS CMC polyelectrolyte membrane was above 800 g/(m 2·h) in 95% EtOH and at 72 ℃. The nature and content of crosslinking agents affected the separation properties of cross linked CS membrane. The total flux of the cross linked CS membrane increased with operating temperature increasing and corresponded to the Arrhenius equation.
