Microporous microspheres can be used as functional nanomaterial carriers for their microporous structure and higher specific surface area. In this study, magnetic fluorescent polymer microspheres were prepared by inco...Microporous microspheres can be used as functional nanomaterial carriers for their microporous structure and higher specific surface area. In this study, magnetic fluorescent polymer microspheres were prepared by incorporating Fe304 nanoparticles and CdSe/ZnS quantum dots（QDs） into hyper-crosslinked microporous polymer micro- spheres（HCMPs） via the in situ coprecipitation method and swelling-diffusion. The HCMPs predominantly have mi- cropores, and their specific surface area is as high as 703.4 m2/g. The magnetic-fluorescent microspheres maintain the superparamagnetic behavior of Fe304, and the saturation magnetization reaches 38.6 A.m2/kg. Moreover, the composite microspheres exhibit an intense emission peak at 530 nm and achieve good fluorescence.展开更多
Polystyrene(PS)is rich in plastic materials,but it produces a large amount of waste every year,causing a huge burden on the environment.Although PS plastic is the source of a common"white pollution"in daily ...Polystyrene(PS)is rich in plastic materials,but it produces a large amount of waste every year,causing a huge burden on the environment.Although PS plastic is the source of a common"white pollution"in daily life,it still has a high utilization value.At the same time,the flammability of PS material determines that it cannot be applicated in places where fire accidents occur frequently.As a result,its application has been greatly limited.In order to realize the efficient utilization of waste PS and broaden its scope of application,PS was modified by hyper-crosslinking in order to improve its fire-retardant performance.In this method,the PS solution with high purity was obtained by dissolving waste PS foam with 1,2-dichloroethane(DCE),and then the hyper-crosslinked polymer with high specific surface area was prepared by adding cross-linking agent formaldehyde dimethyl acetal(FDA)and a Lewis-acid catalyst ferric chloride(FeCl_(3)).Further studies showed that the effects of the amount of cross-linking agent FDA,catalyst FeCl_(3) and PS on the reaction products were different.In addition,compared the as-prepared fire-retardant materials with PS foam from the aspects of flame retardancy and thermal insulation,it can be concluded that the fire-retardant performance of the materials prepared by this method has been significantly enhanced.And it is proved that this method is feasible towards the preparation of a large number of fire-retardant composite materials by using a scale-up experiment.展开更多
Polystyrene crosslinked microspheres were prepared by soap-free emulsion polymerization using styrene (St) and divinylbenzene (DVB) as monomers;then,the microporous structure was knitted by the Friedel-Crafts alkylati...Polystyrene crosslinked microspheres were prepared by soap-free emulsion polymerization using styrene (St) and divinylbenzene (DVB) as monomers;then,the microporous structure was knitted by the Friedel-Crafts alkylation reaction,and the Au nanoparticles (AuNPs) were loaded into the pores through thermal reduction,to obtain AuNPs/ hyper-crosslinked microporous polymer composite microspheres.SEM and particle-size test results show that the microspheres show good monodispersity.The micropore analysis indicates that the specific surface area and the pore volume of the microporous polymer microspheres decrease with increasing DVB content,and when the DVB content is 0.1%,the specific surface area reaches a maximum of 1 174.6 m2/g.After loading AuNPs,the specific surface area and the amount of micropores of the composite microspheres decrease obviously.The results of XRD and XPS analyses suggest that HAuCl4 is reduced to AuNPs.The composite microspheres show a good catalytic performance for the reduction catalyst of 4-nitrophenol.展开更多
Conjugated microporous polymers have excellent skeleton structures but poor electrical conductivity limits their applications in microwave absorption.To solve this problem,a strategy of molecular expansion and confini...Conjugated microporous polymers have excellent skeleton structures but poor electrical conductivity limits their applications in microwave absorption.To solve this problem,a strategy of molecular expansion and confining polymerization is proposed in this work to synthesize conductive hyper-crosslinked conjugated microporous polymer.The topology of the conjugated microporous polymer is changed into a three-dimensional skeleton structure with high specific surface area by using molecular expansion technique,and the controlled growth of polypyrrole in the channel constructs a unique network structure.The balance of excellent composite backbone structure,proper conductivity,attenuation capability and impedance matching enable the material to exhibit electromagnetic wave absorption performance.As a result,with low filler loading of 10 wt%,a strongest reflection loss of-52.68 d B and a maximum effective bandwidth of 5.76 GHz.Additionally,CST simulations of the radar scattering cross section have been carried out to verify the excellent material properties.This study provides new concepts for new conductive polymers and broadens the application of hyper-crosslinked conjugated microporous polymer in the field of electromagnetic wave absorption.展开更多
Using the rigid 3,3-bis（4-hydroxyphenyl）-2-（4-tritylphenyl）isoindolin-l-one with polar functional groups as a building block and formaldehyde dimethyl acetal（FDA） as crossinglinker, a new hyper-crosslinked polym...Using the rigid 3,3-bis（4-hydroxyphenyl）-2-（4-tritylphenyl）isoindolin-l-one with polar functional groups as a building block and formaldehyde dimethyl acetal（FDA） as crossinglinker, a new hyper-crosslinked polymer （HCP） was synthesized via Friedel-Crafts alkylation reaction promoted by anhydrous FeC13. The synthesized HCP is insoluble in boiled water and common organic solvents. Moreover, it shows a good CO2 capture capacity even if its surface area is not very high, and the absolute COz uptake capacity of it is 3.05 mmol/g. This can be attributed to the introduction of polar hydroxyl and lactam groups into the skeleton of the polymer, which provides effective adsorp- tion sites for COz. In addition, the synthesized HCP also exhibits good adsorption capacity for organic dyes in water, especially for crystal violet.展开更多
Fluorinated porous organic networks(F-PONs)have demonstrated unique properties and applications,but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free...Fluorinated porous organic networks(F-PONs)have demonstrated unique properties and applications,but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free and easy handling conditions are still rarely reported.Herein,using polydivinylbenzene(PDVB)as an easily available precursor,a novel and straightforward approach was developed to afford F-PONs via a dehydrative Friedel-Crafts reaction using perfluorinated benzylic alcohols as the cross-linking agent promoted by Bronsted acid(trifluoromethanesulfonic acid).The afforded material(F-PDVB)featured high fluorine content(22 at.%),large surface area(771 m^(2)·g^(-1)),and good chemical/thermal stability,rendering them as promising candidates for the adsorption of CO_(2),hydrocarbons,fluorocarbons,and chlorofluorocarbons,with weight capacities up to 520 wt.%being achieved.This simple methodology can be extended to fabricate fluorinated hyper-crosslinked polymers(F-HCPs)from rigid aromatic monomers.The progress made in this work will open new opportunities to further expand the involvement of fluorinated materials in large scale applications.展开更多
Separation media that combine the desired material properties within a single material for a given process remain an ongoing challenge for the gas separations in industry.Process integration of porous solid adsorbents...Separation media that combine the desired material properties within a single material for a given process remain an ongoing challenge for the gas separations in industry.Process integration of porous solid adsorbents is difficult due to their limited volumetric capacity,whereas issues of volatility and high regeneration temperatures exist for liquid amines and physical solvents.Herein,we report a family of polymer liquids inspired by hyper-crosslinked polymers(HCPs),a class of highly swellable network polymers.Compared with a chemically similar porous solid,the HCP-liquids demonstrate good volumetric capacity and improved selectivity of carbon dioxide over methane.Uptake appears to be enhanced by intramolecular swelling of the HCP-liquids at elevated pressures,while guests are strongly rejected from the HCP-liquids at slightly elevated temperatures,leading to highly efficient regeneration.Heat of adsorption and specific heat capacity of the HCP-liquids are also low,further suggesting favourable process thermodynamics.Additionally being easily prepared at scale,the presented HCP-liquids represent a promising step towards a material with the requisite properties to replace conventional scrubbing solvents to drastically reduce the footprint and energy needs of gas separations.展开更多
Both bottle-point and column-feeding experi-ments involving different solutes and sorbents were carried out to investigate the adsorption selectivity and separation performance of salicylic acid and 5-sulfosalicylic a...Both bottle-point and column-feeding experi-ments involving different solutes and sorbents were carried out to investigate the adsorption selectivity and separation performance of salicylic acid and 5-sulfosalicylic acid.Their adsorption isotherms onto such hypercrosslinked polymeric adsorbents as NDA-100 and NDA-99 could be well described by the Freundlich equations whose characteristics describe extrathermic and favorable adsorption processes.The adsorp-tion towards NDA-100 mainly depended on the p-p interac-tion,while that towards NDA-99 was extremely influenced by the static-electric interaction.Additionally,the adsorptive capacity of salicylic acid on NDA-99 decreased while it increased on NDA-100 with the presence of 5-sulfosalicylic acid in the adsorptive environment as the competitive component.Comparatively,the adsorption capacity of 5-sulfosalicylic acid decreased on both resins with salicylic acid as the competitive component.In fact,the difference in the interaction between adsorbent and adsorbate resulted in the straight antagonism on the effective adsorption sites on the adsorbent.In conclusion,the adsorption selectivity of salicylic acid onto NDA-100 was obviously larger than that onto NDA-99 with the existence of 5-sulfosalicylic acid in the adsorptive environment.A satisfactory separation and recovery of tested solutes in aqueous phase could be foresee-ably achieved by the sequencing adsorption technique involving NDA-100 as well as NDA-99.展开更多
聚酰胺反渗透膜是目前广泛应用的一款商用化水处理膜。然而其表面活性层聚酰胺的结构致密,会导致水通量与截盐率出现“trade-off”现象。针对该问题提出,选择具有多孔结构的、亲水性超交联聚合物复合材料作为添加剂,在界面聚合过程中引...聚酰胺反渗透膜是目前广泛应用的一款商用化水处理膜。然而其表面活性层聚酰胺的结构致密,会导致水通量与截盐率出现“trade-off”现象。针对该问题提出,选择具有多孔结构的、亲水性超交联聚合物复合材料作为添加剂,在界面聚合过程中引入聚酰胺活性层中,为水分子提供更多水通道。同时,纯烃本质的超交联聚合物与聚酰胺的高度相容性,保证了反渗透复合膜的高效截盐性能。经过脱盐性能测试,结果显示添加3.0 mg PDA@HCP-B-SO_(3)H的反渗透复合膜具有最高的水通量为44.4 L·m^(-2)·h^(-1),截盐率高达99.6%。相比于聚酰胺反渗膜,3.0-PDA@HCP-B-SO_(3)H PA RO的水通量提升了26.5%,截盐率基本保持不变;相比于只嫁接-SO_(3)H的HCP-B-SO_(3)H PA RO,水通量提升了11.6%(35.0 L·m^(-2)·h^(-1)上升至39.8 L·m^(-2)·h^(-1)),截盐率基本持平。这说明添加具有多孔结构的、亲水性强的改性超交联聚合物作为添加剂,是一种十分有效地提升聚酰胺反渗透膜性能的方法。展开更多
基金Supported by the National Natural Science Foundation of China（Nos. 11174075, 31303049）.
文摘Microporous microspheres can be used as functional nanomaterial carriers for their microporous structure and higher specific surface area. In this study, magnetic fluorescent polymer microspheres were prepared by incorporating Fe304 nanoparticles and CdSe/ZnS quantum dots（QDs） into hyper-crosslinked microporous polymer micro- spheres（HCMPs） via the in situ coprecipitation method and swelling-diffusion. The HCMPs predominantly have mi- cropores, and their specific surface area is as high as 703.4 m2/g. The magnetic-fluorescent microspheres maintain the superparamagnetic behavior of Fe304, and the saturation magnetization reaches 38.6 A.m2/kg. Moreover, the composite microspheres exhibit an intense emission peak at 530 nm and achieve good fluorescence.
基金Thanks for financial support from the National Natural Science Foun-dation of China(No.51906252)the Natural Science Foundation of Jiangsu Province(NO.BK20190632)China Postdoctoral Science Foun-dation(2019M661980).
文摘Polystyrene(PS)is rich in plastic materials,but it produces a large amount of waste every year,causing a huge burden on the environment.Although PS plastic is the source of a common"white pollution"in daily life,it still has a high utilization value.At the same time,the flammability of PS material determines that it cannot be applicated in places where fire accidents occur frequently.As a result,its application has been greatly limited.In order to realize the efficient utilization of waste PS and broaden its scope of application,PS was modified by hyper-crosslinking in order to improve its fire-retardant performance.In this method,the PS solution with high purity was obtained by dissolving waste PS foam with 1,2-dichloroethane(DCE),and then the hyper-crosslinked polymer with high specific surface area was prepared by adding cross-linking agent formaldehyde dimethyl acetal(FDA)and a Lewis-acid catalyst ferric chloride(FeCl_(3)).Further studies showed that the effects of the amount of cross-linking agent FDA,catalyst FeCl_(3) and PS on the reaction products were different.In addition,compared the as-prepared fire-retardant materials with PS foam from the aspects of flame retardancy and thermal insulation,it can be concluded that the fire-retardant performance of the materials prepared by this method has been significantly enhanced.And it is proved that this method is feasible towards the preparation of a large number of fire-retardant composite materials by using a scale-up experiment.
基金the National Natural Science Foundation of China(No.51303049)。
文摘Polystyrene crosslinked microspheres were prepared by soap-free emulsion polymerization using styrene (St) and divinylbenzene (DVB) as monomers;then,the microporous structure was knitted by the Friedel-Crafts alkylation reaction,and the Au nanoparticles (AuNPs) were loaded into the pores through thermal reduction,to obtain AuNPs/ hyper-crosslinked microporous polymer composite microspheres.SEM and particle-size test results show that the microspheres show good monodispersity.The micropore analysis indicates that the specific surface area and the pore volume of the microporous polymer microspheres decrease with increasing DVB content,and when the DVB content is 0.1%,the specific surface area reaches a maximum of 1 174.6 m2/g.After loading AuNPs,the specific surface area and the amount of micropores of the composite microspheres decrease obviously.The results of XRD and XPS analyses suggest that HAuCl4 is reduced to AuNPs.The composite microspheres show a good catalytic performance for the reduction catalyst of 4-nitrophenol.
基金financially supported by the National Natural Science Foundation of China(No.52273267)the Fundamental Research Funds for the Central Universities(Nos.30920041102 and 30920021107)。
文摘Conjugated microporous polymers have excellent skeleton structures but poor electrical conductivity limits their applications in microwave absorption.To solve this problem,a strategy of molecular expansion and confining polymerization is proposed in this work to synthesize conductive hyper-crosslinked conjugated microporous polymer.The topology of the conjugated microporous polymer is changed into a three-dimensional skeleton structure with high specific surface area by using molecular expansion technique,and the controlled growth of polypyrrole in the channel constructs a unique network structure.The balance of excellent composite backbone structure,proper conductivity,attenuation capability and impedance matching enable the material to exhibit electromagnetic wave absorption performance.As a result,with low filler loading of 10 wt%,a strongest reflection loss of-52.68 d B and a maximum effective bandwidth of 5.76 GHz.Additionally,CST simulations of the radar scattering cross section have been carried out to verify the excellent material properties.This study provides new concepts for new conductive polymers and broadens the application of hyper-crosslinked conjugated microporous polymer in the field of electromagnetic wave absorption.
基金Supported by the National Natural Science Foundation of China（Nos,21171065, 21201077）.
文摘Using the rigid 3,3-bis（4-hydroxyphenyl）-2-（4-tritylphenyl）isoindolin-l-one with polar functional groups as a building block and formaldehyde dimethyl acetal（FDA） as crossinglinker, a new hyper-crosslinked polymer （HCP） was synthesized via Friedel-Crafts alkylation reaction promoted by anhydrous FeC13. The synthesized HCP is insoluble in boiled water and common organic solvents. Moreover, it shows a good CO2 capture capacity even if its surface area is not very high, and the absolute COz uptake capacity of it is 3.05 mmol/g. This can be attributed to the introduction of polar hydroxyl and lactam groups into the skeleton of the polymer, which provides effective adsorp- tion sites for COz. In addition, the synthesized HCP also exhibits good adsorption capacity for organic dyes in water, especially for crystal violet.
基金supported financially by the Division of Chemical Sciences,Geosciences,and Biosciences,Office of Basic Energy Sciences,US Department of Energy.
文摘Fluorinated porous organic networks(F-PONs)have demonstrated unique properties and applications,but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free and easy handling conditions are still rarely reported.Herein,using polydivinylbenzene(PDVB)as an easily available precursor,a novel and straightforward approach was developed to afford F-PONs via a dehydrative Friedel-Crafts reaction using perfluorinated benzylic alcohols as the cross-linking agent promoted by Bronsted acid(trifluoromethanesulfonic acid).The afforded material(F-PDVB)featured high fluorine content(22 at.%),large surface area(771 m^(2)·g^(-1)),and good chemical/thermal stability,rendering them as promising candidates for the adsorption of CO_(2),hydrocarbons,fluorocarbons,and chlorofluorocarbons,with weight capacities up to 520 wt.%being achieved.This simple methodology can be extended to fabricate fluorinated hyper-crosslinked polymers(F-HCPs)from rigid aromatic monomers.The progress made in this work will open new opportunities to further expand the involvement of fluorinated materials in large scale applications.
基金funding from Australian research council(F T1301000345)。
文摘Separation media that combine the desired material properties within a single material for a given process remain an ongoing challenge for the gas separations in industry.Process integration of porous solid adsorbents is difficult due to their limited volumetric capacity,whereas issues of volatility and high regeneration temperatures exist for liquid amines and physical solvents.Herein,we report a family of polymer liquids inspired by hyper-crosslinked polymers(HCPs),a class of highly swellable network polymers.Compared with a chemically similar porous solid,the HCP-liquids demonstrate good volumetric capacity and improved selectivity of carbon dioxide over methane.Uptake appears to be enhanced by intramolecular swelling of the HCP-liquids at elevated pressures,while guests are strongly rejected from the HCP-liquids at slightly elevated temperatures,leading to highly efficient regeneration.Heat of adsorption and specific heat capacity of the HCP-liquids are also low,further suggesting favourable process thermodynamics.Additionally being easily prepared at scale,the presented HCP-liquids represent a promising step towards a material with the requisite properties to replace conventional scrubbing solvents to drastically reduce the footprint and energy needs of gas separations.
基金The work was supported by the Opening Fund of Key Laboratory of Environmental Engineering of Jiangsu Province,China(Grant No.KF0502)by the Opening Fund of Jiangsu Provincial Key Laboratory of Coastal Wetland Bioresources and Environmental Protection(Grant No.JLCBE05005).
文摘Both bottle-point and column-feeding experi-ments involving different solutes and sorbents were carried out to investigate the adsorption selectivity and separation performance of salicylic acid and 5-sulfosalicylic acid.Their adsorption isotherms onto such hypercrosslinked polymeric adsorbents as NDA-100 and NDA-99 could be well described by the Freundlich equations whose characteristics describe extrathermic and favorable adsorption processes.The adsorp-tion towards NDA-100 mainly depended on the p-p interac-tion,while that towards NDA-99 was extremely influenced by the static-electric interaction.Additionally,the adsorptive capacity of salicylic acid on NDA-99 decreased while it increased on NDA-100 with the presence of 5-sulfosalicylic acid in the adsorptive environment as the competitive component.Comparatively,the adsorption capacity of 5-sulfosalicylic acid decreased on both resins with salicylic acid as the competitive component.In fact,the difference in the interaction between adsorbent and adsorbate resulted in the straight antagonism on the effective adsorption sites on the adsorbent.In conclusion,the adsorption selectivity of salicylic acid onto NDA-100 was obviously larger than that onto NDA-99 with the existence of 5-sulfosalicylic acid in the adsorptive environment.A satisfactory separation and recovery of tested solutes in aqueous phase could be foresee-ably achieved by the sequencing adsorption technique involving NDA-100 as well as NDA-99.
文摘聚酰胺反渗透膜是目前广泛应用的一款商用化水处理膜。然而其表面活性层聚酰胺的结构致密,会导致水通量与截盐率出现“trade-off”现象。针对该问题提出,选择具有多孔结构的、亲水性超交联聚合物复合材料作为添加剂,在界面聚合过程中引入聚酰胺活性层中,为水分子提供更多水通道。同时,纯烃本质的超交联聚合物与聚酰胺的高度相容性,保证了反渗透复合膜的高效截盐性能。经过脱盐性能测试,结果显示添加3.0 mg PDA@HCP-B-SO_(3)H的反渗透复合膜具有最高的水通量为44.4 L·m^(-2)·h^(-1),截盐率高达99.6%。相比于聚酰胺反渗膜,3.0-PDA@HCP-B-SO_(3)H PA RO的水通量提升了26.5%,截盐率基本保持不变;相比于只嫁接-SO_(3)H的HCP-B-SO_(3)H PA RO,水通量提升了11.6%(35.0 L·m^(-2)·h^(-1)上升至39.8 L·m^(-2)·h^(-1)),截盐率基本持平。这说明添加具有多孔结构的、亲水性强的改性超交联聚合物作为添加剂,是一种十分有效地提升聚酰胺反渗透膜性能的方法。
基金Project supported by the National Undergraduate Training Program for Innovation and Entrepreneurship(No.201710638031)the Fundamental Research Funds of China West Normal University(No.17C038)and the Meritocracy Research Funds of China West Normal University(No.17Y031)~~
