Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,th...Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,the poor chemical stability and low electron conductivity limited their activity,and single-functional sites in these frameworks hindered them to show multifunctional roles in catalytic systems.Herein,we have constructed novel metal organic polymers(Co-HAT-CN and Ni-HAT-CN)with dual catalytic centers(metal-N_(4) and metal-N_(2))to catalyze oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).By using different metal centers,the catalytic activity and selectivity were well-tuned.Among them,Co-HAT-CN catalyzed the ORR in a 4e^(-)pathway,with a half-wave potential of 0.8 V versus RHE,while the Ni-HAT-CN catalyze ORR in a 2e^(-)pathway with H_(2)O_(2) selectivity over 90%.Moreover,the Co-HAT-CN delivered an overpotential of 350 mV at 10 mA cm^(-2) with a corresponding Tafel slope of 24 mV dec^(-1) for OER in a 1.0 M KOH aqueous solution.The experimental results revealed that the activities toward ORR were due to the M-N_(4) sites in the frameworks,and both M-N_(4) and M-N_(2) sites contributed to the OER.This work gives us a new platform to construct bifunctional catalysts.展开更多
Organic electrode materials are promising for lithium-ion batteries(LIBs) because of their environmental friendliness and structural diversity.However,they always suffer from limited capacity,poor cycling stability,an...Organic electrode materials are promising for lithium-ion batteries(LIBs) because of their environmental friendliness and structural diversity.However,they always suffer from limited capacity,poor cycling stability,and rate performance.Herein,hexaazatrinaphthalene-based azo-linked hyperbranched polymer(HAHP) is designed and synthesized as a cathode for LIBs.However,the densely stacked morphology lowers the chance of the active sites participating in the redox reaction.To address this issue,the singlewalled carbon nanotube(SWCNT) template is used to induce the growth of nanosized HAHP on the surface of SWCNTs.The HAHP@SWCNT nanocomposites have porous structures and highly accessible active sites.Moreover,the strong π-π interaction between HAHP and highly conductive SWCNTs effectively endows the HAHP@SWCNT nanocomposites with improved cycling stability and fast charge-discharge rates.As a result,the HAHP@SWCNT nanocomposite cathode shows a high specific capacity(320.4 mA h g^(-1)at 100 mA g^(-1)),excellent cycling stability(800 cycles;290 mA h g^(-1)at 100 mA g^(-1),capacity retained 91%) and outstanding rate performance(235 mA h g^(-1)at 2000 mA g^(-1),76% capacity retention versus 50 mA g^(-1)).This work provides a strategy to combine the macromolecular structural design and micromorphology control of electrode materials for obtaining organic polymer cathodes for high-performance LIBs.展开更多
Aqueous Mg ion batteries(AMIBs)show great potential in energy storage for their advantages of high capacity,abundant resource,and environmental friendliness.However,the development of AMIBs is limited due to the scarc...Aqueous Mg ion batteries(AMIBs)show great potential in energy storage for their advantages of high capacity,abundant resource,and environmental friendliness.However,the development of AMIBs is limited due to the scarcity of suitable anode materials.In this study,a new polymer anode material(PNTAQ)with flower-like nanosheet structure is synthesized for aqueous Mg-Na hybrid-ion battery(AMNHIB).PNTAQ possess carbonyl functional groups which can be oxidized and reduced reversibly in aqueous solution containing alkaline metal ions.PNTAQ displays a discharge specific capacity of 245 mAh g^(−1)at 50 mA g^(−1)in 1 M MgCl_(2)+0.5 M NaCl electrolyte,which is much higher than that in single 1 M MgCl_(2)or 0.5 M NaCl electrolyte.Even cycling at 1000 mA g^(−1)for 1000 times,the capacity retention can still maintain at 87.2%.A full Mg-Na hybrid-ion cell is assembled by employingβ-MnO_(2)as cathode and PNTAQ as anode material,it exhibits a specific capacity of 91.6 mAh g^(−1)at 100 mA g^(−1).The polymer electrode material well maintains its framework structure during the discharge/charge cycling process of the hybrid-ion battery.展开更多
Separation membrane with high flux is generally encouraged in industrial application,because of the tremendous needs for decreasing membrane areas,usage costs and space requirements.The most effective and direct metho...Separation membrane with high flux is generally encouraged in industrial application,because of the tremendous needs for decreasing membrane areas,usage costs and space requirements.The most effective and direct method for obtaining the high flux is to decrease membrane thickness.Polyamide(PA)nanofiltration membrane is conventionally prepared by the direct interfacial polymerization(IP)on substrate surface,and results in a thick PA layer.In this work,we proposed a strategy that constructing triazine-based porous organic polymer(TRZ-POP)as the interlayer to prepare the ultrathin PA nanofiltration membranes.TRZ-POP is firstly deposited on the polyethersulfone substrate,and then the formed TRZ-POP provides more adhesion sites towards PA based on its high specific surface areas.The chemical bonding between terminal amine group of TRZ-POP and the amide group of PA further improves the binding force,and strengthens the stability of PA layer.More importantly,the high porosity of TRZPOP layer causes the higher polymerization of initial PA owning to the stored sufficient amino monomer;and H-bonding interaction between amine groups of TRZ-POP and piperazine(PIP)can astrict the release of PIP.Thus,IP process is controlled,and the thinnest thickness of prepared PA layer is only<15 nm.As expected,PA/TRZ-POP membrane shows a more excellent water flux of 1414 L·m^(-2)·h^(-1)·MPa^(-1)than that of the state-of-the-art nanofiltration membranes,and without sacrificing dye rejection.The build of TRZPOP interlayer develops a new method for obtaining a high-flux nanofiltration membrane.展开更多
Combining photocatalytic organic reactions with CO_(2)reduction is an efficient solar energy utilization mode,but it is still limited by the organic species that can be matched and the low conversion.Herein,ultrathin ...Combining photocatalytic organic reactions with CO_(2)reduction is an efficient solar energy utilization mode,but it is still limited by the organic species that can be matched and the low conversion.Herein,ultrathin organic polymer with p-πconjugated structure(TPP)was rationally designed and prepared,and showed a high yield of CO(15.2 mmol g^(-1))and conversion of SAS coupled products(100%),far exceeding the organic polymer with P=O structure.The enhanced photoredox activity of TPP is ascribed to the orbital interaction between the p-orbital on phosphorus and theπ-orbitals of aromatic,which can accelerate the photoinduced charge carrier separation and improve the CO_(2)adsorption capacity.TPP can also be used for the dehydrocoupling of various benzyl mercaptans to the corresponding SAS bond products.This work provides a new concept for the efficient synthesis of disulfide bonds combined with CO_(2)reduction in a photoreaction system.展开更多
Compared with traditional aluminum salts, polyaluminum chloride (PACI) has better coagulation-flocculation performance in turbidity removal. However, it is still inferior to organic polymers in terms of bridging fun...Compared with traditional aluminum salts, polyaluminum chloride (PACI) has better coagulation-flocculation performance in turbidity removal. However, it is still inferior to organic polymers in terms of bridging function. In order to improve the aggregating property of PACl, different composite PACl flocculants were prepared with various organic polymers. The effect of organic polymer on the distribution or Al(Ⅲ) species in composite flocculants was studied using ^27TAl NMR and Al-ferron complexation methods. The charge neutralization and surface adsorption characteristics of composite flocculants were also investigated. Jar tests were conducted to evaluate the turbidity removal efficacy of organic polymer modified composite flocculants. The study shows that cationic polymer and anionic polymer have significant influences on the coagulation-flocculation behaviors of PACl. Both cationic and anionic polymers can improve the turbidity removal performancc of PACl but the mechanisms arc much different: cationic organic polymer mainly increases the charge neutralization ability, but anionic polymer mainly enhances the bridging function.展开更多
High flammability of polymers has become a major issue which has restricted its applications.Recently,highly crystalline materials and metal–organic frameworks(MOFs),which consisted of metal ions and organic linkers,...High flammability of polymers has become a major issue which has restricted its applications.Recently,highly crystalline materials and metal–organic frameworks(MOFs),which consisted of metal ions and organic linkers,have been intensively employed as novel fire retardants(FRs)for a variety of polymers(MOF/polymer).The MOFs possessed abundant transition metal species,fire-retardant elements and potential carbon source accompanied with the facile tuning of the structure and property,making MOF,its derivatives and MOF hybrids promising for fire retardancy research.The recent progress and strategies to prepare MOF-based FRs are emphasized and summarized.The fire retardancy mechanisms of MOF/polymer composites are explained,which may guide the future design for efficient MOF-based FRs.Finally,the challenges and prospects related to different MOFbased FRs are also discussed and aim to provide a fast and holistic overview,which is beneficial for researchers to quickly get up to speed with the latest development in this field.展开更多
A series of water-soluble polymers such as poly(ethylene oxide)(PEO), polyacrylamide(PAM) and poly(vinyl pyrrilidone)(PVP) was successfully prepared via the electrospinning of their aqueous solutions without...A series of water-soluble polymers such as poly(ethylene oxide)(PEO), polyacrylamide(PAM) and poly(vinyl pyrrilidone)(PVP) was successfully prepared via the electrospinning of their aqueous solutions without the use of a surfactant. The effects of solution properties on the electrospinning of PEO, PAM and PVP solutions were investigated. The viscosity of the solution, charge density carried by the jet, and the surface tension of the solution are the key factors that influence the morphology and diameter size of the fibers. The viscosity of the solution was measured on a modular compact rheometer. The morphology and the diameter size distribution of the fibers were observed under an environmental scanning electron microscope(ESEM). The results show that the diameters of the nanofibers electro spun from the solutions of these water soluble polymers were uniform and less than 300 nm.展开更多
The organic/inorganic nanocomposites polymer electrolytes were designed and synthesized. The organic/inorganic nanocomposites membrane materials and their lithium salt complexes have been found thermally stable below ...The organic/inorganic nanocomposites polymer electrolytes were designed and synthesized. The organic/inorganic nanocomposites membrane materials and their lithium salt complexes have been found thermally stable below 200 °C. The conductivity of the organic/inorganic nanocomposites polymer electrolytes prepared at room temperature was at magnitude range of 10(?6) S/cm.展开更多
Luminescent porous materials have shown various applications such as electronic devices, gas adsorption, energy materials and photocatalysis. Consequently, we designed and prepared a new type borondipyrromethene(BODIP...Luminescent porous materials have shown various applications such as electronic devices, gas adsorption, energy materials and photocatalysis. Consequently, we designed and prepared a new type borondipyrromethene(BODIPY) based porous organic polymer(POP) by using Sonogashira coupling reaction. This POP-1 exhibits high thermal stability with moderate surface area. In addition, POP-1 is highly emissive in a solid state. Due to enrichment of different kinds of heteroatoms in the skeleton of the porous polymer, POP-1 selectively captures carbon dioxide(CO_2) with relative high adsorption selectivity of CO_2/N_2.展开更多
Rechargeable aluminum batteries are believed as a promising next-generation energy-storage system due to abundant low-cost Al sources and high volumetric specific capacity.The Al-storage cathodes,however,are plagued b...Rechargeable aluminum batteries are believed as a promising next-generation energy-storage system due to abundant low-cost Al sources and high volumetric specific capacity.The Al-storage cathodes,however,are plagued by strong electrostatic interaction between host materials and carrier ions,leading to large overpotential and undesired cycling stability as well as sluggish ion diffusion kinetics.Herein,sulfur-linked carbonyl polymer based on perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA) as the cathode materials for ABs is proposed,which demonstrates a small voltage polarization(135 mV),a reversible capacity of 110 mAh g^(-1) at 100 mA g^(-1) even after 1200 cycles,and rapid Al-storage kinetics.Compared with PTCDA,the sulfide polymer possesses higher working voltage because of its lower LUMO energy level according to theoretical calculation.The ordered carbonyl active sites in sulfide polymer contribute to the maximized material utilization and rapid ion coordination and dissociation,resulting in superior rate capability.Besides,the bridged thioether bonds endow the polysulfide with robust and flexible structure,which inhibits the dissolution of active materials and improves cycling stability.This work implies the importance of ordered arrangement of redox active moieties for organic electrode,which provides the theoretical direction for the structural design of organic materials applied in multivalent-ion batteries.展开更多
Carbon capture,storage,and utilization(CCSU)is recognized as an effective method to reduce the excessive emission of CO_(2).Absorption by amine aqueous solutions is considered highly efficient for CO_(2) capture from ...Carbon capture,storage,and utilization(CCSU)is recognized as an effective method to reduce the excessive emission of CO_(2).Absorption by amine aqueous solutions is considered highly efficient for CO_(2) capture from the flue gas because of the large CO_(2) capture capacity and high selectivity.However,it is often limited by the equipment corrosion and the high desorption energy consumption,and adsorption of CO_(2) using solid adsorbents has been receiving more attention in recent years due to its simplicity and high efficiency.More recently,a great number of porous organic polymers(POPs)have been designed and constructed for CO_(2) capture,and they are proven promising solid adsorbents for CO_(2) capture due to their high Brunauer-Emmett-Teller(BET)surface area(SBET),adjustable pore size and easy functionalization.In particular,they usually have rigid skeleton,permanent porosity,and good physiochemical stability.In this review,we have a detailed review for the different POPs developed in recent years,not only the design strategy,but also the special structure for CO_(2) capture.The outlook of the opportunities and challenges of the POPs is also proposed.展开更多
The lithiated covalent organic framework(named TpPa-SO_(3) Li),which was prepared by a mild chemical lithiation strategy,was introduced in poly(ethylene oxide)(PEO)to produce the composite polymer electrolytes(CPEs).L...The lithiated covalent organic framework(named TpPa-SO_(3) Li),which was prepared by a mild chemical lithiation strategy,was introduced in poly(ethylene oxide)(PEO)to produce the composite polymer electrolytes(CPEs).Li-ion can transfer along the PEO chain or across the layer of TpPa-SO_(3) Li within the nanochannels,resulting in a high Li-ion conductivity of3.01×10^(-4)S/cm at 60℃.When the CPE with 0.75 wt.%TpPa-SO_(3) Li was used in the LiFePO_(4)‖Li solid-state battery,the cell delivered a stable capacity of 125 mA·h/g after 250 cycles at 0.5 C,60℃.In comparison,the cell using the CPE without TpPa-SO_(3) Li exhibited a capacity of only 118 mA·h/g.展开更多
Two non-conjugated polymers PEIE-DBO and PEIE-DCO, prepared by quaternization of polyethyleneimine ethoxylate by 1,8-dibromooctane and 1,8-dichlorooctane respectively, are developed as electron transport layer(ETL) in...Two non-conjugated polymers PEIE-DBO and PEIE-DCO, prepared by quaternization of polyethyleneimine ethoxylate by 1,8-dibromooctane and 1,8-dichlorooctane respectively, are developed as electron transport layer(ETL) in high-performance inverted organic solar cells(OSCs), and the effects of halide ions on polymeric photoelectric performance are fully investigated. PEIE-DBO possesses higher electron mobility(3.68×10-4 cm2 V-1s-1), higher conductivity and more efficient exciton dissociation and electron extraction, attributed to its lower work function(3.94 eV) than that of PEIE-DCO, which results in better photovoltaic performance in OSCs. The inverted OSCs with PTB7-Th: PC71BM as photoactive layer and PEIE-DBO as ETL exhibit higher PCE of 10.52%, 9.45% and 9.09% at the thickness of 9, 35 and 50 nm,respectively. To our knowledge, PEIE-DBO possesses the best thickness-insensitive performance in polymeric ETLs of inverted fullerene-based OSCs. Furthermore, PEIE-DBO was used to fabricate the inverted non-fullerene OSCs(PM6:Y6) and obtained a high PCE of 15.74%, which indicates that PEIE-DBO is effective both in fullerene-based OSCs and fullerene-free OSCs.展开更多
Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2CHSi(OMe)3)n-RF;RF = CF(CF3)OCF7, n = 2, 3;RF-(VM)n-RF] was applied to the preparation of fluoroalkyl end-capped vinyltrimethoxysilane oligomer/α-, β-, ...Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2CHSi(OMe)3)n-RF;RF = CF(CF3)OCF7, n = 2, 3;RF-(VM)n-RF] was applied to the preparation of fluoroalkyl end-capped vinyltrimethoxysilane oligomer/α-, β-, γ-cyclodextrin polymers (α-, β-, γ-CDPs) composites [RF-(VM-SiO2)n-RF/α-, β-, γ-CDPs] by the sol-gel reaction of the corresponding oligomer in the presence of the α-, β-, γ-CDPs under alkaline conditions. The RF-(VM-SiO2)n-RF/α-, β-, γ-CDPs composites thus obtained were found to give a good dispersibility toward the traditional organic media except for water, and were applied to the surface modification of glass to provide a sueperoleophilic/superhydrophobic characteristic on the modified surface, although the corresponding RF-(VM-SiO2)n-RF nanocomposites can give a usual oleophobic/superhydrophobic property on the surface. These composites powders were also found to be applicable to the packing material for the column chromatography to separate the mixture of oil/water and the water in oil (W/O) emulsions. More interestingly, these composite powders were found to have a higher adsorption ability toward not only low-molecular weight aromatic compounds such as bisphenol A and bisphenol AF but also volatile organic compounds, compared to that of the pristine α-, β-, γ-CDPs.展开更多
(E)-2,6-Dimethyl-4-styrylpyridine-3,5-dicarboxylic acid (H2mspda) is firstly employed in coordination chemistry.Two isostructural two-dimensional (2-D) 4-connected metal-organic coordination polymers with a gene...(E)-2,6-Dimethyl-4-styrylpyridine-3,5-dicarboxylic acid (H2mspda) is firstly employed in coordination chemistry.Two isostructural two-dimensional (2-D) 4-connected metal-organic coordination polymers with a general formula of {M2[(mspda)2(bpy)(H2O)2]}n (M=Zn(1) and Co(2)) are assembled from H2mspda,4,4'-bipyridyl (bpy),zinc and cobalt ions under hydrothermal conditions,and characterized by single-crystal X-ray diffraction analyses.Complex 1 crystallizes in monoclinic,space group P21/n with a=14.551(4),b=10.941(3),c=14.945(4),β=98.817(4)o,V=2351.3(1)3,Dc=1.511 g/cm3,μ(MoKα)=1.090 mm-1,F(000)=1104,Z=4,the final R=0.0335 and wR=0.0485 for 3296 observed reflections (I 〉 2σ(I)).In compound 1,mspda2-spacers are only arrayed in a head-to-tail fashion which corresponds to a 2-D coordination polymer.Solid-state H2mspda and complex 1 have expected photoluminescence (λem=475~496 nm) at room temperature.展开更多
The 6-mercapto-1,3,5-triazine-2,4-dithiol monosodium(TTN) compound was used to fabricate an organic film on pure copper. The polymer plating process of TTN on pure copper in Na2CO3 aqueous solution and the growth mech...The 6-mercapto-1,3,5-triazine-2,4-dithiol monosodium(TTN) compound was used to fabricate an organic film on pure copper. The polymer plating process of TTN on pure copper in Na2CO3 aqueous solution and the growth mechanism of poly(6-mercapto-1,3,5-triazine-2,4-dithiol)(PTT) film were studied by means of cyclic voltammetry. The polymer plating under galvanostatic mode at 0.05 mA/cm2 was conducted to generate PTT film on pure copper in the same electrolyte with different polymer-plating time. The film mass was determined by electronic balance and the insoluble fraction in tetrahydrofuran(THF) Is tested. The performance of organic film formed on copper surface was investigated preliminarily by potentiodynamic polarization and electrochemical impedance spectroscopy(EIS). It is found that a slight peak measured at 0 V vs SCE attributes to the oxidation of copper and generated Cu+ or/and Cu2+ to produce Cu-TTN complex,then a strong oxide peak is observed at 0.311 V vs SCE due to the polymerization of TTN for the increase of the film thickness. Electrochemical measurement results reveal that 10 min is an optimum polymer-plated time to obtain high quality film. The results of potentiodynamic polarization show that current density decreases from 1.85 μA/cm2 for bare copper to 0.168 μA/cm2 for polymer-plated copper while polymer-plated time is 10 min. The charge transfer resistances of bare copper and polymer-plated copper are 937 Ω·cm2 and 11.12 kΩ·cm2,respectively. The film capacitor for polymer-plated copper is as low as 1.82 μF·cm2. The EIS results confirm the results of potentiodynamic polarization and reveal that a homogenous and compact film is obtained by polymer plating technique.展开更多
The ferrimagnetism and quantum phase transition of a bipartite lozenge periodic Anderson-like organic polymer, in which the localized f electrons hybridize with the odd site conduction orbitals, are investigated by me...The ferrimagnetism and quantum phase transition of a bipartite lozenge periodic Anderson-like organic polymer, in which the localized f electrons hybridize with the odd site conduction orbitals, are investigated by means of Green's function theory. The ground state turns out to be gapless ferrimagnetism. At a finite temperature, the ferrimagnetic-to- paramagnetic phase transition takes place. The Kondo screenings and Ruderman-Kittel-Kasuya-Yosida (RKKY) inter- action can reduce and increase the transition temperature, respectively. Two Kondo screenings compete with each other, giving rise to the localized f electron spin screened antiferromagnetically. Accordingly, in a magnetic field, all spins are aligned along the chain easily, which is associated with metal-insulator transition. Furthermore, in a temperature-field plane, we reveal the gapless and spin polarized phases, which are characterized by susceptibility and specific heat, and whose behaviours are determined by the competition between the up-spin and down-spin hole excitations.展开更多
The addition of water-soluble polymer to a fine coal slurry to enhance dewatering process is considered to be one of the most effective ways of solving the problems of dewatering of fine coal. A series of tests are co...The addition of water-soluble polymer to a fine coal slurry to enhance dewatering process is considered to be one of the most effective ways of solving the problems of dewatering of fine coal. A series of tests are conducted with a vacuum dewatering apparatus to study the effects of various factors such as the species of polymer, polymer dosage and its ways of addition, and the pH of fine coal slurry on filtrating and dewatering of fine coal.展开更多
基金support from the Natural Science Foundation of Shanghai (20ZR1464000)G.Zeng acknowledges the support from the National Natural Science Foundation of China (21878322,22075309)the Science and Technology Commission of Shanghai Municipality (19ZR1479200,22ZR1470100)。
文摘Metal-organic frameworks and covalent organic frameworks have been widely employed in electrochemical catalysis owing to their designable skeletons,controllable porosities,and well-defined catalytic centers.However,the poor chemical stability and low electron conductivity limited their activity,and single-functional sites in these frameworks hindered them to show multifunctional roles in catalytic systems.Herein,we have constructed novel metal organic polymers(Co-HAT-CN and Ni-HAT-CN)with dual catalytic centers(metal-N_(4) and metal-N_(2))to catalyze oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).By using different metal centers,the catalytic activity and selectivity were well-tuned.Among them,Co-HAT-CN catalyzed the ORR in a 4e^(-)pathway,with a half-wave potential of 0.8 V versus RHE,while the Ni-HAT-CN catalyze ORR in a 2e^(-)pathway with H_(2)O_(2) selectivity over 90%.Moreover,the Co-HAT-CN delivered an overpotential of 350 mV at 10 mA cm^(-2) with a corresponding Tafel slope of 24 mV dec^(-1) for OER in a 1.0 M KOH aqueous solution.The experimental results revealed that the activities toward ORR were due to the M-N_(4) sites in the frameworks,and both M-N_(4) and M-N_(2) sites contributed to the OER.This work gives us a new platform to construct bifunctional catalysts.
基金supported by the National Natural Science Foundation of China(Grant No.51903100)the Science and Technology Development Plan of Jilin Province,China(Grant No.20210402060GH)。
文摘Organic electrode materials are promising for lithium-ion batteries(LIBs) because of their environmental friendliness and structural diversity.However,they always suffer from limited capacity,poor cycling stability,and rate performance.Herein,hexaazatrinaphthalene-based azo-linked hyperbranched polymer(HAHP) is designed and synthesized as a cathode for LIBs.However,the densely stacked morphology lowers the chance of the active sites participating in the redox reaction.To address this issue,the singlewalled carbon nanotube(SWCNT) template is used to induce the growth of nanosized HAHP on the surface of SWCNTs.The HAHP@SWCNT nanocomposites have porous structures and highly accessible active sites.Moreover,the strong π-π interaction between HAHP and highly conductive SWCNTs effectively endows the HAHP@SWCNT nanocomposites with improved cycling stability and fast charge-discharge rates.As a result,the HAHP@SWCNT nanocomposite cathode shows a high specific capacity(320.4 mA h g^(-1)at 100 mA g^(-1)),excellent cycling stability(800 cycles;290 mA h g^(-1)at 100 mA g^(-1),capacity retained 91%) and outstanding rate performance(235 mA h g^(-1)at 2000 mA g^(-1),76% capacity retention versus 50 mA g^(-1)).This work provides a strategy to combine the macromolecular structural design and micromorphology control of electrode materials for obtaining organic polymer cathodes for high-performance LIBs.
基金supported by the China Postdoctoral Science Foundation(2018 M630340,2019 T120254)the Fundamental Research Funds for the Central University
文摘Aqueous Mg ion batteries(AMIBs)show great potential in energy storage for their advantages of high capacity,abundant resource,and environmental friendliness.However,the development of AMIBs is limited due to the scarcity of suitable anode materials.In this study,a new polymer anode material(PNTAQ)with flower-like nanosheet structure is synthesized for aqueous Mg-Na hybrid-ion battery(AMNHIB).PNTAQ possess carbonyl functional groups which can be oxidized and reduced reversibly in aqueous solution containing alkaline metal ions.PNTAQ displays a discharge specific capacity of 245 mAh g^(−1)at 50 mA g^(−1)in 1 M MgCl_(2)+0.5 M NaCl electrolyte,which is much higher than that in single 1 M MgCl_(2)or 0.5 M NaCl electrolyte.Even cycling at 1000 mA g^(−1)for 1000 times,the capacity retention can still maintain at 87.2%.A full Mg-Na hybrid-ion cell is assembled by employingβ-MnO_(2)as cathode and PNTAQ as anode material,it exhibits a specific capacity of 91.6 mAh g^(−1)at 100 mA g^(−1).The polymer electrode material well maintains its framework structure during the discharge/charge cycling process of the hybrid-ion battery.
基金funded by National Key Research and Development Program of China (2021YFC2101202)Bingtuan Science and Technology Program (2022DB025)+3 种基金Beijing Natural Science Foundation (2222015)Hebei Province Key Research and Development Program (21327316D)China Postdoctoral Science Foundation (2021M700011)the long-term subsidy mechanism from the Ministry of Finance and the Ministry of Education of China。
文摘Separation membrane with high flux is generally encouraged in industrial application,because of the tremendous needs for decreasing membrane areas,usage costs and space requirements.The most effective and direct method for obtaining the high flux is to decrease membrane thickness.Polyamide(PA)nanofiltration membrane is conventionally prepared by the direct interfacial polymerization(IP)on substrate surface,and results in a thick PA layer.In this work,we proposed a strategy that constructing triazine-based porous organic polymer(TRZ-POP)as the interlayer to prepare the ultrathin PA nanofiltration membranes.TRZ-POP is firstly deposited on the polyethersulfone substrate,and then the formed TRZ-POP provides more adhesion sites towards PA based on its high specific surface areas.The chemical bonding between terminal amine group of TRZ-POP and the amide group of PA further improves the binding force,and strengthens the stability of PA layer.More importantly,the high porosity of TRZPOP layer causes the higher polymerization of initial PA owning to the stored sufficient amino monomer;and H-bonding interaction between amine groups of TRZ-POP and piperazine(PIP)can astrict the release of PIP.Thus,IP process is controlled,and the thinnest thickness of prepared PA layer is only<15 nm.As expected,PA/TRZ-POP membrane shows a more excellent water flux of 1414 L·m^(-2)·h^(-1)·MPa^(-1)than that of the state-of-the-art nanofiltration membranes,and without sacrificing dye rejection.The build of TRZPOP interlayer develops a new method for obtaining a high-flux nanofiltration membrane.
基金the financial support of the research fund of the Science and Technology Innovation Program of Hunan Province(2020RC2076)the General Project of Education Department of Hunan Province(21C008)+2 种基金the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(2022C02)the Youth Science and Technology Talent Project of Hunan Province(2022RC1197)the Hunan Provincial Natural Science Foundation of China(2021JJ40529)。
文摘Combining photocatalytic organic reactions with CO_(2)reduction is an efficient solar energy utilization mode,but it is still limited by the organic species that can be matched and the low conversion.Herein,ultrathin organic polymer with p-πconjugated structure(TPP)was rationally designed and prepared,and showed a high yield of CO(15.2 mmol g^(-1))and conversion of SAS coupled products(100%),far exceeding the organic polymer with P=O structure.The enhanced photoredox activity of TPP is ascribed to the orbital interaction between the p-orbital on phosphorus and theπ-orbitals of aromatic,which can accelerate the photoinduced charge carrier separation and improve the CO_(2)adsorption capacity.TPP can also be used for the dehydrocoupling of various benzyl mercaptans to the corresponding SAS bond products.This work provides a new concept for the efficient synthesis of disulfide bonds combined with CO_(2)reduction in a photoreaction system.
文摘Compared with traditional aluminum salts, polyaluminum chloride (PACI) has better coagulation-flocculation performance in turbidity removal. However, it is still inferior to organic polymers in terms of bridging function. In order to improve the aggregating property of PACl, different composite PACl flocculants were prepared with various organic polymers. The effect of organic polymer on the distribution or Al(Ⅲ) species in composite flocculants was studied using ^27TAl NMR and Al-ferron complexation methods. The charge neutralization and surface adsorption characteristics of composite flocculants were also investigated. Jar tests were conducted to evaluate the turbidity removal efficacy of organic polymer modified composite flocculants. The study shows that cationic polymer and anionic polymer have significant influences on the coagulation-flocculation behaviors of PACl. Both cationic and anionic polymers can improve the turbidity removal performancc of PACl but the mechanisms arc much different: cationic organic polymer mainly increases the charge neutralization ability, but anionic polymer mainly enhances the bridging function.
基金This research is partly supported by the scholarship from China Scholarship Council under the Grant CSC(201608060071).
文摘High flammability of polymers has become a major issue which has restricted its applications.Recently,highly crystalline materials and metal–organic frameworks(MOFs),which consisted of metal ions and organic linkers,have been intensively employed as novel fire retardants(FRs)for a variety of polymers(MOF/polymer).The MOFs possessed abundant transition metal species,fire-retardant elements and potential carbon source accompanied with the facile tuning of the structure and property,making MOF,its derivatives and MOF hybrids promising for fire retardancy research.The recent progress and strategies to prepare MOF-based FRs are emphasized and summarized.The fire retardancy mechanisms of MOF/polymer composites are explained,which may guide the future design for efficient MOF-based FRs.Finally,the challenges and prospects related to different MOFbased FRs are also discussed and aim to provide a fast and holistic overview,which is beneficial for researchers to quickly get up to speed with the latest development in this field.
基金Supported by the Development Project of Jilin Province Science and Technology of China(No.20080344)
文摘A series of water-soluble polymers such as poly(ethylene oxide)(PEO), polyacrylamide(PAM) and poly(vinyl pyrrilidone)(PVP) was successfully prepared via the electrospinning of their aqueous solutions without the use of a surfactant. The effects of solution properties on the electrospinning of PEO, PAM and PVP solutions were investigated. The viscosity of the solution, charge density carried by the jet, and the surface tension of the solution are the key factors that influence the morphology and diameter size of the fibers. The viscosity of the solution was measured on a modular compact rheometer. The morphology and the diameter size distribution of the fibers were observed under an environmental scanning electron microscope(ESEM). The results show that the diameters of the nanofibers electro spun from the solutions of these water soluble polymers were uniform and less than 300 nm.
文摘The organic/inorganic nanocomposites polymer electrolytes were designed and synthesized. The organic/inorganic nanocomposites membrane materials and their lithium salt complexes have been found thermally stable below 200 °C. The conductivity of the organic/inorganic nanocomposites polymer electrolytes prepared at room temperature was at magnitude range of 10(?6) S/cm.
基金Funded by the Natural Science Foundation of China(Nos.21674129 and 21376272)the Post-doctor Foundation of Central South University(No.140050292)
文摘Luminescent porous materials have shown various applications such as electronic devices, gas adsorption, energy materials and photocatalysis. Consequently, we designed and prepared a new type borondipyrromethene(BODIPY) based porous organic polymer(POP) by using Sonogashira coupling reaction. This POP-1 exhibits high thermal stability with moderate surface area. In addition, POP-1 is highly emissive in a solid state. Due to enrichment of different kinds of heteroatoms in the skeleton of the porous polymer, POP-1 selectively captures carbon dioxide(CO_2) with relative high adsorption selectivity of CO_2/N_2.
基金supported by the Ministry of Science and Technology of China (2019YFA0705600 and 2017YFA0206700)the National Natural Science Foundation of China (21805141,22005155 and 52072186)+2 种基金the 111 Project from the Ministry of Education of China (B12015)the Fundamental Research Funds for the Central Universities (92122001)the Young Elite Scientist Sponsorship Program by CAST (2019QNRC001)。
文摘Rechargeable aluminum batteries are believed as a promising next-generation energy-storage system due to abundant low-cost Al sources and high volumetric specific capacity.The Al-storage cathodes,however,are plagued by strong electrostatic interaction between host materials and carrier ions,leading to large overpotential and undesired cycling stability as well as sluggish ion diffusion kinetics.Herein,sulfur-linked carbonyl polymer based on perylene-3,4,9,10-tetracarboxylic dianhydride(PTCDA) as the cathode materials for ABs is proposed,which demonstrates a small voltage polarization(135 mV),a reversible capacity of 110 mAh g^(-1) at 100 mA g^(-1) even after 1200 cycles,and rapid Al-storage kinetics.Compared with PTCDA,the sulfide polymer possesses higher working voltage because of its lower LUMO energy level according to theoretical calculation.The ordered carbonyl active sites in sulfide polymer contribute to the maximized material utilization and rapid ion coordination and dissociation,resulting in superior rate capability.Besides,the bridged thioether bonds endow the polysulfide with robust and flexible structure,which inhibits the dissolution of active materials and improves cycling stability.This work implies the importance of ordered arrangement of redox active moieties for organic electrode,which provides the theoretical direction for the structural design of organic materials applied in multivalent-ion batteries.
文摘Carbon capture,storage,and utilization(CCSU)is recognized as an effective method to reduce the excessive emission of CO_(2).Absorption by amine aqueous solutions is considered highly efficient for CO_(2) capture from the flue gas because of the large CO_(2) capture capacity and high selectivity.However,it is often limited by the equipment corrosion and the high desorption energy consumption,and adsorption of CO_(2) using solid adsorbents has been receiving more attention in recent years due to its simplicity and high efficiency.More recently,a great number of porous organic polymers(POPs)have been designed and constructed for CO_(2) capture,and they are proven promising solid adsorbents for CO_(2) capture due to their high Brunauer-Emmett-Teller(BET)surface area(SBET),adjustable pore size and easy functionalization.In particular,they usually have rigid skeleton,permanent porosity,and good physiochemical stability.In this review,we have a detailed review for the different POPs developed in recent years,not only the design strategy,but also the special structure for CO_(2) capture.The outlook of the opportunities and challenges of the POPs is also proposed.
基金supported by the State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC)the National Natural Science Foundation of China(Nos.21878216,22005215)+1 种基金Hebei Province Innovation Ability Promotion Project(No.20312201D)the National Key Research and Development Program of China(No.2019YFE0118800)。
文摘The lithiated covalent organic framework(named TpPa-SO_(3) Li),which was prepared by a mild chemical lithiation strategy,was introduced in poly(ethylene oxide)(PEO)to produce the composite polymer electrolytes(CPEs).Li-ion can transfer along the PEO chain or across the layer of TpPa-SO_(3) Li within the nanochannels,resulting in a high Li-ion conductivity of3.01×10^(-4)S/cm at 60℃.When the CPE with 0.75 wt.%TpPa-SO_(3) Li was used in the LiFePO_(4)‖Li solid-state battery,the cell delivered a stable capacity of 125 mA·h/g after 250 cycles at 0.5 C,60℃.In comparison,the cell using the CPE without TpPa-SO_(3) Li exhibited a capacity of only 118 mA·h/g.
基金the support from the National Natural Science Foundation of China (51873177, 51573153, 61564003 and 21875204)the group of Advanced Photoelectricity and Supermolecule Function Materials of Ministry of Education (IRT-17R90)+1 种基金the Hunan 2011 Collaborative Innovation Center of Chemical Engineering & Technology with Environmental Benignity and Effective Resource Utilizationsupport from Guangxi Bagui Scholar Program and Guangxi Natural Science Foundation (2015GXNSFGA139002)。
文摘Two non-conjugated polymers PEIE-DBO and PEIE-DCO, prepared by quaternization of polyethyleneimine ethoxylate by 1,8-dibromooctane and 1,8-dichlorooctane respectively, are developed as electron transport layer(ETL) in high-performance inverted organic solar cells(OSCs), and the effects of halide ions on polymeric photoelectric performance are fully investigated. PEIE-DBO possesses higher electron mobility(3.68×10-4 cm2 V-1s-1), higher conductivity and more efficient exciton dissociation and electron extraction, attributed to its lower work function(3.94 eV) than that of PEIE-DCO, which results in better photovoltaic performance in OSCs. The inverted OSCs with PTB7-Th: PC71BM as photoactive layer and PEIE-DBO as ETL exhibit higher PCE of 10.52%, 9.45% and 9.09% at the thickness of 9, 35 and 50 nm,respectively. To our knowledge, PEIE-DBO possesses the best thickness-insensitive performance in polymeric ETLs of inverted fullerene-based OSCs. Furthermore, PEIE-DBO was used to fabricate the inverted non-fullerene OSCs(PM6:Y6) and obtained a high PCE of 15.74%, which indicates that PEIE-DBO is effective both in fullerene-based OSCs and fullerene-free OSCs.
文摘Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2CHSi(OMe)3)n-RF;RF = CF(CF3)OCF7, n = 2, 3;RF-(VM)n-RF] was applied to the preparation of fluoroalkyl end-capped vinyltrimethoxysilane oligomer/α-, β-, γ-cyclodextrin polymers (α-, β-, γ-CDPs) composites [RF-(VM-SiO2)n-RF/α-, β-, γ-CDPs] by the sol-gel reaction of the corresponding oligomer in the presence of the α-, β-, γ-CDPs under alkaline conditions. The RF-(VM-SiO2)n-RF/α-, β-, γ-CDPs composites thus obtained were found to give a good dispersibility toward the traditional organic media except for water, and were applied to the surface modification of glass to provide a sueperoleophilic/superhydrophobic characteristic on the modified surface, although the corresponding RF-(VM-SiO2)n-RF nanocomposites can give a usual oleophobic/superhydrophobic property on the surface. These composites powders were also found to be applicable to the packing material for the column chromatography to separate the mixture of oil/water and the water in oil (W/O) emulsions. More interestingly, these composite powders were found to have a higher adsorption ability toward not only low-molecular weight aromatic compounds such as bisphenol A and bisphenol AF but also volatile organic compounds, compared to that of the pristine α-, β-, γ-CDPs.
基金Supported by the Key Project of Chinese Ministry of Education (No. 208116)the Scientific and Technological Project of CQEC (No. KJ080829)
文摘(E)-2,6-Dimethyl-4-styrylpyridine-3,5-dicarboxylic acid (H2mspda) is firstly employed in coordination chemistry.Two isostructural two-dimensional (2-D) 4-connected metal-organic coordination polymers with a general formula of {M2[(mspda)2(bpy)(H2O)2]}n (M=Zn(1) and Co(2)) are assembled from H2mspda,4,4'-bipyridyl (bpy),zinc and cobalt ions under hydrothermal conditions,and characterized by single-crystal X-ray diffraction analyses.Complex 1 crystallizes in monoclinic,space group P21/n with a=14.551(4),b=10.941(3),c=14.945(4),β=98.817(4)o,V=2351.3(1)3,Dc=1.511 g/cm3,μ(MoKα)=1.090 mm-1,F(000)=1104,Z=4,the final R=0.0335 and wR=0.0485 for 3296 observed reflections (I 〉 2σ(I)).In compound 1,mspda2-spacers are only arrayed in a head-to-tail fashion which corresponds to a 2-D coordination polymer.Solid-state H2mspda and complex 1 have expected photoluminescence (λem=475~496 nm) at room temperature.
基金Project(50673028) supported by the National Natural Science Foundation of Chinaproject(04020090) supported by Guangdong Natural Science Foundation of Guangdong Province, ChinaProject(2005Z3-I0011) supported by Guangzhou International Science and Technology Cooperation Project
文摘The 6-mercapto-1,3,5-triazine-2,4-dithiol monosodium(TTN) compound was used to fabricate an organic film on pure copper. The polymer plating process of TTN on pure copper in Na2CO3 aqueous solution and the growth mechanism of poly(6-mercapto-1,3,5-triazine-2,4-dithiol)(PTT) film were studied by means of cyclic voltammetry. The polymer plating under galvanostatic mode at 0.05 mA/cm2 was conducted to generate PTT film on pure copper in the same electrolyte with different polymer-plating time. The film mass was determined by electronic balance and the insoluble fraction in tetrahydrofuran(THF) Is tested. The performance of organic film formed on copper surface was investigated preliminarily by potentiodynamic polarization and electrochemical impedance spectroscopy(EIS). It is found that a slight peak measured at 0 V vs SCE attributes to the oxidation of copper and generated Cu+ or/and Cu2+ to produce Cu-TTN complex,then a strong oxide peak is observed at 0.311 V vs SCE due to the polymerization of TTN for the increase of the film thickness. Electrochemical measurement results reveal that 10 min is an optimum polymer-plated time to obtain high quality film. The results of potentiodynamic polarization show that current density decreases from 1.85 μA/cm2 for bare copper to 0.168 μA/cm2 for polymer-plated copper while polymer-plated time is 10 min. The charge transfer resistances of bare copper and polymer-plated copper are 937 Ω·cm2 and 11.12 kΩ·cm2,respectively. The film capacitor for polymer-plated copper is as low as 1.82 μF·cm2. The EIS results confirm the results of potentiodynamic polarization and reveal that a homogenous and compact film is obtained by polymer plating technique.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.11204157 and 11174179)the China Three Gorges University Project (Grant No.KJ2011B068)the Yichang City Project,China (Grant No.A201230229)
文摘The ferrimagnetism and quantum phase transition of a bipartite lozenge periodic Anderson-like organic polymer, in which the localized f electrons hybridize with the odd site conduction orbitals, are investigated by means of Green's function theory. The ground state turns out to be gapless ferrimagnetism. At a finite temperature, the ferrimagnetic-to- paramagnetic phase transition takes place. The Kondo screenings and Ruderman-Kittel-Kasuya-Yosida (RKKY) inter- action can reduce and increase the transition temperature, respectively. Two Kondo screenings compete with each other, giving rise to the localized f electron spin screened antiferromagnetically. Accordingly, in a magnetic field, all spins are aligned along the chain easily, which is associated with metal-insulator transition. Furthermore, in a temperature-field plane, we reveal the gapless and spin polarized phases, which are characterized by susceptibility and specific heat, and whose behaviours are determined by the competition between the up-spin and down-spin hole excitations.
文摘The addition of water-soluble polymer to a fine coal slurry to enhance dewatering process is considered to be one of the most effective ways of solving the problems of dewatering of fine coal. A series of tests are conducted with a vacuum dewatering apparatus to study the effects of various factors such as the species of polymer, polymer dosage and its ways of addition, and the pH of fine coal slurry on filtrating and dewatering of fine coal.