The development of applicable electrolytes is the key point for high-performance rechargeable magnesium batteries(RMBs).The use of liquid electrolyte is prone to safety problems caused by liquid electrolyte leakage.Po...The development of applicable electrolytes is the key point for high-performance rechargeable magnesium batteries(RMBs).The use of liquid electrolyte is prone to safety problems caused by liquid electrolyte leakage.Polymer-based gel electrolytes with high ionic conductivity,great flexibility,easy processing,and high safety have been studied by many scholars in recent years.In this work,a novel porous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membrane is prepared by a phase inversion method.By immersing porous PVDF-HFP membranes in MgCl2-AlCl3/TEGDME(Tetraethylene glycol dimethyl ether)electrolytes,porous PVDF-HFP based electrolytes(PPEs)are formed.The PPE exhibits a high ionic conductivity(4.72×10^(-4) S cm-1,25℃),a high liquid electrolyte uptake of 162%,as well as a wide voltage window(3.1 V).The galvanostatic cycling test of Mg//Mg symmetric cell with PPE reveals that the reversible magnesium ion(Mg^(2+))plating/stripping occurs at low overpotentials(~0.13 V).Excellent long cycle stability(65.5 mAh g^(-1) over 1700 cycles)is achieved for the quasisolid-state RMB assembled with MoS2/C cathode and Mg anode.Compared with the liquid electrolyte,the PPE could effectively reduce the side reactions and make Mg^(2+)plating/stripping more uniformly on the Mg electrode side.This strategy herein provides a new route to fabricate high-performance RMB through suitable cathode material and polymer electrolyte with excellent performance.展开更多
Organic-inorganic hybrid</span><b> </b><span style="font-family:Verdana;">network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquiox...Organic-inorganic hybrid</span><b> </b><span style="font-family:Verdana;">network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquioxane (SQ109) and alkyl diacrylate or diisocyanate compounds. Thiol-ene reaction of SQ109 and 1,4-butanediol diacrylate (BDA) successfully yield porous polymer in toluene initiated by azobis</span></span><span style="font-family:Verdana;">(</span><span style="font-family:Verdana;">isobutyronitrile</span><span style="font-family:Verdana;">)</span><span style="font-family:Verdana;"> (AIBN) at 60</span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. Morphology of the porous polymers was composed by connected globules, and the diameter of the globules decreased with increasing in the monomer concentration </span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">system</span><span style="font-family:""><span style="font-family:Verdana;">. By contrast, the reaction with 1,6-hexanediol diacrylate or </span><span style="font-family:Verdana;">1,5-hexadiene yielded homogeneous clear gels. Thermal analyses of SQ109-BDA</span><span style="font-family:Verdana;"> porous polymers indicated that thermal degradation of ester groups of BDA in the polymer network occurred at around 300</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. The porous polymer was also obtained </span><span style="font-family:Verdana;">by</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">using</span><span style="font-family:""><span style="font-family:Verdana;"> a photo-initiator (Irugacure184) at room temperature, and showed higher Young’s modulus than the corresponding porous polymer obtained with the reaction with AIBN due to the small size of </span><span style="font-family:Verdana;">the globules. Young’s modulus of SQ109-BDA porous polymer increased</span><span style="font-family:Verdana;"> with </span><span style="font-family:Verdana;">increasing in the monomer concentration </span></span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction systems. Thioliso</span><span style="font-family:""><span style="font-family:Verdana;">cyanate addition reactions between SQ109 </span><span style="font-family:Verdana;">and hexamethylene diisocyanate (HDI) or methylenediphenyl 4,4’-diisocyanate</span><span style="font-family:Verdana;"> (MDI) were investigated to obtain network polymers. The reactions in toluene yielded the corresponding homogeneous clear gels. By contrast the reactions in a mixed solvent of toluene (50 vol.%) and </span><i><span style="font-family:Verdana;">N,N</span></i><span style="font-family:Verdana;">-dimethylformamide (50 vol.%) produced porous polymers. The morphology of the porous polymers was composed by connected </span><span style="font-family:Verdana;">globules or aggregated particles. The size of globules and particles in the</span><span style="font-family:Verdana;"> SQ109-HDI porous polymers was larger </span><span style="font-family:Verdana;">than </span></span><span style="font-family:Verdana;">those</span><span style="font-family:Verdana;"> in the SQ109-MDI porous polymers. Thermal degradation of SQ109-HDI and SQ109-MDI porous polymers</span><span style="font-family:Verdana;"> started at round 260</span><span style="font-family:Verdana;">°</span><span style="font-family:""><span style="font-family:Verdana;">C and showed </span><span style="font-family:Verdana;">endothermic peak at around 350</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C derived from degradation of </span><span style="font-family:Verdana;">thio-urethane bond.展开更多
The transformation of CO_(2)into cyclic carbonates via atom-economical cycloadditions with epoxides has recently attracted tremendous attention.On one hand,though many heterogeneous catalysts have been developed for t...The transformation of CO_(2)into cyclic carbonates via atom-economical cycloadditions with epoxides has recently attracted tremendous attention.On one hand,though many heterogeneous catalysts have been developed for this reaction,they typically suffer from disadvantages such as the need for severe reaction conditions,catalyst loss,and large amounts of soluble co-catalysts.On the other hand,the development of heterogeneous catalysts featuring multiple and cooperative active sites,remains challenging and desirable.In this study,we prepared a series of porous organic catalysts(POP-PBnCl-TPPMg-x)via the copolymerization metal-porphyrin compounds and phosphonium salt monomers in various ratios.The resulting materials contain both Lewis-acidic and Lewis-basic active sites.The molecular-level combination of these sites in the same polymer allows these active sites to work synergistically,giving rise to excellent performance in the cycloaddition reaction of CO_(2)with epoxides,under mild conditions(40℃ and 1 atm CO_(2))in the absence of soluble co-catalysts.POP-PBnCl-TPPMg-12 can also efficiently fixate CO_(2)under low-CO_(2)-concentration(15%v/v N2)conditions representative of typical CO_(2)compositions in industrial exhaust gases.More importantly,this catalyst shows excellent recyclability and can easily be separated and reused at least five times while maintaining its activity.In view of their heterogeneous nature and excellent catalytic performance,the obtained catalysts are promising candidates for the transformation of industrially generated CO_(2)into high value-added chemicals.展开更多
Two vinyl‐functionalized chiral2,2'‐bis(diphenylphosphino)‐1,1'‐binaphthyl(BINAP)ligands,(S)‐4,4'‐divinyl‐BINAP and(S)‐5,5'‐divinyl‐BINAP,were successfully synthesized.Chiral BINAP‐based por...Two vinyl‐functionalized chiral2,2'‐bis(diphenylphosphino)‐1,1'‐binaphthyl(BINAP)ligands,(S)‐4,4'‐divinyl‐BINAP and(S)‐5,5'‐divinyl‐BINAP,were successfully synthesized.Chiral BINAP‐based porous organic polymers(POPs),denoted as4‐BINAP@POPs and5‐BINAP@POPs,were efficiently prepared via the copolymerization of vinyl‐functionalized BINAP with divinyl benzene under solvothermal conditions.Thorough characterization using nuclear magnetic resonance spectroscopy,thermogravimetric analysis,extended X‐ray absorption fine structure analysis,and high‐angle annular dark‐field scanning transmission electron microscopy,we confirmed that chiral BINAP groups were successfully incorporated into the structure of the materials considered to contain hierarchical pores.Ru was introduced as a catalytic species into the POPs using different synthetic routes.Systematic investigation of the resultant chiral Ru/POP catalysts for heterogeneous asymmetric hydrogenation ofβ‐keto esters revealed their excellent chiral inducibility as well as high activity and stability.Our work thereby paves a path towards the use of advanced hierarchical porous polymers as solid chiral platforms for heterogeneous asymmetric catalysis.展开更多
Nitrogen-rich porous organic polymers(POPs)with basic features have already shown promising performance in various organic reactions.But the harsh conditions,tedious synthetic methods and the requirement of specific m...Nitrogen-rich porous organic polymers(POPs)with basic features have already shown promising performance in various organic reactions.But the harsh conditions,tedious synthetic methods and the requirement of specific monomers impede their further application.Herein,we introduce isoindoline chemistry into POP community.An isoindoline formation process between aniline and bromomethylbenzenedcoupling nucleophilic substitution,HBr elimination,and intramolecular cyclization in one pot,is utilized for POPs synthesis.Nitrogen-rich isoindolinebased porous polymers(IPPs)were obtained with specific surface areas up to 408 m^(2) g^(-1).Unexpectedly,mechanochemistry could enable the rapid(3 h)and solid-state synthesis of IPP catalysts.Moreover,this nitrogen-rich catalyst presents excellent activity(isolated yield:99%),scalable ability(up to 14 g per run)and recyclability(five runs)towards the Knoevenagel condensation reaction under mild reaction conditions(water as solvent at room temperature).展开更多
Formic acid(FA)has attracted extensive attention as a hydrogen storage material.Here,we develop two heterogeneous catalysts based on porous organic polymers(POPs).After loading the Ru species,the catalyst bearing the ...Formic acid(FA)has attracted extensive attention as a hydrogen storage material.Here,we develop two heterogeneous catalysts based on porous organic polymers(POPs).After loading the Ru species,the catalyst bearing the triphenylphosphine ligand showed excellent performance in terms of activity and stability for the decomposition of FA to produce hydrogen.展开更多
Immobilization of enzymes onto porous membranes has attracted considerable attention in recent years.However,enhancing the enzymolysis efficiency of the resulting enzyme reactors by varying the environmental condition...Immobilization of enzymes onto porous membranes has attracted considerable attention in recent years.However,enhancing the enzymolysis efficiency of the resulting enzyme reactors by varying the environmental conditions poses a great challenge.In this work,poly(styrene-maleic anhydride-N,N-dimethylacrylamide)was prepared and utilized to construct a thermo-sensitive porous polymer membrane-based enzyme reactor(TS-PPMER)after cellulase was immobilized onto the support by covalent bonding.The catalytic activity of the nano-reactor was evaluated by measuring the yield of the product,glucose,at different temperatures with carboxymethylcellulose as the substrate.Interestingly,the polymer chains coiled and formed numerous nano-pores at a high temperature,which induced the confine effect and greatly boosted the enzymolysis efficiency of TS-PPMER.Furthermore,the proposed TS-PPMER was applied in the hydrolysis of green plant leaves in Epipremnum aureum.This work shows great potential in obtaining biological resources by an environmentally friendly approach using smart polymer-based nano-reactors.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
Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD...Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD)2/COD/bpy system,suffering from great instability and high cost.Herein,we developed an in situ reduction of the Ni(II)catalytic system to synthesize PAF-1 in low cost and high yield.The active Ni(0)species produced from the NiCl_(2)/bpy/NaI/Mg catalyst system can effectively catalyze homocoupling of tetrakis(4-bromophenyl)methane at the room temperature to form PAF-1 with high Brunauer-Emmett-Teller(BET)-specific surface area up to 4948 m^(2) g^(−1)(Langmuir surface area,6785 m2 g−1).The possible halogen exchange and dehalogenation coupling mechanisms for this new catalytic process in PAF's synthesis are discussed in detail.The efficiency and universality of this innovative catalyst system have also been demonstrated in other PAFs'synthesis.This work provides a cheap,facile,and efficient method for scalable synthesis of PAFs and explores their application for high-pressure storage of Xe and Kr.展开更多
A novel porous coordination polymer,iron naphthalenedicarboxylate Fe(OH)(1,4-NDC)·2H2O is hydrothermally synthesized by the reaction of FeSO4·7H2O and 1,4-naphthalenedicarboxylic acid(1,4-H2NDC) at 150...A novel porous coordination polymer,iron naphthalenedicarboxylate Fe(OH)(1,4-NDC)·2H2O is hydrothermally synthesized by the reaction of FeSO4·7H2O and 1,4-naphthalenedicarboxylic acid(1,4-H2NDC) at 150℃.The compound crystallizes in a tetragonal space group P42/nmc:a=2.1447(4) nm,c=0.68849(14) nm,V=3.1669(11) nm3,Z=8,R=0.0845,wR=0.1829.The crystal structure exhibits a three-dimensional framework which is composed of infinite chains of corner-sharing octahedral Fe(OH)2O4 with 1,4-NDC ligands forming two types of channels with square-shaped cross-sections.The large channels present a cross-section of 0.76 nm×0.76 nm,while the small channels are about 0.30 nm×0.30 nm.No structural transformation occurs after removing the guest water molecules,while a robust structure generates with permanent porosity.The adsorption measurements show that the anhydrous sample of the compound can adsorb CO2 into its pores.The adsorption isotherms for methanol,acetone,tetrahydrofuran and benzene are also measured.展开更多
Porous polymers have been recently recog- nized as one of the most important precursors for fabrication of heteroatom-doped porous carbons due to the intrinsic porous structure, easy available heteroatom- containing m...Porous polymers have been recently recog- nized as one of the most important precursors for fabrication of heteroatom-doped porous carbons due to the intrinsic porous structure, easy available heteroatom- containing monomers and versatile polymerization meth- ods. However, the heteroatom elements in as-produced porous carbons are quite relied on monomers. So far, the manipulating of heteroatom in porous polymer derived porous carbons are still very rare and challenge. In this work, a sulfur-enriched porous polymer, which was prepared from a diacetylene-linked porous polymer, was used as precursor to prepare S-doped and/or N-doped porous carbons under nitrogen and/or ammonia atmo- spheres. Remarkably, S content can sharply decrease from 36.3% to 0.05% after ammonia treatment. The N content and specific surface area of as-fabricated porous carbons can reach up to 1.32% and 1508 m^2·g^-1, respectively. As the electrode materials for electrical double-layer capacitors, as-fabricated porous carbons exhibit high specific capacitance of up to 431.6 F·g^-1 at 5 mW·s^-1 and excellent cycling stability of 99.74% capacitance retention after 3000 cycles at 100 mV·s^-1. Furthermore, as the electro- chemical catalysts for oxygen reduction reaction, as- fabricated porous carbons presented ultralow half-wave- potential of 0.78 V versus RHE. This work not only offers a new strategy for manipulating S and N doping features for the porous carbons derived from S-containing porous polymers, but also paves the way for the structure- performance interrelationship study of heteroatoms co- doped porous carbon for energy applications.展开更多
Design and fabrication of the micro/nanostructures of the network units is a critical issue for porous nanonetwork structured materials. Significant progress has been attained in construction of the network units with...Design and fabrication of the micro/nanostructures of the network units is a critical issue for porous nanonetwork structured materials. Significant progress has been attained in construction of the network units with zero-dimensional spherical shapes.However, owing to the limitations of synthetic methods, construction of porous building blocks in one dimension featuring high aspect ratios for porous nanonetwork structured polymer(PNSP) remains largely unexplored. Here we present the successful design and preparation of PNSP with a novel type of one-dimensional network unit, i.e., microporous heterogeneous nanowire. Well-defined core-shell polymer nanoobjects prepared from a gelable block copolymer, poly(3-(triethoxysilyl)propyl methacrylate)-block-polystyrene are employed as building blocks, and facilely transformed into PNSP via hypercrosslinking of polystyrene shell. The as-prepared PNSP exhibits unique three-dimensional hierarchical nanonetwork morphologies with large surface area. These findings could provide a new avenue for fabrication of unique well-defined PNSP, and thus generate valuable breakthroughs in many applications.展开更多
A series of benzimidazole-linked porous polymers are obtained by the condensation reaction between the o-aminobenzol end groups of building blocks(2,3,6,7,10,11-hexaaminotriphenylene,3,3'-diaminobenzidine or 1,2,4...A series of benzimidazole-linked porous polymers are obtained by the condensation reaction between the o-aminobenzol end groups of building blocks(2,3,6,7,10,11-hexaaminotriphenylene,3,3'-diaminobenzidine or 1,2,4,5-benzenetetraamine)and the aldehyde groups of building blocks[terephthalicaldehyde,4,4'-biphenyl-dicarboxaldehyde,1,3,5-tris(4-acetylphenyl)benzene or 1,3,5-tris(4-formylbiphenyl)amine]in one-pot synthesis without employing any catalyst or template.The existence of the imidazole ring in the obtained polymers could be identified by Fourier transform infrared and solid-state^(13)C CP/MAS NMR spectroscopy.The sphere-shaped mor-phology of the obtained polymers is observed through scanning electron microscopy.The polymers possess Brunauer-Emmett-Teller specific surface area values over 600 m^(2)·g^(-1),showing hydrogen storage(up to 1.6 wt%,at 77 K and 1×10^(5)Pa)and carbon dioxide capture(up to 12.6 wt%,at 273 K and 1×10^(5)Pa)properties.Such poly-mers would possess good performance in the applications of gas storage and separation.展开更多
Porous polymer beads(PPBs) containing hierarchical bimodal pore structure with gigapores and meso-macropores were prepared by polymerization-induced phase separation(PIPS) and emulsion-template technique in a glas...Porous polymer beads(PPBs) containing hierarchical bimodal pore structure with gigapores and meso-macropores were prepared by polymerization-induced phase separation(PIPS) and emulsion-template technique in a glass capillary microfluidic device(GCMD). Fabrication procedure involved the preparation of water-in-oil emulsion by emulsifying aqueous solution into the monomer solution that contains porogen. The emulsion was added into the GCMD to fabricate the(water-in-oil)-in-water double emulsion droplets. The flow rate of the carrier continuous phase strongly influenced the formation mechanism and size of droplets. Formation mechanism transformed from dripping to jetting and size of droplets decreased from 550 μm to 250 μm with the increase in flow rate of the carrier continuous phase. The prepared droplets were initiated for polymerization by on-line UV-irradiation to form PPBs. The meso-macropores in these beads were generated by PIPS because of the presence of porogen and gigapores obtained from the emulsion-template. The pore morphology and pore size distribution of the PPBs were investigated extensively by scanning electron microscopy and mercury intrusion porosimetry(MIP). New pore morphology was formed at the edge of the beads different from traditional theory because of different osmolarities between the water phase of the emulsion and the carrier continuous phase. The morphology and proportion of bimodal pore structure can be tuned by changing the kind and amount of porogen.展开更多
The widespread use of bisphenol A(BPA)poses a serious threat to the environment and human health.However,efficient removal of BPA in water is incredibly challenging,owing to the inert chemical nature and electrical ne...The widespread use of bisphenol A(BPA)poses a serious threat to the environment and human health.However,efficient removal of BPA in water is incredibly challenging,owing to the inert chemical nature and electrical neutrality of BPA.In order to solve this problem,for the first time,we propose that a strategy of designing conjugated porous polymers with the pore size matching the size of BPA can greatly enhance the binding force of BPA.On this basis,we developed a novel conjugated poly 1,3,5-tri[4-(diphenylamino)phenyl]benzene(MPDPB)with intrinsic pore matching the size of BPA and multi-stage porous structure by editing polymerization with nitrobenzene.The binding energy of MPDPB to BPA is the highest at present(37.84 kcal/mol),which is 2.3 times that of the most powerful adsorbent previously reported and five times that of the conventional adsorbent.These advantages make MPDPB have super-high adsorption performance towards BPA and high absorbing stability under extreme environments.Impressively,MPDPB could be easily loaded on a non-woven fabric to generate point-of-use devices,which could eliminate more than 99.8%of BPA,making it the best BPA candidate adsorbent material.We believe that the proposed material design derived from the specific structure of the contaminant molecule can be extended to exploring further innovative adsorbents.展开更多
Metal-organic frameworks(MOFs) show great potential for various applications, but many of them suffer from the drawbacks of hydrolysis propensity and poor processability. Herein, we employ polymers of intrinsic microp...Metal-organic frameworks(MOFs) show great potential for various applications, but many of them suffer from the drawbacks of hydrolysis propensity and poor processability. Herein, we employ polymers of intrinsic microporosity(PIMs) with hydrophobic pores to decorate MOFs toward substantially improved water stability and shapeability. Through simple PIM-1 decoration, the sub-5 nm polymer layers can be uniformly deposited on MOF surfaces with almost no deterioration in porosity. Owing to the existence of superhydrophobic coating and the obstruction of water entrance into MOFs, the PIM-1 coated Cu BTC exhibits impressive water resistance and excellent pore preservation ability after exposure in water, even in acidic and alkaline solutions. Moreover, polymer decoration improves the processability of MOFs, while various MOF/PIM-1 bulk wafers and oil-water separators can be obtained straightforwardly.展开更多
Conjugated porous polymers exhibit considerable advantage as attractive candidate for carbon dioxide(CO_(2)) capture. However, the regeneration of the CO_(2) still faces the problem of high energy cost. Here we synthe...Conjugated porous polymers exhibit considerable advantage as attractive candidate for carbon dioxide(CO_(2)) capture. However, the regeneration of the CO_(2) still faces the problem of high energy cost. Here we synthesize a near-infrared region(NIR) light responsive conjugated porous polymer(PDPP-Gu) [DPP=3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione] by constructing porous amorphous networks with a side chain engineering strategy to regulate CO_(2) adsorption and release through photothermal conversion. The PDPP-Gu is featured by a torsional conjugated backbone as well as a functional side chain of guanidino group. The donor-acceptor configuration of PDPP-Gu afforded strong absorption in the NIR and an excellent photothermal conversion capability of up to 48.8%, as well as a high surface energy. Moreover, guanidine modified side chain further enhanced the CO_(2)-polymers interactions, resulting in a high CO_(2) selective adsorption capacity(0.8 mmol/g) at 273 K, 1 bar(1 bar=105 Pa). The adsorbed CO_(2) can be released under NIR light irradiation. This strategy of molecule design combined the dual features of photothermal conversion and gas adsorption, which is beneficial for the development of materials to dynamically control the adsorption and release of CO_(2) through NIR light.展开更多
Micro/nano-porous polymeric material is considered a unique industrial material due to its extremelylow thermal conductivity, low density, and high surface area. Therefore, it is necessary to establishan accurate ther...Micro/nano-porous polymeric material is considered a unique industrial material due to its extremelylow thermal conductivity, low density, and high surface area. Therefore, it is necessary to establishan accurate thermal conductivity prediction model suiting their applicable conditions and provide atheoretical basis for expanding their applications. In this work, the development of the calculationmodel of equivalent thermal conductivity of micro/nano-porous polymeric materials in recent yearsis summarized. Firstly, it reviews the process of establishing the overall equivalent thermal conductivity calculation model for micro/nanoporous polymers. Then, the predicted calculation models ofthermal conductivity are introduced separately according to the conductive and radiative thermalconductivity models. In addition, the thermal conduction part is divided into the gaseous thermalconductivity model, solid thermal conductivity model and gas-solid coupling model. Finally, it isconcluded that, compared with other porous materials, there are few studies on heat transfer of micro/nanoporous polymers, especially on the particular heat transfer mechanisms such as scale effectsat the micro/nanoscale. In particular, the following aspects of porous polymers still need to be furtherstudied: micro scaled thermal radiation, heat transfer characteristics of particular morphologies at thenanoscales, heat transfer mechanism and impact factors of micro/nanoporous polymers. Such studieswould provide a more accurate prediction of thermal conductivity and a broader application in energyconversion and storage systems.展开更多
A shape-persistent dendritic molecule,tris(4-(2,7-dibromo-9-phenyl-9-fluoren-9-yl)phenyl)amine (TF-6Br),has been readily synthesized in high yield through a concise Friedel-Crafts reaction from triphenylamine and 2,7-...A shape-persistent dendritic molecule,tris(4-(2,7-dibromo-9-phenyl-9-fluoren-9-yl)phenyl)amine (TF-6Br),has been readily synthesized in high yield through a concise Friedel-Crafts reaction from triphenylamine and 2,7-dibromo(9-phenyl-fluoren-9-ol).It was further employed as the key building block to achieve the synthesis of conjugated porous polymer via Sonogashira coupling with 1,4-diethynylbenzene.Under experimental reaction conditions,the resulting porous polymer shows exceptionally nanotubular morphology,which further allows for a template-free synthesis of porous carbon nanotubes via thermal treatment at high temperature.The obtained nitrogen-doped carbon nanotubes feature with an improved porosity and high surface area.展开更多
Immobilization of enzymes onto carriers is a rapidly growing research area aimed at increasing the stability,reusability and enzymolysis efficiency of free enzymes.In this work,the role of phaseseparation and a pH-res...Immobilization of enzymes onto carriers is a rapidly growing research area aimed at increasing the stability,reusability and enzymolysis efficiency of free enzymes.In this work,the role of phaseseparation and a pH-responsive"hairy"brush,which greatly affected the topography of porous polymer membrane enzyme reactors(PMER),was explored.The porous polymer membrane was fabricated by phase-separation of poly(styrene-co-maleic anhydride-acrylic acid)and poly(styrene-ethylene glycol).Notably,the topography and pores size of the PMER could be controlled by phase-separation and a pHresponsive"hairy"brush.For evaluating the enzymolysis efficiency of D-amino acid oxidase(DAAO)immobilized carrier(DAAO@PMER),a chiral ligand exchange capillary electrophoresis method was developed with D-methionine as the substrate.The DAAO@PMER showed good reusability and stability after five continuous runs.Notably,comparing with free DAAO in solution,the DAAO@PMER exhibited a17.7-folds increase in catalytic velocity,which was attributed to its tailorable topography and pHresponsive property.The poly(acrylic acid)moiety of poly(styrene-co-maleic anhydride-acrylic acid)as the pH-responsive"hairy"brush generated topography changing domains upon adjusting the buffer pH,which enable the enzymolysis efficiency of DAAO@PMER to be tuned based upon the well-defined architectures of the PMER.This approach demonstrated that the topographical changes formed by phaseseparation and the pH-responsive"hairy"brush indeed made the proposed porous polymer membrane as suitable supports for enzyme immobilization and fitting for enzymolysis applications,achieving high catalytic performance.展开更多
基金supported by the National Key Research and Development Program of China(2017YFE0113500)the National Natural Science Foundation of China(51872027)。
文摘The development of applicable electrolytes is the key point for high-performance rechargeable magnesium batteries(RMBs).The use of liquid electrolyte is prone to safety problems caused by liquid electrolyte leakage.Polymer-based gel electrolytes with high ionic conductivity,great flexibility,easy processing,and high safety have been studied by many scholars in recent years.In this work,a novel porous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membrane is prepared by a phase inversion method.By immersing porous PVDF-HFP membranes in MgCl2-AlCl3/TEGDME(Tetraethylene glycol dimethyl ether)electrolytes,porous PVDF-HFP based electrolytes(PPEs)are formed.The PPE exhibits a high ionic conductivity(4.72×10^(-4) S cm-1,25℃),a high liquid electrolyte uptake of 162%,as well as a wide voltage window(3.1 V).The galvanostatic cycling test of Mg//Mg symmetric cell with PPE reveals that the reversible magnesium ion(Mg^(2+))plating/stripping occurs at low overpotentials(~0.13 V).Excellent long cycle stability(65.5 mAh g^(-1) over 1700 cycles)is achieved for the quasisolid-state RMB assembled with MoS2/C cathode and Mg anode.Compared with the liquid electrolyte,the PPE could effectively reduce the side reactions and make Mg^(2+)plating/stripping more uniformly on the Mg electrode side.This strategy herein provides a new route to fabricate high-performance RMB through suitable cathode material and polymer electrolyte with excellent performance.
文摘Organic-inorganic hybrid</span><b> </b><span style="font-family:Verdana;">network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquioxane (SQ109) and alkyl diacrylate or diisocyanate compounds. Thiol-ene reaction of SQ109 and 1,4-butanediol diacrylate (BDA) successfully yield porous polymer in toluene initiated by azobis</span></span><span style="font-family:Verdana;">(</span><span style="font-family:Verdana;">isobutyronitrile</span><span style="font-family:Verdana;">)</span><span style="font-family:Verdana;"> (AIBN) at 60</span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. Morphology of the porous polymers was composed by connected globules, and the diameter of the globules decreased with increasing in the monomer concentration </span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">system</span><span style="font-family:""><span style="font-family:Verdana;">. By contrast, the reaction with 1,6-hexanediol diacrylate or </span><span style="font-family:Verdana;">1,5-hexadiene yielded homogeneous clear gels. Thermal analyses of SQ109-BDA</span><span style="font-family:Verdana;"> porous polymers indicated that thermal degradation of ester groups of BDA in the polymer network occurred at around 300</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C. The porous polymer was also obtained </span><span style="font-family:Verdana;">by</span><span style="font-family:Verdana;"> the reaction </span><span style="font-family:Verdana;">using</span><span style="font-family:""><span style="font-family:Verdana;"> a photo-initiator (Irugacure184) at room temperature, and showed higher Young’s modulus than the corresponding porous polymer obtained with the reaction with AIBN due to the small size of </span><span style="font-family:Verdana;">the globules. Young’s modulus of SQ109-BDA porous polymer increased</span><span style="font-family:Verdana;"> with </span><span style="font-family:Verdana;">increasing in the monomer concentration </span></span><span style="font-family:Verdana;">of</span><span style="font-family:Verdana;"> the reaction systems. Thioliso</span><span style="font-family:""><span style="font-family:Verdana;">cyanate addition reactions between SQ109 </span><span style="font-family:Verdana;">and hexamethylene diisocyanate (HDI) or methylenediphenyl 4,4’-diisocyanate</span><span style="font-family:Verdana;"> (MDI) were investigated to obtain network polymers. The reactions in toluene yielded the corresponding homogeneous clear gels. By contrast the reactions in a mixed solvent of toluene (50 vol.%) and </span><i><span style="font-family:Verdana;">N,N</span></i><span style="font-family:Verdana;">-dimethylformamide (50 vol.%) produced porous polymers. The morphology of the porous polymers was composed by connected </span><span style="font-family:Verdana;">globules or aggregated particles. The size of globules and particles in the</span><span style="font-family:Verdana;"> SQ109-HDI porous polymers was larger </span><span style="font-family:Verdana;">than </span></span><span style="font-family:Verdana;">those</span><span style="font-family:Verdana;"> in the SQ109-MDI porous polymers. Thermal degradation of SQ109-HDI and SQ109-MDI porous polymers</span><span style="font-family:Verdana;"> started at round 260</span><span style="font-family:Verdana;">°</span><span style="font-family:""><span style="font-family:Verdana;">C and showed </span><span style="font-family:Verdana;">endothermic peak at around 350</span></span><span style="font-family:Verdana;">°</span><span style="font-family:Verdana;">C derived from degradation of </span><span style="font-family:Verdana;">thio-urethane bond.
文摘The transformation of CO_(2)into cyclic carbonates via atom-economical cycloadditions with epoxides has recently attracted tremendous attention.On one hand,though many heterogeneous catalysts have been developed for this reaction,they typically suffer from disadvantages such as the need for severe reaction conditions,catalyst loss,and large amounts of soluble co-catalysts.On the other hand,the development of heterogeneous catalysts featuring multiple and cooperative active sites,remains challenging and desirable.In this study,we prepared a series of porous organic catalysts(POP-PBnCl-TPPMg-x)via the copolymerization metal-porphyrin compounds and phosphonium salt monomers in various ratios.The resulting materials contain both Lewis-acidic and Lewis-basic active sites.The molecular-level combination of these sites in the same polymer allows these active sites to work synergistically,giving rise to excellent performance in the cycloaddition reaction of CO_(2)with epoxides,under mild conditions(40℃ and 1 atm CO_(2))in the absence of soluble co-catalysts.POP-PBnCl-TPPMg-12 can also efficiently fixate CO_(2)under low-CO_(2)-concentration(15%v/v N2)conditions representative of typical CO_(2)compositions in industrial exhaust gases.More importantly,this catalyst shows excellent recyclability and can easily be separated and reused at least five times while maintaining its activity.In view of their heterogeneous nature and excellent catalytic performance,the obtained catalysts are promising candidates for the transformation of industrially generated CO_(2)into high value-added chemicals.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020400)~~
文摘Two vinyl‐functionalized chiral2,2'‐bis(diphenylphosphino)‐1,1'‐binaphthyl(BINAP)ligands,(S)‐4,4'‐divinyl‐BINAP and(S)‐5,5'‐divinyl‐BINAP,were successfully synthesized.Chiral BINAP‐based porous organic polymers(POPs),denoted as4‐BINAP@POPs and5‐BINAP@POPs,were efficiently prepared via the copolymerization of vinyl‐functionalized BINAP with divinyl benzene under solvothermal conditions.Thorough characterization using nuclear magnetic resonance spectroscopy,thermogravimetric analysis,extended X‐ray absorption fine structure analysis,and high‐angle annular dark‐field scanning transmission electron microscopy,we confirmed that chiral BINAP groups were successfully incorporated into the structure of the materials considered to contain hierarchical pores.Ru was introduced as a catalytic species into the POPs using different synthetic routes.Systematic investigation of the resultant chiral Ru/POP catalysts for heterogeneous asymmetric hydrogenation ofβ‐keto esters revealed their excellent chiral inducibility as well as high activity and stability.Our work thereby paves a path towards the use of advanced hierarchical porous polymers as solid chiral platforms for heterogeneous asymmetric catalysis.
基金Thousand Talent Program,National Natural Science Foundation of China(Grant No.21776174)the Open Foundation of the State Key Laboratory of Ocean Engineering(Shanghai Jiao Tong University of China)(No.1809)China Shipbuilding Industry Corporation for the support.
文摘Nitrogen-rich porous organic polymers(POPs)with basic features have already shown promising performance in various organic reactions.But the harsh conditions,tedious synthetic methods and the requirement of specific monomers impede their further application.Herein,we introduce isoindoline chemistry into POP community.An isoindoline formation process between aniline and bromomethylbenzenedcoupling nucleophilic substitution,HBr elimination,and intramolecular cyclization in one pot,is utilized for POPs synthesis.Nitrogen-rich isoindolinebased porous polymers(IPPs)were obtained with specific surface areas up to 408 m^(2) g^(-1).Unexpectedly,mechanochemistry could enable the rapid(3 h)and solid-state synthesis of IPP catalysts.Moreover,this nitrogen-rich catalyst presents excellent activity(isolated yield:99%),scalable ability(up to 14 g per run)and recyclability(five runs)towards the Knoevenagel condensation reaction under mild reaction conditions(water as solvent at room temperature).
基金supported by the National Key R&D Program of China(2017YFB0602203,2017YFB0602501)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21020300,XDB17020400)~~
文摘Formic acid(FA)has attracted extensive attention as a hydrogen storage material.Here,we develop two heterogeneous catalysts based on porous organic polymers(POPs).After loading the Ru species,the catalyst bearing the triphenylphosphine ligand showed excellent performance in terms of activity and stability for the decomposition of FA to produce hydrogen.
基金supported by the National Natural Science Foundation of China(No.21727809)。
文摘Immobilization of enzymes onto porous membranes has attracted considerable attention in recent years.However,enhancing the enzymolysis efficiency of the resulting enzyme reactors by varying the environmental conditions poses a great challenge.In this work,poly(styrene-maleic anhydride-N,N-dimethylacrylamide)was prepared and utilized to construct a thermo-sensitive porous polymer membrane-based enzyme reactor(TS-PPMER)after cellulase was immobilized onto the support by covalent bonding.The catalytic activity of the nano-reactor was evaluated by measuring the yield of the product,glucose,at different temperatures with carboxymethylcellulose as the substrate.Interestingly,the polymer chains coiled and formed numerous nano-pores at a high temperature,which induced the confine effect and greatly boosted the enzymolysis efficiency of TS-PPMER.Furthermore,the proposed TS-PPMER was applied in the hydrolysis of green plant leaves in Epipremnum aureum.This work shows great potential in obtaining biological resources by an environmentally friendly approach using smart polymer-based nano-reactors.
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National Natural Science Foundation of China,Grant/Award Numbers:21975096,22178280Key Laboratory of Nuclear Data Foundation,Grant/Award Number:JCKY2021201C151Young Talent Support Plan,Grant/Award Number:HG6J001。
文摘Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD)2/COD/bpy system,suffering from great instability and high cost.Herein,we developed an in situ reduction of the Ni(II)catalytic system to synthesize PAF-1 in low cost and high yield.The active Ni(0)species produced from the NiCl_(2)/bpy/NaI/Mg catalyst system can effectively catalyze homocoupling of tetrakis(4-bromophenyl)methane at the room temperature to form PAF-1 with high Brunauer-Emmett-Teller(BET)-specific surface area up to 4948 m^(2) g^(−1)(Langmuir surface area,6785 m2 g−1).The possible halogen exchange and dehalogenation coupling mechanisms for this new catalytic process in PAF's synthesis are discussed in detail.The efficiency and universality of this innovative catalyst system have also been demonstrated in other PAFs'synthesis.This work provides a cheap,facile,and efficient method for scalable synthesis of PAFs and explores their application for high-pressure storage of Xe and Kr.
基金The Natural Science Foundation of Jiangsu Province(No.BK2009262)the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry
文摘A novel porous coordination polymer,iron naphthalenedicarboxylate Fe(OH)(1,4-NDC)·2H2O is hydrothermally synthesized by the reaction of FeSO4·7H2O and 1,4-naphthalenedicarboxylic acid(1,4-H2NDC) at 150℃.The compound crystallizes in a tetragonal space group P42/nmc:a=2.1447(4) nm,c=0.68849(14) nm,V=3.1669(11) nm3,Z=8,R=0.0845,wR=0.1829.The crystal structure exhibits a three-dimensional framework which is composed of infinite chains of corner-sharing octahedral Fe(OH)2O4 with 1,4-NDC ligands forming two types of channels with square-shaped cross-sections.The large channels present a cross-section of 0.76 nm×0.76 nm,while the small channels are about 0.30 nm×0.30 nm.No structural transformation occurs after removing the guest water molecules,while a robust structure generates with permanent porosity.The adsorption measurements show that the anhydrous sample of the compound can adsorb CO2 into its pores.The adsorption isotherms for methanol,acetone,tetrahydrofuran and benzene are also measured.
文摘Porous polymers have been recently recog- nized as one of the most important precursors for fabrication of heteroatom-doped porous carbons due to the intrinsic porous structure, easy available heteroatom- containing monomers and versatile polymerization meth- ods. However, the heteroatom elements in as-produced porous carbons are quite relied on monomers. So far, the manipulating of heteroatom in porous polymer derived porous carbons are still very rare and challenge. In this work, a sulfur-enriched porous polymer, which was prepared from a diacetylene-linked porous polymer, was used as precursor to prepare S-doped and/or N-doped porous carbons under nitrogen and/or ammonia atmo- spheres. Remarkably, S content can sharply decrease from 36.3% to 0.05% after ammonia treatment. The N content and specific surface area of as-fabricated porous carbons can reach up to 1.32% and 1508 m^2·g^-1, respectively. As the electrode materials for electrical double-layer capacitors, as-fabricated porous carbons exhibit high specific capacitance of up to 431.6 F·g^-1 at 5 mW·s^-1 and excellent cycling stability of 99.74% capacitance retention after 3000 cycles at 100 mV·s^-1. Furthermore, as the electro- chemical catalysts for oxygen reduction reaction, as- fabricated porous carbons presented ultralow half-wave- potential of 0.78 V versus RHE. This work not only offers a new strategy for manipulating S and N doping features for the porous carbons derived from S-containing porous polymers, but also paves the way for the structure- performance interrelationship study of heteroatoms co- doped porous carbon for energy applications.
基金supported by the National Natural Science Foundation of China(51422307,51372280,51232005)National Program for Support of Top-notch Young Professionals,Guangdong Natural Science Funds for Distinguished Young Scholar(S2013050014408),Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program(2014TQ01C337)+1 种基金Fundamental Research Funds for the Central Universities(15lgjc17)National Key Basic Research Program of China(2014CB932400)
文摘Design and fabrication of the micro/nanostructures of the network units is a critical issue for porous nanonetwork structured materials. Significant progress has been attained in construction of the network units with zero-dimensional spherical shapes.However, owing to the limitations of synthetic methods, construction of porous building blocks in one dimension featuring high aspect ratios for porous nanonetwork structured polymer(PNSP) remains largely unexplored. Here we present the successful design and preparation of PNSP with a novel type of one-dimensional network unit, i.e., microporous heterogeneous nanowire. Well-defined core-shell polymer nanoobjects prepared from a gelable block copolymer, poly(3-(triethoxysilyl)propyl methacrylate)-block-polystyrene are employed as building blocks, and facilely transformed into PNSP via hypercrosslinking of polystyrene shell. The as-prepared PNSP exhibits unique three-dimensional hierarchical nanonetwork morphologies with large surface area. These findings could provide a new avenue for fabrication of unique well-defined PNSP, and thus generate valuable breakthroughs in many applications.
基金support of the National Science Foun-dation of China (Nos.21374024 and 61261130092)the Ministry of Science and Technology of China (Nos.2014CB932200 and 2011CB932500)is acknowledged.
文摘A series of benzimidazole-linked porous polymers are obtained by the condensation reaction between the o-aminobenzol end groups of building blocks(2,3,6,7,10,11-hexaaminotriphenylene,3,3'-diaminobenzidine or 1,2,4,5-benzenetetraamine)and the aldehyde groups of building blocks[terephthalicaldehyde,4,4'-biphenyl-dicarboxaldehyde,1,3,5-tris(4-acetylphenyl)benzene or 1,3,5-tris(4-formylbiphenyl)amine]in one-pot synthesis without employing any catalyst or template.The existence of the imidazole ring in the obtained polymers could be identified by Fourier transform infrared and solid-state^(13)C CP/MAS NMR spectroscopy.The sphere-shaped mor-phology of the obtained polymers is observed through scanning electron microscopy.The polymers possess Brunauer-Emmett-Teller specific surface area values over 600 m^(2)·g^(-1),showing hydrogen storage(up to 1.6 wt%,at 77 K and 1×10^(5)Pa)and carbon dioxide capture(up to 12.6 wt%,at 273 K and 1×10^(5)Pa)properties.Such poly-mers would possess good performance in the applications of gas storage and separation.
文摘Porous polymer beads(PPBs) containing hierarchical bimodal pore structure with gigapores and meso-macropores were prepared by polymerization-induced phase separation(PIPS) and emulsion-template technique in a glass capillary microfluidic device(GCMD). Fabrication procedure involved the preparation of water-in-oil emulsion by emulsifying aqueous solution into the monomer solution that contains porogen. The emulsion was added into the GCMD to fabricate the(water-in-oil)-in-water double emulsion droplets. The flow rate of the carrier continuous phase strongly influenced the formation mechanism and size of droplets. Formation mechanism transformed from dripping to jetting and size of droplets decreased from 550 μm to 250 μm with the increase in flow rate of the carrier continuous phase. The prepared droplets were initiated for polymerization by on-line UV-irradiation to form PPBs. The meso-macropores in these beads were generated by PIPS because of the presence of porogen and gigapores obtained from the emulsion-template. The pore morphology and pore size distribution of the PPBs were investigated extensively by scanning electron microscopy and mercury intrusion porosimetry(MIP). New pore morphology was formed at the edge of the beads different from traditional theory because of different osmolarities between the water phase of the emulsion and the carrier continuous phase. The morphology and proportion of bimodal pore structure can be tuned by changing the kind and amount of porogen.
基金This work was supported by the National Key Research and Development Program of China(2016YFA0203200)the National Natural Science Foundation of China(21635007,21974134),K.C.Wong Education Foundation and Computing Centre of Jilin Province.
文摘The widespread use of bisphenol A(BPA)poses a serious threat to the environment and human health.However,efficient removal of BPA in water is incredibly challenging,owing to the inert chemical nature and electrical neutrality of BPA.In order to solve this problem,for the first time,we propose that a strategy of designing conjugated porous polymers with the pore size matching the size of BPA can greatly enhance the binding force of BPA.On this basis,we developed a novel conjugated poly 1,3,5-tri[4-(diphenylamino)phenyl]benzene(MPDPB)with intrinsic pore matching the size of BPA and multi-stage porous structure by editing polymerization with nitrobenzene.The binding energy of MPDPB to BPA is the highest at present(37.84 kcal/mol),which is 2.3 times that of the most powerful adsorbent previously reported and five times that of the conventional adsorbent.These advantages make MPDPB have super-high adsorption performance towards BPA and high absorbing stability under extreme environments.Impressively,MPDPB could be easily loaded on a non-woven fabric to generate point-of-use devices,which could eliminate more than 99.8%of BPA,making it the best BPA candidate adsorbent material.We believe that the proposed material design derived from the specific structure of the contaminant molecule can be extended to exploring further innovative adsorbents.
基金financially supported by National Natural Science Foundation of China (No. 51708252)Guangdong Basic and Applied Basic Research Foundation (Nos. 2020B1515120036,2021A1515010187)。
文摘Metal-organic frameworks(MOFs) show great potential for various applications, but many of them suffer from the drawbacks of hydrolysis propensity and poor processability. Herein, we employ polymers of intrinsic microporosity(PIMs) with hydrophobic pores to decorate MOFs toward substantially improved water stability and shapeability. Through simple PIM-1 decoration, the sub-5 nm polymer layers can be uniformly deposited on MOF surfaces with almost no deterioration in porosity. Owing to the existence of superhydrophobic coating and the obstruction of water entrance into MOFs, the PIM-1 coated Cu BTC exhibits impressive water resistance and excellent pore preservation ability after exposure in water, even in acidic and alkaline solutions. Moreover, polymer decoration improves the processability of MOFs, while various MOF/PIM-1 bulk wafers and oil-water separators can be obtained straightforwardly.
基金supported by the National Natural Science Foundation of China (Nos.21905072,22077025)the Natural Science Foundation of Hebei Province,China (Nos.B2020202062,B2020202086).
文摘Conjugated porous polymers exhibit considerable advantage as attractive candidate for carbon dioxide(CO_(2)) capture. However, the regeneration of the CO_(2) still faces the problem of high energy cost. Here we synthesize a near-infrared region(NIR) light responsive conjugated porous polymer(PDPP-Gu) [DPP=3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione] by constructing porous amorphous networks with a side chain engineering strategy to regulate CO_(2) adsorption and release through photothermal conversion. The PDPP-Gu is featured by a torsional conjugated backbone as well as a functional side chain of guanidino group. The donor-acceptor configuration of PDPP-Gu afforded strong absorption in the NIR and an excellent photothermal conversion capability of up to 48.8%, as well as a high surface energy. Moreover, guanidine modified side chain further enhanced the CO_(2)-polymers interactions, resulting in a high CO_(2) selective adsorption capacity(0.8 mmol/g) at 273 K, 1 bar(1 bar=105 Pa). The adsorbed CO_(2) can be released under NIR light irradiation. This strategy of molecule design combined the dual features of photothermal conversion and gas adsorption, which is beneficial for the development of materials to dynamically control the adsorption and release of CO_(2) through NIR light.
基金the National Natural Science Foundation of China(Nos.51776050 and 51536001).
文摘Micro/nano-porous polymeric material is considered a unique industrial material due to its extremelylow thermal conductivity, low density, and high surface area. Therefore, it is necessary to establishan accurate thermal conductivity prediction model suiting their applicable conditions and provide atheoretical basis for expanding their applications. In this work, the development of the calculationmodel of equivalent thermal conductivity of micro/nano-porous polymeric materials in recent yearsis summarized. Firstly, it reviews the process of establishing the overall equivalent thermal conductivity calculation model for micro/nanoporous polymers. Then, the predicted calculation models ofthermal conductivity are introduced separately according to the conductive and radiative thermalconductivity models. In addition, the thermal conduction part is divided into the gaseous thermalconductivity model, solid thermal conductivity model and gas-solid coupling model. Finally, it isconcluded that, compared with other porous materials, there are few studies on heat transfer of micro/nanoporous polymers, especially on the particular heat transfer mechanisms such as scale effectsat the micro/nanoscale. In particular, the following aspects of porous polymers still need to be furtherstudied: micro scaled thermal radiation, heat transfer characteristics of particular morphologies at thenanoscales, heat transfer mechanism and impact factors of micro/nanoporous polymers. Such studieswould provide a more accurate prediction of thermal conductivity and a broader application in energyconversion and storage systems.
基金financially supported by the National Natural Science Foundation of China(21174083)the China Postdoctoral Science Foundation(2011M500767)+1 种基金the Key Program of Science and Technology Commission Foundation of Shanghai(11JC1405400)Shanghai Jiao Tong University(211 Project)
文摘A shape-persistent dendritic molecule,tris(4-(2,7-dibromo-9-phenyl-9-fluoren-9-yl)phenyl)amine (TF-6Br),has been readily synthesized in high yield through a concise Friedel-Crafts reaction from triphenylamine and 2,7-dibromo(9-phenyl-fluoren-9-ol).It was further employed as the key building block to achieve the synthesis of conjugated porous polymer via Sonogashira coupling with 1,4-diethynylbenzene.Under experimental reaction conditions,the resulting porous polymer shows exceptionally nanotubular morphology,which further allows for a template-free synthesis of porous carbon nanotubes via thermal treatment at high temperature.The obtained nitrogen-doped carbon nanotubes feature with an improved porosity and high surface area.
基金the financial support from the National Natural Science Foundation of China(Nos.21874138,22074148,21727809,21635008)。
文摘Immobilization of enzymes onto carriers is a rapidly growing research area aimed at increasing the stability,reusability and enzymolysis efficiency of free enzymes.In this work,the role of phaseseparation and a pH-responsive"hairy"brush,which greatly affected the topography of porous polymer membrane enzyme reactors(PMER),was explored.The porous polymer membrane was fabricated by phase-separation of poly(styrene-co-maleic anhydride-acrylic acid)and poly(styrene-ethylene glycol).Notably,the topography and pores size of the PMER could be controlled by phase-separation and a pHresponsive"hairy"brush.For evaluating the enzymolysis efficiency of D-amino acid oxidase(DAAO)immobilized carrier(DAAO@PMER),a chiral ligand exchange capillary electrophoresis method was developed with D-methionine as the substrate.The DAAO@PMER showed good reusability and stability after five continuous runs.Notably,comparing with free DAAO in solution,the DAAO@PMER exhibited a17.7-folds increase in catalytic velocity,which was attributed to its tailorable topography and pHresponsive property.The poly(acrylic acid)moiety of poly(styrene-co-maleic anhydride-acrylic acid)as the pH-responsive"hairy"brush generated topography changing domains upon adjusting the buffer pH,which enable the enzymolysis efficiency of DAAO@PMER to be tuned based upon the well-defined architectures of the PMER.This approach demonstrated that the topographical changes formed by phaseseparation and the pH-responsive"hairy"brush indeed made the proposed porous polymer membrane as suitable supports for enzyme immobilization and fitting for enzymolysis applications,achieving high catalytic performance.