The urgent demand for renewable energy solutions,propelled by the global energy crisis and environmental concerns,has spurred the creation of innovative materials for solar thermal storage.Photothermal phase change ma...The urgent demand for renewable energy solutions,propelled by the global energy crisis and environmental concerns,has spurred the creation of innovative materials for solar thermal storage.Photothermal phase change materials(PTPCMs)represent a novel type of composite phase change material(PCM)aimed at improving thermal storage efficiency by incorporating photothermal materials into traditional PCMs and encapsulating them within porous structures.Various porous encapsulation materials have been studied,including porous carbon,expanded graphite,and ceramics,but issues like brittleness hinder their practical use.To overcome these limitations,flexible PTPCMs using organic porous polymers—like foams,hydrogels,and porous wood—have emerged,offering high porosity and lightweight characteristics.This review examines recent advancements in the preparation of PTPCMs based on porous polymer supports through techniques like impregnation and in situ polymerization,assessing the impact of different porous polymer materials on PCM performance and clarifying the mechanisms of photothermal conversion and heat storage.Subsequently,the most recent advancements in the applications of porous polymer-based PTPCMs are systematically summarized,and future research challenges and possible solutions are discussed.This review aims to foster awareness about the potential of PTPCMs in promoting environmentally friendly energy practices and catalyzing further research in this promising field.展开更多
Photocatalytic CO_(2)reduction reaction(CO_(2)RR)is one of the promising strategies for sustainably producing solar fuels.The precise identification of catalytic sites and the enhancement of photocatalytic CO_(2)conve...Photocatalytic CO_(2)reduction reaction(CO_(2)RR)is one of the promising strategies for sustainably producing solar fuels.The precise identification of catalytic sites and the enhancement of photocatalytic CO_(2)conversion is imperative yet quite challenging.This critical review summarizes recent advances in porous photo-responsive polymers,including covalent organic frameworks(COFs),covalent triazine frameworks(CTFs),and conjugated microporous polymers(CMPs),those can be rationally designed from the molecular level for visible-light-driven photocatalytic CO_(2)reduction.Additionally,special emphasis is placed on how the well-defined active sites on these polymers can influence their properties and photocatalytic performance.The precise regulation and control of microenvironments and electronic properties of metal active centers are crucial for boosting catalytic efficiency and selectivity,as well as for the design of better photocatalysts for CO_(2)reduction.展开更多
Adsorption-photocatalytic degradation of organic pollutants in water is an advantageous method for environmental purification.Herein,a feasible strategy is developed to construct a novel dual S-scheme heterojunctions ...Adsorption-photocatalytic degradation of organic pollutants in water is an advantageous method for environmental purification.Herein,a feasible strategy is developed to construct a novel dual S-scheme heterojunctions Cu_(7)S_(4)-TiO_(2)-conjugated polymer with a donor-acceptor structure.There are abundant adsorption active sites for adsorption in the porous structure of the composites,which can rapidly capture pollutants through hydrogen bonding and π-π interactions.In addition,the dual S-scheme heterojunctions effectively improve carrier separation while maintaining a strong redox ability.Thus,the optimized 1.5% CST-130 catalysts can adsorb 71% of 20 ppm BPA in 15 min and completely remove it within 30 min with high adsorption capacity and photodegradation efficiency.Therefore,this study provides a new inspiration for synergistic adsorption and degradation of BPA and the construction of dual S-scheme heterojunction.展开更多
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
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
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
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
Organic-inorganic hybrid <span style="font-family:Verdana;">network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquioxane (SQ109) and alkyl diacrylate...Organic-inorganic hybrid <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 style="font-family:Verdana;">(<span style="font-family:Verdana;">isobutyronitrile<span style="font-family:Verdana;">)<span style="font-family:Verdana;"> (AIBN) at 60<span style="font-family:Verdana;">°<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 style="font-family:Verdana;">of<span style="font-family:Verdana;"> the reaction <span style="font-family:Verdana;">system<span style="font-family:""><span style="font-family:Verdana;">. By contrast, the reaction with 1,6-hexanediol diacrylate or <span style="font-family:Verdana;">1,5-hexadiene yielded homogeneous clear gels. Thermal analyses of SQ109-BDA<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 style="font-family:Verdana;">°<span style="font-family:Verdana;">C. The porous polymer was also obtained <span style="font-family:Verdana;">by<span style="font-family:Verdana;"> the reaction <span style="font-family:Verdana;">using<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 style="font-family:Verdana;">the globules. Young’s modulus of SQ109-BDA porous polymer increased<span style="font-family:Verdana;"> with <span style="font-family:Verdana;">increasing in the monomer concentration <span style="font-family:Verdana;">of<span style="font-family:Verdana;"> the reaction systems. Thioliso<span style="font-family:""><span style="font-family:Verdana;">cyanate addition reactions between SQ109 <span style="font-family:Verdana;">and hexamethylene diisocyanate (HDI) or methylenediphenyl 4,4’-diisocyanate<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 style="font-family:Verdana;">N,N<span style="font-family:Verdana;">-dimethylformamide (50 vol.%) produced porous polymers. The morphology of the porous polymers was composed by connected <span style="font-family:Verdana;">globules or aggregated particles. The size of globules and particles in the<span style="font-family:Verdana;"> SQ109-HDI porous polymers was larger <span style="font-family:Verdana;">than <span style="font-family:Verdana;">those<span style="font-family:Verdana;"> in the SQ109-MDI porous polymers. Thermal degradation of SQ109-HDI and SQ109-MDI porous polymers<span style="font-family:Verdana;"> started at round 260<span style="font-family:Verdana;">°<span style="font-family:""><span style="font-family:Verdana;">C and showed <span style="font-family:Verdana;">endothermic peak at around 350<span style="font-family:Verdana;">°<span style="font-family:Verdana;">C derived from degradation of <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
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
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
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
Aqueous zinc-ion batteries(AZIBs)are recognized for their commercial viability due to their low cost,high safety,and substantial theoretical capacity.However,the challenges posed by dendrite growth and side reactions ...Aqueous zinc-ion batteries(AZIBs)are recognized for their commercial viability due to their low cost,high safety,and substantial theoretical capacity.However,the challenges posed by dendrite growth and side reactions of zinc ions hinder the widespread adoption of AZIBs.In this work,a new porous phenolphthalein-based polymer(PPH-CN)is synthesized through the polymerization of phenolphthalein and 2,6-difluorobenzonitrile and served as a protective layer of zinc anode.The PPH-CN layer not only effectively separates the zinc anode from aqueous electrolyte to suppress side reactions,but also provides abundant zincophilic sites to facilitate the deposition of zinc ions.As a result,the Zn@PPH-CN symmetric batteries achieve a notably stable cycle lifespan of 1820 h at a current density of 1 mA cm^(-2),which is thirteen times longer than that of bare Zn.Under the protection of PPH-CN,the zinc anode exhibits a high average Coulombic efficiency(CE)of 99.7%after 3550 cycles in the Zn@PPH-CN//Cu asymmetric battery.The capacity retention rate of Zn@PPH-CN//NH_(4)V_(4)O_(10)full batteries reaches 89.6%after 1000 cycles at 1 Ag^(-1).Furthermore,density functional theory(DFT)simulations identified the Zn^(2+)storage sites of PPH-CN,thereby demonstrating the viability of PPH-CN as interface coatings of zinc anode.This work offers valuable insights into the development of high-performance aqueous battery.展开更多
Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)ca...Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)capable of capturing NIR light.As a NIR photon conversion platform,AQ-TVB-CPPs exhibit three functions:photogenerated electron and hole transfer,photothermal conversion,and singlet oxygen(^(1)O_(2))production under 760 nm LED irradiation.This multifunctional material serves as a heterogeneous photocatalyst for NIR light-driven cyanation ofα-amino C(sp^(3))-H bonds.Controlled experiments indicate that ^(1)O_(2)and photothermal effects are crucial for the reaction and its selective regulation.Compared to visible light,this NIR photocatalytic system achieves higher yields and superior selectivity in the cyanation ofα-amino C(sp^(3))-H bonds,particularly for challenging substrates such as molecules with multiple active sites and organic dyes,as well as in gram-scale reactions.Notably,this strategy also enables the cyanation ofα-amino C(sp^(3))-H bonds under natural sunlight.This metal-free,recyclable,and highly stable multifunctional conjugated porous polymer(CPP)offers a new approach to utilizing NIR light and sunlight for organic synthesis.展开更多
Direct synthesis of high-value-added chemicals from low-carbon molecules is of great research importance.The C(sp^(3))–H bonds in alkanes exhibit a high bond dissociation energy and a very low polarity;consequently,a...Direct synthesis of high-value-added chemicals from low-carbon molecules is of great research importance.The C(sp^(3))–H bonds in alkanes exhibit a high bond dissociation energy and a very low polarity;consequently,achieving highly selective synthesis of esters through alkoxy carbonylation in heterogeneous catalysis is a particularly challenging process.Herein,we describe the immobilization of a single-atom palladium catalyst supported by porous organic polymers for highly selective ester formation in cycloalkane carbonylation,which achieves a selectivity as high as 82% and a benzyl alcohol conversion of up to 96%.Various catalytic characterization methods,including XRD,XPS,TEM,SEM,and FTIR,indicate that palladium species are uniformly distributed in the polymer.This work suggests a promising method for the design of hybrid catalytic systems and offers meaningful insights into the development of bifunctional catalysts for selective alkoxy carbonylation.展开更多
Methyl parathion is a highly hazardous organophosphorus pesticide widely used in agriculture,and its environmental residues pose a significant threat to the ecosystem.Achieving highly efficient and selective adsorptio...Methyl parathion is a highly hazardous organophosphorus pesticide widely used in agriculture,and its environmental residues pose a significant threat to the ecosystem.Achieving highly efficient and selective adsorption removal is an important challenge.Inspired by the adsorption filtration function of the kidney by its hierarchical porous organ structure,we have fabricated a bioinspired hierarchical porous polymer(P5HPP)by introducing the intrinsic molecular cavity of pillar[5]arene to porous organic polymers using a photoclick reaction.P5HPP possesses hierarchical nanoporous structures,abundant adsorption sites,and remarkable host-vip interactions.It can achieve the highly efficient and selective adsorption of methyl parathion in various pesticide solutions by specific host-vip binding(π-πinteractions)between pillar[5]arene and methyl parathion.The adsorption efficiency of methyl parathion(10-4M)can achieve nearly 99.1%by 0.5 mg mL-1P5HPP,and the maximum adsorption capacity reaches up to 148.58 mg g^(-1),which is far superior to other reported pesticide adsorbents.In practical applications,P5HPP is used as the packing material of the adsorption columns to efficiently and rapidly remove 98.6%of methyl parathion(10-4M)from water and alleviate pesticide poison for aquatic organisms.Because of its excellent adsorption performance,good stability,easy recyclability,and low cost,P5HPP is a superb adsorbent for pesticide pollutant treatment with great potential for application in water resource protection.展开更多
A multifunctional porous organic polymer of POP-Nixantphos-PPh_(3)-PhSO_(3)Na was prepared by free radical tricopolymerization.Further loading of Pd(OAc)2 led to the catalyst of Pd/POP-Nixantphos-PPh_(3)-PhSO_(3)Na.In...A multifunctional porous organic polymer of POP-Nixantphos-PPh_(3)-PhSO_(3)Na was prepared by free radical tricopolymerization.Further loading of Pd(OAc)2 led to the catalyst of Pd/POP-Nixantphos-PPh_(3)-PhSO_(3)Na.In this catalyst,Nixantphos ligand moieties were employed to enhance the catalytic hydrocarboxylation activity of palladium.Additionally,PPh_(3)ligand moieties were utilized to construct a porous framework of catalyst that facilitated the dispersion of Pd nanoparticles as well as the diffusion of reactants and products.Furthermore,the incorporation of PhSO_(3)Na moieties improved the hydrophilicity of the support.With H_(2)O as the reaction solvent,under the initial CO pressure of 0.1 MPa,Pd/POP-Nixantphos-PPh3-PhSO3Na-catalyzed hydrocarboxylation of alkynes to afford the correspondingα,β-unsaturated carboxylic acids in good yields(76%~96%).Various alkynes,such as diaromatic alkynes,arylalkyl alkynes and dialkyl alkynes,worked well in the process.Additionally,the catalyst showed excellent recyclability with no significant yield loss over five cycles.展开更多
Adsorptive separation holds important prospect for the challenging recovery of C_(2)H_(6) and C_(3)H_(8) from natural gas and the separation efficiency is primarily determined by a high-performance adsorbent.In this w...Adsorptive separation holds important prospect for the challenging recovery of C_(2)H_(6) and C_(3)H_(8) from natural gas and the separation efficiency is primarily determined by a high-performance adsorbent.In this work,we reported the synthesis of a novel porous organic polymer,FOSU-POP-1 for the separation of CH_(4)/C_(2)H_(6)/C_(3)H_(8).The FOSU-POP-1 was synthesized from tetrakis(4-azidophenyl)methane and 1,3,5-triethynylbenzene via click reaction with a Brunauer-Emmett-Teller(BET)surface area of 1038 m^(2)·g^(-1).Exhibiting stronger affinity towards C_(3)H_(8) and C_(2)H_(6) than CH_(4),2.85 mmol·g^(-1) for C_(3)H_(8) and 2.14 mmol·g^(-1) for C_(2)H_(6) were achieved on the FOSU-POP-1 at 0.1 MPa,298 K,with an ideal adsorbed solution theory selectivity of 227 for C_(3)H_(8)/CH_(4).The breakthrough experiment confirmed the good dynamic separation performance and recyclability of FOSU-POP-1 for CH_(4)/C_(2)H_(6)/C_(3)H_(8) ternary mixture.The density functional theory calculation further revealed that the N atom in triazole ring interacted strongly with the C_(3)H_(8) and C_(2)H_(6).This work highlighted the promising capability of FOSU-POP-1 for efficiently separating CH_(4)/C_(2)H_(6)/C_(3)H_(8) mixture.展开更多
The utilization of nuclear power will persist as a prominent energy source in the foreseeable future.However,it presents substantial challenges concerning waste disposal and the potential emission of untreated radioac...The utilization of nuclear power will persist as a prominent energy source in the foreseeable future.However,it presents substantial challenges concerning waste disposal and the potential emission of untreated radioactive substances,such as radioactive 129I and 131I.The transportation of radioactive iodine poses a significant threat to both the environment and human health.Nevertheless,effectively,rapidly removing iodine ion from water using porous adsorbents remains a crucial challenge.In this work,three kinds of multiple sites porous organic polymers(POPs,POP-1,POP-2,and POP-3)have been developed using a monomer pre-modification strategy for highly efficient and fast I_(3) absorption from water.It is found that the POPs exhibited exceptional performance in terms of I3 adsorption,achieving a top-performing adsorption capacity of 5.25 g g^(-1) and the fastest average adsorption rate(K_(80%)=4.25 g g^(-1) h^(-1))with POP-1.Moreover,POP-1 exhibited exceptional capacity for the removal of I3 fromflowing aqueous solutions,with 95%removal efficiency observed even at 0.0005 mol L^(-1).Such results indicate that this material has the potential to be utilized for the emergency preparation of potable water in areas contaminated with radioactive iodine.The adsorption process can be effectively characterized by the Freundlich model and the pseudo-second-order model.The exceptional I_(3) absorption capacity is primarily attributed to the incorporation of a substantial number of active adsorption sites,including bromine,carbonyl,and amide groups.展开更多
As promising high-temperature proton exchange membranes,phosphoric acid(PA)doped polybenzimidazole(PBI)membranes still face challenges,including excessive PA leaching and limited long-term stability.The preparation of...As promising high-temperature proton exchange membranes,phosphoric acid(PA)doped polybenzimidazole(PBI)membranes still face challenges,including excessive PA leaching and limited long-term stability.The preparation of mixed matrix membranes(MMMs)has emerged as a viable strategy to address these limitations,which can combine the excellent mechanical properties of polymers with the structural advantages of porous fillers.Among various filler materials,nitrogen-containing porous organic polymers(POPs)have shown particular promise because of their excellent compatibility with polymers.Therefore,in this work,a new pyridine-based POP called Py-POP was synthesized.Py-POP was mixed with commercial poly[2,2′-(p-oxidiphenylene)-5,5′-benzimidazole](OPBI)to prepare MMMs.Theoretical calculations indicate that the pyridine groups exhibit strong interactions with PA,significantly enhancing both PA retention and proton conduction efficiency.Remarkably,the PA retention rate of the composite membrane doped with 10 wt%Py-POP is 77.2%at 80/40%RH,which is much higher than that of the OPBI(62.7%).Furthermore,the membrane achieves an outstanding proton conductivity of 0.173 S cm^(-1)at 180℃,which is 4.2 times higher than that of the OPBI membrane.The peak power density of the composite membrane can achieve 915.1 mW cm^(-2) and remains at 891.5 mW cm^(-2) after 80 cycles of testing at 180℃.展开更多
基金supported by the National Natural Science Foundation of China(No.52103093,52103205)the Taishan Scholar Project of Shandong Province(No.tsqn202312187)+2 种基金the Natural Science Foundation of Shandong Province(ZR2024QE220)the Young Elite Scientists Sponsorship Program by CAST(No.2021QNRC001)the Jiangxi Provincial Natural Science Foundation(20232BAB214031,20242BAB25237).
文摘The urgent demand for renewable energy solutions,propelled by the global energy crisis and environmental concerns,has spurred the creation of innovative materials for solar thermal storage.Photothermal phase change materials(PTPCMs)represent a novel type of composite phase change material(PCM)aimed at improving thermal storage efficiency by incorporating photothermal materials into traditional PCMs and encapsulating them within porous structures.Various porous encapsulation materials have been studied,including porous carbon,expanded graphite,and ceramics,but issues like brittleness hinder their practical use.To overcome these limitations,flexible PTPCMs using organic porous polymers—like foams,hydrogels,and porous wood—have emerged,offering high porosity and lightweight characteristics.This review examines recent advancements in the preparation of PTPCMs based on porous polymer supports through techniques like impregnation and in situ polymerization,assessing the impact of different porous polymer materials on PCM performance and clarifying the mechanisms of photothermal conversion and heat storage.Subsequently,the most recent advancements in the applications of porous polymer-based PTPCMs are systematically summarized,and future research challenges and possible solutions are discussed.This review aims to foster awareness about the potential of PTPCMs in promoting environmentally friendly energy practices and catalyzing further research in this promising field.
基金National Natural Science Foundation of China(No.22005154)for financial support。
文摘Photocatalytic CO_(2)reduction reaction(CO_(2)RR)is one of the promising strategies for sustainably producing solar fuels.The precise identification of catalytic sites and the enhancement of photocatalytic CO_(2)conversion is imperative yet quite challenging.This critical review summarizes recent advances in porous photo-responsive polymers,including covalent organic frameworks(COFs),covalent triazine frameworks(CTFs),and conjugated microporous polymers(CMPs),those can be rationally designed from the molecular level for visible-light-driven photocatalytic CO_(2)reduction.Additionally,special emphasis is placed on how the well-defined active sites on these polymers can influence their properties and photocatalytic performance.The precise regulation and control of microenvironments and electronic properties of metal active centers are crucial for boosting catalytic efficiency and selectivity,as well as for the design of better photocatalysts for CO_(2)reduction.
基金supports provided by the National Key R&D Program of China (2020YFC1808401, 2020YFC1808403)National Natural Science Foundation of China (22078213, 21938006, 51973148)+3 种基金Basic Research Project of Cutting-Edge Technology in Jiangsu Province, China (BK20202012)Prospective Application Research Project of Suzhou, China (SYC2022042)Water Research and Technology Project of Suzhou, China (2022006)the Priority Academic Program Development of Jiangsu Higher Education Institutions, China (PAPD)。
文摘Adsorption-photocatalytic degradation of organic pollutants in water is an advantageous method for environmental purification.Herein,a feasible strategy is developed to construct a novel dual S-scheme heterojunctions Cu_(7)S_(4)-TiO_(2)-conjugated polymer with a donor-acceptor structure.There are abundant adsorption active sites for adsorption in the porous structure of the composites,which can rapidly capture pollutants through hydrogen bonding and π-π interactions.In addition,the dual S-scheme heterojunctions effectively improve carrier separation while maintaining a strong redox ability.Thus,the optimized 1.5% CST-130 catalysts can adsorb 71% of 20 ppm BPA in 15 min and completely remove it within 30 min with high adsorption capacity and photodegradation efficiency.Therefore,this study provides a new inspiration for synergistic adsorption and degradation of BPA and the construction of dual S-scheme heterojunction.
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.
文摘Organic-inorganic hybrid <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 style="font-family:Verdana;">(<span style="font-family:Verdana;">isobutyronitrile<span style="font-family:Verdana;">)<span style="font-family:Verdana;"> (AIBN) at 60<span style="font-family:Verdana;">°<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 style="font-family:Verdana;">of<span style="font-family:Verdana;"> the reaction <span style="font-family:Verdana;">system<span style="font-family:""><span style="font-family:Verdana;">. By contrast, the reaction with 1,6-hexanediol diacrylate or <span style="font-family:Verdana;">1,5-hexadiene yielded homogeneous clear gels. Thermal analyses of SQ109-BDA<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 style="font-family:Verdana;">°<span style="font-family:Verdana;">C. The porous polymer was also obtained <span style="font-family:Verdana;">by<span style="font-family:Verdana;"> the reaction <span style="font-family:Verdana;">using<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 style="font-family:Verdana;">the globules. Young’s modulus of SQ109-BDA porous polymer increased<span style="font-family:Verdana;"> with <span style="font-family:Verdana;">increasing in the monomer concentration <span style="font-family:Verdana;">of<span style="font-family:Verdana;"> the reaction systems. Thioliso<span style="font-family:""><span style="font-family:Verdana;">cyanate addition reactions between SQ109 <span style="font-family:Verdana;">and hexamethylene diisocyanate (HDI) or methylenediphenyl 4,4’-diisocyanate<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 style="font-family:Verdana;">N,N<span style="font-family:Verdana;">-dimethylformamide (50 vol.%) produced porous polymers. The morphology of the porous polymers was composed by connected <span style="font-family:Verdana;">globules or aggregated particles. The size of globules and particles in the<span style="font-family:Verdana;"> SQ109-HDI porous polymers was larger <span style="font-family:Verdana;">than <span style="font-family:Verdana;">those<span style="font-family:Verdana;"> in the SQ109-MDI porous polymers. Thermal degradation of SQ109-HDI and SQ109-MDI porous polymers<span style="font-family:Verdana;"> started at round 260<span style="font-family:Verdana;">°<span style="font-family:""><span style="font-family:Verdana;">C and showed <span style="font-family:Verdana;">endothermic peak at around 350<span style="font-family:Verdana;">°<span style="font-family:Verdana;">C derived from degradation of <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 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financially supported by the National Natural Science Foundation of China(Nos.22475035 and 22071021)
文摘Aqueous zinc-ion batteries(AZIBs)are recognized for their commercial viability due to their low cost,high safety,and substantial theoretical capacity.However,the challenges posed by dendrite growth and side reactions of zinc ions hinder the widespread adoption of AZIBs.In this work,a new porous phenolphthalein-based polymer(PPH-CN)is synthesized through the polymerization of phenolphthalein and 2,6-difluorobenzonitrile and served as a protective layer of zinc anode.The PPH-CN layer not only effectively separates the zinc anode from aqueous electrolyte to suppress side reactions,but also provides abundant zincophilic sites to facilitate the deposition of zinc ions.As a result,the Zn@PPH-CN symmetric batteries achieve a notably stable cycle lifespan of 1820 h at a current density of 1 mA cm^(-2),which is thirteen times longer than that of bare Zn.Under the protection of PPH-CN,the zinc anode exhibits a high average Coulombic efficiency(CE)of 99.7%after 3550 cycles in the Zn@PPH-CN//Cu asymmetric battery.The capacity retention rate of Zn@PPH-CN//NH_(4)V_(4)O_(10)full batteries reaches 89.6%after 1000 cycles at 1 Ag^(-1).Furthermore,density functional theory(DFT)simulations identified the Zn^(2+)storage sites of PPH-CN,thereby demonstrating the viability of PPH-CN as interface coatings of zinc anode.This work offers valuable insights into the development of high-performance aqueous battery.
基金supported by the Guangxi Science and Technology Major Program(Guike AA24263012)the National Natural Science Foundation of China(22471046,22301048,22201049)the Bagui Outstanding Youth Talent Project。
文摘Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)capable of capturing NIR light.As a NIR photon conversion platform,AQ-TVB-CPPs exhibit three functions:photogenerated electron and hole transfer,photothermal conversion,and singlet oxygen(^(1)O_(2))production under 760 nm LED irradiation.This multifunctional material serves as a heterogeneous photocatalyst for NIR light-driven cyanation ofα-amino C(sp^(3))-H bonds.Controlled experiments indicate that ^(1)O_(2)and photothermal effects are crucial for the reaction and its selective regulation.Compared to visible light,this NIR photocatalytic system achieves higher yields and superior selectivity in the cyanation ofα-amino C(sp^(3))-H bonds,particularly for challenging substrates such as molecules with multiple active sites and organic dyes,as well as in gram-scale reactions.Notably,this strategy also enables the cyanation ofα-amino C(sp^(3))-H bonds under natural sunlight.This metal-free,recyclable,and highly stable multifunctional conjugated porous polymer(CPP)offers a new approach to utilizing NIR light and sunlight for organic synthesis.
基金supported by the National Natural Science Foundation of China (U22A20393,22202216)the Lanzhou Institute of Chemical Physics (E40199SR)。
文摘Direct synthesis of high-value-added chemicals from low-carbon molecules is of great research importance.The C(sp^(3))–H bonds in alkanes exhibit a high bond dissociation energy and a very low polarity;consequently,achieving highly selective synthesis of esters through alkoxy carbonylation in heterogeneous catalysis is a particularly challenging process.Herein,we describe the immobilization of a single-atom palladium catalyst supported by porous organic polymers for highly selective ester formation in cycloalkane carbonylation,which achieves a selectivity as high as 82% and a benzyl alcohol conversion of up to 96%.Various catalytic characterization methods,including XRD,XPS,TEM,SEM,and FTIR,indicate that palladium species are uniformly distributed in the polymer.This work suggests a promising method for the design of hybrid catalytic systems and offers meaningful insights into the development of bifunctional catalysts for selective alkoxy carbonylation.
基金financially supported by the National Key Research and Development Program of China(2021YFA0716702,2023YFF0717100)the National Natural Science Foundation of China(22371086,22071074)+1 种基金Self-Determined Research Funds of CCNU from the colleges'basic research and operation of MOEsupported by Researchers Supporting Project number(RSPD2025R675),King Saud University,Riyadh,Saudi Arabia。
文摘Methyl parathion is a highly hazardous organophosphorus pesticide widely used in agriculture,and its environmental residues pose a significant threat to the ecosystem.Achieving highly efficient and selective adsorption removal is an important challenge.Inspired by the adsorption filtration function of the kidney by its hierarchical porous organ structure,we have fabricated a bioinspired hierarchical porous polymer(P5HPP)by introducing the intrinsic molecular cavity of pillar[5]arene to porous organic polymers using a photoclick reaction.P5HPP possesses hierarchical nanoporous structures,abundant adsorption sites,and remarkable host-vip interactions.It can achieve the highly efficient and selective adsorption of methyl parathion in various pesticide solutions by specific host-vip binding(π-πinteractions)between pillar[5]arene and methyl parathion.The adsorption efficiency of methyl parathion(10-4M)can achieve nearly 99.1%by 0.5 mg mL-1P5HPP,and the maximum adsorption capacity reaches up to 148.58 mg g^(-1),which is far superior to other reported pesticide adsorbents.In practical applications,P5HPP is used as the packing material of the adsorption columns to efficiently and rapidly remove 98.6%of methyl parathion(10-4M)from water and alleviate pesticide poison for aquatic organisms.Because of its excellent adsorption performance,good stability,easy recyclability,and low cost,P5HPP is a superb adsorbent for pesticide pollutant treatment with great potential for application in water resource protection.
文摘A multifunctional porous organic polymer of POP-Nixantphos-PPh_(3)-PhSO_(3)Na was prepared by free radical tricopolymerization.Further loading of Pd(OAc)2 led to the catalyst of Pd/POP-Nixantphos-PPh_(3)-PhSO_(3)Na.In this catalyst,Nixantphos ligand moieties were employed to enhance the catalytic hydrocarboxylation activity of palladium.Additionally,PPh_(3)ligand moieties were utilized to construct a porous framework of catalyst that facilitated the dispersion of Pd nanoparticles as well as the diffusion of reactants and products.Furthermore,the incorporation of PhSO_(3)Na moieties improved the hydrophilicity of the support.With H_(2)O as the reaction solvent,under the initial CO pressure of 0.1 MPa,Pd/POP-Nixantphos-PPh3-PhSO3Na-catalyzed hydrocarboxylation of alkynes to afford the correspondingα,β-unsaturated carboxylic acids in good yields(76%~96%).Various alkynes,such as diaromatic alkynes,arylalkyl alkynes and dialkyl alkynes,worked well in the process.Additionally,the catalyst showed excellent recyclability with no significant yield loss over five cycles.
基金financially supported by the National Natural Science Foundation of China(22208050,22108034)Guangdong Provincial Natural Science Foundation Project(2023A1515012151)Scientific Research Project of Guangdong Provincial Department of Education(2023KTSCX132).
文摘Adsorptive separation holds important prospect for the challenging recovery of C_(2)H_(6) and C_(3)H_(8) from natural gas and the separation efficiency is primarily determined by a high-performance adsorbent.In this work,we reported the synthesis of a novel porous organic polymer,FOSU-POP-1 for the separation of CH_(4)/C_(2)H_(6)/C_(3)H_(8).The FOSU-POP-1 was synthesized from tetrakis(4-azidophenyl)methane and 1,3,5-triethynylbenzene via click reaction with a Brunauer-Emmett-Teller(BET)surface area of 1038 m^(2)·g^(-1).Exhibiting stronger affinity towards C_(3)H_(8) and C_(2)H_(6) than CH_(4),2.85 mmol·g^(-1) for C_(3)H_(8) and 2.14 mmol·g^(-1) for C_(2)H_(6) were achieved on the FOSU-POP-1 at 0.1 MPa,298 K,with an ideal adsorbed solution theory selectivity of 227 for C_(3)H_(8)/CH_(4).The breakthrough experiment confirmed the good dynamic separation performance and recyclability of FOSU-POP-1 for CH_(4)/C_(2)H_(6)/C_(3)H_(8) ternary mixture.The density functional theory calculation further revealed that the N atom in triazole ring interacted strongly with the C_(3)H_(8) and C_(2)H_(6).This work highlighted the promising capability of FOSU-POP-1 for efficiently separating CH_(4)/C_(2)H_(6)/C_(3)H_(8) mixture.
基金support from the National Natural Science Foundation of China(No.22273016,22273017,22233006)Plan for Henan Province University Science and Technology Innovation Team(No.25IRTSTHN002)+1 种基金Young Backbone Teacher Training Program of Henan Province(2023GGJS036)the 111 project(No.D17007).
文摘The utilization of nuclear power will persist as a prominent energy source in the foreseeable future.However,it presents substantial challenges concerning waste disposal and the potential emission of untreated radioactive substances,such as radioactive 129I and 131I.The transportation of radioactive iodine poses a significant threat to both the environment and human health.Nevertheless,effectively,rapidly removing iodine ion from water using porous adsorbents remains a crucial challenge.In this work,three kinds of multiple sites porous organic polymers(POPs,POP-1,POP-2,and POP-3)have been developed using a monomer pre-modification strategy for highly efficient and fast I_(3) absorption from water.It is found that the POPs exhibited exceptional performance in terms of I3 adsorption,achieving a top-performing adsorption capacity of 5.25 g g^(-1) and the fastest average adsorption rate(K_(80%)=4.25 g g^(-1) h^(-1))with POP-1.Moreover,POP-1 exhibited exceptional capacity for the removal of I3 fromflowing aqueous solutions,with 95%removal efficiency observed even at 0.0005 mol L^(-1).Such results indicate that this material has the potential to be utilized for the emergency preparation of potable water in areas contaminated with radioactive iodine.The adsorption process can be effectively characterized by the Freundlich model and the pseudo-second-order model.The exceptional I_(3) absorption capacity is primarily attributed to the incorporation of a substantial number of active adsorption sites,including bromine,carbonyl,and amide groups.
基金the Natural Science Foundation of Gansu Province(No.24JRRA391).
文摘As promising high-temperature proton exchange membranes,phosphoric acid(PA)doped polybenzimidazole(PBI)membranes still face challenges,including excessive PA leaching and limited long-term stability.The preparation of mixed matrix membranes(MMMs)has emerged as a viable strategy to address these limitations,which can combine the excellent mechanical properties of polymers with the structural advantages of porous fillers.Among various filler materials,nitrogen-containing porous organic polymers(POPs)have shown particular promise because of their excellent compatibility with polymers.Therefore,in this work,a new pyridine-based POP called Py-POP was synthesized.Py-POP was mixed with commercial poly[2,2′-(p-oxidiphenylene)-5,5′-benzimidazole](OPBI)to prepare MMMs.Theoretical calculations indicate that the pyridine groups exhibit strong interactions with PA,significantly enhancing both PA retention and proton conduction efficiency.Remarkably,the PA retention rate of the composite membrane doped with 10 wt%Py-POP is 77.2%at 80/40%RH,which is much higher than that of the OPBI(62.7%).Furthermore,the membrane achieves an outstanding proton conductivity of 0.173 S cm^(-1)at 180℃,which is 4.2 times higher than that of the OPBI membrane.The peak power density of the composite membrane can achieve 915.1 mW cm^(-2) and remains at 891.5 mW cm^(-2) after 80 cycles of testing at 180℃.
