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
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
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
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
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
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
Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the...Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.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
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
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
Volatile organic compounds(VOCs)with high toxicity and carcinogenicity are emitted from kinds of industries,which endanger human health and the environment.Adsorption is a promising method for the treatment of VOCs du...Volatile organic compounds(VOCs)with high toxicity and carcinogenicity are emitted from kinds of industries,which endanger human health and the environment.Adsorption is a promising method for the treatment of VOCs due to its low cost and high efficiency.In recent years,activated carbons,zeolites,and mesoporous materials are widely used to remove VOCs because of their high specific surface area and abundant porosity.However,the hydrophilic nature and low desorption rate of those materials limit their commercial application.Furthermore,the adsorption capacities of VOCs still need to be improved.Porous organic polymers(POPs)with extremely high porosity,structural diversity,and hydrophobic have been considered as one of the most promising candidates for VOCs adsorption.This review generalized the superiority of POPs for VOCs adsorption compared to other porous materials and summarized the studies of VOCs adsorption on different types of POPs.Moreover,the mechanism of competitive adsorption between water and VOCs on the POPs was discussed.Finally,a concise outlook for utilizing POPs for VOCs adsorption was discussed,noting areas in which further work is needed to develop the next-generation POPs for practical applications.展开更多
In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxyme...In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural（EMF） in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran（THF）. The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H（100） at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers（PCPs） for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.展开更多
A new chiral monomer,(S)‐5,5′‐divinyl‐BINAP,was successfully synthesized and embedded intotwo different porous organic polymers(Poly‐1and Poly‐2).After loading a Rh species,the catalystswere applied for the hete...A new chiral monomer,(S)‐5,5′‐divinyl‐BINAP,was successfully synthesized and embedded intotwo different porous organic polymers(Poly‐1and Poly‐2).After loading a Rh species,the catalystswere applied for the heterogeneous asymmetric hydroformylation of styrene.Compared with thehomogeneous BINAP analogue,the enantioselectivity of Rh/Poly‐1catalyst was drastically increasedby approximately70%.The improved enantioselectivity of the porous Rh/BINAP polymerswas attributed to the presence of flexible chiral nanopockets resulting from the increased bulk ofthe R groups near the catalytic center.展开更多
A series of thiophene-based conjugated microporous polymers （ThPOPs） have been synthesized on the basis of ferric chloride-catalyzed oxidative coupling polymerization of muRi-thienyl monomers. The structures of ThPO...A series of thiophene-based conjugated microporous polymers （ThPOPs） have been synthesized on the basis of ferric chloride-catalyzed oxidative coupling polymerization of muRi-thienyl monomers. The structures of ThPOPs were confirmed via solid-state t3C CP/MAS NMR spectroscopy and Fourier-transform infrared spectroscopy. The ThPOPs possess high porosities and their high Brunauer-Emmett-Teller specific surface area results vary between 350 and 1320mZg . The presence of abundant ultra-micronores at 0.50-0.63 nm allows ThPOPs efficient gas （carbon dioxide, methane, and hydrogen） adsorption.展开更多
Carbon capture,storage,and utilization(CCSU)is recognized as an effective method to reduce the excessive emission of CO_(2).Absorption by amine aqueous solutions is considered highly efficient for CO_(2) capture from ...Carbon capture,storage,and utilization(CCSU)is recognized as an effective method to reduce the excessive emission of CO_(2).Absorption by amine aqueous solutions is considered highly efficient for CO_(2) capture from the flue gas because of the large CO_(2) capture capacity and high selectivity.However,it is often limited by the equipment corrosion and the high desorption energy consumption,and adsorption of CO_(2) using solid adsorbents has been receiving more attention in recent years due to its simplicity and high efficiency.More recently,a great number of porous organic polymers(POPs)have been designed and constructed for CO_(2) capture,and they are proven promising solid adsorbents for CO_(2) capture due to their high Brunauer-Emmett-Teller(BET)surface area(SBET),adjustable pore size and easy functionalization.In particular,they usually have rigid skeleton,permanent porosity,and good physiochemical stability.In this review,we have a detailed review for the different POPs developed in recent years,not only the design strategy,but also the special structure for CO_(2) capture.The outlook of the opportunities and challenges of the POPs is also proposed.展开更多
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 porous organic polymer named FC-POP was facilely synthesized with extraordinary porosity and excellent stability. Further covalent incorporation of various amines including single amine group, multi-amine groups of ...A porous organic polymer named FC-POP was facilely synthesized with extraordinary porosity and excellent stability. Further covalent incorporation of various amines including single amine group, multi-amine groups of diethylenediamine （DETA）, and poly-amine groups of polyethylenimine （PEI） to the network gave rise to task-specific modification of the microenvironments to make them more suitable for CO2 capture. As a result, significant boost of CO2 adsorption capacity of 4.5 mmol/g （for FC-POP-CH2DETA, 273 K, 1 bar） and the CO2/N2 selectivity of 736.1 （for FC- POP-CH2PEI） were observed after the post-synthesis amine modifications. Furthermore, these materials can be regener- ated in elevated temperature under vacuum without apparent loss of CO2 adsorption capacity.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
Porous ionic polymers have demonstrated great potential for high-performance separation by the merits of their unique molecular recognition,but the preparation of anion-functionalized ionic polymers for the separation...Porous ionic polymers have demonstrated great potential for high-performance separation by the merits of their unique molecular recognition,but the preparation of anion-functionalized ionic polymers for the separation of bioactive molecules with highly similar structures remains a challenge.Here,through the facile Friedel-Crafts alkylation between benzylimidazole ionic liquids(ILs)and crosslinkers,several anion-functionalized hypercrosslinked ionic porous polymers(HIPs)are reported,which are well decorated with strongly basic carboxylate anions as well as feature tubular morphology and excellent thermal stability.High adsorption capacity(103.6 mg g^(−1) for tocopherol homologues)and selectivity(S_(βγ/α),4.26;S_(δ/α),3.19)for bioactive compounds with high structural similarity have been realized,superior to those of commercial adsorbents,hypercrosslinked polymer without ILs,and HIPs with common ILs.This study manifests a new synthetic strategy and rational molecular design for functionalized adsorbents,as well as offers new opportunities to enable high-performance separation.展开更多
Pyrylium salts are a type of representative and convincing example of versatility and variety not only as a nodal point in organic transformations but also as an attractive building block in functional organic materia...Pyrylium salts are a type of representative and convincing example of versatility and variety not only as a nodal point in organic transformations but also as an attractive building block in functional organic materials. Herein, we report an effective synthetic protocol to fabricate a new pyrylium-containing porous organic polymers(POPs), named TMP-P, via Knoevenagel condensation with 2,4,6-trimethylpyrylium salt(TMP) as the key building block and 1,4-phthalaldehyde as the linker. The resulting ionic polymer TMPP exhibited efficient visible-light-driven heterogeneous photodegradation of Rhodamine B, owing to the presence of wide visible light absorption and a narrow optical band gap triggered pyrylium core in the framework.展开更多
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.
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.
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.
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financially supported by the International Cooperation Program of the Ministry of Science and Technology of Hubei Province(No.2023EHA069)Shenzhen Science and Technology Program(No.JCYJ20230807143702005)the National Foreign Experts Program(No.G2022027015L)。
文摘Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.
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.
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supported by the National Key R&D Pro-gram of China(Nos.2019YFC1904100,2019YFC1904102,2019YFC1903902,and 2016YFC0205300)the National En-gineering Laboratory for Mobile Source Emission Control Technology of China(No.NELMS2017A03)+3 种基金the Natural Na-tional Science Foundation of China(Nos.21503144,21690083)Tianjin Research Program of Ecological Environmental Treat-ment(Nos.18ZXSZSF00210,18ZXSZSF00060)the Tianjin Research Program of Application Foundation and Advanced Technique(No.16JCQNJC05400)Major Science and Tech-nology Project for Ecological Environment Management in Tianjin(No.18ZXSZSF00210)。
文摘Volatile organic compounds(VOCs)with high toxicity and carcinogenicity are emitted from kinds of industries,which endanger human health and the environment.Adsorption is a promising method for the treatment of VOCs due to its low cost and high efficiency.In recent years,activated carbons,zeolites,and mesoporous materials are widely used to remove VOCs because of their high specific surface area and abundant porosity.However,the hydrophilic nature and low desorption rate of those materials limit their commercial application.Furthermore,the adsorption capacities of VOCs still need to be improved.Porous organic polymers(POPs)with extremely high porosity,structural diversity,and hydrophobic have been considered as one of the most promising candidates for VOCs adsorption.This review generalized the superiority of POPs for VOCs adsorption compared to other porous materials and summarized the studies of VOCs adsorption on different types of POPs.Moreover,the mechanism of competitive adsorption between water and VOCs on the POPs was discussed.Finally,a concise outlook for utilizing POPs for VOCs adsorption was discussed,noting areas in which further work is needed to develop the next-generation POPs for practical applications.
基金financially supported by the Natural Science Foundation of China(no.21576059)the Key Technologies R&D Program(no.2011BAE06B02)+1 种基金the International Science&Technology Cooperation Program of China(2010DFB60840)the Science and Technology Project of Guizhou Province(nos.[2012]6012 and[2011]3016)
文摘In this work, a series of MIL-101-SO3H（x） polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural（EMF） in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran（THF）. The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO;H（100） at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers（PCPs） for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.
基金supported by the Strategic priority Research Program of the Chinese Academy of Sciences (XDB17020400)~~
文摘A new chiral monomer,(S)‐5,5′‐divinyl‐BINAP,was successfully synthesized and embedded intotwo different porous organic polymers(Poly‐1and Poly‐2).After loading a Rh species,the catalystswere applied for the heterogeneous asymmetric hydroformylation of styrene.Compared with thehomogeneous BINAP analogue,the enantioselectivity of Rh/Poly‐1catalyst was drastically increasedby approximately70%.The improved enantioselectivity of the porous Rh/BINAP polymerswas attributed to the presence of flexible chiral nanopockets resulting from the increased bulk ofthe R groups near the catalytic center.
基金supported by the National Natural Science Foundation of China(21474027,21574032)
文摘A series of thiophene-based conjugated microporous polymers （ThPOPs） have been synthesized on the basis of ferric chloride-catalyzed oxidative coupling polymerization of muRi-thienyl monomers. The structures of ThPOPs were confirmed via solid-state t3C CP/MAS NMR spectroscopy and Fourier-transform infrared spectroscopy. The ThPOPs possess high porosities and their high Brunauer-Emmett-Teller specific surface area results vary between 350 and 1320mZg . The presence of abundant ultra-micronores at 0.50-0.63 nm allows ThPOPs efficient gas （carbon dioxide, methane, and hydrogen） adsorption.
文摘Carbon capture,storage,and utilization(CCSU)is recognized as an effective method to reduce the excessive emission of CO_(2).Absorption by amine aqueous solutions is considered highly efficient for CO_(2) capture from the flue gas because of the large CO_(2) capture capacity and high selectivity.However,it is often limited by the equipment corrosion and the high desorption energy consumption,and adsorption of CO_(2) using solid adsorbents has been receiving more attention in recent years due to its simplicity and high efficiency.More recently,a great number of porous organic polymers(POPs)have been designed and constructed for CO_(2) capture,and they are proven promising solid adsorbents for CO_(2) capture due to their high Brunauer-Emmett-Teller(BET)surface area(SBET),adjustable pore size and easy functionalization.In particular,they usually have rigid skeleton,permanent porosity,and good physiochemical stability.In this review,we have a detailed review for the different POPs developed in recent years,not only the design strategy,but also the special structure for CO_(2) capture.The outlook of the opportunities and challenges of the POPs is also proposed.
基金supported by the 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.
文摘A porous organic polymer named FC-POP was facilely synthesized with extraordinary porosity and excellent stability. Further covalent incorporation of various amines including single amine group, multi-amine groups of diethylenediamine （DETA）, and poly-amine groups of polyethylenimine （PEI） to the network gave rise to task-specific modification of the microenvironments to make them more suitable for CO2 capture. As a result, significant boost of CO2 adsorption capacity of 4.5 mmol/g （for FC-POP-CH2DETA, 273 K, 1 bar） and the CO2/N2 selectivity of 736.1 （for FC- POP-CH2PEI） were observed after the post-synthesis amine modifications. Furthermore, these materials can be regener- ated in elevated temperature under vacuum without apparent loss of CO2 adsorption capacity.
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 the National Natural Science Foundation of China(21908191,21938011,21890764)Zhejiang Provincial Natural Science Foundation of China(LR20B060001)the Entrepreneur Team Introduction Program of Zhejiang(2019R01006)。
文摘Porous ionic polymers have demonstrated great potential for high-performance separation by the merits of their unique molecular recognition,but the preparation of anion-functionalized ionic polymers for the separation of bioactive molecules with highly similar structures remains a challenge.Here,through the facile Friedel-Crafts alkylation between benzylimidazole ionic liquids(ILs)and crosslinkers,several anion-functionalized hypercrosslinked ionic porous polymers(HIPs)are reported,which are well decorated with strongly basic carboxylate anions as well as feature tubular morphology and excellent thermal stability.High adsorption capacity(103.6 mg g^(−1) for tocopherol homologues)and selectivity(S_(βγ/α),4.26;S_(δ/α),3.19)for bioactive compounds with high structural similarity have been realized,superior to those of commercial adsorbents,hypercrosslinked polymer without ILs,and HIPs with common ILs.This study manifests a new synthetic strategy and rational molecular design for functionalized adsorbents,as well as offers new opportunities to enable high-performance separation.
基金financial support from the Natural Science Foundation of Liaoning Province (No. 2019-MS-046)。
文摘Pyrylium salts are a type of representative and convincing example of versatility and variety not only as a nodal point in organic transformations but also as an attractive building block in functional organic materials. Herein, we report an effective synthetic protocol to fabricate a new pyrylium-containing porous organic polymers(POPs), named TMP-P, via Knoevenagel condensation with 2,4,6-trimethylpyrylium salt(TMP) as the key building block and 1,4-phthalaldehyde as the linker. The resulting ionic polymer TMPP exhibited efficient visible-light-driven heterogeneous photodegradation of Rhodamine B, owing to the presence of wide visible light absorption and a narrow optical band gap triggered pyrylium core in the framework.
