Triglyceride oil of plant seed cannot be used on its own without further modification. The fatty acids must be suitably functionalized in order to add polymerisable functionalities which will help in the curing proces...Triglyceride oil of plant seed cannot be used on its own without further modification. The fatty acids must be suitably functionalized in order to add polymerisable functionalities which will help in the curing process. The purpose of these modifications is to reach a higher level of molecular weight and cross-link density, and also to incorporate chemical functionalities known to impart stiffness in a polymer network. The modification can go through various path ways which were described in this study.展开更多
Synthetic polymers are the most widely used materials for packaging because of their ease of processing,low cost,and low density.However,many of these materials are not easily recyclable and are difficult to degrade c...Synthetic polymers are the most widely used materials for packaging because of their ease of processing,low cost,and low density.However,many of these materials are not easily recyclable and are difficult to degrade completely in nature,creating environmental problems.Thus,there is a tendency to substitute such polymers with natural polymers and copolymers that are easily bio-degraded and less likely to cause environmental pollution.There has been a greater interest in poly-lactic acid(PLA),poly-hydroxyalkanoates(PHAs),cellulose and starch based polymers and copolymers as the emerging biodegradable material candidates for the future.This paper reviews the present state-of-the-art biodegradable polymers made from renewable resources and discusses the main features of their properties and design.展开更多
Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O...Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.展开更多
Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
Epoxy resins are widely employed in wind turbine blades,drone rotors,and automotive interiors due to their excel-lent mechani-cal proper-ties and long service life.However,their insoluble and infusible cross-linked ne...Epoxy resins are widely employed in wind turbine blades,drone rotors,and automotive interiors due to their excel-lent mechani-cal proper-ties and long service life.However,their insoluble and infusible cross-linked networks pose a significant re-cycling challenge,particularly with the impending retirement of the first generation of wind turbine blades.In this work,we reported a fully bio-based epoxy Vitrimer(FEP)incorporat-ing a dual-dynamic covalent network design and systematically investigated the influence of the 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)catalyst on its curing kinetics,thermal/mechan-ical properties,dynamic exchange behavior,and degradation performance in a mild alkaline solution.Compared to conventional epoxy resins,FEP exhibited superior tensile strength and elongation at break at an optimal TBD concentration(2 wt%),achieving an excellent strength-toughness balance.The presence of TBD accelerated the exchange rates of both disulfide and ester bonds,endowing FEP with notable stress relaxation at elevated tempera-tures.Moreover,FEP demonstrated complete dissolution in 1 mol/L NaOH within 6 h at 25℃.These results underscored the exceptional strength,toughness,and recyclability of FEP,positioning it as a promising,environmentally friendly matrix resin for next-generation appli-cations in the new energy sector.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
Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need fo...Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.展开更多
The structural design and performance characteristics of the diaphragm have a decisive impact on the safety and electrochemical performance of lithium-ion batteries(LIBs).However,traditional polyolefin diaphragms stil...The structural design and performance characteristics of the diaphragm have a decisive impact on the safety and electrochemical performance of lithium-ion batteries(LIBs).However,traditional polyolefin diaphragms still face challenges in simultaneously improving the ion transport efficiency and thermal stability.Here,we report an in situ dynamic lithium compensation strategy for manufacturing a biobased furan aramid/ceramic diaphragm(BAS)with higher thermal stability and ion transport efficiency.Specifically,exchangeable carboxyl groups(–COOH)are introduced into the bio-based furan aramid(BA)framework,which are in situ converted into–COOLi groups to form lithium ions(Li^(+))transport channels,achieving dynamic compensation of active Li^(+).The dual transmission system of ion exchange and physical pore channels synergistically enhances the ionic conductivity of BAS to 1.536 mS cm^(-1).The high polarity structure of the furan ring and the electrolyte have excellent compatibility,significantly reducing the solid–liquid interfacial energy,making BAS have extremely high electrolyte wettability(contact angle of 0°).The BA amide group forms a multi-scale bonding network with the nano-ceramics.The BAS prepared by the water-coating process exhibits excellent thermal stability(with a thermal shrinkage rate of less than 1%after 1 h at 150℃).The LiFePO_(4)|Li half-cell assembled with BAS shows a capacity retention rate of up to 91.7%after 280 cycles at 1C,with a Coulomb efficiency of 99%,demonstrating excellent cycling stability.This design and development based on bio-materials provides a new approach for high safety and high energy density battery systems.展开更多
Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2...Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.展开更多
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polym...To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.展开更多
Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid an...Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid antibiotic removal.However,their low concentrations limit mass transfer efficiency,resulting in suboptimal performance.Adsorption is crucial for enhancing photocatalytic efficiency.In this study,a series of binary heterojunction catalysts(x%BWO@STHP)were synthesized,consisting of Bi_(2)WO_(6)(BWO)grafted with sulfonated triptycene-based hypercrosslinked polymer(STHP).The high specific surface area of STHP,combined withπ-πconjugation and ionic interactions with antibiotics,significantly enhances adsorption capacity.This facilitates effective contact between low-concentration pollutants in aqueous solutions and the active sites of the catalyst.The formation of a Z-scheme heterojunction between BWO and STHP facilitates photogenerated charge separation,and further significantly improves photocatalytic degradation performance.Specifically,the 20%BWO@STHP catalyst achieved rapid adsorption equilibrium for oxytetracycline(OTC),doxycycline(DOX),and tetracycline(TC)within 2 min and completely degraded them after 15 min of irradiation.Compared to pristine BWO,the photocatalytic reaction rate constants are significantly increased,being 9.69 times higher for OTC and 13.45 times higher for DOX.The catalyst exhibits excellent reusability and holds promising potential for practical applications.展开更多
Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and...Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and achieving efficient phosphorescent emission in RTP conjugated polymers(CPs)remains a significant challenge.Herein,we developed two RTP CPs(P(PSe ZPh-p-Ph)and P(PSe ZPh-m-Ph))by linking the phenoselenazine units with the para-and meta-phenylene units,respectively,to form the conjugated main chains.The phenylene linker with different lingking mode manipulates the effictiveπ-conjugation of the polymer backbones.Comparing with the para-linked P(PSe ZPh-pPh),meta-linked P(PSe ZPh-m-Ph)exhibit the decreased effectiveπ-conjugation and the enhanced contribution of selenium atoms to the frontier orbitals,leading to the larger spin-orbit coupling(SOC)constants and the accelerated phosphorescence radiative decay process.The P(PSe ZPhm-Ph)achieves a phosphorescence quantum yield of 21.4%in doped polystyrene films,which is among the highest efficiencies reported to date for pure organic RTP CPs.These CPs are applied to construct phosphorescent film sensors for oxygen detection with the high quenching constants(K_(sv))up to 14.80 kPa^(-1)and low detection of limit of 0.84 ppm,demostrating the potential for application in oxygen film sensors.展开更多
Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cat...Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cationic ring-opening polymerization.The ratio of blocks,the order of their attachment to the core,and arm length were varied.Conformation of synthesized stars was determined by methods of molecular hydrodynamics and optics.It has been shown that star-shaped molecules were characterized by high intramolecular density,and the arm folding increased with their lengthening.The influence of the structure of block copolymers and their molar mass on the critical micelle concentration has been established.Complexes of synthesized star-shaped block copolymers with curcumin were obtained and the efficient binding of curcumin to polymer molecules was demonstrated.The behavior of the aqueous solutions of the prepared polymer stars and their complexes with curcumin was investigated by light scattering and turbidimetry methods.The influence of the structure and molar mass of star polymers on their thermoresponsiveness and the phase separation temperatures in aqueous solutions was analyzed.A slight increase in the phase separation temperature was found on passage from polymer solutions to solutions of polymer complexes with hydrophobic curcumin.展开更多
Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we dev...Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we develop a constitutive model that explicitly couples the solvent concentration,structural relaxation,and mechanical response.This framework is built on a multiplicative decomposition of deformation and an Eyring-type flow rule,with structural evolution described by an effective temperature.A generalized shift factor is introduced to quantify how the solvent concentration and effective temperature jointly affect the relaxation time,thereby integrating physical aging and plasticization.The model is subsequently applied to methacrylate(MA)-based copolymer networks immersed in phosphate-buffered saline for up to nine months.Simulations accurately capture key experimental features,including the strong softening of highly swellable networks,the partial recovery due to aging,and the mitigating role of hydrophobic crosslinking in reducing solvent uptake.While the current single-mode description cannot reproduce the full relaxation spectrum,it establishes an efficient framework for predicting the long-term mechanical performance under coupled environmental and mechanical loading.This study provides a constitutive description of solvent-swollen glassy polymers,offering mechanistic insight into the interplay between plasticization and aging.Beyond biomedical MA networks,this framework establishes a foundation for predicting the long-term performance of polymer glasses under coupled aqueous environmental and mechanical loading.展开更多
Organic room-temperature phosphorescence(RTP)materials are promising for bioimaging applications due to their tunable structures,excellent biocompatibility,and long-lived luminescence.However,the development of highly...Organic room-temperature phosphorescence(RTP)materials are promising for bioimaging applications due to their tunable structures,excellent biocompatibility,and long-lived luminescence.However,the development of highly efficient organic RTP materials for aqueous systems remains challenging,as the organic phosphorescence is prone to being quenched by the dissolved oxygen in water.Herein,heteroaromatic carboxylic acids serve as ligand vips to construct a series of host-vip composites with nontoxic,dense EDTA-M(M=Ca,Mg,and Al)coordination polymer in water.These composites exhibit ultra-long pure RTP of vip molecules with phosphorescence quantum yield up to 53%,and lifetime up to 589.7 ms,due to the synergistic effect of dual-network structure:a coordinatively cross-linked network of EDTA-M,and a non-covalent bonded network formed by ligands and water molecules.The phosphorescence intensity is more than three times that of the composite with a single coordination network.Notably,the dual-network configuration can form a rigid and dense structure and block the intrusion of external H_(2)O and O_(2) molecules to avoid phosphorescence quenching in water.As a result,the RTP of the composites remains unchanged after 1 month in water.Furthermore,the nanoparticles fabricated from composites and anionic surfactants can be successfully applied in in vivo imaging of mice for the stable RTP in water.This work provides a novel strategy for the development of high-performance RTP materials in aqueous systems.展开更多
Conformational entropy,one of the central concepts of polymer physics,is the key to revealing physical characteristics of polymers.Despite an increased repertoire of conformational-entropy effects in the structural fo...Conformational entropy,one of the central concepts of polymer physics,is the key to revealing physical characteristics of polymers.Despite an increased repertoire of conformational-entropy effects in the structural formation,transition,and properties of polymer systems,the physical origin of conformational entropy remains less understood compared to interaction energy and other types of entropy.This review seeks to provide a conceptual framework unveiling several principles and rules of conformational entropy in governing the structures and properties of polymers,from the perspective of fundamental physics and statistical mechanics.First,we focus on the fundamentals of entropy in thermodynamics,leading to the theoretical basis for the elucidation of conformational entropy.Second,we delineate the physical nature of statistics and dissipation of conformational entropy and its essential dependence on the environmental heat bath.Next,we explore the principles of conformational entropy in driving the ordering transitions of various systems of polymers and their nanocomposites,elucidating the emergent and collective behaviors as well as the interplay between energetic interactions and entropy.Moreover,we demonstrate how the concept of conformational entropy is generalized to the biological systems and other soft matters.Finally,we discuss future directions to signify this framework originated from polymers.展开更多
Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrat...Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrate that bio-based benzaldehyde,a noteworthy high-value chemical,is able to be directionally prepared from lignocellulosic biomass.This new control-lable transformation was materialized by uniting catalytic-pyrolysis of lignocellulose to toluene intermediate and catalytic oxidation of toluene intermediate to bio-based benzalde-hyde.This work also developed a highly active magnetic catalyst(CoFe_(2)O_(4)@Biochar(HTR)),achieving 77.1%benzaldehyde selectivity and 46.7%benzaldehyde yield using this catalyst.It was found that introducing the biochar carrier into the cobalt iron composite metal oxide cat-alyst enhanced hydroxyl radical formation and bio-based benzaldehyde synthesis.Based on catalyst characterizations and hydroxyl radical analysis,potential reaction mechanism for bio-based benzaldehyde synthesis was proposed.This strategy may provide a beneficial pathway for developing high-value bio-based chemical(benzaldehyde)using renewable lignocellulosic biomass.展开更多
Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives.However,it is challenging to develop environmenta...Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives.However,it is challenging to develop environmentally friendly catalytic systems,especially in constructing efficient and recyclable catalysts under water or solvent-free conditions.Here,we designed two novel coordination polymers Cd-CPs and Fe-CPs to investigate their catalytic performance in water.Gratifyingly,it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions,while it was effective for the synthesis of1,3,5-triazines through acceptorless dehydrogenative coupling strategies.The features of broad substrate,high atom efficiency,and good catalyst reusability highlight the feasibility of this transformation.In additional,we demonstrated the spindle-like structures Fe-P,derived from the Fe-CPs via phosphorylation,which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability.This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction,and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.展开更多
In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminate...In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminated PBC(PBC-OH)prepolymers with 1,6-hexmethylene diisocyanate(HDI)as a chain extender.The effects of the prepolymer molecular weight and content on the structure and application properties of the PES-b-PBC copolymers were systematically investigated using various techniques.It was found that the compatibility of PES and PBC blocks in PES-b-PBC copolymers can be greatly enhanced by lowering the length of the prepolymers,and the amorphous phase of the PES and PBC chain segments in the PES-b-PBC copolymer would transform from immiscibility and partial miscibility to miscibility when the number-average molecular weight(M_(n))of the PES-OH and PBC-OH prepolymers is less than 2000 g/mol.Only the crystal structure of bare PES can be observed in the wide-angle X-ray diffraction(WAXD)spectrum of the PES-b-PBC copolymers,but their crystallinity degrees were found to decrease with increasing PBC fraction.The thermal behavior,crystallization performance,rheological properties,mechanical properties,and degradation properties of the PES-b-PBC multiblock copolymers can be easily modulated by altering the block length and composition of the prepolymers,offering potential applications in biodegradable materials.展开更多
Redox-active covalent organic polymers(COPs)have emerged as appealing renewable electrode materials for next-generation Li-ion batteries,but their performance is limited by insufficient redox sites and inadequate Li-i...Redox-active covalent organic polymers(COPs)have emerged as appealing renewable electrode materials for next-generation Li-ion batteries,but their performance is limited by insufficient redox sites and inadequate Li-ion diffusion.Here,we develop a novel class of mesoporous covalent organic polymer(namely TF-Azo-COP)bearing multiple redox sites and explore its first use as efficient 18-electron-redox anodes for superior Li-ion storage in both coin-type and fiber-type batteries.The newly produced TF-Azo-COP involves three types of active sites including C=N in triazines and imines,N=N in azo,and C6-ring aromatics to enable 18-Li-ion storage on one repeatable segment,while affording extendedπ-conjugation for fast electron transfer and a pore size of~2.5 nm for facilitated ion diffusion with a high coefficient up to~10^(-10)cm^(2)s^(-1)—superior to some reported organic electrodes.Meriting from the above,pairing TF-Azo-COP with metal Li endows a coin cell with good cycling stability and a large reversible capacity of 795.4 mAh g^(-1)at 0.1 A g^(-1)—representing one of the best performances among reported organic electrodes.When coupled with fiber-shaped LiFePO_(4)cathodes,the assembled fiber cell delivers an excellent combination of linear capacity(0.23 mAh cm^(-1)),energy density(0.55 mWh cm^(-1)),cycling stability(250 cycles),and good flexibility.展开更多
文摘Triglyceride oil of plant seed cannot be used on its own without further modification. The fatty acids must be suitably functionalized in order to add polymerisable functionalities which will help in the curing process. The purpose of these modifications is to reach a higher level of molecular weight and cross-link density, and also to incorporate chemical functionalities known to impart stiffness in a polymer network. The modification can go through various path ways which were described in this study.
基金support from the NSERC Strategic Network-Innovative Green Wood Fibre Product(Canada)Natural Science Foundation of China(Grant No.21466005)are gratefully acknowledged.
文摘Synthetic polymers are the most widely used materials for packaging because of their ease of processing,low cost,and low density.However,many of these materials are not easily recyclable and are difficult to degrade completely in nature,creating environmental problems.Thus,there is a tendency to substitute such polymers with natural polymers and copolymers that are easily bio-degraded and less likely to cause environmental pollution.There has been a greater interest in poly-lactic acid(PLA),poly-hydroxyalkanoates(PHAs),cellulose and starch based polymers and copolymers as the emerging biodegradable material candidates for the future.This paper reviews the present state-of-the-art biodegradable polymers made from renewable resources and discusses the main features of their properties and design.
文摘Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
基金support from the National Natural Science Foundation of China(Nos.22293011,T2341001)the Major Science and Technology Project of Anhui Province(202203a06020010).
文摘Epoxy resins are widely employed in wind turbine blades,drone rotors,and automotive interiors due to their excel-lent mechani-cal proper-ties and long service life.However,their insoluble and infusible cross-linked networks pose a significant re-cycling challenge,particularly with the impending retirement of the first generation of wind turbine blades.In this work,we reported a fully bio-based epoxy Vitrimer(FEP)incorporat-ing a dual-dynamic covalent network design and systematically investigated the influence of the 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)catalyst on its curing kinetics,thermal/mechan-ical properties,dynamic exchange behavior,and degradation performance in a mild alkaline solution.Compared to conventional epoxy resins,FEP exhibited superior tensile strength and elongation at break at an optimal TBD concentration(2 wt%),achieving an excellent strength-toughness balance.The presence of TBD accelerated the exchange rates of both disulfide and ester bonds,endowing FEP with notable stress relaxation at elevated tempera-tures.Moreover,FEP demonstrated complete dissolution in 1 mol/L NaOH within 6 h at 25℃.These results underscored the exceptional strength,toughness,and recyclability of FEP,positioning it as a promising,environmentally friendly matrix resin for next-generation appli-cations in the new energy sector.
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supported by the National Natural Science Foundation of China(Nos.22322107,22101169 and 22071144)by Shanghai Scientific and Technological Committee(No.22010500300).
文摘Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.
基金the financial support from the National Natural Science Foundation of China(22293011,T2341001)the Major Science and Technology Project of Anhui Province(202203a06020010)+1 种基金the Horizontal Project Provided by Jiangsu Zhuogao New Materials Technology Co.,Ltd.(Td00923003H)Joint Laboratory by China Power Investment Ronghe New Energy Technology Co.,Ltd.and the Central Government Guiding Special Fund Project for Local Science and Technology Development(202407a12020008)。
文摘The structural design and performance characteristics of the diaphragm have a decisive impact on the safety and electrochemical performance of lithium-ion batteries(LIBs).However,traditional polyolefin diaphragms still face challenges in simultaneously improving the ion transport efficiency and thermal stability.Here,we report an in situ dynamic lithium compensation strategy for manufacturing a biobased furan aramid/ceramic diaphragm(BAS)with higher thermal stability and ion transport efficiency.Specifically,exchangeable carboxyl groups(–COOH)are introduced into the bio-based furan aramid(BA)framework,which are in situ converted into–COOLi groups to form lithium ions(Li^(+))transport channels,achieving dynamic compensation of active Li^(+).The dual transmission system of ion exchange and physical pore channels synergistically enhances the ionic conductivity of BAS to 1.536 mS cm^(-1).The high polarity structure of the furan ring and the electrolyte have excellent compatibility,significantly reducing the solid–liquid interfacial energy,making BAS have extremely high electrolyte wettability(contact angle of 0°).The BA amide group forms a multi-scale bonding network with the nano-ceramics.The BAS prepared by the water-coating process exhibits excellent thermal stability(with a thermal shrinkage rate of less than 1%after 1 h at 150℃).The LiFePO_(4)|Li half-cell assembled with BAS shows a capacity retention rate of up to 91.7%after 280 cycles at 1C,with a Coulomb efficiency of 99%,demonstrating excellent cycling stability.This design and development based on bio-materials provides a new approach for high safety and high energy density battery systems.
文摘Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.
基金the support from the Jiangsu Provincial Senior Talent Program (Dengfeng,Jiangsu University)the support from the National Key R&D Program of China (No.2024YFB3612600)+3 种基金the National Natural Science Foundation of China (Nos.22275098,62288102)Basic Research Program of Jiangsu (No.BK20243057)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (No.NY222097)the National Natural Science Foundation of China (No.62205035)。
文摘To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
基金the financial support provided by the National Natural Science Foundation of China(22478267,22438009,U24A20535)Basic Research Program of Jiangsu province(BK20243002)+1 种基金Prospective Application Research Project of Suzhou(SYC2022042)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid antibiotic removal.However,their low concentrations limit mass transfer efficiency,resulting in suboptimal performance.Adsorption is crucial for enhancing photocatalytic efficiency.In this study,a series of binary heterojunction catalysts(x%BWO@STHP)were synthesized,consisting of Bi_(2)WO_(6)(BWO)grafted with sulfonated triptycene-based hypercrosslinked polymer(STHP).The high specific surface area of STHP,combined withπ-πconjugation and ionic interactions with antibiotics,significantly enhances adsorption capacity.This facilitates effective contact between low-concentration pollutants in aqueous solutions and the active sites of the catalyst.The formation of a Z-scheme heterojunction between BWO and STHP facilitates photogenerated charge separation,and further significantly improves photocatalytic degradation performance.Specifically,the 20%BWO@STHP catalyst achieved rapid adsorption equilibrium for oxytetracycline(OTC),doxycycline(DOX),and tetracycline(TC)within 2 min and completely degraded them after 15 min of irradiation.Compared to pristine BWO,the photocatalytic reaction rate constants are significantly increased,being 9.69 times higher for OTC and 13.45 times higher for DOX.The catalyst exhibits excellent reusability and holds promising potential for practical applications.
基金supported by the National Natural Science Foundation of China(Nos.22275182,22075272,51973211,51833009,21674111 and 52261135541)the Ministry of Science and Technology of the People’s Republic of China(the National Key R&D Program of China,No.2022YFB4200400)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0520102)。
文摘Pure organic room-temperature phosphorescent(RTP)polymers possess good processability and flexibility over small molecular crystals.However,most of RTP polymers reported so far are based on non-conjugated polymers,and achieving efficient phosphorescent emission in RTP conjugated polymers(CPs)remains a significant challenge.Herein,we developed two RTP CPs(P(PSe ZPh-p-Ph)and P(PSe ZPh-m-Ph))by linking the phenoselenazine units with the para-and meta-phenylene units,respectively,to form the conjugated main chains.The phenylene linker with different lingking mode manipulates the effictiveπ-conjugation of the polymer backbones.Comparing with the para-linked P(PSe ZPh-pPh),meta-linked P(PSe ZPh-m-Ph)exhibit the decreased effectiveπ-conjugation and the enhanced contribution of selenium atoms to the frontier orbitals,leading to the larger spin-orbit coupling(SOC)constants and the accelerated phosphorescence radiative decay process.The P(PSe ZPhm-Ph)achieves a phosphorescence quantum yield of 21.4%in doped polystyrene films,which is among the highest efficiencies reported to date for pure organic RTP CPs.These CPs are applied to construct phosphorescent film sensors for oxygen detection with the high quenching constants(K_(sv))up to 14.80 kPa^(-1)and low detection of limit of 0.84 ppm,demostrating the potential for application in oxygen film sensors.
基金financially supported by the Russian Science Foundation(No.23-13-00205)。
文摘Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cationic ring-opening polymerization.The ratio of blocks,the order of their attachment to the core,and arm length were varied.Conformation of synthesized stars was determined by methods of molecular hydrodynamics and optics.It has been shown that star-shaped molecules were characterized by high intramolecular density,and the arm folding increased with their lengthening.The influence of the structure of block copolymers and their molar mass on the critical micelle concentration has been established.Complexes of synthesized star-shaped block copolymers with curcumin were obtained and the efficient binding of curcumin to polymer molecules was demonstrated.The behavior of the aqueous solutions of the prepared polymer stars and their complexes with curcumin was investigated by light scattering and turbidimetry methods.The influence of the structure and molar mass of star polymers on their thermoresponsiveness and the phase separation temperatures in aqueous solutions was analyzed.A slight increase in the phase separation temperature was found on passage from polymer solutions to solutions of polymer complexes with hydrophobic curcumin.
基金the funding support from the Smart Medicine and Engineering Interdisciplinary Innovation Project of Ningbo University(No.ZHYG003)。
文摘Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we develop a constitutive model that explicitly couples the solvent concentration,structural relaxation,and mechanical response.This framework is built on a multiplicative decomposition of deformation and an Eyring-type flow rule,with structural evolution described by an effective temperature.A generalized shift factor is introduced to quantify how the solvent concentration and effective temperature jointly affect the relaxation time,thereby integrating physical aging and plasticization.The model is subsequently applied to methacrylate(MA)-based copolymer networks immersed in phosphate-buffered saline for up to nine months.Simulations accurately capture key experimental features,including the strong softening of highly swellable networks,the partial recovery due to aging,and the mitigating role of hydrophobic crosslinking in reducing solvent uptake.While the current single-mode description cannot reproduce the full relaxation spectrum,it establishes an efficient framework for predicting the long-term mechanical performance under coupled environmental and mechanical loading.This study provides a constitutive description of solvent-swollen glassy polymers,offering mechanistic insight into the interplay between plasticization and aging.Beyond biomedical MA networks,this framework establishes a foundation for predicting the long-term performance of polymer glasses under coupled aqueous environmental and mechanical loading.
基金supported by the Startup Funds for Introduced Talents of Wuyi University(YJ202304)the National Natural Science Foundation of China(22375044).
文摘Organic room-temperature phosphorescence(RTP)materials are promising for bioimaging applications due to their tunable structures,excellent biocompatibility,and long-lived luminescence.However,the development of highly efficient organic RTP materials for aqueous systems remains challenging,as the organic phosphorescence is prone to being quenched by the dissolved oxygen in water.Herein,heteroaromatic carboxylic acids serve as ligand vips to construct a series of host-vip composites with nontoxic,dense EDTA-M(M=Ca,Mg,and Al)coordination polymer in water.These composites exhibit ultra-long pure RTP of vip molecules with phosphorescence quantum yield up to 53%,and lifetime up to 589.7 ms,due to the synergistic effect of dual-network structure:a coordinatively cross-linked network of EDTA-M,and a non-covalent bonded network formed by ligands and water molecules.The phosphorescence intensity is more than three times that of the composite with a single coordination network.Notably,the dual-network configuration can form a rigid and dense structure and block the intrusion of external H_(2)O and O_(2) molecules to avoid phosphorescence quenching in water.As a result,the RTP of the composites remains unchanged after 1 month in water.Furthermore,the nanoparticles fabricated from composites and anionic surfactants can be successfully applied in in vivo imaging of mice for the stable RTP in water.This work provides a novel strategy for the development of high-performance RTP materials in aqueous systems.
基金financially supported by the National Natural Science Foundation of China (Nos. 22533003 and 22025302)financial support from the Ministry of Science and Technology of China (No. 2022YFA1203203)State Key Laboratory of Chemical Engineering (No. SKL-ChE23T01).
文摘Conformational entropy,one of the central concepts of polymer physics,is the key to revealing physical characteristics of polymers.Despite an increased repertoire of conformational-entropy effects in the structural formation,transition,and properties of polymer systems,the physical origin of conformational entropy remains less understood compared to interaction energy and other types of entropy.This review seeks to provide a conceptual framework unveiling several principles and rules of conformational entropy in governing the structures and properties of polymers,from the perspective of fundamental physics and statistical mechanics.First,we focus on the fundamentals of entropy in thermodynamics,leading to the theoretical basis for the elucidation of conformational entropy.Second,we delineate the physical nature of statistics and dissipation of conformational entropy and its essential dependence on the environmental heat bath.Next,we explore the principles of conformational entropy in driving the ordering transitions of various systems of polymers and their nanocomposites,elucidating the emergent and collective behaviors as well as the interplay between energetic interactions and entropy.Moreover,we demonstrate how the concept of conformational entropy is generalized to the biological systems and other soft matters.Finally,we discuss future directions to signify this framework originated from polymers.
基金supported by the National Natural Sci-ence Foundation of China(Nos.U21A20288 and 21978280).
文摘Developing green and efficient methods to acquire lignocellulose-based chemicals with high added value is beneficial for facilitating green chemistry and sustainable development.The goal of this study is to demonstrate that bio-based benzaldehyde,a noteworthy high-value chemical,is able to be directionally prepared from lignocellulosic biomass.This new control-lable transformation was materialized by uniting catalytic-pyrolysis of lignocellulose to toluene intermediate and catalytic oxidation of toluene intermediate to bio-based benzalde-hyde.This work also developed a highly active magnetic catalyst(CoFe_(2)O_(4)@Biochar(HTR)),achieving 77.1%benzaldehyde selectivity and 46.7%benzaldehyde yield using this catalyst.It was found that introducing the biochar carrier into the cobalt iron composite metal oxide cat-alyst enhanced hydroxyl radical formation and bio-based benzaldehyde synthesis.Based on catalyst characterizations and hydroxyl radical analysis,potential reaction mechanism for bio-based benzaldehyde synthesis was proposed.This strategy may provide a beneficial pathway for developing high-value bio-based chemical(benzaldehyde)using renewable lignocellulosic biomass.
基金financial support of this work by the National Natural Science Foundation of China(No.21861039)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX24_2530)the Fundamental Research Funds for the Central Universities。
文摘Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives.However,it is challenging to develop environmentally friendly catalytic systems,especially in constructing efficient and recyclable catalysts under water or solvent-free conditions.Here,we designed two novel coordination polymers Cd-CPs and Fe-CPs to investigate their catalytic performance in water.Gratifyingly,it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions,while it was effective for the synthesis of1,3,5-triazines through acceptorless dehydrogenative coupling strategies.The features of broad substrate,high atom efficiency,and good catalyst reusability highlight the feasibility of this transformation.In additional,we demonstrated the spindle-like structures Fe-P,derived from the Fe-CPs via phosphorylation,which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability.This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction,and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.
基金financially supported by the Science and Technology Projects of Changji Prefecture(No.2023112258)Shihezi Coal Chemical Industry Common Technology Research Institute Project(No.MGJY0104)the Program for Young Innovative Talents of Shihezi University(No.CXFZ202302).
文摘In this study,a series of poly(ethylene succinate)-b-poly(butylene carbonate)(PES-b-PBC)multiblock copolymers were prepared through the chain-extension reaction of hydroxyl-terminated PES(PES-OH)and hydroxyl-terminated PBC(PBC-OH)prepolymers with 1,6-hexmethylene diisocyanate(HDI)as a chain extender.The effects of the prepolymer molecular weight and content on the structure and application properties of the PES-b-PBC copolymers were systematically investigated using various techniques.It was found that the compatibility of PES and PBC blocks in PES-b-PBC copolymers can be greatly enhanced by lowering the length of the prepolymers,and the amorphous phase of the PES and PBC chain segments in the PES-b-PBC copolymer would transform from immiscibility and partial miscibility to miscibility when the number-average molecular weight(M_(n))of the PES-OH and PBC-OH prepolymers is less than 2000 g/mol.Only the crystal structure of bare PES can be observed in the wide-angle X-ray diffraction(WAXD)spectrum of the PES-b-PBC copolymers,but their crystallinity degrees were found to decrease with increasing PBC fraction.The thermal behavior,crystallization performance,rheological properties,mechanical properties,and degradation properties of the PES-b-PBC multiblock copolymers can be easily modulated by altering the block length and composition of the prepolymers,offering potential applications in biodegradable materials.
基金support from Guangdong Basic and Applied Basic Research Foundation(2020B1515420001 and 2023B1515040027)Fundamental Research Funds for the Central Universities,Sun Yat-sen University(23yxqntd002)the Postdoctoral Fellowship Program of CPSF(GZC20242066).
文摘Redox-active covalent organic polymers(COPs)have emerged as appealing renewable electrode materials for next-generation Li-ion batteries,but their performance is limited by insufficient redox sites and inadequate Li-ion diffusion.Here,we develop a novel class of mesoporous covalent organic polymer(namely TF-Azo-COP)bearing multiple redox sites and explore its first use as efficient 18-electron-redox anodes for superior Li-ion storage in both coin-type and fiber-type batteries.The newly produced TF-Azo-COP involves three types of active sites including C=N in triazines and imines,N=N in azo,and C6-ring aromatics to enable 18-Li-ion storage on one repeatable segment,while affording extendedπ-conjugation for fast electron transfer and a pore size of~2.5 nm for facilitated ion diffusion with a high coefficient up to~10^(-10)cm^(2)s^(-1)—superior to some reported organic electrodes.Meriting from the above,pairing TF-Azo-COP with metal Li endows a coin cell with good cycling stability and a large reversible capacity of 795.4 mAh g^(-1)at 0.1 A g^(-1)—representing one of the best performances among reported organic electrodes.When coupled with fiber-shaped LiFePO_(4)cathodes,the assembled fiber cell delivers an excellent combination of linear capacity(0.23 mAh cm^(-1)),energy density(0.55 mWh cm^(-1)),cycling stability(250 cycles),and good flexibility.
