Three-dimensional(3 D)printing has revolutionized the design and production of customized scaffolds,but the minimally invasive implantation of 3 D-printed structures into the human body remains challenging.This has pr...Three-dimensional(3 D)printing has revolutionized the design and production of customized scaffolds,but the minimally invasive implantation of 3 D-printed structures into the human body remains challenging.This has prompted the exploration of innovative materials and technical solutions.Shape-memory polymers,as advanced intelligent materials,exhibit considerable potential in minimally invasive surgical applications.Herein,we developed a novel thermosetting shape-memory polymer,poly(L-lactic acid)-trimethylene carbonate-glycolic acid(PLLA-TMC-GA),for the fabrication of bioengineered scaffolds with body temperature-activated shape-memory functionality.We comprehensively evaluated the mechanical properties,thermal stability,shape-memory capabilities,biocompatibility,biodegradability,and 3 D printing performance of PLLA-TMC-GA terpolymers with various compositions.The results indicate that PLLA-TMC-GA exhibits exceptional shape-memory performance,adjustable material properties,favorable biocompatibility,and the potential for controlled biodegradation and reabsorption.The use of PLLA-TMC-GA as a biodegradable shape-memory polymer allows the reduction of implant volume,simplifies implantation,and enables on-demand activation at body temperature.These characteristics present new opportunities for the advancement of minimally invasive surgical techniques.展开更多
Interest in temperature-responsive polymers has steadily grown over the past several decades, and numerous studies have been dedicated to developing temperature sensitive polymers that can be constructed into new smar...Interest in temperature-responsive polymers has steadily grown over the past several decades, and numerous studies have been dedicated to developing temperature sensitive polymers that can be constructed into new smart materials for biomedical applications. Phase behavior of a temperature-responsive polymer plays a pivotal role in determining its biological performance in certain conditions. In addition to the additives （such as salts and proteins） in aqueous solutions, molecular weight, molecular weight distribution, and structural or compositional factors can also significantly affect the transition temperatures of the polymers. This review comprehensively describes well-established and newly developed synthetic strategies for preparing temperature-responsive polymers. The structural and compositional parameters that affect the transition temperatures and self-assembly behavior are discussed. Finally, the biomedical applications of the temperature-responsive polymers in drug delivery, immunotherapy, tissue engineering, and diagnosis are summarized.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
The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polyme...The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polymer(Emim)2[Cu(BBTZ)_(2)(β-Mo_(8)O_(26))](Mo_(8)-CP).Mo_(8)-CP was characterized by elemental analysis,thermogravime-try,IR,powder X-ray diffraction,and single-crystal X-ray diffraction.In Mo_(8)-CP,structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain.These chains are further bridged by(β-Mo_(8)O_(26))^(4-)to construct a 3D coordination polymer.Notably,(Emim)^(+)acts as a structure-directing agent,occupying the channels of the 3D coordination polymer.Based on this unique structure,the ion exchange properties of Mo_(8)-CP toward rare-earth ions were investigated.It has been found that the luminescent color of the material can be successfully regulat-ed by introducing Eu^(3+)or Tb^(3+)through ion exchange.CCDC:2475110,Mo_(8)-CP.展开更多
The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the effici...The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the efficiency of OSCs.Herein,two bridging polymer acceptors(PAs)—benzodithiophene-(2-ethylhexyl)oxy(BDT-C2C4)and benzodithiophene-octyloxy(BDT-C_(8))—are designed and synthesized by combining a benzodithiophene(BDT)unit as the donor moiety[poly({4,8-bis[5-(2-ethylhexyl)-4-fluorothiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}){5,8-bis[4-(2-butyloctyl)thiophen-2-yl]dithieno[3',2':3,4]},D18],and a 2,2′-((2Z,2′Z)-{[12,13-Bis(2-butyloctyl)-12,13-dihydro-3,9-dinonylthieno[2,3]thieno[3,2-b]pyrrolo[4,5-g]thieno[2,3-b]indole-2,10-diyl]bis(methanylylidene)}bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(Y6)derivative as the acceptor moiety.BDT-C2C4 and BDT-C_(8) are functionalized with(2-ethylhexyl)oxy and octyloxy side chains on the BDT unit,respectively.Both PAs show complementary absorption and cascaded energy levels with the donor D18 and the acceptor 2,2′-((2Z,2′Z)-{[12,13-bis(3-ethylheptyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″∶4′,5′]thieno[2′,3′∶4,5]pyrrolo[3,2-g]thieno[2′,3′∶4,5]thieno[3,2-b]indole-2,10-diyl]bis(meth⁃aneylylidene)}bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(N3),but BDT-C_(8) exhibits better compatibility with D18 and N3 compared to BDT-C2C4.When incorporated as a third component into the D18∶N3 blend,both PAs improve the active layer morphology.In particular,the D18∶N3∶BDT-C_(8) blend shows significantly optimized morphology,featuring reduced phase separation and a fibrous network structure.As a result,the device based on D18∶N3∶BDT-C_(8) achieves a power conversion efficiency of 18.18%,significantly higher than that of the device based on D18∶N3(ca.17.37%).This work presents a compatibilizer strategy for optimizing blend morphology towards high-performance ternary OSCs.展开更多
A new principle for producing fire-resistant polymer materials with increased deformation properties using a flame retardant not as a heterogeneous additive,but as a thermoplastic flame retardant in a hybrid polymer m...A new principle for producing fire-resistant polymer materials with increased deformation properties using a flame retardant not as a heterogeneous additive,but as a thermoplastic flame retardant in a hybrid polymer mixture with a polyhydrocarbon is considered.Hybrid polymer blends of low-molecular ammonium polyphosphate(APP)with an ethylene-vinyl acetate copolymer(EVA)with an APP content of 80 wt%with enhanced deformation properties were obtained by extrusion mixing at various temperatures in the range from 200°C to 250°C.A chemical scheme for the transformations of the components during the formation of the composite is proposed.X-ray diffraction analysis showed the formation of new crystalline structures of APP.The phase structure of the systems corresponding to the model of a dispersed-filled composite in which EVA plays the role of a matrix,determining the deformation of the mixture,and the filler is ammonium polyphosphate,was studied by scanning electron microscopy(SEM).The method of FTIR microscopy showed chemical interactions between EVA and APP with the formation of amide groups.The conditions for obtaining compositions characterized by heat resistance of 210°C,oxygen index of 55 and ultimate elongation at drawing of 213%were established.展开更多
Temperature is one of the main causes of spontaneous coal combustion.To improve the flame retardant performance,CaCl2,ammonium polyphosphate(APP),and calcium phosphate(CaHP)were compounded to control the temperature r...Temperature is one of the main causes of spontaneous coal combustion.To improve the flame retardant performance,CaCl2,ammonium polyphosphate(APP),and calcium phosphate(CaHP)were compounded to control the temperature response of different stages of coal spontaneous combustion through physical and chemical synergy.Simultaneous thermal analysis,thermogravimetric-Fourier infrared spectroscopy(TG-FTIR),in-situ FTIR and electron paramagnetic resonance(EPR)were used to study the multitemperature stage synergistic inhibition of coal spontaneous combustion.The results show that the proposed method is effective.By obtaining the characteristics of the spontaneous combustion reaction stage of coal in advance,the method of configuring an appropriate composite inhibitor can effectively realize the intelligent control of the temperature response of coal spontaneous combustion.The ignition point of long-flame coal increased by 37.15℃.The inhibition rate of the gas phase products was more than 20%,and the inhibition rate of the functional groups was more than 30%.It has a good quenching effect on free radicals and can effectively inhibit the oxidation activity of active free radicals such as H,HO,and O.The results provide experimental and theoretical support for the study of temperature-responsive composite flame retardants for coal with different metamorphic degrees.展开更多
Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)...Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)owing to its excellent hydrophilicity and swelling capacity.However,calcium bentonite(CaB),which is much more abundant worldwide,is rarely used for containment applications owing to its poor hydrophilicity.This study proposed a polymerization method that transforms sodium-activated calcium bentonite(NCB)into PMB to achieve low hydraulic conductivity(k)to aggressive liquids.The mechanism for its low k was revealed through characterization techniques and analyses(e.g.X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM),and Brunauer-Emmett-Teller(BET)).The results showed that the PMB had a small amount of polymer elution(indicating better interface stability)and thus exhibited excellent barrier properties under chemically aggressive conditions,with the k of<10^(-11) m/s for 0.6 mol/L NaCl solution,which is four orders of magnitude lower than that of the NCB(k=3×10^(-7) m/s).Various microscopic analyses indicated that the selected monomers were successfully polymerized,and intercalated into and grafted onto the montmorillonite layers of bentonite.The formed polymer network increased the swelling capability of PMB granules,decreased the pore size,and created narrow and tortuous flow pathways leading to a very low k to aggressive liquids.展开更多
Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth a...Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth and unstable interfacial reactions,rarely perform beyond coin-cell demonstrations.To address these shortcomings,a multifunctional composite quasi-solid polymer electrolyte(QSPE)that incorporates boron nitride(BN)as an engineered filler in a highly conductive polymer blend system has been developed.The optimized formation(15BN QSPE)delivers a room-temperature ionic conductivity of 2.15 m S cm^(-1)and a sodium-ion transference number of 0.80.Molecular dynamics simulations elucidate the coordination environment and show improved transport in the presence of BN.BN is chemically active and bifunctional:boron acts as an electron acceptor,interacting with solvents and macromolecules,while nitrogen coordinates with sodium ions,tailoring the solvation environment and transport pathways to promote efficient ion migration.The 15BN QSPE is self-extinguishing,resists oxidative thermal degradation,and enables stable cycling in symmetric sodium cells for>1400 h at0.5 m A cm^(-2).A Prussian blue full cell achieves>1500 stable cycles at 1C with -99% Coulombic efficiency in coin-cell configuration.A two-layer pouch cell with dual 15BN QSPE layers delivers 600 stable cycles at 0.125C and withstands rigorous mechanical abuse.These results position 15BN QSPE as a scalable,highperformance electrolyte offering enhanced safety and efficiency for next-generation sodium metal batteries.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
With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial c...With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.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
Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimen...Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimensional optimization strategy to alleviate the side reactions between SN and Li metal,and develop a highly stable poly-vinylethylene carbonate-based PPCE(PPCE-VEC).Moreover,we identify the intrinsic factors of multi-dimensional polymer structures on the electrolyte stability by three typical classes of polyesters.The PPCE-VEC constructed by in situ polymerization exhibits much better stability than poly-vinylene carbonate-based PPCE(PPCE-VCA)and poly-trifluoroethyl acrylate-based PPCE(PPCE-TFA),which is verified by its fewer SN-decomposition species in X-ray photoelectron spectroscopy(XPS)and outstanding full cell performance.The PPCE-VEC-enabled LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell achieve 73.7%capacity retention after 1400 cycles,which outperforms PPCE-VCA-and PPCE-TFA-enabled full cells(61.9%and 46.9%).Spectral analysis and theoretical calculation reveal that the high solvation ability of the carbonyl site,flexible polymer chain,and homogeneous electrolyte phase of PPCE-VEC are favorable to maximizing competition coordination with Li^(+)to weaken the Li^(+)–SN binding and shape an anion-rich solvation structure.This optimized polymer-involved Li^(+)solvation enhances SN stability and facilitates the formation of B/F enriched solid-electrolyte interphase(SEI),thus significantly improving PPCE stability.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
Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are ga...Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are gaining prominence due to their unique combination of mechanical flexibility,environmental compatibility,and solution-processable fabrication.A notable candidate in this field is poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene)(PBTTT),a liquid-crystalline conjugated polymer,with high charge carrier mobility and adaptability to melt-processing techniques.Recent advancements have propelled PBTTT’s figure of merit from below 0.1 to a remarkable 1.28 at 368 K,showcasing its potential for practical applications.This review systematically examines strategies to enhance PBTTT’s TE performance through doping(solution,vapor,and anion exchange doping),composite engineering,and aggregation state controlling.Recent key breakthroughs include ion exchange doping for stable charge modulation,multi-heterojunction architectures reducing thermal conductivity,and proton-coupled electron transfer doping for precise Fermi-level tuning.Despite great progress,challenges still persist in enhancing TE conversion efficiency,balancing or decoupling electrical conductivity,Seebeck coefficient and thermal conductivity,and leveraging melt-processing scalability of PBTTT.By bridging fundamental insights with applied research,this work provides a roadmap for advancing PBTTT-based TE materials toward efficient energy harvesting and wearable electronics.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
In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skel...In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skeletal structures with their homologues carbon and silicon,whereas the polymers containing germanium and tin show unique properties derived from their large atomic radii and weak binding energies.For example,polygermane and polystannane exhibited light absorption in the UV–visible region and conductivity because of theσ-conjugation through the polymer main-chain constructed byσ-bonds between heavy elements.Theσ-conjugation was affected by the conformational change of the polymer main-chain,and thermochromic properties can be induced.Furthermore,the weak bonds were able to be cleaved homolytically upon photoirradiation,and radicals were subsequently generated.By incorporating hypervalent heavy elements into theπ-conjugated system,it was possible to modulate the electronic structures of theπ-conjugated system throughσ*–π*conjugation with highly coordinated elements.Finally,applications for organic solar cells,organic lightemitting materials,and chemical sensors have been achieved.Herein,representative synthetic methods and unique properties for creating smart materials with germanium and tin will be explained.展开更多
Efficient photo-patterning of polymer semiconductors with cross-linkers has emerged as a promising route to fabricate organic integrated circuits via all-solution processing techniques.Herein,we report a new four-arme...Efficient photo-patterning of polymer semiconductors with cross-linkers has emerged as a promising route to fabricate organic integrated circuits via all-solution processing techniques.Herein,we report a new four-armed diazo-based oligomer photo-crosslinker 2DPP4N_(2)for the patterning of semiconducting polymers by UV light-induced crossing-linking reaction.After blending 2DPP4N_(2)with polymer semiconductors such as PDPP4T(p-type),PDPP3T(ambipolar)and N2200(n-type),we prepared various patterns with a resolution of 6μm by irradiating through a photo-mask with 254 nm UV light for 160 s.Notably,the interchain packing and surface morphology remained nearly unchanged after photo-patterning,as characterized by atomic force microscopy(AFM)and grazing incidence wide-angle X-ray scattering(GIWAXS).Consequently,the charge transport property of the patterned thin film was largely maintained in comparison to that of its pristine thin film.These results reveal that 2DPP4N_(2)is a viable and promising candidate for application in all-solution-processable flexible integrated electronic devices.展开更多
基金supported by the National Natural Science Foundation of China(Nos.82402822,82360427,82372425,82072443,and 32200559)the Priority Union Foundation of Yunnan Provincial Science and Technology Department and Kunming Medical University(No.202301AY070001-164)+1 种基金the Natural Science Foundation of Sichuan Province(No.23NSFSC5880)the Central Government of Sichuan Province Guiding the Special Project of Local Science and Technology Development(No.2024ZYD0155).
文摘Three-dimensional(3 D)printing has revolutionized the design and production of customized scaffolds,but the minimally invasive implantation of 3 D-printed structures into the human body remains challenging.This has prompted the exploration of innovative materials and technical solutions.Shape-memory polymers,as advanced intelligent materials,exhibit considerable potential in minimally invasive surgical applications.Herein,we developed a novel thermosetting shape-memory polymer,poly(L-lactic acid)-trimethylene carbonate-glycolic acid(PLLA-TMC-GA),for the fabrication of bioengineered scaffolds with body temperature-activated shape-memory functionality.We comprehensively evaluated the mechanical properties,thermal stability,shape-memory capabilities,biocompatibility,biodegradability,and 3 D printing performance of PLLA-TMC-GA terpolymers with various compositions.The results indicate that PLLA-TMC-GA exhibits exceptional shape-memory performance,adjustable material properties,favorable biocompatibility,and the potential for controlled biodegradation and reabsorption.The use of PLLA-TMC-GA as a biodegradable shape-memory polymer allows the reduction of implant volume,simplifies implantation,and enables on-demand activation at body temperature.These characteristics present new opportunities for the advancement of minimally invasive surgical techniques.
基金This work was supported by the National Natural Science Foundation of China （Nos. 21374026 and 51573032）, the National Science Fund for Distinguished Young Scholars （No. 51725302）, Science Fund for Creative Research Groups of the National Natural Science Foundation of China （No. 11621505）, CAS Key Research Program for Frontier Sciences （No. QYZDJ-SSW-SLH022）, Key Project of Chinese Academy of Sciences in Cooperation with Foreign Enterprises （No. GJHZ1541）, and CAS Interdisciplinary Innovation Team.
文摘Interest in temperature-responsive polymers has steadily grown over the past several decades, and numerous studies have been dedicated to developing temperature sensitive polymers that can be constructed into new smart materials for biomedical applications. Phase behavior of a temperature-responsive polymer plays a pivotal role in determining its biological performance in certain conditions. In addition to the additives （such as salts and proteins） in aqueous solutions, molecular weight, molecular weight distribution, and structural or compositional factors can also significantly affect the transition temperatures of the polymers. This review comprehensively describes well-established and newly developed synthetic strategies for preparing temperature-responsive polymers. The structural and compositional parameters that affect the transition temperatures and self-assembly behavior are discussed. Finally, the biomedical applications of the temperature-responsive polymers in drug delivery, immunotherapy, tissue engineering, and diagnosis are summarized.
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.
文摘The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polymer(Emim)2[Cu(BBTZ)_(2)(β-Mo_(8)O_(26))](Mo_(8)-CP).Mo_(8)-CP was characterized by elemental analysis,thermogravime-try,IR,powder X-ray diffraction,and single-crystal X-ray diffraction.In Mo_(8)-CP,structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain.These chains are further bridged by(β-Mo_(8)O_(26))^(4-)to construct a 3D coordination polymer.Notably,(Emim)^(+)acts as a structure-directing agent,occupying the channels of the 3D coordination polymer.Based on this unique structure,the ion exchange properties of Mo_(8)-CP toward rare-earth ions were investigated.It has been found that the luminescent color of the material can be successfully regulat-ed by introducing Eu^(3+)or Tb^(3+)through ion exchange.CCDC:2475110,Mo_(8)-CP.
文摘The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs).However,binary blends often suffer from suboptimal phase separation,which limits the efficiency of OSCs.Herein,two bridging polymer acceptors(PAs)—benzodithiophene-(2-ethylhexyl)oxy(BDT-C2C4)and benzodithiophene-octyloxy(BDT-C_(8))—are designed and synthesized by combining a benzodithiophene(BDT)unit as the donor moiety[poly({4,8-bis[5-(2-ethylhexyl)-4-fluorothiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}){5,8-bis[4-(2-butyloctyl)thiophen-2-yl]dithieno[3',2':3,4]},D18],and a 2,2′-((2Z,2′Z)-{[12,13-Bis(2-butyloctyl)-12,13-dihydro-3,9-dinonylthieno[2,3]thieno[3,2-b]pyrrolo[4,5-g]thieno[2,3-b]indole-2,10-diyl]bis(methanylylidene)}bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(Y6)derivative as the acceptor moiety.BDT-C2C4 and BDT-C_(8) are functionalized with(2-ethylhexyl)oxy and octyloxy side chains on the BDT unit,respectively.Both PAs show complementary absorption and cascaded energy levels with the donor D18 and the acceptor 2,2′-((2Z,2′Z)-{[12,13-bis(3-ethylheptyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″∶4′,5′]thieno[2′,3′∶4,5]pyrrolo[3,2-g]thieno[2′,3′∶4,5]thieno[3,2-b]indole-2,10-diyl]bis(meth⁃aneylylidene)}bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(N3),but BDT-C_(8) exhibits better compatibility with D18 and N3 compared to BDT-C2C4.When incorporated as a third component into the D18∶N3 blend,both PAs improve the active layer morphology.In particular,the D18∶N3∶BDT-C_(8) blend shows significantly optimized morphology,featuring reduced phase separation and a fibrous network structure.As a result,the device based on D18∶N3∶BDT-C_(8) achieves a power conversion efficiency of 18.18%,significantly higher than that of the device based on D18∶N3(ca.17.37%).This work presents a compatibilizer strategy for optimizing blend morphology towards high-performance ternary OSCs.
基金financially supported by Ministry of Science and Higher Education of the Russian Federation.
文摘A new principle for producing fire-resistant polymer materials with increased deformation properties using a flame retardant not as a heterogeneous additive,but as a thermoplastic flame retardant in a hybrid polymer mixture with a polyhydrocarbon is considered.Hybrid polymer blends of low-molecular ammonium polyphosphate(APP)with an ethylene-vinyl acetate copolymer(EVA)with an APP content of 80 wt%with enhanced deformation properties were obtained by extrusion mixing at various temperatures in the range from 200°C to 250°C.A chemical scheme for the transformations of the components during the formation of the composite is proposed.X-ray diffraction analysis showed the formation of new crystalline structures of APP.The phase structure of the systems corresponding to the model of a dispersed-filled composite in which EVA plays the role of a matrix,determining the deformation of the mixture,and the filler is ammonium polyphosphate,was studied by scanning electron microscopy(SEM).The method of FTIR microscopy showed chemical interactions between EVA and APP with the formation of amide groups.The conditions for obtaining compositions characterized by heat resistance of 210°C,oxygen index of 55 and ultimate elongation at drawing of 213%were established.
基金financial support from the National Natural Science Foundation of China(Nos.52174183 and 52374203).
文摘Temperature is one of the main causes of spontaneous coal combustion.To improve the flame retardant performance,CaCl2,ammonium polyphosphate(APP),and calcium phosphate(CaHP)were compounded to control the temperature response of different stages of coal spontaneous combustion through physical and chemical synergy.Simultaneous thermal analysis,thermogravimetric-Fourier infrared spectroscopy(TG-FTIR),in-situ FTIR and electron paramagnetic resonance(EPR)were used to study the multitemperature stage synergistic inhibition of coal spontaneous combustion.The results show that the proposed method is effective.By obtaining the characteristics of the spontaneous combustion reaction stage of coal in advance,the method of configuring an appropriate composite inhibitor can effectively realize the intelligent control of the temperature response of coal spontaneous combustion.The ignition point of long-flame coal increased by 37.15℃.The inhibition rate of the gas phase products was more than 20%,and the inhibition rate of the functional groups was more than 30%.It has a good quenching effect on free radicals and can effectively inhibit the oxidation activity of active free radicals such as H,HO,and O.The results provide experimental and theoretical support for the study of temperature-responsive composite flame retardants for coal with different metamorphic degrees.
基金supported by the National Natural Science Foundation of China(Grant Nos.52478351,52208329)the Shenzhen Science and Technology Innovation Commission(Grant No.JCYJ20240813143306009)support is gratefully acknowledged.
文摘Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)owing to its excellent hydrophilicity and swelling capacity.However,calcium bentonite(CaB),which is much more abundant worldwide,is rarely used for containment applications owing to its poor hydrophilicity.This study proposed a polymerization method that transforms sodium-activated calcium bentonite(NCB)into PMB to achieve low hydraulic conductivity(k)to aggressive liquids.The mechanism for its low k was revealed through characterization techniques and analyses(e.g.X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM),and Brunauer-Emmett-Teller(BET)).The results showed that the PMB had a small amount of polymer elution(indicating better interface stability)and thus exhibited excellent barrier properties under chemically aggressive conditions,with the k of<10^(-11) m/s for 0.6 mol/L NaCl solution,which is four orders of magnitude lower than that of the NCB(k=3×10^(-7) m/s).Various microscopic analyses indicated that the selected monomers were successfully polymerized,and intercalated into and grafted onto the montmorillonite layers of bentonite.The formed polymer network increased the swelling capability of PMB granules,decreased the pore size,and created narrow and tortuous flow pathways leading to a very low k to aggressive liquids.
基金a seed grant from IIT Delhi(SGNF148)supported by the JST-ERATO Yamauchi Materials SpaceTectonics Project(JPMJER2003)+2 种基金the ARC Australian Laureate Fellowship(FL230100095)the UQ-Yonsei International Joint Research Projectthe support from JSPS Postdoctoral Fellowships for Research in Japan。
文摘Commercial-level sodium metal batteries require electrolytes with high ionic mobility and excellent thermo-mechanical and electrochemical stability.Conventional flammable liquid electrolytes,prone to dendrite growth and unstable interfacial reactions,rarely perform beyond coin-cell demonstrations.To address these shortcomings,a multifunctional composite quasi-solid polymer electrolyte(QSPE)that incorporates boron nitride(BN)as an engineered filler in a highly conductive polymer blend system has been developed.The optimized formation(15BN QSPE)delivers a room-temperature ionic conductivity of 2.15 m S cm^(-1)and a sodium-ion transference number of 0.80.Molecular dynamics simulations elucidate the coordination environment and show improved transport in the presence of BN.BN is chemically active and bifunctional:boron acts as an electron acceptor,interacting with solvents and macromolecules,while nitrogen coordinates with sodium ions,tailoring the solvation environment and transport pathways to promote efficient ion migration.The 15BN QSPE is self-extinguishing,resists oxidative thermal degradation,and enables stable cycling in symmetric sodium cells for>1400 h at0.5 m A cm^(-2).A Prussian blue full cell achieves>1500 stable cycles at 1C with -99% Coulombic efficiency in coin-cell configuration.A two-layer pouch cell with dual 15BN QSPE layers delivers 600 stable cycles at 0.125C and withstands rigorous mechanical abuse.These results position 15BN QSPE as a scalable,highperformance electrolyte offering enhanced safety and efficiency for next-generation sodium metal batteries.
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(52103299)。
文摘With the global push for energy conservation and the rapid development of low-power,flexible and wearable optical displays,the demand for electrochromic technology has surged.Gel polymer electrolytes(GPEs),a crucial component of electrochromic devices(ECDs),show great promise in applications.This is attributed to their efficient ion-transport capabilities,excellent mechanical properties and strong adhesion.All of these characteristics are conducive to enhancing the safety of the devices,streamlining the packaging process,significantly improving the electrochromic performance of ECDs and boosting their commercial application potential.This review provides a comprehensive overview of GPEs for ECDs,focusing on their basic designs,functional modifications and practical applications.Firstly,this review outlines the fundamental design of GPEs for ECDs,encompassing key performance index,classification,gelation mechanism and preparation methods.Building on this foundation,it provides an in-depth discussion of functionalized GPEs developed to enhance device performance or expand functionality,including electrochromic,temperature-responsive,photo-responsive and stretchable self-healing GPE.Furthermore,the integration of GPEs into various ECD applications,including smart windows,displays,energy storage devices and wearable electronic,are summarized to highlight the advantages that the design of GPEs brings to the practical application of ECDs.Finally,based on the summary of GPEs employed for ECDs,the challenges and development expectations in this direction were indicated.
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supported by the National Natural Science Foundation of China(22072048)the Guangdong Provincial Department of Science and Technology(2021A1515010128 and 2022A0505050013).
文摘Succinonitrile(SN)-based polymer plastic crystal electrolytes(PPCEs)are regarded as promising candidates for lithium metal batteries but suffer from serious side reactions with Li metal.Herein,we propose a multi-dimensional optimization strategy to alleviate the side reactions between SN and Li metal,and develop a highly stable poly-vinylethylene carbonate-based PPCE(PPCE-VEC).Moreover,we identify the intrinsic factors of multi-dimensional polymer structures on the electrolyte stability by three typical classes of polyesters.The PPCE-VEC constructed by in situ polymerization exhibits much better stability than poly-vinylene carbonate-based PPCE(PPCE-VCA)and poly-trifluoroethyl acrylate-based PPCE(PPCE-TFA),which is verified by its fewer SN-decomposition species in X-ray photoelectron spectroscopy(XPS)and outstanding full cell performance.The PPCE-VEC-enabled LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)full cell achieve 73.7%capacity retention after 1400 cycles,which outperforms PPCE-VCA-and PPCE-TFA-enabled full cells(61.9%and 46.9%).Spectral analysis and theoretical calculation reveal that the high solvation ability of the carbonyl site,flexible polymer chain,and homogeneous electrolyte phase of PPCE-VEC are favorable to maximizing competition coordination with Li^(+)to weaken the Li^(+)–SN binding and shape an anion-rich solvation structure.This optimized polymer-involved Li^(+)solvation enhances SN stability and facilitates the formation of B/F enriched solid-electrolyte interphase(SEI),thus significantly improving PPCE stability.
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financial support by Guangdong Basic and Applied Basic Research Foundation(2025A1515012415)National Natural Science Foundation of China(52242305)the Stable Support Project of Shenzhen(Project No.20231122125728001).
文摘Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are gaining prominence due to their unique combination of mechanical flexibility,environmental compatibility,and solution-processable fabrication.A notable candidate in this field is poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene)(PBTTT),a liquid-crystalline conjugated polymer,with high charge carrier mobility and adaptability to melt-processing techniques.Recent advancements have propelled PBTTT’s figure of merit from below 0.1 to a remarkable 1.28 at 368 K,showcasing its potential for practical applications.This review systematically examines strategies to enhance PBTTT’s TE performance through doping(solution,vapor,and anion exchange doping),composite engineering,and aggregation state controlling.Recent key breakthroughs include ion exchange doping for stable charge modulation,multi-heterojunction architectures reducing thermal conductivity,and proton-coupled electron transfer doping for precise Fermi-level tuning.Despite great progress,challenges still persist in enhancing TE conversion efficiency,balancing or decoupling electrical conductivity,Seebeck coefficient and thermal conductivity,and leveraging melt-processing scalability of PBTTT.By bridging fundamental insights with applied research,this work provides a roadmap for advancing PBTTT-based TE materials toward efficient energy harvesting and wearable electronics.
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 Japan Society for the Promotion of Science(JSPS),a Grant-in-Aid for Scientific Research(B)(JP23K23398)(for M.G.)and(JP24K01570)(for K.T.).
文摘In this review,the synthesis,functions,and applications of the polymers containing germanium and tin,which are heavy group 14 elements,in their polymer frameworks are summarized.Germanium and tin can form similar skeletal structures with their homologues carbon and silicon,whereas the polymers containing germanium and tin show unique properties derived from their large atomic radii and weak binding energies.For example,polygermane and polystannane exhibited light absorption in the UV–visible region and conductivity because of theσ-conjugation through the polymer main-chain constructed byσ-bonds between heavy elements.Theσ-conjugation was affected by the conformational change of the polymer main-chain,and thermochromic properties can be induced.Furthermore,the weak bonds were able to be cleaved homolytically upon photoirradiation,and radicals were subsequently generated.By incorporating hypervalent heavy elements into theπ-conjugated system,it was possible to modulate the electronic structures of theπ-conjugated system throughσ*–π*conjugation with highly coordinated elements.Finally,applications for organic solar cells,organic lightemitting materials,and chemical sensors have been achieved.Herein,representative synthetic methods and unique properties for creating smart materials with germanium and tin will be explained.
基金supported by the National Natural Science Foundation of China(No.22205242)。
文摘Efficient photo-patterning of polymer semiconductors with cross-linkers has emerged as a promising route to fabricate organic integrated circuits via all-solution processing techniques.Herein,we report a new four-armed diazo-based oligomer photo-crosslinker 2DPP4N_(2)for the patterning of semiconducting polymers by UV light-induced crossing-linking reaction.After blending 2DPP4N_(2)with polymer semiconductors such as PDPP4T(p-type),PDPP3T(ambipolar)and N2200(n-type),we prepared various patterns with a resolution of 6μm by irradiating through a photo-mask with 254 nm UV light for 160 s.Notably,the interchain packing and surface morphology remained nearly unchanged after photo-patterning,as characterized by atomic force microscopy(AFM)and grazing incidence wide-angle X-ray scattering(GIWAXS).Consequently,the charge transport property of the patterned thin film was largely maintained in comparison to that of its pristine thin film.These results reveal that 2DPP4N_(2)is a viable and promising candidate for application in all-solution-processable flexible integrated electronic devices.
