Acrylonitrile-sodium styrene sulfonate copolymer/layered double hydroxides nanocomposites were prepared by in situ aqueous precipitation copolymerization of acrylonitrile （AN） and sodium styrene sulfonate （SSS） in...Acrylonitrile-sodium styrene sulfonate copolymer/layered double hydroxides nanocomposites were prepared by in situ aqueous precipitation copolymerization of acrylonitrile （AN） and sodium styrene sulfonate （SSS） in the presence of 4-vinylbenzene sulfonate intercalated layered double hydroxides （MgA1-VBS LDHs） and transferred to acrylonitrile-styrene sulfonic acid （AN-SSA） copolymer/LDHs nanocomposites as a proton-conducting polymer electrolyte. MgA1-VBS LDHs were prepared by a coprecipitation method, and the structure and composition of MgAl-VBS LDHs were determined by X-ray diffraction （XRD）, infrared spectroscopy, and elemental analysis. X-ray diffraction result of AN-SSS copolymer/LDHs nanocomposites indicated that the LDHs layers were well dispersed in the AN-SSS copolymer matrix. All the AN-SSS copolymer/LDHs nanocomposites showed significant enhancement of the decomposition temperatures compared with the pristine AN-SSS copolymer, as identified by the thermogravimetric analysis. The methanol crossover was decreased and the proton conductivity was highly enhanced for the AN-SSA copolymer/LDHs nanocomposite electrolyte systems. In the case of the nanocomposite electrolyte containing 2% （by mass） LDHs, the proton conductivity of 2.60×10^- 3 S·m^-1 was achieved for the polymer electrolyte.展开更多
Electrodeposited organic light-emitting diode(OLED)technology requires a spin-coating-free hole-injection layer that simultaneously provides smooth surface morphology,stable energy levels,and compatibility with high-r...Electrodeposited organic light-emitting diode(OLED)technology requires a spin-coating-free hole-injection layer that simultaneously provides smooth surface morphology,stable energy levels,and compatibility with high-resolution pixel architectures.In this study,electropolymerization of 3,4-ethylenedioxythiophene(EDOT)in poly(styrene sulfonate)(PSS-)surfactant-solubilized colloidal media is shown to afford poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)films with robust surface uniformity and stable energy levels suitable for application as hole-injection layers in OLEDs.Systematic investigation reveals that the hole-injection properties of these films are governed primarily by the colloidal chemistry of EDOT/PSS-surfactant-solubilized systems,rather than by conventional electrochemical parameters.This colloidal regulation modulates the film work function over a practically useful range.Incorporation of optimized films into OLEDs leads to enhanced hole injection and improved device performance,with external quantum efficiency increasing from 2.2%to 7.4%and minimal roll-off.Overall,this work demonstrates a feasible example of realizing spin-coating-free hole-injection layers,offering a potential direction for the development of electrodeposited injection layers for OLEDs.展开更多
In recent decades,annual urban fire incidents,including those involving ancient wooden buildings burned,transportation,and solar panels,have increased,leading to significant loss of human life and property.Addressing ...In recent decades,annual urban fire incidents,including those involving ancient wooden buildings burned,transportation,and solar panels,have increased,leading to significant loss of human life and property.Addressing this issue without altering the surface morphology or interfering with optical behavior of flammable materials poses a substantial challenge.Herein,we present a transparent,low thickness,ceramifiable nanosystem coating composed of a highly adhesive base(poly(SSS1-co-HEMA1)),nanoscale layered double hydroxide sheets as ceramic precursors,and supramolecular melamine di-borate as an accelerator.We demonstrate that this hybrid coating can transform into a porous,fire-resistant protective layer with a highly thermostable vitreous phase upon exposure to flame/heat source.A nanosystem coating of just~100μm thickness can significantly increase the limiting oxygen index of wood(Pine)to 37.3%,dramatically reduce total heat release by 78.6%,and maintain low smoke toxicity(CIT_G=0.016).Detailed molecular force analysis,combined with a comprehensive examination of the underlying flame-retardant mechanisms,underscores the effectiveness of this coating.This work offers a strategy for creating efficient,environmentally friendly coatings with fire safety applications across various industries.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
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
NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsi...NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.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
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
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
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
Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,t...Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,to create a functionally graded cathode during precursor synthesis.Based on thermodynamic principles of bulk insolubility and phase separation kinetics,we achieved the selective precipitation of Co onto the surface of a Ni-rich hydroxide precursor.Upon high-temperature lithiation,this engineered precursor spontaneously forms a unique,bifunctional Co-rich spinel-like layer on the final LiNi_(0.88)Co_(0.06)Mn_(0.06)O_(2)(NCM)cathode.This architecture suppresses detrimental Li/Ni cation mixing and protects the active material.Consequently,the IP-driven NCM cathode demonstrates vastly superior rate capability,delivering 140.8 m A h g^(-1)at 5C,compared to 112.9 mA h g^(-1)for its conventionally prepared counterpart.This enhancement is attributed to significantly lower charge-transfer resistance and faster kinetics.Remarkably,in a full-cell configuration,the IP-driven NCM cathode maintains 81.5%capacity after 1000 cycles at an aggressive 5C rate.This work presents a thermodynamically driven,scalable strategy for designing advanced cathodes with exceptional high-power performance and stability.展开更多
Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabl...Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabling topological functionalities in the post-Moore era.Here we review recent progress on two-dimensional(2D)magnetism in LTMCs,emphasizing material taxonomy,intrinsic magnetic properties,and external-field controls.This review first presents a classification of LTMCs by crystal structure and chemistry—binary halides,chalcogenides,and ternary families(e.g.,MPX_(3),M_(m)X_(n)Te_(k),MnBi_(2)Te_(4))—followed by a summary of their coupling mechanisms,ordering temperatures,and dimensional effects.It then analyzes the modulation of exchange interactions,magnetic anisotropy,and topological states by electric-field gating,strain engineering,and ion intercalation,with representative experimental demonstrations.Notable advances include room-temperature ferromagnetic metals and semiconductors,observation of the quantum anomalous Hall effect(QAHE)in MnBi2Te4,and synergistic control of magnetic-topological states under multiple external stimuli.Persistent challenges involve the limited availability of intrinsic 2D magnetic semiconductors with high Curie temperatures(Tc),incomplete understanding of the microscopic couplings at interfaces and under quantum confinement,and device-level stability.We conclude by outlining opportunities that lie in the integration of multiscale characterization,first-principles theory,and cross-scale fabrication to precisely co-engineer magnetism,topology,and electronic structure,thereby advancing LTMCs toward spintronic and topological-quantum applications.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
基金Supported by Program for New Century Excellent Talents in University(NCET-07-0738)
文摘Acrylonitrile-sodium styrene sulfonate copolymer/layered double hydroxides nanocomposites were prepared by in situ aqueous precipitation copolymerization of acrylonitrile （AN） and sodium styrene sulfonate （SSS） in the presence of 4-vinylbenzene sulfonate intercalated layered double hydroxides （MgA1-VBS LDHs） and transferred to acrylonitrile-styrene sulfonic acid （AN-SSA） copolymer/LDHs nanocomposites as a proton-conducting polymer electrolyte. MgA1-VBS LDHs were prepared by a coprecipitation method, and the structure and composition of MgAl-VBS LDHs were determined by X-ray diffraction （XRD）, infrared spectroscopy, and elemental analysis. X-ray diffraction result of AN-SSS copolymer/LDHs nanocomposites indicated that the LDHs layers were well dispersed in the AN-SSS copolymer matrix. All the AN-SSS copolymer/LDHs nanocomposites showed significant enhancement of the decomposition temperatures compared with the pristine AN-SSS copolymer, as identified by the thermogravimetric analysis. The methanol crossover was decreased and the proton conductivity was highly enhanced for the AN-SSA copolymer/LDHs nanocomposite electrolyte systems. In the case of the nanocomposite electrolyte containing 2% （by mass） LDHs, the proton conductivity of 2.60×10^- 3 S·m^-1 was achieved for the polymer electrolyte.
基金supported by the National Key R&D Program of China(No.2020YFA0714604)the Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(No.2023B1212060003)+1 种基金the SSL Sci-tech Commissioner Program(No.20234383-01KCJ-G)the National Natural Science Foundation of China(No.92463310)。
文摘Electrodeposited organic light-emitting diode(OLED)technology requires a spin-coating-free hole-injection layer that simultaneously provides smooth surface morphology,stable energy levels,and compatibility with high-resolution pixel architectures.In this study,electropolymerization of 3,4-ethylenedioxythiophene(EDOT)in poly(styrene sulfonate)(PSS-)surfactant-solubilized colloidal media is shown to afford poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)films with robust surface uniformity and stable energy levels suitable for application as hole-injection layers in OLEDs.Systematic investigation reveals that the hole-injection properties of these films are governed primarily by the colloidal chemistry of EDOT/PSS-surfactant-solubilized systems,rather than by conventional electrochemical parameters.This colloidal regulation modulates the film work function over a practically useful range.Incorporation of optimized films into OLEDs leads to enhanced hole injection and improved device performance,with external quantum efficiency increasing from 2.2%to 7.4%and minimal roll-off.Overall,this work demonstrates a feasible example of realizing spin-coating-free hole-injection layers,offering a potential direction for the development of electrodeposited injection layers for OLEDs.
基金the financial support from the National Natural Science Foundation of China(524B2168,U22A20149,52173081,and 52273275)。
文摘In recent decades,annual urban fire incidents,including those involving ancient wooden buildings burned,transportation,and solar panels,have increased,leading to significant loss of human life and property.Addressing this issue without altering the surface morphology or interfering with optical behavior of flammable materials poses a substantial challenge.Herein,we present a transparent,low thickness,ceramifiable nanosystem coating composed of a highly adhesive base(poly(SSS1-co-HEMA1)),nanoscale layered double hydroxide sheets as ceramic precursors,and supramolecular melamine di-borate as an accelerator.We demonstrate that this hybrid coating can transform into a porous,fire-resistant protective layer with a highly thermostable vitreous phase upon exposure to flame/heat source.A nanosystem coating of just~100μm thickness can significantly increase the limiting oxygen index of wood(Pine)to 37.3%,dramatically reduce total heat release by 78.6%,and maintain low smoke toxicity(CIT_G=0.016).Detailed molecular force analysis,combined with a comprehensive examination of the underlying flame-retardant mechanisms,underscores the effectiveness of this coating.This work offers a strategy for creating efficient,environmentally friendly coatings with fire safety applications across various industries.
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.
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.
基金supported by the Natural Science Foundation of China Grant No.52272289 and 5240223,and JSPS(Japan Society for the Promotion of Science)of Grant No.22K19088,23H00313,24H02202,and 24H02205。
文摘NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.
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.
基金supported by grants from the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(MSIT)(RS-2024-00407116)+1 种基金by the Ministry of Education(NRF-2018R1A6A1A03024231)support from the NRF grant funded by the MSIT(RS-2024-00406724)。
文摘Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,to create a functionally graded cathode during precursor synthesis.Based on thermodynamic principles of bulk insolubility and phase separation kinetics,we achieved the selective precipitation of Co onto the surface of a Ni-rich hydroxide precursor.Upon high-temperature lithiation,this engineered precursor spontaneously forms a unique,bifunctional Co-rich spinel-like layer on the final LiNi_(0.88)Co_(0.06)Mn_(0.06)O_(2)(NCM)cathode.This architecture suppresses detrimental Li/Ni cation mixing and protects the active material.Consequently,the IP-driven NCM cathode demonstrates vastly superior rate capability,delivering 140.8 m A h g^(-1)at 5C,compared to 112.9 mA h g^(-1)for its conventionally prepared counterpart.This enhancement is attributed to significantly lower charge-transfer resistance and faster kinetics.Remarkably,in a full-cell configuration,the IP-driven NCM cathode maintains 81.5%capacity after 1000 cycles at an aggressive 5C rate.This work presents a thermodynamically driven,scalable strategy for designing advanced cathodes with exceptional high-power performance and stability.
基金supported by the National KeyR&D Program of China(Grant No.2024YFB3817400)the National Natural Science Foundation of China(Grants No.12274276 and No.U24A6002)+1 种基金the Natural Science Foundation of Shanxi Province(China)(Grant No.202403021223008)Supported by Scientific and Technology Innovation Programs of Higher Education Institutions in Shanxi(Grant No.2024Q017 and No.2025L043).
文摘Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabling topological functionalities in the post-Moore era.Here we review recent progress on two-dimensional(2D)magnetism in LTMCs,emphasizing material taxonomy,intrinsic magnetic properties,and external-field controls.This review first presents a classification of LTMCs by crystal structure and chemistry—binary halides,chalcogenides,and ternary families(e.g.,MPX_(3),M_(m)X_(n)Te_(k),MnBi_(2)Te_(4))—followed by a summary of their coupling mechanisms,ordering temperatures,and dimensional effects.It then analyzes the modulation of exchange interactions,magnetic anisotropy,and topological states by electric-field gating,strain engineering,and ion intercalation,with representative experimental demonstrations.Notable advances include room-temperature ferromagnetic metals and semiconductors,observation of the quantum anomalous Hall effect(QAHE)in MnBi2Te4,and synergistic control of magnetic-topological states under multiple external stimuli.Persistent challenges involve the limited availability of intrinsic 2D magnetic semiconductors with high Curie temperatures(Tc),incomplete understanding of the microscopic couplings at interfaces and under quantum confinement,and device-level stability.We conclude by outlining opportunities that lie in the integration of multiscale characterization,first-principles theory,and cross-scale fabrication to precisely co-engineer magnetism,topology,and electronic structure,thereby advancing LTMCs toward spintronic and topological-quantum applications.
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.
