In the present work,by virtue of the synergistic and independent effects of Janus structure,an asymmetric nickel-chain/multiwall carbon nanotube/polyimide(Ni/MWCNTs/PI)composite foam with absorption-dominated electrom...In the present work,by virtue of the synergistic and independent effects of Janus structure,an asymmetric nickel-chain/multiwall carbon nanotube/polyimide(Ni/MWCNTs/PI)composite foam with absorption-dominated electromagnetic interference(EMI)shielding and thermal insulation performances was successfully fabricated through an ordered casting and directional freeze-drying strategy.Water-soluble polyamic acid(PAA)was chosen to match the oriented freeze-drying method to acquire oriented pores,and the thermal imidization process from PAA to PI exactly eliminated the interface of the multilayered structure.By controlling the electro-magnetic gradient and propagation path of the incident microwaves in the MWCNT/PI and Ni/PI layers,the PI composite foam exhibited an efficient EMI SE of 55.8 dB in the X-band with extremely low reflection characteristics(R=0.22).The asymmetric conductive net-work also greatly preserved the thermal insulation properties of PI.The thermal conductivity(TC)of the Ni/MWCNT/PI composite foam was as low as 0.032 W/(m K).In addition,owing to the elimination of MWCNT/PI and Ni/PI interfaces during the thermal imidization process,the composite foam showed satisfactory compressive strength.The fabricated PI composite foam could provide reliable electromagnetic protection in complex applications and withstand high temperatures,which has great potential in cuttingedge applications such as advanced aircraft.展开更多
In this study,a novel linear polyimide chain(PTCDA-DCH)was used as an electrochemiluminescence(ECL)emitter,employing a chiral metal-organic framework(MOF)(Zn-Dcam-dabco)as the chiral selector and ferrocene(Fc)as a que...In this study,a novel linear polyimide chain(PTCDA-DCH)was used as an electrochemiluminescence(ECL)emitter,employing a chiral metal-organic framework(MOF)(Zn-Dcam-dabco)as the chiral selector and ferrocene(Fc)as a quencher to construct a chiral sensor for detecting histidine(His)enantiomers.Competitive interactions between Fc and His induce partial Fc desorption from the sensor surface,leading to ECL signal recovery.Differential Fc release due to the distinct binding affinities of Zn-Dcam-dabco for His enantiomers enabled precise chiral discrimination.Notably,the sensor achieved the quantitative detection of His enantiomers with an limits of detection(LOD)of 8μmol/L.Furthermore,the sensor demonstrated excellent recovery rates of 98.0%–104%for l-histidine(L-His)and 92.0%–95.9%for D-His in spiked milk samples,validating its reliability for real-sample analysis.This study provides a promising platform for ECL-based chiral recognition,bioanalysis,and the rapid assessment of amino acids in food products.展开更多
Conjugated microporous polymers(CMPs)have attracted considerable attention as potential organic anode materials for sodium-ion batteries(SIBs)due to their flexible chemical structure,high porosity,environmental friend...Conjugated microporous polymers(CMPs)have attracted considerable attention as potential organic anode materials for sodium-ion batteries(SIBs)due to their flexible chemical structure,high porosity,environmental friendliness,and cost effectiveness.However,the inherent shortcomings of organic electrodes,such as low conductivity,high solubility in electrolyte,narrow material utilization,etc.,limit their further development.In this work,we successfully prepared a novel porous polyimide PPD containing multicarbonyl active centers via the polycondensation of pyromellitic dianhydride(PMDA)and2,6-diaminoanthraquinone(DAAQ).The stable conjugated structure and multiple redox centers give the polymer high reversible specific capacity(244.6 m Ah/g after 100 cycles at 100 m A/g),ultra-long cycle stability(100.7 m Ah/g after 2000 cycles at 1.0 A/g),and predominant rate capability.Meanwhile,the sodium storage mechanism of the electrode materials during the charging and discharging process is investigated by ex-situ XPS/FTIR analysis.Due to the exceptional electrochemical properties and simple synthesis method,this work may shed light on the preparation of polyimide-based anodes for high specific capacity and rate capability secondary batteries.展开更多
Hydrophobic nanofiber composite membranes comprising polyimide and metal-organic frameworks are developed for desalination via direct contact membrane distillation(DCMD).Our study demonstrates the synthesis of hydroph...Hydrophobic nanofiber composite membranes comprising polyimide and metal-organic frameworks are developed for desalination via direct contact membrane distillation(DCMD).Our study demonstrates the synthesis of hydrophobic polyimides with trifluoromethyl groups,along with superhydrophobic UiO-66(hMOF)prepared by phenylsilane modification on the metal-oxo nodes.These components are then combined to create nanofiber membranes with improved hydro ph obi city,ensuring long-term stability while preserving a high water flux.Integration of hMOF into the polymer matrix further increases membrane hydrophobic properties and provides additional pathways for vapor transport during MD.The resulting nanofiber composite membranes containing 20 wt%of hMOFs(PI-1-hMOF-20)were able to desalinate hypersaline feed solution of up to 17 wt%NaCl solution,conditions that are beyond the capability of reverse osmosis systems.These membranes demonstrated a water flux of 68.1 kg m^(-2)h^(-1) with a rejection rate of 99.98%for a simulated seawater solution of 3.5 wt%NaCl at 70℃,while maintaining consistent desalination performance for 250 h.展开更多
It is urgent to develop high-performance polyimide(PI)films that simultaneously exhibit high transparency,exceptional thermal stability,mechanical robustness,and low dielectric to fulfil the requirements of flexible d...It is urgent to develop high-performance polyimide(PI)films that simultaneously exhibit high transparency,exceptional thermal stability,mechanical robustness,and low dielectric to fulfil the requirements of flexible display technologies.Herein,a series of fluorinated polyimide films(FPIs)were fabricated by the condensation of 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione)(6FDA)and the fluorinated triphenylmethane diamine monomer(EDA,MEDA and DMEDA)with heat-crosslinkable tetrafluorostyrene side groups,which was incorporated by different numbers of methyl groups pendant in the ortho position of amino groups.Subsequently,the FPI films underwent heating to produce crosslinking FPIs(C-FPIs)through the self-crosslinking of double bonds in the tetrafluorostyrene.The transparency,solvent resistance,thermal stability,mechanical robustness and dielectric properties of FPI and C-FPI films can be tuned by the number of methyl groups and crosslinking,which were deeply investigated by virtue of molecular dynamics(MD)simulations and density functional theory(DFT).As a result,all the films exhibited exceptional optically colorless and transparent,with transmittance in the visible region of 450-700 nm exceeding 79.9%,and the cut-off wavelengths(λ_(off))were nearly 350 nm.The thermal decomposition temperatures at 5% weight loss(T_(d5%))for all samples exceeded 504℃.These films exhibited a wide range of tunable tensile strength(46.5-75.1 MPa).Significantly,they showed exceptional dielectric properties with the dielectric constant of 2.3-2.5 at full frequency(10^(7)-20 Hz).This study not only highlights the relationship between the polymer molecular structure and properties,but offer insights for balancing optical transparency,heat resistance and low dielectric constant in PI films.展开更多
Designing and manufacturing compatible multi-band stealth materials remains a great challenge. In this work, a silver-metalized polyimide photochromic composite foam is successfully fabricated by self-activating elect...Designing and manufacturing compatible multi-band stealth materials remains a great challenge. In this work, a silver-metalized polyimide photochromic composite foam is successfully fabricated by self-activating electroless silver-plating on the surface of the polyimide skeleton and followed by applying a photochromic coating on the upper surface. The effective loading of silver nanoparticles facilitates the rational construction of a conductive network in foam, improving the efficient dissipation of incident electromagnetic waves. In addition, the interconnected conductive network successfully endows it with an excellent Joule heating capability, which can be employed to effectively remove ice and/or mitigate the impact of water vapor on radar stealth performance in cold and wet weather. Besides, the low emissivity silver plating combined with superior thermal insulation of foam enables the material with excellent infrared stealth performance. Moreover, the modulation of self-adaptive photochromic coating brings a prominent visual stealth performance under different sunlight backgrounds. As a result, such excellent radar and infrared stealth performance combined with the adaptive color-switching capability provides the foam with great potential for preparing compatible multi-band materials.展开更多
Designing and fabricating a compatible low-reflectivity electromagnetic interference(EMI)shielding/high-temperature resistant infrared stealth material possesses a critical significance in the field of military.Hence,...Designing and fabricating a compatible low-reflectivity electromagnetic interference(EMI)shielding/high-temperature resistant infrared stealth material possesses a critical significance in the field of military.Hence,a hierarchical polyimide(PI)nonwoven fabric is fabricated by alkali treatment,in-situ growth of magnetic particles and"self-activated"electroless Ag plating process.Especially,the hierarchical impedance matching can be constructed by systematically assembling Fe_(3)O_(4)/Ag-loaded PI nonwoven fabric(PFA)and pure Ag-coated PI nonwoven fabric(PA),endowing it with an ultralowreflectivity EMI shielding performance.In addition,thermal insulation of fluffy three-dimensional(3D)space structure in PFA and low infrared emissivity of PA originated from Ag plating bring an excellent infrared stealth performance.More importantly,the strong bonding interaction between Fe_(3)O_(4),Ag,and PI fiber improves thermal stability in EMI shielding and high-temperature resistant infrared stealth performance.Such excellent comprehensive performance makes it promising for military tents to protect internal equipment from electromagnetic interference stemmed from adjacent equipment and/or enemy,and inhibit external infrared detection.展开更多
In high-frequency electrical energy systems,polyimide(PI)composite insulation materials need to possess a low dielectric constant,sufficient thermal conductivity,and robust interfacial adhesion to ensure reliable perf...In high-frequency electrical energy systems,polyimide(PI)composite insulation materials need to possess a low dielectric constant,sufficient thermal conductivity,and robust interfacial adhesion to ensure reliable performance under elevated temperatures and pressures.These aspects are crucial for preventing local overheating and electrical breakdown,thereby ensuring reliable equipment operation.Traditional PI insulation materials often exhibit high dielectric constants and pronounced dielectric losses,compromising their insulation efficiency.In this study,molecular dynamics simulations were employed to incorporate polyhedral oligomeric silsesquioxanes(POSS)into PI through physical blending and chemical bonding to enhance dielectric properties.Key parameters of the PI/POSS composite system,including dielectric constant,thermal conductivity,glass transition temperature,Young’s modulus,Poisson’s ratio,and interfacial adhesion energy,were systematically evaluated for both doping methods.The degradation behavior of the PI composites under high-temperature and electric field conditions was also simulated to elucidate degradation pathways and product distributions,providing insights for designing low-dielectric insulation materials.Doping with POSS significantly reduces the dielectric constant of PI,thereby improving insulation performance,thermal stability,mechanical strength,and interfacial adhesion.At an optimal POSS doping ratio,the thermal conductivity of PI is enhanced.Compared with the physical blending system,the chemical bonding system yields more substantial improvements across all evaluated properties.Under high-temperature and strong electric field conditions,POSS doping enhances interfacial adhesion and thermal stability,effectively suppressing the cleavage of key chemical bonds,reducingCOemissions,and increasing the formation of oxygen-containing intermediates and water molecules,which contributes to improved environmental sustainability.展开更多
The development of intelligent electronic power systems necessitates advanced flexible pressure sensors.Despite improved compressibility through surface micro-structures or bulk pores,conventional capacitive pressure ...The development of intelligent electronic power systems necessitates advanced flexible pressure sensors.Despite improved compressibility through surface micro-structures or bulk pores,conventional capacitive pressure sensors face limitations due to their low dielectric constant and poor temperature tolerance of most elastomers.Herein,we constructed oriented polyimide-based aerogels with mechanical robustness and notable changes in dielectric constant under compression.The enhancement is attributed to the doping of surface-modified dielectric nanoparticles and graphene oxide sheets,which interact with polymer molecular chains.The resulting aerogels,with their excellent temperature resistance,were used to assemble high-performance capacitive pressure sensors.The sensor exhibits a maximum sensitivity of 1.41 kPa^(−1)over a wide working range of 0-200 kPa.Meanwhile,the sensor can operate in environments up to 150℃during 2000 compression/release cycles.Furthermore,the aerogel-based sensor demonstrates proximity sensing capabilities,showing great potential for applications in non-contact sensing and extreme environment detection.展开更多
Aqueous zinc-ion hybrid capacitors(ZIHCs)are promising electrochemical energy storage systems with advantages of high-energy density,low cost,safety and environmental friendliness.However,application of carbon-based c...Aqueous zinc-ion hybrid capacitors(ZIHCs)are promising electrochemical energy storage systems with advantages of high-energy density,low cost,safety and environmental friendliness.However,application of carbon-based cathodes is limited by their low-energy density due to the lack of active sites.Herein,a chemisorption sites modulating strategy is proposed to construct nitrogen-doped polyimide carbon nanoflowers with abundant oxygen vacancies and carbonyl functionalization via high-temperature calcination and subsequent acid processing.The synergistic effect of oxygen vacancies,carbonyl groups,enhanced surface area and porous structure enables stable zinc-ion storage with high capacity.Remarkably,the carbon materials can circulate 20,000 cycles stably at a current density of 2 A·g^(-1).After 10,000 cycles at a high rate of 3 A·g^(-1),a capacity retention rate of 64%can still be achieved.The as-prepared ZIHCs provide an energy density of 65.61 Wh·kg^(-1)at the power density of 197.82 W·kg^(-1).Current research shows that polyimide-derived carbon material synthesized by acid activation provides a new idea for developing cathodes in aqueous ZIHCs.展开更多
The dual system capable of solar-driven interfacial steam production and all-weather hydropower generation is emerging as a potential way to alleviate freshwater shortage and energy crisis.However,the intrinsic mechan...The dual system capable of solar-driven interfacial steam production and all-weather hydropower generation is emerging as a potential way to alleviate freshwater shortage and energy crisis.However,the intrinsic mechanism of hydroelectricity generation powered by the interaction between seawater and material structure is vague,and it remains challenging to develop dual-functional evaporators with high photothermal conversion efficiency and ionic selectivity.Herein,an all-weather dual-function evaporator based on porous carbon fiber-like(PCF)is acquired through the pyrolysis of barium-based metal-organic framework(Ba-BTEC),which is originated from waste polyimide.The PCF-based evaporator/device exhibits a high steam generation rate of 2.93 kg m^(-2)h^(-1)in seawater under 1 kW m^(-2)irradiation,along with the notable opencircuit voltage of 0.32 V,owing to the good light absorption ability,optimal wettability,and suitable aperture size.Moreover,molecular dynamics simulation result reveals that Na+tends to migrate rapidly within the nanoporous channels of PCF,owing to a strong affinity between oxygen-containing functional group and water molecules.This work not only proposes an eco-friendly strategy for constructing low-cost fulltime freshwater-hydroelectric co-generation device,but also contributes to the understanding of evaporation-driven energy harvesting technology.展开更多
Demand for high-performance power devices continues to grow with the continuous development of power electronics and high-end field applications.Although packaging materials based on epoxy resins and silica gels have ...Demand for high-performance power devices continues to grow with the continuous development of power electronics and high-end field applications.Although packaging materials based on epoxy resins and silica gels have been widely developed,higher operating temperatures and operating voltages are still critical to the performance of power devices.Here,a composite film containing functionalized meso-porous hollow silica particles(MH-SiO_(2))and polyimide(PI)was prepared by a template method and layer-by-layer coating strategy to address the current bottlenecks in packaging material development.The electrical breakdown strength of the prepared PI/SiO_(2) composite film was 323.41 kV/mm,while the mass fraction of MH-SiO_(2) was only 5%.This indicates that the mesoporous structure can effectively inhibit electron collisions with nano-restricted domains.The simulation results also indicate that the size variation of inorganic fillers and the interaction of organic/inorganic heterogeneous interfaces are the main reasons affecting the performance of the composites.Meanwhile,the PI/SiO_(2) composite films achieved other properties required for practical applications,such as matched coefficient of thermal ex-pansion(CTE)(23.5 ppm/℃),excellent thermal stability(T_(5)%=559.0℃)and low dielectric constant(2.27@1 M Hz).These results highlight the great potential of inorganic phase-specific structural designs for the preparation of high-performance power device packaging materials.展开更多
Enhancing the mechanical properties is crucial for polyimide films,but the mechanical properties(Young's modulus,tensile strength,and elongation at break)mutually constrain each other,complicating simultaneous enh...Enhancing the mechanical properties is crucial for polyimide films,but the mechanical properties(Young's modulus,tensile strength,and elongation at break)mutually constrain each other,complicating simultaneous enhancement via traditional trial-and-error methods.In this work,we proposed a materials genome approach to design and screen phenylethynyl-terminated polyimides for films with enhanced mechani-cal properties.We first established machine learning models to predict Young's modulus,tensile strength,and elongation at break to explore the chemical space containing thousands of candidate structures.The accuracies of the machine learning models were verified by molecular dynamics simulations on screened polyimides and experimental testing on three representative polyimide films.The performance advantages of the best-selected polyimides were analyzed by comparing well-known polyimides based on molecular dynamics simulations,and the structural rationale was revealed by"gene"analysis and feature importance evaluation.This work provides a cost-effective strategy for designing polyimide films withenhancedmechanical properties.展开更多
Polyimide(PI)is widely used in high-tech fields such as microelectronics,aerospace,and national defense because of its excellent optical properties,high-and low-temperature resistance,and good dimensional stability.To...Polyimide(PI)is widely used in high-tech fields such as microelectronics,aerospace,and national defense because of its excellent optical properties,high-and low-temperature resistance,and good dimensional stability.To achieve the desired properties of PI,the monomers 2,6-diaminopyrimidin-4-ol(DAPD)and 6-(2,3,5,6-tetrafluoro-4-vinylphenoxy)pyrimidin-2,4-diamine(DAFPD),which contains crosslinkable functional groups,were designed and synthesized successfully and copolymerized with 4,4'-oxydianiline(ODA)and 4,4-hexafluoroisopropylphthalic anhydride(6FDA).The prepared PI film(PI-3),with rigid backbones and loose packing had excellent heat resistance(Td5%=489℃)and optical properties(T450=82%).Furthermore,a crosslinked PI film(c-PI-3)with more heat-resistant(Td5%=524℃)and better mechanical properties(σ=125.46MPa),can be obtained through thermal crosslinking of tetrafluorostyrene.In addition,the changes in the properties caused by the proportion of DAFPD added during copolymerization are discussed comprehensively.This study provides a promising candidate for heat-resistant PI materials.展开更多
High performance is always the research objective in developing triboelectric nanogenerators(TENGs)for future versatile applications.In this study,flexible triboelectric membranes were prepared based on polyimide(PI)m...High performance is always the research objective in developing triboelectric nanogenerators(TENGs)for future versatile applications.In this study,flexible triboelectric membranes were prepared based on polyimide(PI)membranes doped with barium titanate(BTO)nanoparticles and multi-walled carbon nanotubes(MWCNTs).The piezoelectric BTO nanoparticles were incorporated to boost the electric outputs by the synergistic effect of piezoelectricity and triboelectricity and MWCNTs were incorporated to provide a microcapacitor structure for enhancing the performance of TENGs.When the mass fraction of the BTO nanoparticle was 10%and the mass fraction of the MWCNT was 0.1%,the corresponding TENG achieved optimum electric outputs(an open-circuit voltage of around 65 V,a short-circuit current of about 20.0μA and a transferred charge of about 25.0 nC),much higher than those of the TENG with a single PI membrane.The TENG is potentially used to supply energy for commercial light-emitting diodes and as self-powered sensors to monitor human physical training conditions.This research provides a guideline for developing TENGs with high performance,which is crucial for their long-term use.展开更多
Modified polyimides(MPIs)possess excellent thermal stability,chemical stability,and mechanical properties,and are considered to be a kind of dielectric material for high-frequency communication.Enhancing the rigidity ...Modified polyimides(MPIs)possess excellent thermal stability,chemical stability,and mechanical properties,and are considered to be a kind of dielectric material for high-frequency communication.Enhancing the rigidity of the polymer chains and intermolecular interactions can ensure low D_(k)/D_(f)at high frequency,which is attributed to the effective restriction of dipole orientations.However,it is difficult to achieve tight chain packing in an overly rigid polymer chain,whereas an overly flexible polymer chain might be insufficient to restrain small-scale molecular motions below T_(g).To balance the trade-off between the rigidity of the polymer chains and tight chain packing,MPI was developed with a rigidsoft structure based on a naphthalene-alkyl-based diamine.On the one hand,incorporating the soft unit can enhance the movability of polymer chains to achieve dense chain packing for polyimides(PIs).On the other hand,the presence of rigid aromatic units can enhance intermolecular interactions and further restrict the motion of polar imide groups below T_(g).As a result,the resultant MPI can prevent small-scale molecular motion below T_(g).In contrast to the reference PI-TFMB-6FDA,D_(k)/D_(f)is significantly reduced from 2.72/0.0075 to 2.73/0.005 at a high frequency of 10 GHz Furthermore,the rigid-soft structure endows PIs with good thermoplasticity owing to the good chain flexibility above T_(g).In addition,PIs based on rigid-soft structures can preserve favorable thermal stability.展开更多
Polyimides(PIs)are widely used in the microelectronics field due to their excellent comprehensive performance and the diversity and designability of their structures.In flexible substrate applications,designing the mo...Polyimides(PIs)are widely used in the microelectronics field due to their excellent comprehensive performance and the diversity and designability of their structures.In flexible substrate applications,designing the molecular structure to balance thermodynamic and optical properties is the most critical part of the PI design process.To accelerate the discovery of high-performance PIs,we established predictive models for glass transition temperature(T_(g)),cut-off wavelength(CW),and coefficient of thermal expansion(CTE)using various machine learning algorithms.The optimal predictive models for the three properties demonstrated high accuracy and stability in both test set predictions and cross-validation results.Additionally,the interpretability of the three optimal models was analyzed using the SHAP method,and the accuracy and generalization ability of the models were validated using several novel PIs.By combining the three models,predictions were made for multiple PIs,leading to the selection and synthesis of PIs with excellent comprehensive performance.135 novel PIs were designed and their key properties were obtained without the need for experimental verification.The predictive models established in this study can assist researchers in quickly determining the T_(g),CW and CTE of PIs,thereby facilitating the swift identification of promising candidates for further development.展开更多
Organo-soluble alicyclic polyimides (ALPIs) were synthesized from an alicyclic dianhydride, 1,8-dimethyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DMEA) and several multialkyl-substituted 4,4'-d...Organo-soluble alicyclic polyimides (ALPIs) were synthesized from an alicyclic dianhydride, 1,8-dimethyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DMEA) and several multialkyl-substituted 4,4'-diaminodiphenylmethane compounds, including 3,3'-dimethyl-4,4'-diaminodiphenyt methane (DMDA), 3,31,5,5'-tetramethyl-4,4'-diaminodiphenyl methane (TMDA) and 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane (TEDA). For comparison, the aromatic polyimides (ARPIs) were synthesized from the aromatic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and the same diamines. The ALPIs exhibited better solubility and transparency, but worse thermal stabilities and mechanical properties than those of the ARPIs. And the ALPIs could be dissolved in common organic solvents, such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), chloroform, tetrahydrofuran, m-cresol and so on. The ALPI films had an UV-Vis cut-off at 320 nm and a transmittance of higher than 80% in the visible region. In addition, the ALPIs showed thermal decomposition temperatures (T-d) of about 450degreesC, which was nearly 100degreesC lower than that of the ARPIs.展开更多
A novel Pd electrocatalyst with flowerlike micro-nanostructures was synthesized by electrochemical deposition on a flexible graphene/polyimide（Gr/PI） composite membrane and characterized by scanning electron microsc...A novel Pd electrocatalyst with flowerlike micro-nanostructures was synthesized by electrochemical deposition on a flexible graphene/polyimide（Gr/PI） composite membrane and characterized by scanning electron microscopy（SEM）,X-ray diffraction（XRD）.The Pd micro-nanoparticles were prepared on a COOH-CNTs/PI membrane as a comparative sample.The XRD and SEM investigations for Pd electrodeposition demonstrate that the particle size of Gr/PI composite membrane is smaller than that of COOH-CNTs/PI membrane,while the uniform and dense distribution of Pd micro-nanoparticles on the Gr/PI composite membrane is greater than that on the COOH-CNTs/PI membrane.The electrocatalytic properties of Pd/Gr/PI and Pd/COOH-CNTs/PI catalysts for the oxidation of formic acid were investigated by cyclic voltammetry（CV） and chronoamperometry（CA）.It is found that the electrocatalytic activity and stability of Pd/Gr/PI are superior to those of Pd/COOH-CNTs/PI catalyst.This is because smaller metal particles and higher dense distribution desirably provide abundant catalytic sites and mean higher catalytic activity.Therefore,the Pd/Gr/PI catalyst has better catalytic performance for formic acid oxidation than the Pd/COOH-CNTs/PI catalyst.展开更多
The fluorine-containing organic polymer was synthesized from 3, 3＇, 4, 4＇-Bisphenyltetracarboxylic （BPDA）, and 2,2-Bis （3-amino-4-hydroxyyphenyl） hexafluoropropane （6FHP）. It is a first-step preparation of a p...The fluorine-containing organic polymer was synthesized from 3, 3＇, 4, 4＇-Bisphenyltetracarboxylic （BPDA）, and 2,2-Bis （3-amino-4-hydroxyyphenyl） hexafluoropropane （6FHP）. It is a first-step preparation of a preimided hydroxy-containing polyimide, followed by the covalent bonding of an active chromophore, dispersed red 19 （DR19）, onto the backbone of the polyimide via the Mitsunobu reaction. The nonlinear optical （NLO） containing polyimide was synthesized. The differential scanning calorimeter （DSC）and thermal gravimetric analysis （TGA） exhibited Tg and the temperature Tg at which 5 % mass losses occurring of polymer were 248 and 309 ℃, respectively. A reflective electro-optic （EO） modulator using this polymer was fabricated. The optical nonlinearities were determined to be d33 = 5. 209×10^-9 esu （poling voltage of 3.6 kV, 205 ℃） and d33 =7. 418×10^-9esu （poling voltage of 3. 8 kV, 210 ℃） by the second harmonic generation method in in-situ condition at a fundamental wavelength of 1 064 nm. The EO coefficients 733 of the polymer layer in the EO modulator were determined to be 2. 182 pm/V （poling voltage of 3.6 kV, 205 ℃） and 3. 107 pm/V （poling voltage of 3.8 kV, 210 ℃） at 1064 nm by an attenuated-total-reflection （ATR） method.展开更多
基金supported by the Natural Science Foundation of Shanxi Province(Nos.20210302123015 and 20210302123035)the Opening Project of State Key Laboratory of Polymer Materials Engineering(Sichuan University)(No.sklpme2022-4-06)the Open Foundation of China-Belarus Belt and Road Joint Laboratory on Electromagnetic Environment Effect(No.ZBKF2022030301).
文摘In the present work,by virtue of the synergistic and independent effects of Janus structure,an asymmetric nickel-chain/multiwall carbon nanotube/polyimide(Ni/MWCNTs/PI)composite foam with absorption-dominated electromagnetic interference(EMI)shielding and thermal insulation performances was successfully fabricated through an ordered casting and directional freeze-drying strategy.Water-soluble polyamic acid(PAA)was chosen to match the oriented freeze-drying method to acquire oriented pores,and the thermal imidization process from PAA to PI exactly eliminated the interface of the multilayered structure.By controlling the electro-magnetic gradient and propagation path of the incident microwaves in the MWCNT/PI and Ni/PI layers,the PI composite foam exhibited an efficient EMI SE of 55.8 dB in the X-band with extremely low reflection characteristics(R=0.22).The asymmetric conductive net-work also greatly preserved the thermal insulation properties of PI.The thermal conductivity(TC)of the Ni/MWCNT/PI composite foam was as low as 0.032 W/(m K).In addition,owing to the elimination of MWCNT/PI and Ni/PI interfaces during the thermal imidization process,the composite foam showed satisfactory compressive strength.The fabricated PI composite foam could provide reliable electromagnetic protection in complex applications and withstand high temperatures,which has great potential in cuttingedge applications such as advanced aircraft.
基金financially supported by the Natural Science Foundation of Shandong Province,China(Nos.ZR2020QB065 and ZR2021MB121)。
文摘In this study,a novel linear polyimide chain(PTCDA-DCH)was used as an electrochemiluminescence(ECL)emitter,employing a chiral metal-organic framework(MOF)(Zn-Dcam-dabco)as the chiral selector and ferrocene(Fc)as a quencher to construct a chiral sensor for detecting histidine(His)enantiomers.Competitive interactions between Fc and His induce partial Fc desorption from the sensor surface,leading to ECL signal recovery.Differential Fc release due to the distinct binding affinities of Zn-Dcam-dabco for His enantiomers enabled precise chiral discrimination.Notably,the sensor achieved the quantitative detection of His enantiomers with an limits of detection(LOD)of 8μmol/L.Furthermore,the sensor demonstrated excellent recovery rates of 98.0%–104%for l-histidine(L-His)and 92.0%–95.9%for D-His in spiked milk samples,validating its reliability for real-sample analysis.This study provides a promising platform for ECL-based chiral recognition,bioanalysis,and the rapid assessment of amino acids in food products.
基金supported by National Natural Science Foundation,China(Nos.52071132,U21A20284 and 52261135632)Natural Science Foundation of Henan,China(Nos.232300421080,242300421035)+2 种基金Program for Innovative Team(in Science and Technology)in University of Henan Province,China(No.24IRTSTHN006)Key Scientific Research Programs in Universities of Henan Province,China–Special Projects for Basic Research(No.23ZX008)the Natural Science Foundation of Hunan Province,China(No.2023JJ50287)。
文摘Conjugated microporous polymers(CMPs)have attracted considerable attention as potential organic anode materials for sodium-ion batteries(SIBs)due to their flexible chemical structure,high porosity,environmental friendliness,and cost effectiveness.However,the inherent shortcomings of organic electrodes,such as low conductivity,high solubility in electrolyte,narrow material utilization,etc.,limit their further development.In this work,we successfully prepared a novel porous polyimide PPD containing multicarbonyl active centers via the polycondensation of pyromellitic dianhydride(PMDA)and2,6-diaminoanthraquinone(DAAQ).The stable conjugated structure and multiple redox centers give the polymer high reversible specific capacity(244.6 m Ah/g after 100 cycles at 100 m A/g),ultra-long cycle stability(100.7 m Ah/g after 2000 cycles at 1.0 A/g),and predominant rate capability.Meanwhile,the sodium storage mechanism of the electrode materials during the charging and discharging process is investigated by ex-situ XPS/FTIR analysis.Due to the exceptional electrochemical properties and simple synthesis method,this work may shed light on the preparation of polyimide-based anodes for high specific capacity and rate capability secondary batteries.
基金supported by the Australian Research Council Discovery Early Career Researcher Award Scheme(DE220100135 and DE220100435)。
文摘Hydrophobic nanofiber composite membranes comprising polyimide and metal-organic frameworks are developed for desalination via direct contact membrane distillation(DCMD).Our study demonstrates the synthesis of hydrophobic polyimides with trifluoromethyl groups,along with superhydrophobic UiO-66(hMOF)prepared by phenylsilane modification on the metal-oxo nodes.These components are then combined to create nanofiber membranes with improved hydro ph obi city,ensuring long-term stability while preserving a high water flux.Integration of hMOF into the polymer matrix further increases membrane hydrophobic properties and provides additional pathways for vapor transport during MD.The resulting nanofiber composite membranes containing 20 wt%of hMOFs(PI-1-hMOF-20)were able to desalinate hypersaline feed solution of up to 17 wt%NaCl solution,conditions that are beyond the capability of reverse osmosis systems.These membranes demonstrated a water flux of 68.1 kg m^(-2)h^(-1) with a rejection rate of 99.98%for a simulated seawater solution of 3.5 wt%NaCl at 70℃,while maintaining consistent desalination performance for 250 h.
基金financially supported by the Natural Science Foundation of Shandong Province(Nos.ZR2021ME055,ZR2022QB170 and ZR2022MB034)the Foundation(No.GZKF202128)of State Key Laboratory of Biobased Material and Green Papermaking,Qilu University of Technology,Shandong Academy of Sciencesthe Development Program Project of Young Innovation Team of Institutions of Higher Learning in Shandong Province.
文摘It is urgent to develop high-performance polyimide(PI)films that simultaneously exhibit high transparency,exceptional thermal stability,mechanical robustness,and low dielectric to fulfil the requirements of flexible display technologies.Herein,a series of fluorinated polyimide films(FPIs)were fabricated by the condensation of 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione)(6FDA)and the fluorinated triphenylmethane diamine monomer(EDA,MEDA and DMEDA)with heat-crosslinkable tetrafluorostyrene side groups,which was incorporated by different numbers of methyl groups pendant in the ortho position of amino groups.Subsequently,the FPI films underwent heating to produce crosslinking FPIs(C-FPIs)through the self-crosslinking of double bonds in the tetrafluorostyrene.The transparency,solvent resistance,thermal stability,mechanical robustness and dielectric properties of FPI and C-FPI films can be tuned by the number of methyl groups and crosslinking,which were deeply investigated by virtue of molecular dynamics(MD)simulations and density functional theory(DFT).As a result,all the films exhibited exceptional optically colorless and transparent,with transmittance in the visible region of 450-700 nm exceeding 79.9%,and the cut-off wavelengths(λ_(off))were nearly 350 nm.The thermal decomposition temperatures at 5% weight loss(T_(d5%))for all samples exceeded 504℃.These films exhibited a wide range of tunable tensile strength(46.5-75.1 MPa).Significantly,they showed exceptional dielectric properties with the dielectric constant of 2.3-2.5 at full frequency(10^(7)-20 Hz).This study not only highlights the relationship between the polymer molecular structure and properties,but offer insights for balancing optical transparency,heat resistance and low dielectric constant in PI films.
基金supported by the National Natural Science Foundation of China(Nos.52373077,52003106,52233006,and 52161135302)the Research Foundation Flanders(No.G0F2322N)+1 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.SJCX23_1236)the Innovation Program of Shanghai Municipal Education Commission(No.2021-01-07-00-03-E00108).
文摘Designing and manufacturing compatible multi-band stealth materials remains a great challenge. In this work, a silver-metalized polyimide photochromic composite foam is successfully fabricated by self-activating electroless silver-plating on the surface of the polyimide skeleton and followed by applying a photochromic coating on the upper surface. The effective loading of silver nanoparticles facilitates the rational construction of a conductive network in foam, improving the efficient dissipation of incident electromagnetic waves. In addition, the interconnected conductive network successfully endows it with an excellent Joule heating capability, which can be employed to effectively remove ice and/or mitigate the impact of water vapor on radar stealth performance in cold and wet weather. Besides, the low emissivity silver plating combined with superior thermal insulation of foam enables the material with excellent infrared stealth performance. Moreover, the modulation of self-adaptive photochromic coating brings a prominent visual stealth performance under different sunlight backgrounds. As a result, such excellent radar and infrared stealth performance combined with the adaptive color-switching capability provides the foam with great potential for preparing compatible multi-band materials.
基金support from the National Natural Science Foundation of China(52373077,52003106,52103074,52233006,52161135302)the Research Foundation Flanders(G0F2322N)Innovation Program of Shanghai Municipal Education Commission(2021-01-07-00-03-E00108).
文摘Designing and fabricating a compatible low-reflectivity electromagnetic interference(EMI)shielding/high-temperature resistant infrared stealth material possesses a critical significance in the field of military.Hence,a hierarchical polyimide(PI)nonwoven fabric is fabricated by alkali treatment,in-situ growth of magnetic particles and"self-activated"electroless Ag plating process.Especially,the hierarchical impedance matching can be constructed by systematically assembling Fe_(3)O_(4)/Ag-loaded PI nonwoven fabric(PFA)and pure Ag-coated PI nonwoven fabric(PA),endowing it with an ultralowreflectivity EMI shielding performance.In addition,thermal insulation of fluffy three-dimensional(3D)space structure in PFA and low infrared emissivity of PA originated from Ag plating bring an excellent infrared stealth performance.More importantly,the strong bonding interaction between Fe_(3)O_(4),Ag,and PI fiber improves thermal stability in EMI shielding and high-temperature resistant infrared stealth performance.Such excellent comprehensive performance makes it promising for military tents to protect internal equipment from electromagnetic interference stemmed from adjacent equipment and/or enemy,and inhibit external infrared detection.
基金financially supported by the Natural Science Foundation of Shandong Province(No.ZR2021ME011)State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources(No.LAPS20001)。
文摘In high-frequency electrical energy systems,polyimide(PI)composite insulation materials need to possess a low dielectric constant,sufficient thermal conductivity,and robust interfacial adhesion to ensure reliable performance under elevated temperatures and pressures.These aspects are crucial for preventing local overheating and electrical breakdown,thereby ensuring reliable equipment operation.Traditional PI insulation materials often exhibit high dielectric constants and pronounced dielectric losses,compromising their insulation efficiency.In this study,molecular dynamics simulations were employed to incorporate polyhedral oligomeric silsesquioxanes(POSS)into PI through physical blending and chemical bonding to enhance dielectric properties.Key parameters of the PI/POSS composite system,including dielectric constant,thermal conductivity,glass transition temperature,Young’s modulus,Poisson’s ratio,and interfacial adhesion energy,were systematically evaluated for both doping methods.The degradation behavior of the PI composites under high-temperature and electric field conditions was also simulated to elucidate degradation pathways and product distributions,providing insights for designing low-dielectric insulation materials.Doping with POSS significantly reduces the dielectric constant of PI,thereby improving insulation performance,thermal stability,mechanical strength,and interfacial adhesion.At an optimal POSS doping ratio,the thermal conductivity of PI is enhanced.Compared with the physical blending system,the chemical bonding system yields more substantial improvements across all evaluated properties.Under high-temperature and strong electric field conditions,POSS doping enhances interfacial adhesion and thermal stability,effectively suppressing the cleavage of key chemical bonds,reducingCOemissions,and increasing the formation of oxygen-containing intermediates and water molecules,which contributes to improved environmental sustainability.
基金financially supported by the National Key Research&Development Program of China(No.2022YFA1205200).
文摘The development of intelligent electronic power systems necessitates advanced flexible pressure sensors.Despite improved compressibility through surface micro-structures or bulk pores,conventional capacitive pressure sensors face limitations due to their low dielectric constant and poor temperature tolerance of most elastomers.Herein,we constructed oriented polyimide-based aerogels with mechanical robustness and notable changes in dielectric constant under compression.The enhancement is attributed to the doping of surface-modified dielectric nanoparticles and graphene oxide sheets,which interact with polymer molecular chains.The resulting aerogels,with their excellent temperature resistance,were used to assemble high-performance capacitive pressure sensors.The sensor exhibits a maximum sensitivity of 1.41 kPa^(−1)over a wide working range of 0-200 kPa.Meanwhile,the sensor can operate in environments up to 150℃during 2000 compression/release cycles.Furthermore,the aerogel-based sensor demonstrates proximity sensing capabilities,showing great potential for applications in non-contact sensing and extreme environment detection.
基金supported by the National Natural Science Foundation of China(Nos.52272211 and 52072145)the Funding of Jilin Province Development and Reform Commission(Nos.2024C018-11 and 2020C026-2)+3 种基金the Scientific and Technological Developing Project of Jilin Province(Nos.20230508046RC,20240602023RC,YDZJ202101ZYTS185 and YDZJ202201ZYTS372)Jilin Talent Development Funding(No.2021Y027)the Funds for Special Projects of the Central Government in Guidance of Local Science and Technology Development(No.202002017JC)the Research Program on Science and Technology from the Education Department of Jilin Province(Nos.JJKH20220439KJ and JJKH20210550KJ).
文摘Aqueous zinc-ion hybrid capacitors(ZIHCs)are promising electrochemical energy storage systems with advantages of high-energy density,low cost,safety and environmental friendliness.However,application of carbon-based cathodes is limited by their low-energy density due to the lack of active sites.Herein,a chemisorption sites modulating strategy is proposed to construct nitrogen-doped polyimide carbon nanoflowers with abundant oxygen vacancies and carbonyl functionalization via high-temperature calcination and subsequent acid processing.The synergistic effect of oxygen vacancies,carbonyl groups,enhanced surface area and porous structure enables stable zinc-ion storage with high capacity.Remarkably,the carbon materials can circulate 20,000 cycles stably at a current density of 2 A·g^(-1).After 10,000 cycles at a high rate of 3 A·g^(-1),a capacity retention rate of 64%can still be achieved.The as-prepared ZIHCs provide an energy density of 65.61 Wh·kg^(-1)at the power density of 197.82 W·kg^(-1).Current research shows that polyimide-derived carbon material synthesized by acid activation provides a new idea for developing cathodes in aqueous ZIHCs.
基金supported by National Natural Science Foundation of China(No.52373099)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(No.B21003)。
文摘The dual system capable of solar-driven interfacial steam production and all-weather hydropower generation is emerging as a potential way to alleviate freshwater shortage and energy crisis.However,the intrinsic mechanism of hydroelectricity generation powered by the interaction between seawater and material structure is vague,and it remains challenging to develop dual-functional evaporators with high photothermal conversion efficiency and ionic selectivity.Herein,an all-weather dual-function evaporator based on porous carbon fiber-like(PCF)is acquired through the pyrolysis of barium-based metal-organic framework(Ba-BTEC),which is originated from waste polyimide.The PCF-based evaporator/device exhibits a high steam generation rate of 2.93 kg m^(-2)h^(-1)in seawater under 1 kW m^(-2)irradiation,along with the notable opencircuit voltage of 0.32 V,owing to the good light absorption ability,optimal wettability,and suitable aperture size.Moreover,molecular dynamics simulation result reveals that Na+tends to migrate rapidly within the nanoporous channels of PCF,owing to a strong affinity between oxygen-containing functional group and water molecules.This work not only proposes an eco-friendly strategy for constructing low-cost fulltime freshwater-hydroelectric co-generation device,but also contributes to the understanding of evaporation-driven energy harvesting technology.
基金supported by the National Natural Science Foundation of China(Nos.52377026 and 52301192)the Taishan Scholars and Young Experts Program of Shandong Province(No.tsqn202103057)+1 种基金the Natural Science Foundation of Shandong Province(Nos.ZR2024ME046 and ZR2024QE313)the China Postdoctoral Science Foundation(No.2024M761554).
文摘Demand for high-performance power devices continues to grow with the continuous development of power electronics and high-end field applications.Although packaging materials based on epoxy resins and silica gels have been widely developed,higher operating temperatures and operating voltages are still critical to the performance of power devices.Here,a composite film containing functionalized meso-porous hollow silica particles(MH-SiO_(2))and polyimide(PI)was prepared by a template method and layer-by-layer coating strategy to address the current bottlenecks in packaging material development.The electrical breakdown strength of the prepared PI/SiO_(2) composite film was 323.41 kV/mm,while the mass fraction of MH-SiO_(2) was only 5%.This indicates that the mesoporous structure can effectively inhibit electron collisions with nano-restricted domains.The simulation results also indicate that the size variation of inorganic fillers and the interaction of organic/inorganic heterogeneous interfaces are the main reasons affecting the performance of the composites.Meanwhile,the PI/SiO_(2) composite films achieved other properties required for practical applications,such as matched coefficient of thermal ex-pansion(CTE)(23.5 ppm/℃),excellent thermal stability(T_(5)%=559.0℃)and low dielectric constant(2.27@1 M Hz).These results highlight the great potential of inorganic phase-specific structural designs for the preparation of high-performance power device packaging materials.
基金supported by the National Key R&D Program of China(No.2022YFB3707302)the National Natural Science Foundation of China(Nos.52394271 , 52394270).
文摘Enhancing the mechanical properties is crucial for polyimide films,but the mechanical properties(Young's modulus,tensile strength,and elongation at break)mutually constrain each other,complicating simultaneous enhancement via traditional trial-and-error methods.In this work,we proposed a materials genome approach to design and screen phenylethynyl-terminated polyimides for films with enhanced mechani-cal properties.We first established machine learning models to predict Young's modulus,tensile strength,and elongation at break to explore the chemical space containing thousands of candidate structures.The accuracies of the machine learning models were verified by molecular dynamics simulations on screened polyimides and experimental testing on three representative polyimide films.The performance advantages of the best-selected polyimides were analyzed by comparing well-known polyimides based on molecular dynamics simulations,and the structural rationale was revealed by"gene"analysis and feature importance evaluation.This work provides a cost-effective strategy for designing polyimide films withenhancedmechanical properties.
基金supported by the National Key Research and Development Program of China(No.2022YFB3603101)。
文摘Polyimide(PI)is widely used in high-tech fields such as microelectronics,aerospace,and national defense because of its excellent optical properties,high-and low-temperature resistance,and good dimensional stability.To achieve the desired properties of PI,the monomers 2,6-diaminopyrimidin-4-ol(DAPD)and 6-(2,3,5,6-tetrafluoro-4-vinylphenoxy)pyrimidin-2,4-diamine(DAFPD),which contains crosslinkable functional groups,were designed and synthesized successfully and copolymerized with 4,4'-oxydianiline(ODA)and 4,4-hexafluoroisopropylphthalic anhydride(6FDA).The prepared PI film(PI-3),with rigid backbones and loose packing had excellent heat resistance(Td5%=489℃)and optical properties(T450=82%).Furthermore,a crosslinked PI film(c-PI-3)with more heat-resistant(Td5%=524℃)and better mechanical properties(σ=125.46MPa),can be obtained through thermal crosslinking of tetrafluorostyrene.In addition,the changes in the properties caused by the proportion of DAFPD added during copolymerization are discussed comprehensively.This study provides a promising candidate for heat-resistant PI materials.
基金National Natural Science Foundation of China(No.52103267)。
文摘High performance is always the research objective in developing triboelectric nanogenerators(TENGs)for future versatile applications.In this study,flexible triboelectric membranes were prepared based on polyimide(PI)membranes doped with barium titanate(BTO)nanoparticles and multi-walled carbon nanotubes(MWCNTs).The piezoelectric BTO nanoparticles were incorporated to boost the electric outputs by the synergistic effect of piezoelectricity and triboelectricity and MWCNTs were incorporated to provide a microcapacitor structure for enhancing the performance of TENGs.When the mass fraction of the BTO nanoparticle was 10%and the mass fraction of the MWCNT was 0.1%,the corresponding TENG achieved optimum electric outputs(an open-circuit voltage of around 65 V,a short-circuit current of about 20.0μA and a transferred charge of about 25.0 nC),much higher than those of the TENG with a single PI membrane.The TENG is potentially used to supply energy for commercial light-emitting diodes and as self-powered sensors to monitor human physical training conditions.This research provides a guideline for developing TENGs with high performance,which is crucial for their long-term use.
基金supported by the National Natural Science Foundation of China(Nos.U20A20340 and 52001068)Key-Area Research and Development Program of Guangdong Province(No.2020B010182001)+3 种基金Dongguan Key Research&Development Program(No.20231200300192)Science and Technology Projects in Guangzhou(No.2025A04J3832)Foshan Introducing Innovative and Entrepreneurial Teams(No.1920001000108)Guangzhou Hongmian Project(No.HMJH-2020-0012)。
文摘Modified polyimides(MPIs)possess excellent thermal stability,chemical stability,and mechanical properties,and are considered to be a kind of dielectric material for high-frequency communication.Enhancing the rigidity of the polymer chains and intermolecular interactions can ensure low D_(k)/D_(f)at high frequency,which is attributed to the effective restriction of dipole orientations.However,it is difficult to achieve tight chain packing in an overly rigid polymer chain,whereas an overly flexible polymer chain might be insufficient to restrain small-scale molecular motions below T_(g).To balance the trade-off between the rigidity of the polymer chains and tight chain packing,MPI was developed with a rigidsoft structure based on a naphthalene-alkyl-based diamine.On the one hand,incorporating the soft unit can enhance the movability of polymer chains to achieve dense chain packing for polyimides(PIs).On the other hand,the presence of rigid aromatic units can enhance intermolecular interactions and further restrict the motion of polar imide groups below T_(g).As a result,the resultant MPI can prevent small-scale molecular motion below T_(g).In contrast to the reference PI-TFMB-6FDA,D_(k)/D_(f)is significantly reduced from 2.72/0.0075 to 2.73/0.005 at a high frequency of 10 GHz Furthermore,the rigid-soft structure endows PIs with good thermoplasticity owing to the good chain flexibility above T_(g).In addition,PIs based on rigid-soft structures can preserve favorable thermal stability.
基金supported by the National Key Research and Development Program of China(2022YFB3603100).
文摘Polyimides(PIs)are widely used in the microelectronics field due to their excellent comprehensive performance and the diversity and designability of their structures.In flexible substrate applications,designing the molecular structure to balance thermodynamic and optical properties is the most critical part of the PI design process.To accelerate the discovery of high-performance PIs,we established predictive models for glass transition temperature(T_(g)),cut-off wavelength(CW),and coefficient of thermal expansion(CTE)using various machine learning algorithms.The optimal predictive models for the three properties demonstrated high accuracy and stability in both test set predictions and cross-validation results.Additionally,the interpretability of the three optimal models was analyzed using the SHAP method,and the accuracy and generalization ability of the models were validated using several novel PIs.By combining the three models,predictions were made for multiple PIs,leading to the selection and synthesis of PIs with excellent comprehensive performance.135 novel PIs were designed and their key properties were obtained without the need for experimental verification.The predictive models established in this study can assist researchers in quickly determining the T_(g),CW and CTE of PIs,thereby facilitating the swift identification of promising candidates for further development.
基金This work was supported by the National Natural Science Foundation of China under the Grant for Distinguished YoungScholars (No. 59925310).
文摘Organo-soluble alicyclic polyimides (ALPIs) were synthesized from an alicyclic dianhydride, 1,8-dimethyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DMEA) and several multialkyl-substituted 4,4'-diaminodiphenylmethane compounds, including 3,3'-dimethyl-4,4'-diaminodiphenyt methane (DMDA), 3,31,5,5'-tetramethyl-4,4'-diaminodiphenyl methane (TMDA) and 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane (TEDA). For comparison, the aromatic polyimides (ARPIs) were synthesized from the aromatic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and the same diamines. The ALPIs exhibited better solubility and transparency, but worse thermal stabilities and mechanical properties than those of the ARPIs. And the ALPIs could be dissolved in common organic solvents, such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), chloroform, tetrahydrofuran, m-cresol and so on. The ALPI films had an UV-Vis cut-off at 320 nm and a transmittance of higher than 80% in the visible region. In addition, the ALPIs showed thermal decomposition temperatures (T-d) of about 450degreesC, which was nearly 100degreesC lower than that of the ARPIs.
基金Project(51372106)supported by the National Natural Science Foundation of China
文摘A novel Pd electrocatalyst with flowerlike micro-nanostructures was synthesized by electrochemical deposition on a flexible graphene/polyimide（Gr/PI） composite membrane and characterized by scanning electron microscopy（SEM）,X-ray diffraction（XRD）.The Pd micro-nanoparticles were prepared on a COOH-CNTs/PI membrane as a comparative sample.The XRD and SEM investigations for Pd electrodeposition demonstrate that the particle size of Gr/PI composite membrane is smaller than that of COOH-CNTs/PI membrane,while the uniform and dense distribution of Pd micro-nanoparticles on the Gr/PI composite membrane is greater than that on the COOH-CNTs/PI membrane.The electrocatalytic properties of Pd/Gr/PI and Pd/COOH-CNTs/PI catalysts for the oxidation of formic acid were investigated by cyclic voltammetry（CV） and chronoamperometry（CA）.It is found that the electrocatalytic activity and stability of Pd/Gr/PI are superior to those of Pd/COOH-CNTs/PI catalyst.This is because smaller metal particles and higher dense distribution desirably provide abundant catalytic sites and mean higher catalytic activity.Therefore,the Pd/Gr/PI catalyst has better catalytic performance for formic acid oxidation than the Pd/COOH-CNTs/PI catalyst.
基金Jiangsu Planned Projects for Postdoctoral ResearchFunds(No0602037B)the Natural Science Foundation of Higher Edu-cation Institutions of Jiangsu Province (No05KJB150016)+1 种基金the Nation-al Natural Science Foundation of China (No50377005)the Fund ofJiangsu University (No06JDG015)
文摘The fluorine-containing organic polymer was synthesized from 3, 3＇, 4, 4＇-Bisphenyltetracarboxylic （BPDA）, and 2,2-Bis （3-amino-4-hydroxyyphenyl） hexafluoropropane （6FHP）. It is a first-step preparation of a preimided hydroxy-containing polyimide, followed by the covalent bonding of an active chromophore, dispersed red 19 （DR19）, onto the backbone of the polyimide via the Mitsunobu reaction. The nonlinear optical （NLO） containing polyimide was synthesized. The differential scanning calorimeter （DSC）and thermal gravimetric analysis （TGA） exhibited Tg and the temperature Tg at which 5 % mass losses occurring of polymer were 248 and 309 ℃, respectively. A reflective electro-optic （EO） modulator using this polymer was fabricated. The optical nonlinearities were determined to be d33 = 5. 209×10^-9 esu （poling voltage of 3.6 kV, 205 ℃） and d33 =7. 418×10^-9esu （poling voltage of 3. 8 kV, 210 ℃） by the second harmonic generation method in in-situ condition at a fundamental wavelength of 1 064 nm. The EO coefficients 733 of the polymer layer in the EO modulator were determined to be 2. 182 pm/V （poling voltage of 3.6 kV, 205 ℃） and 3. 107 pm/V （poling voltage of 3.8 kV, 210 ℃） at 1064 nm by an attenuated-total-reflection （ATR） method.
