The key parameters that characterize the morphological quality of multi-layer and multi-pass metal laser deposited parts are the surface roughness and the error between the actual printing height and the theoretical m...The key parameters that characterize the morphological quality of multi-layer and multi-pass metal laser deposited parts are the surface roughness and the error between the actual printing height and the theoretical model height.The Taguchi method was employed to establish the correlations between process parameter combinations and multi-objective characterization of metal deposition morphology(height error and roughness).Results show that using the signal-to-noise ratio and grey relational analysis,the optimal parameter combination for multi-layer and multi-pass deposition is determined as follows:laser power of 800 W,powder feeding rate of 0.3 r/min,step distance of 1.6 mm,and scanning speed of 20 mm/s.Subsequently,a Genetic Bayesian-back propagation(GB-BP)network is constructed to predict multi-objective responses.Compared with the traditional back propagation network,the GB-back propagation network improves the prediction accuracy of height error and surface roughness by 43.14%and 71.43%,respectively.This network can accurately predict the multi-objective characterization of morphological quality of multi-layer and multi-pass metal deposited parts.展开更多
As businesses develop and expand with a significant volume of data,data protection and privacy become increasingly important.Research has shown a tremendous increase in phishing activities during and after COVID-19.Th...As businesses develop and expand with a significant volume of data,data protection and privacy become increasingly important.Research has shown a tremendous increase in phishing activities during and after COVID-19.This research aimed to improve the existing approaches to detecting phishing activities on the internet.We designed a multi-layered phish detection algorithm to detect and prevent phishing applications on the internet using URLs.In the algorithm,we considered technical dimensions of phishing attack prevention and mitigation on the internet.In our approach,we merge,Phishtank,Blacklist,Blocklist,and Whitelist to form our framework.A web application system and browser extension were developed to implement the algorithm.The multi-layer phish detector evaluated ten thousandURLs gathered randomly from the internet(five thousand phishing and five thousand legitimate URLs).The system was estimated to detect levels of accuracy,true-positive and false-positive values.The system level accuracy was recorded to be 98.16%.Approximately 49.6%of the websites were detected as illegitimate,whilst 49.8%were seen as legitimate.展开更多
At present,the emerging solid-phase friction-based additive manufacturing technology,including friction rolling additive man-ufacturing(FRAM),can only manufacture simple single-pass components.In this study,multi-laye...At present,the emerging solid-phase friction-based additive manufacturing technology,including friction rolling additive man-ufacturing(FRAM),can only manufacture simple single-pass components.In this study,multi-layer multi-pass FRAM-deposited alumin-um alloy samples were successfully prepared using a non-shoulder tool head.The material flow behavior and microstructure of the over-lapped zone between adjacent layers and passes during multi-layer multi-pass FRAM deposition were studied using the hybrid 6061 and 5052 aluminum alloys.The results showed that a mechanical interlocking structure was formed between the adjacent layers and the adja-cent passes in the overlapped center area.Repeated friction and rolling of the tool head led to different degrees of lateral flow and plastic deformation of the materials in the overlapped zone,which made the recrystallization degree in the left and right edge zones of the over-lapped zone the highest,followed by the overlapped center zone and the non-overlapped zone.The tensile strength of the overlapped zone exceeded 90%of that of the single-pass deposition sample.It is proved that although there are uneven grooves on the surface of the over-lapping area during multi-layer and multi-pass deposition,they can be filled by the flow of materials during the deposition of the next lay-er,thus ensuring the dense microstructure and excellent mechanical properties of the overlapping area.The multi-layer multi-pass FRAM deposition overcomes the limitation of deposition width and lays the foundation for the future deposition of large-scale high-performance components.展开更多
The growing incidence of cyberattacks necessitates a robust and effective Intrusion Detection Systems(IDS)for enhanced network security.While conventional IDSs can be unsuitable for detecting different and emerging at...The growing incidence of cyberattacks necessitates a robust and effective Intrusion Detection Systems(IDS)for enhanced network security.While conventional IDSs can be unsuitable for detecting different and emerging attacks,there is a demand for better techniques to improve detection reliability.This study introduces a new method,the Deep Adaptive Multi-Layer Attention Network(DAMLAN),to boost the result of intrusion detection on network data.Due to its multi-scale attention mechanisms and graph features,DAMLAN aims to address both known and unknown intrusions.The real-world NSL-KDD dataset,a popular choice among IDS researchers,is used to assess the proposed model.There are 67,343 normal samples and 58,630 intrusion attacks in the training set,12,833 normal samples,and 9711 intrusion attacks in the test set.Thus,the proposed DAMLAN method is more effective than the standard models due to the consideration of patterns by the attention layers.The experimental performance of the proposed model demonstrates that it achieves 99.26%training accuracy and 90.68%testing accuracy,with precision reaching 98.54%on the training set and 96.64%on the testing set.The recall and F1 scores again support the model with training set values of 99.90%and 99.21%and testing set values of 86.65%and 91.37%.These results provide a strong basis for the claims made regarding the model’s potential to identify intrusion attacks and affirm its relatively strong overall performance,irrespective of type.Future work would employ more attempts to extend the scalability and applicability of DAMLAN for real-time use in intrusion detection systems.展开更多
The huge impact kinetic energy cannot be quickly dissipated by the energy-absorbing structure and transferred to the other vehicle through the car body structure,which will cause structural damage and threaten the liv...The huge impact kinetic energy cannot be quickly dissipated by the energy-absorbing structure and transferred to the other vehicle through the car body structure,which will cause structural damage and threaten the lives of the occupants.Therefore,it is necessary to understand the laws of energy conversion,dissipation and transfer during train collisions.This study proposes a multi-layer progressive analysis method of energy flow during train collisions,considering the characteristics of the train.In this method,the train collision system is divided into conversion,dissipation,and transfer layers from the perspective of the train,collision interface,and car body structure to analyze the energy conversion,dissipation and transfer characteristics.Taking the collision process of a rail train as an example,a train collision energy transfer path analysis model was established based on power flow theory.The results show that when the maximum mean acceleration of the vehicle meets the standard requirements,the jerk may exceed the allowable limit of the human body,and there is a risk of injury to the occupants of a secondary collision.The decay rate of the collision energy along the direction of train operation reaches 79%.As the collision progresses,the collision energy gradually converges in the structure with holes,and the structure deforms when the gathered energy is greater than the maximum energy the structure can withstand.The proposed method helps to understand the train collision energy flow law and provides theoretical support for the train crashworthiness design in the future.展开更多
In practical engineering construction,multi-layered barriers containing geomembranes are extensively applied to retard the migration of pollutants.However,the associated analytical theory on pollutants diffusion still...In practical engineering construction,multi-layered barriers containing geomembranes are extensively applied to retard the migration of pollutants.However,the associated analytical theory on pollutants diffusion still needs to be further improved.In this work,general analytical solutions are derived for one-dimensional diffusion of degradable organic contaminant(DOC)in the multi-layered media containing geomembranes under a time-varying concentration boundary condition,where the variable substitution and separated variable approaches are employed.These analytical solutions with clear expressions can be used not only to study the diffusion behaviors of DOC in bottom and vertical composite barrier systems,but also to verify other complex numerical models.The proposed general analytical solutions are then fully validated via three comparative analyses,including comparisons with the experimental measurements,an existing analytical solution,and a finite-difference solution.Ultimately,the influences of different factors on the composite cutoff wall’s(CCW,which consists of two soil-bentonite layers and a geomembrane)service performance are investigated through a composite vertical barrier system as the application example.The findings obtained from this investigation can provide scientific guidance for the barrier performance evaluation and the engineering design of CCWs.This application example also exhibits the necessity and effectiveness of the developed analytical solutions.展开更多
This study proposes a general imperfect thermal contact model to predict the thermal contact resistance at the interface among multi-layered composite structures.Based on the Green-Lindsay(GL)thermoelastic theory,semi...This study proposes a general imperfect thermal contact model to predict the thermal contact resistance at the interface among multi-layered composite structures.Based on the Green-Lindsay(GL)thermoelastic theory,semi analytical solutions of temperature increment and displacement of multi-layered composite structures are obtained by using the Laplace transform method,upon which the effects of thermal resistance coefficient,partition coefficient,thermal conductivity ratio and heat capacity ratio on the responses are studied.The results show that the generalized imperfect thermal contact model can realistically describe the imperfect thermal contact problem.Accordingly,it may degenerate into other thermal contact models by adjusting the thermal resistance coefficient and partition coefficient.展开更多
Transportation structures such as composite pavements and railway foundations typically consist of multi-layered media designed to withstand high bearing capacity.A theoretical understanding of load transfer mechanism...Transportation structures such as composite pavements and railway foundations typically consist of multi-layered media designed to withstand high bearing capacity.A theoretical understanding of load transfer mechanisms in these multi-layer composites is essential,as it offers intuitive insights into parametric influences and facilitates enhanced structural performance.This paper employs an improved transfer matrix method to address the limitations of existing theoretical approaches for analyzing multi-layer composite structures.By establishing a twodimensional composite pavement model,it investigates load transfer characteristics and validates the accuracy through finite element simulation.The proposed method offers a straightforward analytical approach for examining internal interactions between structural layers.Case studies indicate that the concrete surface layer is the main load-bearing layer for most vertical normal and shear stresses.The soil base layer reduces the overall mechanical response of the substructure,while horizontal actions increase the risk of interfacial slip and cracking.Structural optimization analysis demonstrates that increasing the thickness of the concrete surface layer,enhancing the thickness and stiffness of the soil base layer,or incorporating gradient layers can significantly mitigate these risks of interfacial slip and cracking.The findings of this study can guide the optimization design,parameter analysis,and damage prevention of multi-layer composite structures.展开更多
Low Earth Orbit(LEO)mega-constellation networks,exemplified by Starlink,are poised to play a pivotal role in future mobile communication networks,due to their low latency and high capacity.With the massively deployed ...Low Earth Orbit(LEO)mega-constellation networks,exemplified by Starlink,are poised to play a pivotal role in future mobile communication networks,due to their low latency and high capacity.With the massively deployed satellites,ground users now can be covered by multiple visible satellites,but also face complex handover issues with such massive high-mobility satellites in multi-layer.The end-to-end routing is also affected by the handover behavior.In this paper,we propose an intelligent handover strategy dedicated to multi-layer LEO mega-constellation networks.Firstly,an analytic model is utilized to rapidly estimate the end-to-end propagation latency as a key handover factor to construct a multi-objective optimization model.Subsequently,an intelligent handover strategy is proposed by employing the Dueling Double Deep Q Network(D3QN)-based deep reinforcement learning algorithm for single-layer constellations.Moreover,an optimal crosslayer handover scheme is proposed by predicting the latency-jitter and minimizing the cross-layer overhead.Simulation results demonstrate the superior performance of the proposed method in the multi-layer LEO mega-constellation,showcasing reductions of up to 8.2%and 59.5%in end-to-end latency and jitter respectively,when compared to the existing handover strategies.展开更多
Stab-resistant textiles play a critical role in personal protection,necessitating a deeper understanding of how structural and layering factors influence their performance.The current study experimentally examines the...Stab-resistant textiles play a critical role in personal protection,necessitating a deeper understanding of how structural and layering factors influence their performance.The current study experimentally examines the effects of textile structure,layering,and ply orientation on the stab resistance of multi-layer textiles.Three 3D warp interlock(3DWI)structures({f1},{f2},{f3})and a 2D woven fabric({f4}),all made of high-performance p-aramid yarns,were engineered and manufactured.Multi-layer specimens were prepared and subjected to drop-weight stabbing tests following HOSBD standards.Stabbing performance metrics,including Depth of Trauma(DoT),Depth of Penetration(DoP),and trauma deformation(Ymax,Xmax),were investigated and analyzed.Statistical analyses(Two-and One-Way ANOVA)indicated that fabric type and layer number significantly impacted DoP(P<0.05),while ply orientation significantly affected DoP(P<0.05)but not DoT(P>0.05).Further detailed analysis revealed that 2D woven fabrics exhibited greater trauma deformation than 3D WIF structures.Increasing the number of layers reduced both DoP and DoT across all fabric structures,with f3 demonstrating the best performance in multi-layer configurations.Aligned ply orientations also enhanced stab resistance,underscoring the importance of alignment in dissipating impact energy.展开更多
Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully construct...Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.展开更多
High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carb...High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carboxylic group enriched COF by post-functionalization with detecting antibody(Ab1)and ferrocene(Fc),and used for electrochemical detection of AFP.Due to the small,homogeneous pore size of the COF,Ab1 with a big size was immobilized on the surface of the COF,while Fc with a small size was covalently modified both on the surface and in the pores of COF.The covalently immobilized Ab1 was quite stable and beneficial to specifically detect AFP biomarkers.Meanwhile,the enriched Fc molecules not only improved the conductivity of the COF,but also effectively transferred and amplified the electrochemical signal.This proposed immunosensor exhibited high sensitivity in detecting AFP with a detection limit of 0.39 pg/mL(S/N of 3:1)and a wide linear response range spanning from 1 pg/mL to 100 ng/mL when plotted against logarithmic concentrations.Furthermore,this immunosensor showed excellent selectivity,stability and reproducibility in the testing of real samples.This study presents an innovative prototype for construction of a precious metal-free,antibody-directly-immobilized,simple and stable electrochemical immunoprobe.展开更多
Accelerating the development of new quality productive forces(NQPF),with innovation at its core,has become essential for firm growth in the new era.Drawing on financial data from China's A-share listed companies s...Accelerating the development of new quality productive forces(NQPF),with innovation at its core,has become essential for firm growth in the new era.Drawing on financial data from China's A-share listed companies spanning the period 2010–2023,this study empirically investigates the impact of entrepreneurial spirit on firm-level NQPF.The results indicate that entrepreneurial spirit significantly promotes firm-level NQPF.Mechanism analysis indicates that entrepreneurial effort—underpinned by technological capital accumulation,effective incentive and constraint mechanisms,and a competitive market environment—plays a mediating role in this relationship.Further heterogeneity analysis reveals that,amid China's economic transition,the positive effects of entrepreneurial spirit are more pronounced in non-state-owned enterprises,high-tech firms,and newly established firms.Accordingly,systematic efforts should be pursued across the technological,organizational,and environmental(TOE)dimensions to optimize the cultivation of entrepreneurial spirit.In particular,greater emphasis should be placed on productive entrepreneurial spirit and the constructive role of entrepreneurial effort,so as to fully leverage their contribution to the advancement of firm-level NQPF.展开更多
The development of efficient photocatalysts for crucial organic transformation,such as aerobic oxidation,remains challenging.Although powdered porous materials offer abundant accessible active sites,their application ...The development of efficient photocatalysts for crucial organic transformation,such as aerobic oxidation,remains challenging.Although powdered porous materials offer abundant accessible active sites,their application in liquid-phase catalysis is often limited by insufficient light absorption and inevitable charge recombination,which are inherent drawbacks of conventional heterogeneous catalysts.Here,through rational design and nanoscale-engineering of porous aromatic frameworks(PAFs)comprising porphyrin and porous organic cage,a quasi-homogeneous porous photocatalyst with high catalytic activity and controllable dimension was developed.The interface-directed growth in oil-in-water emulsion shaped the morphology of photoactive PAFs from powders to nanoflakes,which facilitated the light absorbance and catalyst-substrate interaction.Compared with PAF powders,PAF nanoflakes exhibited superior photocatalytic activity for aerobic oxidation.For mustard gas simulant(2-chloroethyl ethyl sulfide,CEES),PAF nanoflakes exhibited ultrafast detoxification rates in room air with a half-life(t_(1/2))as fast as 26s,which even exceeded other catalysts in pure oxygen.It also completely catalyzed the aerobic oxidation of thioether within 15 min,which is almost the fastest rate among any reported organic photocatalysts.Furthermore,the efficient catalytic performance under mild conditions caused by improved light enrichment,surface charge transfer and carrier lifetime was elucidated.展开更多
The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative p...The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.展开更多
This study presents a novel polyoxometalate(POM)constructed crystalline inorganic framework,featuring a 2D layered architecture with irregular porosity and inherent proton sources.This unique configuration establishes...This study presents a novel polyoxometalate(POM)constructed crystalline inorganic framework,featuring a 2D layered architecture with irregular porosity and inherent proton sources.This unique configuration establishes an intrinsic hydrogen bonding network that facilitates proton hopping(Grotthuss mechanism),achieving a[100]directional proton conductivity of 1.75×10^(-3)S cm^(-1)under a low relative humidity(RH)of 35%at 298 K.Notably,under elevated conditions(338 K,95%RH),it attains a superprotonic conductivity of 1.61 S cm^(-1),representing one of the highest values recorded for framework materials to date.Analysis of the molecular structure,pore geometry characteristics and topological connectivity,and water vapor adsorption experiment(offering proton diffusion coefficient),indicates that the exceptional water-mediated proton dynamics stem from the interlayer S-shaped irregular pore channels,which probably induce a siphon-like effect to significantly enhance the transport of hydrated protons under the vehicle mechanism.This work not only proposes a POM strategy for constructing 2D inorganic frameworks but also reveals the irregular pore channel-enhanced proton dynamics,providing new insights into the optimization of proton conductors.展开更多
Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystall...Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystallinity and surface area of COFs,are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation,catalysis,chemical sensing,and energy storage.Therefore,it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development.In this review,we offer a comprehensive overview of recent advancements in PI-COFs,emphasizing their synthesis methods,design principles and applications.Finally,our brief outlooks on the current challenges and future developments of PI-COFs are provided.Overall,this review aims to guide the recent and future development of PI-COFs.展开更多
Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fund...Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fundamental trade-off between haze and transparency,coupled with impractical thicknesses(≥1 mm).Inspired by squid’s skin-peeling mechanism,this work develops a peroxyformic acid(HCOOOH)-enabled precision peeling strategy to isolate intact 10-μm-thick bamboo green(BG)frameworks—100×thinner than wood-based counterparts while achieving an unprecedented optical performance(88%haze with 80%transparency).This performance surpasses delignified biomass(transparency<40%at 1 mm)and matches engineered cellulose composites,yet requires no energy-intensive nanofibrillation.The preserved native cellulose I crystalline structure(64.76%crystallinity)and wax-coated uniaxial fibril alignment(Hermans factor:0.23)contribute to high mechanical strength(903 MPa modulus)and broadband light scattering.As a light-management layer in polycrystalline silicon solar cells,the BG framework boosts photoelectric conversion efficiency by 0.41%absolute(18.74%→19.15%),outperforming synthetic anti-reflective coatings.The work establishes a scalable,waste-to-wealth route for optical-grade cellulose materials in next-generation optoelectronics.展开更多
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability...Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.展开更多
The separation of propylene(C_(3)H_(6))and propane(C_(3)H_(8))presents a significant industrial challenge due to their similar molecular dimensions and physicochemical properties.Among various separation methods,molec...The separation of propylene(C_(3)H_(6))and propane(C_(3)H_(8))presents a significant industrial challenge due to their similar molecular dimensions and physicochemical properties.Among various separation methods,molecular sieving emerges as the most promising approach,but it will be significantly compromised at high temperatures due to the significant thermal motion.Here,we report a thermally robust zinc-based metal-organic framework(MOF)that can be synthesized on sub-kilogram scale and achieve exceptional C_(3)H_(6)/C_(3)H_(8) separation performances across a broad temperature range(298–353 K).Unlike conventional MOFs suffering from thermal lattice expansion to give poorer selectivity,this new MOF gives the adsorption capacity of C_(3)H_(6)essentially unchanged and that of C_(3)H_(8) negligible at elevated temperatures,outperforming most state-of-the-art adsorbents,in virtue of multiple hydrogen bonds at the aperture.Column breakthrough experiments confirmed the excellent separation capability,and showed no performance degradation over multi-round adsorption-desorption cycles at 353 K.This study addresses the critical challenge of the trade-off between temperature and selectivity in adsorptive separation,which offers new insights into the design of porous structures for highly effective separation at high temperatures.展开更多
基金National Natural Science Foundation of China(52175237)。
文摘The key parameters that characterize the morphological quality of multi-layer and multi-pass metal laser deposited parts are the surface roughness and the error between the actual printing height and the theoretical model height.The Taguchi method was employed to establish the correlations between process parameter combinations and multi-objective characterization of metal deposition morphology(height error and roughness).Results show that using the signal-to-noise ratio and grey relational analysis,the optimal parameter combination for multi-layer and multi-pass deposition is determined as follows:laser power of 800 W,powder feeding rate of 0.3 r/min,step distance of 1.6 mm,and scanning speed of 20 mm/s.Subsequently,a Genetic Bayesian-back propagation(GB-BP)network is constructed to predict multi-objective responses.Compared with the traditional back propagation network,the GB-back propagation network improves the prediction accuracy of height error and surface roughness by 43.14%and 71.43%,respectively.This network can accurately predict the multi-objective characterization of morphological quality of multi-layer and multi-pass metal deposited parts.
文摘As businesses develop and expand with a significant volume of data,data protection and privacy become increasingly important.Research has shown a tremendous increase in phishing activities during and after COVID-19.This research aimed to improve the existing approaches to detecting phishing activities on the internet.We designed a multi-layered phish detection algorithm to detect and prevent phishing applications on the internet using URLs.In the algorithm,we considered technical dimensions of phishing attack prevention and mitigation on the internet.In our approach,we merge,Phishtank,Blacklist,Blocklist,and Whitelist to form our framework.A web application system and browser extension were developed to implement the algorithm.The multi-layer phish detector evaluated ten thousandURLs gathered randomly from the internet(five thousand phishing and five thousand legitimate URLs).The system was estimated to detect levels of accuracy,true-positive and false-positive values.The system level accuracy was recorded to be 98.16%.Approximately 49.6%of the websites were detected as illegitimate,whilst 49.8%were seen as legitimate.
基金supported by the National Key Research and Development Program of China(No.2022YFB3404700)the National Natural Science Foundation of China(Nos.52105313 and 52275299)+2 种基金the Research and Development Program of Beijing Municipal Education Commission,China(No.KM202210005036)the Natural Science Foundation of Chongqing,China(No.CSTB2023NSCQ-MSX0701)the National Defense Basic Research Projects of China(No.JCKY2022405C002).
文摘At present,the emerging solid-phase friction-based additive manufacturing technology,including friction rolling additive man-ufacturing(FRAM),can only manufacture simple single-pass components.In this study,multi-layer multi-pass FRAM-deposited alumin-um alloy samples were successfully prepared using a non-shoulder tool head.The material flow behavior and microstructure of the over-lapped zone between adjacent layers and passes during multi-layer multi-pass FRAM deposition were studied using the hybrid 6061 and 5052 aluminum alloys.The results showed that a mechanical interlocking structure was formed between the adjacent layers and the adja-cent passes in the overlapped center area.Repeated friction and rolling of the tool head led to different degrees of lateral flow and plastic deformation of the materials in the overlapped zone,which made the recrystallization degree in the left and right edge zones of the over-lapped zone the highest,followed by the overlapped center zone and the non-overlapped zone.The tensile strength of the overlapped zone exceeded 90%of that of the single-pass deposition sample.It is proved that although there are uneven grooves on the surface of the over-lapping area during multi-layer and multi-pass deposition,they can be filled by the flow of materials during the deposition of the next lay-er,thus ensuring the dense microstructure and excellent mechanical properties of the overlapping area.The multi-layer multi-pass FRAM deposition overcomes the limitation of deposition width and lays the foundation for the future deposition of large-scale high-performance components.
基金Nourah bint Abdulrahman University for funding this project through the Researchers Supporting Project(PNURSP2025R319)Riyadh,Saudi Arabia and Prince Sultan University for covering the article processing charges(APC)associated with this publication.Special acknowledgement to Automated Systems&Soft Computing Lab(ASSCL),Prince Sultan University,Riyadh,Saudi Arabia.
文摘The growing incidence of cyberattacks necessitates a robust and effective Intrusion Detection Systems(IDS)for enhanced network security.While conventional IDSs can be unsuitable for detecting different and emerging attacks,there is a demand for better techniques to improve detection reliability.This study introduces a new method,the Deep Adaptive Multi-Layer Attention Network(DAMLAN),to boost the result of intrusion detection on network data.Due to its multi-scale attention mechanisms and graph features,DAMLAN aims to address both known and unknown intrusions.The real-world NSL-KDD dataset,a popular choice among IDS researchers,is used to assess the proposed model.There are 67,343 normal samples and 58,630 intrusion attacks in the training set,12,833 normal samples,and 9711 intrusion attacks in the test set.Thus,the proposed DAMLAN method is more effective than the standard models due to the consideration of patterns by the attention layers.The experimental performance of the proposed model demonstrates that it achieves 99.26%training accuracy and 90.68%testing accuracy,with precision reaching 98.54%on the training set and 96.64%on the testing set.The recall and F1 scores again support the model with training set values of 99.90%and 99.21%and testing set values of 86.65%and 91.37%.These results provide a strong basis for the claims made regarding the model’s potential to identify intrusion attacks and affirm its relatively strong overall performance,irrespective of type.Future work would employ more attempts to extend the scalability and applicability of DAMLAN for real-time use in intrusion detection systems.
基金Supported by the National Natural Science Foundation of China(Grant No.52172409)Postdoctoral Innovation Talents Support Program(Grant No.BX20240298)+1 种基金the Fundamental Research Funds for the Central Universities(Grant No.2682024GF023)Heilongjiang Province Postdoctoral Foundation Project(Grant No.LBH-Z23041).
文摘The huge impact kinetic energy cannot be quickly dissipated by the energy-absorbing structure and transferred to the other vehicle through the car body structure,which will cause structural damage and threaten the lives of the occupants.Therefore,it is necessary to understand the laws of energy conversion,dissipation and transfer during train collisions.This study proposes a multi-layer progressive analysis method of energy flow during train collisions,considering the characteristics of the train.In this method,the train collision system is divided into conversion,dissipation,and transfer layers from the perspective of the train,collision interface,and car body structure to analyze the energy conversion,dissipation and transfer characteristics.Taking the collision process of a rail train as an example,a train collision energy transfer path analysis model was established based on power flow theory.The results show that when the maximum mean acceleration of the vehicle meets the standard requirements,the jerk may exceed the allowable limit of the human body,and there is a risk of injury to the occupants of a secondary collision.The decay rate of the collision energy along the direction of train operation reaches 79%.As the collision progresses,the collision energy gradually converges in the structure with holes,and the structure deforms when the gathered energy is greater than the maximum energy the structure can withstand.The proposed method helps to understand the train collision energy flow law and provides theoretical support for the train crashworthiness design in the future.
基金Project(2023YFC3707800)supported by the National Key Research and Development Program of China。
文摘In practical engineering construction,multi-layered barriers containing geomembranes are extensively applied to retard the migration of pollutants.However,the associated analytical theory on pollutants diffusion still needs to be further improved.In this work,general analytical solutions are derived for one-dimensional diffusion of degradable organic contaminant(DOC)in the multi-layered media containing geomembranes under a time-varying concentration boundary condition,where the variable substitution and separated variable approaches are employed.These analytical solutions with clear expressions can be used not only to study the diffusion behaviors of DOC in bottom and vertical composite barrier systems,but also to verify other complex numerical models.The proposed general analytical solutions are then fully validated via three comparative analyses,including comparisons with the experimental measurements,an existing analytical solution,and a finite-difference solution.Ultimately,the influences of different factors on the composite cutoff wall’s(CCW,which consists of two soil-bentonite layers and a geomembrane)service performance are investigated through a composite vertical barrier system as the application example.The findings obtained from this investigation can provide scientific guidance for the barrier performance evaluation and the engineering design of CCWs.This application example also exhibits the necessity and effectiveness of the developed analytical solutions.
基金Projects(42477162,52108347,52178371,52168046,52178321,52308383)supported by the National Natural Science Foundation of ChinaProjects(2023C03143,2022C01099,2024C01219,2022C03151)supported by the Zhejiang Key Research and Development Plan,China+6 种基金Project(LQ22E080010)supported by the Exploring Youth Project of Zhejiang Natural Science Foundation,ChinaProject(LR21E080005)supported by the Outstanding Youth Project of Natural Science Foundation of Zhejiang Province,ChinaProject(2022M712964)supported by the Postdoctoral Science Foundation of ChinaProject(2023AFB008)supported by the Natural Science Foundation of Hubei Province for Youth,ChinaProject(202203)supported by Engineering Research Centre of Rock-Soil Drilling&Excavation and Protection,Ministry of Education,ChinaProject(202305-2)supported by the Science and Technology Project of Zhejiang Provincial Communication Department,ChinaProject(2021K256)supported by the Construction Research Founds of Department of Housing and Urban-Rural Development of Zhejiang Province,China。
文摘This study proposes a general imperfect thermal contact model to predict the thermal contact resistance at the interface among multi-layered composite structures.Based on the Green-Lindsay(GL)thermoelastic theory,semi analytical solutions of temperature increment and displacement of multi-layered composite structures are obtained by using the Laplace transform method,upon which the effects of thermal resistance coefficient,partition coefficient,thermal conductivity ratio and heat capacity ratio on the responses are studied.The results show that the generalized imperfect thermal contact model can realistically describe the imperfect thermal contact problem.Accordingly,it may degenerate into other thermal contact models by adjusting the thermal resistance coefficient and partition coefficient.
基金supported by Fundamental Research Funds for the Central Universities(No.lzujbky-2024-05)Innovation Foundation of Provincial Education Department of Gansu(2024B-005)+2 种基金Scientific Department of Gansu(24CXGA083,24CXGA024,JK2024-28,JK2024-32 and 23CXJA0007)Industrial Support Plan Project of Provincial Education Department of Gansu(2025CYZC-003 and CYZC-2024-10)the Hunan Natural Science Foundation Science and Education Joint Fund Project(2022JJ60109).
文摘Transportation structures such as composite pavements and railway foundations typically consist of multi-layered media designed to withstand high bearing capacity.A theoretical understanding of load transfer mechanisms in these multi-layer composites is essential,as it offers intuitive insights into parametric influences and facilitates enhanced structural performance.This paper employs an improved transfer matrix method to address the limitations of existing theoretical approaches for analyzing multi-layer composite structures.By establishing a twodimensional composite pavement model,it investigates load transfer characteristics and validates the accuracy through finite element simulation.The proposed method offers a straightforward analytical approach for examining internal interactions between structural layers.Case studies indicate that the concrete surface layer is the main load-bearing layer for most vertical normal and shear stresses.The soil base layer reduces the overall mechanical response of the substructure,while horizontal actions increase the risk of interfacial slip and cracking.Structural optimization analysis demonstrates that increasing the thickness of the concrete surface layer,enhancing the thickness and stiffness of the soil base layer,or incorporating gradient layers can significantly mitigate these risks of interfacial slip and cracking.The findings of this study can guide the optimization design,parameter analysis,and damage prevention of multi-layer composite structures.
基金supported by the National Natural Science Foundation of China(No.62401597)Natural Science Foundation of Hunan Province,China(No.2024JJ6469)the Research Project of National University of Defense Technology,China(No.ZK22-02).
文摘Low Earth Orbit(LEO)mega-constellation networks,exemplified by Starlink,are poised to play a pivotal role in future mobile communication networks,due to their low latency and high capacity.With the massively deployed satellites,ground users now can be covered by multiple visible satellites,but also face complex handover issues with such massive high-mobility satellites in multi-layer.The end-to-end routing is also affected by the handover behavior.In this paper,we propose an intelligent handover strategy dedicated to multi-layer LEO mega-constellation networks.Firstly,an analytic model is utilized to rapidly estimate the end-to-end propagation latency as a key handover factor to construct a multi-objective optimization model.Subsequently,an intelligent handover strategy is proposed by employing the Dueling Double Deep Q Network(D3QN)-based deep reinforcement learning algorithm for single-layer constellations.Moreover,an optimal crosslayer handover scheme is proposed by predicting the latency-jitter and minimizing the cross-layer overhead.Simulation results demonstrate the superior performance of the proposed method in the multi-layer LEO mega-constellation,showcasing reductions of up to 8.2%and 59.5%in end-to-end latency and jitter respectively,when compared to the existing handover strategies.
文摘Stab-resistant textiles play a critical role in personal protection,necessitating a deeper understanding of how structural and layering factors influence their performance.The current study experimentally examines the effects of textile structure,layering,and ply orientation on the stab resistance of multi-layer textiles.Three 3D warp interlock(3DWI)structures({f1},{f2},{f3})and a 2D woven fabric({f4}),all made of high-performance p-aramid yarns,were engineered and manufactured.Multi-layer specimens were prepared and subjected to drop-weight stabbing tests following HOSBD standards.Stabbing performance metrics,including Depth of Trauma(DoT),Depth of Penetration(DoP),and trauma deformation(Ymax,Xmax),were investigated and analyzed.Statistical analyses(Two-and One-Way ANOVA)indicated that fabric type and layer number significantly impacted DoP(P<0.05),while ply orientation significantly affected DoP(P<0.05)but not DoT(P>0.05).Further detailed analysis revealed that 2D woven fabrics exhibited greater trauma deformation than 3D WIF structures.Increasing the number of layers reduced both DoP and DoT across all fabric structures,with f3 demonstrating the best performance in multi-layer configurations.Aligned ply orientations also enhanced stab resistance,underscoring the importance of alignment in dissipating impact energy.
文摘Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.
基金the Natural Science Foundation of ZhejiangProvince(No.LZ24B020005)the National Natural Science Foundation of China(No.22071040)for financial support.
文摘High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carboxylic group enriched COF by post-functionalization with detecting antibody(Ab1)and ferrocene(Fc),and used for electrochemical detection of AFP.Due to the small,homogeneous pore size of the COF,Ab1 with a big size was immobilized on the surface of the COF,while Fc with a small size was covalently modified both on the surface and in the pores of COF.The covalently immobilized Ab1 was quite stable and beneficial to specifically detect AFP biomarkers.Meanwhile,the enriched Fc molecules not only improved the conductivity of the COF,but also effectively transferred and amplified the electrochemical signal.This proposed immunosensor exhibited high sensitivity in detecting AFP with a detection limit of 0.39 pg/mL(S/N of 3:1)and a wide linear response range spanning from 1 pg/mL to 100 ng/mL when plotted against logarithmic concentrations.Furthermore,this immunosensor showed excellent selectivity,stability and reproducibility in the testing of real samples.This study presents an innovative prototype for construction of a precious metal-free,antibody-directly-immobilized,simple and stable electrochemical immunoprobe.
基金Liaoning Provincial Social Science Fund Key Disciplines Development Project,Research on the New Supply Function of Entrepreneurs Based on Innovation Ecosystems Driven by Data(Grant No.L22ZD061)。
文摘Accelerating the development of new quality productive forces(NQPF),with innovation at its core,has become essential for firm growth in the new era.Drawing on financial data from China's A-share listed companies spanning the period 2010–2023,this study empirically investigates the impact of entrepreneurial spirit on firm-level NQPF.The results indicate that entrepreneurial spirit significantly promotes firm-level NQPF.Mechanism analysis indicates that entrepreneurial effort—underpinned by technological capital accumulation,effective incentive and constraint mechanisms,and a competitive market environment—plays a mediating role in this relationship.Further heterogeneity analysis reveals that,amid China's economic transition,the positive effects of entrepreneurial spirit are more pronounced in non-state-owned enterprises,high-tech firms,and newly established firms.Accordingly,systematic efforts should be pursued across the technological,organizational,and environmental(TOE)dimensions to optimize the cultivation of entrepreneurial spirit.In particular,greater emphasis should be placed on productive entrepreneurial spirit and the constructive role of entrepreneurial effort,so as to fully leverage their contribution to the advancement of firm-level NQPF.
基金supported by the National Natural Science Foundation of China(22075040,U21A20330,22131004)the National Key R&D Program of China(2022YFB3805900)+2 种基金the Jilin Provincial Scientific and Technological Development Program(20240602105RC)the Innovation Platform for Academicians of Hainan Provincethe Specific Research Fund of the Innovation Platform for Academicians of Hainan Province(YSPTZX202321)。
文摘The development of efficient photocatalysts for crucial organic transformation,such as aerobic oxidation,remains challenging.Although powdered porous materials offer abundant accessible active sites,their application in liquid-phase catalysis is often limited by insufficient light absorption and inevitable charge recombination,which are inherent drawbacks of conventional heterogeneous catalysts.Here,through rational design and nanoscale-engineering of porous aromatic frameworks(PAFs)comprising porphyrin and porous organic cage,a quasi-homogeneous porous photocatalyst with high catalytic activity and controllable dimension was developed.The interface-directed growth in oil-in-water emulsion shaped the morphology of photoactive PAFs from powders to nanoflakes,which facilitated the light absorbance and catalyst-substrate interaction.Compared with PAF powders,PAF nanoflakes exhibited superior photocatalytic activity for aerobic oxidation.For mustard gas simulant(2-chloroethyl ethyl sulfide,CEES),PAF nanoflakes exhibited ultrafast detoxification rates in room air with a half-life(t_(1/2))as fast as 26s,which even exceeded other catalysts in pure oxygen.It also completely catalyzed the aerobic oxidation of thioether within 15 min,which is almost the fastest rate among any reported organic photocatalysts.Furthermore,the efficient catalytic performance under mild conditions caused by improved light enrichment,surface charge transfer and carrier lifetime was elucidated.
基金supported by the National Natural Science Foundation of China(No.52304329)the Yunnan Fundamental Research Projects(No.202201BE070001-003),Guo Lin would like to acknowledge Xing Dian talent support program of Yunnan Province.
文摘The recovery of precious metals(PMs)from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization.This review systematically examines the transformative potential of metal-organic frameworks(MOFs)as next-generation adsorbents for PM recovery,focusing on their synthesis,functionalization,and multiscale adsorption mechanisms.We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity,energy consumption,and secondary pollution.In contrast,MOFs offer tunable porosity,abundant active sites,and tunable surface chemistry,enabling efficient PM capture via synergistic physical and chemical adsorption.Advanced modification techniques,including direct synthesis and post-synthetic modification,are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au,Ag,Pt,and Pd.Key structure-property relationships are established through multiscale characterization and thermodynamic models,revealing the critical roles of hierarchical porosity,soft donor atoms,and framework stability.Industrial challenges,such as aqueous stability and scalability,are addressed via Zr-O bond strengthening,hydrophobic functionalization,and support immobilization.This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.
基金supported by the National Natural Science Foundation of China(22271075,22171071)。
文摘This study presents a novel polyoxometalate(POM)constructed crystalline inorganic framework,featuring a 2D layered architecture with irregular porosity and inherent proton sources.This unique configuration establishes an intrinsic hydrogen bonding network that facilitates proton hopping(Grotthuss mechanism),achieving a[100]directional proton conductivity of 1.75×10^(-3)S cm^(-1)under a low relative humidity(RH)of 35%at 298 K.Notably,under elevated conditions(338 K,95%RH),it attains a superprotonic conductivity of 1.61 S cm^(-1),representing one of the highest values recorded for framework materials to date.Analysis of the molecular structure,pore geometry characteristics and topological connectivity,and water vapor adsorption experiment(offering proton diffusion coefficient),indicates that the exceptional water-mediated proton dynamics stem from the interlayer S-shaped irregular pore channels,which probably induce a siphon-like effect to significantly enhance the transport of hydrated protons under the vehicle mechanism.This work not only proposes a POM strategy for constructing 2D inorganic frameworks but also reveals the irregular pore channel-enhanced proton dynamics,providing new insights into the optimization of proton conductors.
基金supported by the National Key R&D Program of China(No.2023YFA1507204)National Natural Science Foundation ofChina(Nos.22475074,22171139,22225109,22302055)+4 种基金Natural Science Foundation of Guangdong Province(No.2023B1515020076)Key Scientific Research Project Plan of Colleges and Universities of Henan Province(No.24B150004)The Double Thousand Talents Plan of Jiangxi Province(No.jxsq2023102003)Project supported by the Guangdong Provincial Key Laboratory of Carbon Dioxide Resource Utilization(No.2024B121201001)Project supportedby the Major Research plan of the National Natural Science Foundation of China(No.92461310).
文摘Polyimide-linkage covalent organic frameworks(PI-COFs),as a subclass of the COFs material family,featuring the unique combination of excellent thermal stability of polyimide,tunable pore sizes,as well as high crystallinity and surface area of COFs,are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation,catalysis,chemical sensing,and energy storage.Therefore,it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development.In this review,we offer a comprehensive overview of recent advancements in PI-COFs,emphasizing their synthesis methods,design principles and applications.Finally,our brief outlooks on the current challenges and future developments of PI-COFs are provided.Overall,this review aims to guide the recent and future development of PI-COFs.
基金supported by National Natural Science Foundation of China(32494793).
文摘Cellulose frameworks have emerged as promising materials for light management due to their exceptional light-scattering capabilities and sustainable nature.Conventional biomass-derived cellulose frameworks face a fundamental trade-off between haze and transparency,coupled with impractical thicknesses(≥1 mm).Inspired by squid’s skin-peeling mechanism,this work develops a peroxyformic acid(HCOOOH)-enabled precision peeling strategy to isolate intact 10-μm-thick bamboo green(BG)frameworks—100×thinner than wood-based counterparts while achieving an unprecedented optical performance(88%haze with 80%transparency).This performance surpasses delignified biomass(transparency<40%at 1 mm)and matches engineered cellulose composites,yet requires no energy-intensive nanofibrillation.The preserved native cellulose I crystalline structure(64.76%crystallinity)and wax-coated uniaxial fibril alignment(Hermans factor:0.23)contribute to high mechanical strength(903 MPa modulus)and broadband light scattering.As a light-management layer in polycrystalline silicon solar cells,the BG framework boosts photoelectric conversion efficiency by 0.41%absolute(18.74%→19.15%),outperforming synthetic anti-reflective coatings.The work establishes a scalable,waste-to-wealth route for optical-grade cellulose materials in next-generation optoelectronics.
基金The National Natural Science Foundation of China (NSFC,Nos.92256201,52273006,22071041,92356302,and 21971052)Natural Science Foundation of Jilin Province (No.20240101181JC) are gratefully appreciated for financial the supportssupported by the User Experiment Assist System of Shanghai Synchrotron Radiation Facility (SSRF)。
文摘Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.
基金supported by the National Natural Science Foundation of China(22475240,22090061,22488101)the State Key Laboratory of Catalysis(2024SKL-A-010)。
文摘The separation of propylene(C_(3)H_(6))and propane(C_(3)H_(8))presents a significant industrial challenge due to their similar molecular dimensions and physicochemical properties.Among various separation methods,molecular sieving emerges as the most promising approach,but it will be significantly compromised at high temperatures due to the significant thermal motion.Here,we report a thermally robust zinc-based metal-organic framework(MOF)that can be synthesized on sub-kilogram scale and achieve exceptional C_(3)H_(6)/C_(3)H_(8) separation performances across a broad temperature range(298–353 K).Unlike conventional MOFs suffering from thermal lattice expansion to give poorer selectivity,this new MOF gives the adsorption capacity of C_(3)H_(6)essentially unchanged and that of C_(3)H_(8) negligible at elevated temperatures,outperforming most state-of-the-art adsorbents,in virtue of multiple hydrogen bonds at the aperture.Column breakthrough experiments confirmed the excellent separation capability,and showed no performance degradation over multi-round adsorption-desorption cycles at 353 K.This study addresses the critical challenge of the trade-off between temperature and selectivity in adsorptive separation,which offers new insights into the design of porous structures for highly effective separation at high temperatures.
