Over the past decades, two-dimensional（2D） nanomaterials possessing planar layered architecture and unique electronic structures have been being quickly developed, due to their wide potential application in the fiel...Over the past decades, two-dimensional（2D） nanomaterials possessing planar layered architecture and unique electronic structures have been being quickly developed, due to their wide potential application in the fields of chemistry, physics, and materials science. As a new family of 2D nanomaterials, 2D polymerbased nanosheets, featuring excellent characters, such as tunable framework structures, light weight, flexibility, high specific surface, and good semiconducting properties, have been emerging as one kind of promising functional materials for optoelectronics, gas separation, catalysis and sensing, etc. In this review, the recent progress in synthetic approach and characterization of 2D polymer-based nanosheets were summarized, and their current advances in electrochemical energy storage and conversion including second batteries, supercapacitors, oxygen reduction and hydrogen evolution were discussed systematically.展开更多
Two-dimensional polymers(2DPs)are emerging crystalline 2D organic material comprising free-standing,single-atom/monomer-thick,planar,and covalent networks with long-ranging structural order.Benefiting from their intri...Two-dimensional polymers(2DPs)are emerging crystalline 2D organic material comprising free-standing,single-atom/monomer-thick,planar,and covalent networks with long-ranging structural order.Benefiting from their intrinsic porosity,crystallinity,and electrical properties,2DPs have displayed great potential for separation,energy conversion and electronic fields.In this mini review,we aim to provide the recent progress in crystalline 2DPs films form synthesis strategies to characterization methods,as well as the future trends.We first present the synthesis strategy of single-crystalline 2DPs films including crystal engineering approaches and surface science.Also,we summarize the characterization methods of 2DPs films and highlight the advantages and limitations of different methods focusing on chemical bonding,morphology,and crystal structure.Finally,we will present the current challenges and trends regarding the future developments of crystallinity,monomer design,synthesis strategy and characterization.展开更多
Recent years have witnessed the rise of an emerging class of synthetic twodimensional(2D)materials-2D polymers.The combination of organic chemistry and rational design of polymeric crystals has stimulated tremendous r...Recent years have witnessed the rise of an emerging class of synthetic twodimensional(2D)materials-2D polymers.The combination of organic chemistry and rational design of polymeric crystals has stimulated tremendous research efforts in the controlled synthesis of 2D polymers.However,despite the advancement in synthetic methodologies,the structural characterization of 2D polymers remains a significant challenge.Although aberration-corrected high-resolution transmission electron microscopy(AC-HRTEM)is capable of direct imaging of atomic structures with sub-Ångström resolution,electron radiation damage poses a substantial limit on the achievable image resolution due to instant decomposition of the molecular framework.In this Perspective,we will briefly discuss radiation damage mitigation strategies,which may eventually result in AC-HRTEM imaging of 2D polymers down to the atomic scale.展开更多
Molecular weaving is a powerful approach to make molecularly woven materials that have showed unprecedented characteristics and properties intrinsically distinct to those of non-woven materials.We here report a facile...Molecular weaving is a powerful approach to make molecularly woven materials that have showed unprecedented characteristics and properties intrinsically distinct to those of non-woven materials.We here report a facile and efficient approach for the synthesis of 2D woven supramolecular polymers by differentiated self-assembly through orthogonal noncovalent interactions.Importantly,the difference in binding strength of two orthogonal noncovalent interactions can be used to control the process of molecular weaving.Consequently,single-layered 2D woven supramolecular polymers were synthesized and fully characterized by various techniques.This study demonstrates a controllable method for molecular weaving,and will significantly hasten the development of molecularly woven materials.展开更多
Expanding the structural diversity of crystalline two-dimensional polymers(2DPs) is highly desired but remains a considerable challenge. Herein we report the first synthesis of novel crystalline secondary amine-linked...Expanding the structural diversity of crystalline two-dimensional polymers(2DPs) is highly desired but remains a considerable challenge. Herein we report the first synthesis of novel crystalline secondary amine-linked triazine-based 2DPs(SAT-2DPs) by using benzidine or 4, 4′′-diamino-p-terphenyl and cyanuric chloride under solvothermal conditions. We find the structures of diamine-based monomers play a crucial role in deciding whether the synthesized material is crystalline 2DPs nanosheets or amorphous nanoparticles, which is unexpected and provides an important understanding of the 2D polymerization mechanism.The obtained SAT-2DPs not only show a lateral size of micrometers and an ultrathin thickness of a few nanometers, but also demonstrate high crystallinity with a unique ABC stacking configuration, excellent solvent dispersibility and superior thermal stability. In addition, the resultant SAT-2DPs are used to guide uniform lithium-ion deposition due to their abundant nitrogen atoms and ordered open channels. The assembled asymmetric coin cells(Li|Cu) with SAT-2DPs realize the average coulombic efficient up to 99.3% during discharge-charge cycles. This work provides valuable insights into the synthesis of new 2DPs for various applications.展开更多
Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
As emerging two-dimensional(2D)materials,carbides and nitrides(MXenes)could be solid solutions or organized structures made up of multi-atomic layers.With remarkable and adjustable electrical,optical,mechanical,and el...As emerging two-dimensional(2D)materials,carbides and nitrides(MXenes)could be solid solutions or organized structures made up of multi-atomic layers.With remarkable and adjustable electrical,optical,mechanical,and electrochemical characteristics,MXenes have shown great potential in brain-inspired neuromorphic computing electronics,including neuromorphic gas sensors,pressure sensors and photodetectors.This paper provides a forward-looking review of the research progress regarding MXenes in the neuromorphic sensing domain and discussed the critical challenges that need to be resolved.Key bottlenecks such as insufficient long-term stability under environmental exposure,high costs,scalability limitations in large-scale production,and mechanical mismatch in wearable integration hinder their practical deployment.Furthermore,unresolved issues like interfacial compatibility in heterostructures and energy inefficiency in neu-romorphic signal conversion demand urgent attention.The review offers insights into future research directions enhance the fundamental understanding of MXene properties and promote further integration into neuromorphic computing applications through the convergence with various emerging technologies.展开更多
Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are ga...Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are gaining prominence due to their unique combination of mechanical flexibility,environmental compatibility,and solution-processable fabrication.A notable candidate in this field is poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene)(PBTTT),a liquid-crystalline conjugated polymer,with high charge carrier mobility and adaptability to melt-processing techniques.Recent advancements have propelled PBTTT’s figure of merit from below 0.1 to a remarkable 1.28 at 368 K,showcasing its potential for practical applications.This review systematically examines strategies to enhance PBTTT’s TE performance through doping(solution,vapor,and anion exchange doping),composite engineering,and aggregation state controlling.Recent key breakthroughs include ion exchange doping for stable charge modulation,multi-heterojunction architectures reducing thermal conductivity,and proton-coupled electron transfer doping for precise Fermi-level tuning.Despite great progress,challenges still persist in enhancing TE conversion efficiency,balancing or decoupling electrical conductivity,Seebeck coefficient and thermal conductivity,and leveraging melt-processing scalability of PBTTT.By bridging fundamental insights with applied research,this work provides a roadmap for advancing PBTTT-based TE materials toward efficient energy harvesting and wearable electronics.展开更多
Two-dimensional conjugated metal-organic framework(2D c-MOF)nanosheets have garnered significant research interest owing to their suite of distinctive properties.Consequently,diverse synthetic methodologies have been ...Two-dimensional conjugated metal-organic framework(2D c-MOF)nanosheets have garnered significant research interest owing to their suite of distinctive properties.Consequently,diverse synthetic methodologies have been established for the fabrication of 2D c-MOFs exhibiting welldefined nanosheet morphology.In addition,the structural engineering of 2D c-MOF nanosheets for energy storage and conversion has emerged as a prominent research focus.This review comprehensively summarizes recent advancements in 2D c-MOF nanosheets.We commence with a concise overview of diverse synthesis strategies for these materials.Subsequently,progress in their utilization as electrode materials or catalysts for batteries,supercapacitors,and electrocatalysis/photocatalysis is systematically examined.Finally,prevailing challenges and prospective research directions are discussed.Collectively,this review aims to stimulate the development of sophisticated 2D c-MOF nanosheets for high-performance energy applications.展开更多
To investigate the pore structure of graphene oxide modified polymer cement mortar(GOPM)under salt-freeze-thaw(SFT)coupling effects and its impact on deterioration,this study modifies polymer cement mortar(EMCM)with g...To investigate the pore structure of graphene oxide modified polymer cement mortar(GOPM)under salt-freeze-thaw(SFT)coupling effects and its impact on deterioration,this study modifies polymer cement mortar(EMCM)with graphene oxide(GO).The micro-pore structure of GOPM is characterized using LF-NMR and SEM.Fractal theory is applied to calculate the fractal dimension of pore volume,and the deterioration patterns are analyzed based on the evolution characteristics of capillary pores.The experimental results indicate that,after 25 salt-freeze-thaw cycles(SFTc),SO2-4 ions penetrate the matrix,generating corrosion products that fill existing pores and enhance the compactness of the specimen.As the number of cycles increases,the ongoing formation and expansion of corrosion products within the matrix,combined with persistent freezing forces,and result in the degradation of the pore structure.Therefore,the mass loss rate(MLR)of the specimens shows a trend of first decreasing and then increasing,while the relative dynamic elastic modulus(RDEM)initially increases and then decreases.Compared to the PC group specimens,the G3PM group specimens show a 28.71% reduction in MLR and a 31.42% increase in RDEM after 150 SFTc.The fractal dimensions of the transition pores,capillary pores,and macropores in the G3PM specimens first increase and then decrease as the number of SFTc increases.Among them,the capillary pores show the highest correlation with MLR and RDEM,with correlation coefficients of 0.97438 and 0.98555,respectively.展开更多
Nanoscale confinement environments often affect the transport mechanisms of nanofluids.Understanding the dynamic behavior of molecules in two-dimensional(2D)confined channels is of great importance in the areas of sen...Nanoscale confinement environments often affect the transport mechanisms of nanofluids.Understanding the dynamic behavior of molecules in two-dimensional(2D)confined channels is of great importance in the areas of sensing,catalysis and energy storage.As a popular candidate for a new type of gas sensing material,MXenes have the problem of nonselectivity towards polar gases with slow responses,which severely limits their applications.Here,we report a study on regulating the confinement effect of 2D channels between MXene layers through annealing treatment and ion(Na^(+))intercalation for high-performance ammonia(NH_(3))sensing.Firstly,the annealing treatment accurately modulates the size of the 2D channels to effectively block the entry of large-size gas molecules and improve the selectivity for NH_(3).Ab initio molecular dynamics(AIMD)also confirms that the modulated channel size has a special"nano-pumping effect",which can accelerate the dynamic behavior of NH_(3) molecules in the 2D confined space.Moreover,the intercalation of Na+ions increases the adsorption capacity of NH_(3).Therefore,the"nano-pumping effect"and theintercalation of Na+ions effectively enhance the response speed and sensitivity of MXene to NH_(3),respectively.The experimental results show that the modified Ti_(3)C_(2) exhibits high sensitivity(0.17),rapid response(181 s),excellent selectivity and stability towards NH_(3).展开更多
Bone regeneration for non-load-bearing defects remains a significant clinical challenge requiring advanced biomaterials and cellular strategies.Adiposederived mesenchymal stem cells(AD-MSCs)have garnered significant i...Bone regeneration for non-load-bearing defects remains a significant clinical challenge requiring advanced biomaterials and cellular strategies.Adiposederived mesenchymal stem cells(AD-MSCs)have garnered significant interest in bone tissue engineering(BTE)because of their abundant availability,minimally invasive harvesting procedures,and robust differentiation potential into osteogenic lineages.Unlike bone marrow-derived mesenchymal stem cells,AD-MSCs can be easily obtained in large quantities,making them appealing alternatives for therapeutic applications.This review explores hydrogels containing polymers,such as chitosan,collagen,gelatin,and hyaluronic acid,and their composites,tailored for BTE,and emphasizes the importance of these hydrogels as scaffolds for the delivery of AD-MSCs.Various hydrogel fabrication techniques and biocompatibility assessments are discussed,along with innovative modifications to enhance osteogenesis.This review also briefly outlines AD-MSC isolation methods and advanced embedding techniques for precise cell placement,such as direct encapsulation and three-dimensional bioprinting.We discuss the mechanisms of bone regeneration in the AD-MSC-laden hydrogels,including osteoinduction,vascularization,and extracellular matrix remodeling.We also review the preclinical and clinical applications of AD-MSC-hydrogel systems,emphasizing their success and limitations.In this review,we provide a comprehensive overview of AD-MSC-based hydrogel systems to guide the development of effective therapies for bone regeneration.展开更多
Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving...Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.展开更多
As a promising graphene analogue,two-dimensional(2D)polymer nanosheets with unique 2D features,diversified topological structures and as well as tunable electronic properties,have received extensive attention in recen...As a promising graphene analogue,two-dimensional(2D)polymer nanosheets with unique 2D features,diversified topological structures and as well as tunable electronic properties,have received extensive attention in recent years.Here in this review,we summarized the recent research progress in the preparation methods of 2D polymer nanosheets,mainly including interfacial polymerization and solution polymerization.We also discussed the recent research advancements of 2D polymer nanosheets in the fields of energy storage and conversion applications,such as batteries,supercapacitors,electrocatalysis and photocatalysis.Finally,on the basis of their current development,we put forward the existing challenges and some personal perspectives.展开更多
Two-dimensional(2D) materials have been demonstrated to exhibit unique properties originating from its 2D nature. In recent years, the construction of 2D materials has become a topic of great interest. This article su...Two-dimensional(2D) materials have been demonstrated to exhibit unique properties originating from its 2D nature. In recent years, the construction of 2D materials has become a topic of great interest. This article summarizes the recent advance of 2D supramolecular organic frameworks(SOFs) which are homogeneously constructed in solution phase through self-assembly of rationally designed building blocks. These 2D SOFs are soluble and still maintain stable network structures in solutions, which exhibit uniqueness not only in structures but also in properties. In this concise review, the SOFs-related background is briefly introduced firstly, followed by outlining the research progress of soluble 2D SOFs from the perspective of monomer design, assembly, and structural characterization.The article ends with a personal outlook on the future development of this new class of supramolecular polymers.展开更多
Generalized two-dimensional correlation spectroscopy （2DCOS） and its derivate technique, perturbation correlation moving window （PCMW）, have found great potential in studying a series of physico-chemical phenomena...Generalized two-dimensional correlation spectroscopy （2DCOS） and its derivate technique, perturbation correlation moving window （PCMW）, have found great potential in studying a series of physico-chemical phenomena in stimuli-responsive polymeric systems. By spreading peaks along a second dimension, 2DCOS can significantly enhance spectral resolution and discern the sequence of group dynamics applicable to various external perturbation-induced spectroscopic changes, especially in infrared （IR）, near-infrared （NIR） and Raman spectroscopy. On the basis of 2DCOS synchronous power spectra changing, PCMW proves to be a powerful tool to monitor complicated spectral variations and to find transition points and ranges. This article reviews the recent work of our research group in the application of 2DCOS and PCMW in thermoresponsive polymers, mainly focused on liquid crystalline polymers and lower critical solution temperature （LCST）-type polymers. Details of group motions and chain conformational changes upon temperature perturbation can thus be elucidated at the molecular level, which contribute to the understanding of their phase transition nature.展开更多
A metal-organic coordination polymer [Cd（tdc）（bimb）（μ2-H2O）]n （H2tdc = thiophe-ne-2,5-dicarboxylic acid, bimb = 1,4-bis（imidazol-l-yl）-butane） 1 has been hydrothermally synthe- sized and characterized by el...A metal-organic coordination polymer [Cd（tdc）（bimb）（μ2-H2O）]n （H2tdc = thiophe-ne-2,5-dicarboxylic acid, bimb = 1,4-bis（imidazol-l-yl）-butane） 1 has been hydrothermally synthe- sized and characterized by elemental analysis, IR, TG, luminescence spectrum and single-crystal X-ray diffraction. Colorless crystals crystallize in the triclinic system, space group P^-1 with a = 5.8945（3）, b = 10.3129（5）, c = 11.2226（5） A, a = 95.1430（10）,β = 97.9020（10）, γ = 90.5910（10）°, V = 672.84（6） A^3, C11H11CdN2O5S, Mr= 395.68, De = 1.953 g/cm^3, μ（MoKa） = 1.797 mm^-1, F（000） = 390, Z = 2, the final R = 0.0209 and wR = 0.0508 for 2514 observed reflections （I 〉 2σ（I））. The structure of 1 exhibits a two-dimensional layer-like structure.展开更多
A new coordination polymer, [Mn（L）（1,4-bdc）] （L = 11-fluoro-dipyrido[3,2- a：2＂,3 ＂- c]phenazine, 1,4-bdc - benzene-1,4-dicarboxylate）, has been synthesized through the hydrothermal method and characterized by...A new coordination polymer, [Mn（L）（1,4-bdc）] （L = 11-fluoro-dipyrido[3,2- a：2＂,3 ＂- c]phenazine, 1,4-bdc - benzene-1,4-dicarboxylate）, has been synthesized through the hydrothermal method and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.7544（9）, b = 10.8254（10）, c = 11.5288（10） A, a = 114.1300（10）, β = 96.6110（10）, y = 105.0390（10）°, V= 1038.62（16）/k3, Z= 2, C26H13FMnN404, Mr = 519.34, Dc = 1.661 g/cm3, F（000） = 526, ,u（MoKa） = 0.691 mm^-, R = 0.0405 and wR = 0.0977. The 1,4-bdc dianions link the neighboring Mn（II） atoms to yield a two-dimensional layer structure. The L ligands are attached on both sides of the layer. The π-π interactions between the L ligands of neighboring layers result in a three-dimensional supramolecular architecture.展开更多
In recent years,as a new class of two-dimensional polymer,covalent organic frameworks（COFs） have attracted intensive attention and developed rapidly.This review provides an overview of a type of COFs which can be ut...In recent years,as a new class of two-dimensional polymer,covalent organic frameworks（COFs） have attracted intensive attention and developed rapidly.This review provides an overview of a type of COFs which can be utilized as organic semiconductors.Carefully choosing monomers as the building blocks will bestow different types of semiconducting character on COFs.We summarize the p-type,n-type and ambipolar semiconducting COFs and highlight the effects of π-functional building blocks on the photoconductive behaviors of the semiconducting COFs.展开更多
Self-healing materials have been developed over the past decade with the recovery ability after damage.However,most researches focused on the self-healing process at three-dimension.Herein,we prepare monolayer self-he...Self-healing materials have been developed over the past decade with the recovery ability after damage.However,most researches focused on the self-healing process at three-dimension.Herein,we prepare monolayer self-healing hydrogen-bond-based supramolecular polymer film and explore the self-healing process at the two-dimensional limit.The healing process,which can be reversibly repeated for at least three times,is influenced by the temperature,the molecule-substrate interaction and the substrate roughness.In the application,the monolayer self-healing polymer film can be used to modify the SiO2 dielectric for copper phthalocyanine field effect transistor with improved mobility.This work will be valuable for developing two-dimensional functional self-healing materials in the future.展开更多
基金financially supported by the National Natural Science Foundation of China(51403126,21574080,61306018 and 21504057)Shanghai Committee of Science and Technology(15JC1490500,16JC1400703,and 17ZR1441700)+1 种基金Open Project Program of the State Key Laboratory of Photocatalysis on Energy and Environment(SKLPEE-KF201702,Fuzhou University)State Key Laboratory of Supramolecular Structure and Materials(sklssm201732,Jinlin University)
文摘Over the past decades, two-dimensional（2D） nanomaterials possessing planar layered architecture and unique electronic structures have been being quickly developed, due to their wide potential application in the fields of chemistry, physics, and materials science. As a new family of 2D nanomaterials, 2D polymerbased nanosheets, featuring excellent characters, such as tunable framework structures, light weight, flexibility, high specific surface, and good semiconducting properties, have been emerging as one kind of promising functional materials for optoelectronics, gas separation, catalysis and sensing, etc. In this review, the recent progress in synthetic approach and characterization of 2D polymer-based nanosheets were summarized, and their current advances in electrochemical energy storage and conversion including second batteries, supercapacitors, oxygen reduction and hydrogen evolution were discussed systematically.
基金supported by the Zhejiang Provincial Natural Science Foundation of China(No.LR21E030001).
文摘Two-dimensional polymers(2DPs)are emerging crystalline 2D organic material comprising free-standing,single-atom/monomer-thick,planar,and covalent networks with long-ranging structural order.Benefiting from their intrinsic porosity,crystallinity,and electrical properties,2DPs have displayed great potential for separation,energy conversion and electronic fields.In this mini review,we aim to provide the recent progress in crystalline 2DPs films form synthesis strategies to characterization methods,as well as the future trends.We first present the synthesis strategy of single-crystalline 2DPs films including crystal engineering approaches and surface science.Also,we summarize the characterization methods of 2DPs films and highlight the advantages and limitations of different methods focusing on chemical bonding,morphology,and crystal structure.Finally,we will present the current challenges and trends regarding the future developments of crystallinity,monomer design,synthesis strategy and characterization.
基金gratefully acknowledge the funding from the Germany Research Foundation(DFG)in SFB-1415(Grant No.417590517)from the European Union's Horizon 2020 research and innovation programme under Grant Agreement Nos.881603,785291(GrapheneCore3).
文摘Recent years have witnessed the rise of an emerging class of synthetic twodimensional(2D)materials-2D polymers.The combination of organic chemistry and rational design of polymeric crystals has stimulated tremendous research efforts in the controlled synthesis of 2D polymers.However,despite the advancement in synthetic methodologies,the structural characterization of 2D polymers remains a significant challenge.Although aberration-corrected high-resolution transmission electron microscopy(AC-HRTEM)is capable of direct imaging of atomic structures with sub-Ångström resolution,electron radiation damage poses a substantial limit on the achievable image resolution due to instant decomposition of the molecular framework.In this Perspective,we will briefly discuss radiation damage mitigation strategies,which may eventually result in AC-HRTEM imaging of 2D polymers down to the atomic scale.
基金supported by the National Natural Science Foundation of China(Nos.92156012 and 22071078).
文摘Molecular weaving is a powerful approach to make molecularly woven materials that have showed unprecedented characteristics and properties intrinsically distinct to those of non-woven materials.We here report a facile and efficient approach for the synthesis of 2D woven supramolecular polymers by differentiated self-assembly through orthogonal noncovalent interactions.Importantly,the difference in binding strength of two orthogonal noncovalent interactions can be used to control the process of molecular weaving.Consequently,single-layered 2D woven supramolecular polymers were synthesized and fully characterized by various techniques.This study demonstrates a controllable method for molecular weaving,and will significantly hasten the development of molecularly woven materials.
基金support by the National Natural Science Foundation of China (51873039, 51673042)the Young Elite Scientist Sponsorship Program by CAST (2017QNRC001)。
文摘Expanding the structural diversity of crystalline two-dimensional polymers(2DPs) is highly desired but remains a considerable challenge. Herein we report the first synthesis of novel crystalline secondary amine-linked triazine-based 2DPs(SAT-2DPs) by using benzidine or 4, 4′′-diamino-p-terphenyl and cyanuric chloride under solvothermal conditions. We find the structures of diamine-based monomers play a crucial role in deciding whether the synthesized material is crystalline 2DPs nanosheets or amorphous nanoparticles, which is unexpected and provides an important understanding of the 2D polymerization mechanism.The obtained SAT-2DPs not only show a lateral size of micrometers and an ultrathin thickness of a few nanometers, but also demonstrate high crystallinity with a unique ABC stacking configuration, excellent solvent dispersibility and superior thermal stability. In addition, the resultant SAT-2DPs are used to guide uniform lithium-ion deposition due to their abundant nitrogen atoms and ordered open channels. The assembled asymmetric coin cells(Li|Cu) with SAT-2DPs realize the average coulombic efficient up to 99.3% during discharge-charge cycles. This work provides valuable insights into the synthesis of new 2DPs for various applications.
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
基金supported by the NSFC(12474071)Natural Science Foundation of Shandong Province(ZR2024YQ051,ZR2025QB50)+6 种基金Guangdong Basic and Applied Basic Research Foundation(2025A1515011191)the Shanghai Sailing Program(23YF1402200,23YF1402400)funded by Basic Research Program of Jiangsu(BK20240424)Open Research Fund of State Key Laboratory of Crystal Materials(KF2406)Taishan Scholar Foundation of Shandong Province(tsqn202408006,tsqn202507058)Young Talent of Lifting engineering for Science and Technology in Shandong,China(SDAST2024QTB002)the Qilu Young Scholar Program of Shandong University。
文摘As emerging two-dimensional(2D)materials,carbides and nitrides(MXenes)could be solid solutions or organized structures made up of multi-atomic layers.With remarkable and adjustable electrical,optical,mechanical,and electrochemical characteristics,MXenes have shown great potential in brain-inspired neuromorphic computing electronics,including neuromorphic gas sensors,pressure sensors and photodetectors.This paper provides a forward-looking review of the research progress regarding MXenes in the neuromorphic sensing domain and discussed the critical challenges that need to be resolved.Key bottlenecks such as insufficient long-term stability under environmental exposure,high costs,scalability limitations in large-scale production,and mechanical mismatch in wearable integration hinder their practical deployment.Furthermore,unresolved issues like interfacial compatibility in heterostructures and energy inefficiency in neu-romorphic signal conversion demand urgent attention.The review offers insights into future research directions enhance the fundamental understanding of MXene properties and promote further integration into neuromorphic computing applications through the convergence with various emerging technologies.
基金financial support by Guangdong Basic and Applied Basic Research Foundation(2025A1515012415)National Natural Science Foundation of China(52242305)the Stable Support Project of Shenzhen(Project No.20231122125728001).
文摘Thermoelectric(TE)materials,being capable of converting waste heat into electricity,are pivotal for sustainable energy solutions.Among emerging TE materials,organic TE materials,particularly conjugated polymers,are gaining prominence due to their unique combination of mechanical flexibility,environmental compatibility,and solution-processable fabrication.A notable candidate in this field is poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene)(PBTTT),a liquid-crystalline conjugated polymer,with high charge carrier mobility and adaptability to melt-processing techniques.Recent advancements have propelled PBTTT’s figure of merit from below 0.1 to a remarkable 1.28 at 368 K,showcasing its potential for practical applications.This review systematically examines strategies to enhance PBTTT’s TE performance through doping(solution,vapor,and anion exchange doping),composite engineering,and aggregation state controlling.Recent key breakthroughs include ion exchange doping for stable charge modulation,multi-heterojunction architectures reducing thermal conductivity,and proton-coupled electron transfer doping for precise Fermi-level tuning.Despite great progress,challenges still persist in enhancing TE conversion efficiency,balancing or decoupling electrical conductivity,Seebeck coefficient and thermal conductivity,and leveraging melt-processing scalability of PBTTT.By bridging fundamental insights with applied research,this work provides a roadmap for advancing PBTTT-based TE materials toward efficient energy harvesting and wearable electronics.
基金supported by the National Natural Science Foundation of China(Nos.22205196 and 52371240)the Natural Science Foundation of Jiangsu Province(No.BK20210790)the start-up fundings from Yangzhou University.
文摘Two-dimensional conjugated metal-organic framework(2D c-MOF)nanosheets have garnered significant research interest owing to their suite of distinctive properties.Consequently,diverse synthetic methodologies have been established for the fabrication of 2D c-MOFs exhibiting welldefined nanosheet morphology.In addition,the structural engineering of 2D c-MOF nanosheets for energy storage and conversion has emerged as a prominent research focus.This review comprehensively summarizes recent advancements in 2D c-MOF nanosheets.We commence with a concise overview of diverse synthesis strategies for these materials.Subsequently,progress in their utilization as electrode materials or catalysts for batteries,supercapacitors,and electrocatalysis/photocatalysis is systematically examined.Finally,prevailing challenges and prospective research directions are discussed.Collectively,this review aims to stimulate the development of sophisticated 2D c-MOF nanosheets for high-performance energy applications.
基金Funded by the National Natural Science Foundation of China(Nos.5226804252468035)。
文摘To investigate the pore structure of graphene oxide modified polymer cement mortar(GOPM)under salt-freeze-thaw(SFT)coupling effects and its impact on deterioration,this study modifies polymer cement mortar(EMCM)with graphene oxide(GO).The micro-pore structure of GOPM is characterized using LF-NMR and SEM.Fractal theory is applied to calculate the fractal dimension of pore volume,and the deterioration patterns are analyzed based on the evolution characteristics of capillary pores.The experimental results indicate that,after 25 salt-freeze-thaw cycles(SFTc),SO2-4 ions penetrate the matrix,generating corrosion products that fill existing pores and enhance the compactness of the specimen.As the number of cycles increases,the ongoing formation and expansion of corrosion products within the matrix,combined with persistent freezing forces,and result in the degradation of the pore structure.Therefore,the mass loss rate(MLR)of the specimens shows a trend of first decreasing and then increasing,while the relative dynamic elastic modulus(RDEM)initially increases and then decreases.Compared to the PC group specimens,the G3PM group specimens show a 28.71% reduction in MLR and a 31.42% increase in RDEM after 150 SFTc.The fractal dimensions of the transition pores,capillary pores,and macropores in the G3PM specimens first increase and then decrease as the number of SFTc increases.Among them,the capillary pores show the highest correlation with MLR and RDEM,with correlation coefficients of 0.97438 and 0.98555,respectively.
基金supported by the National Natural Science Foundation of China(Nos.52422505 and 12274124)the Innovative Research Group Project of the National Natural Science Foundation of China(No.52321002).
文摘Nanoscale confinement environments often affect the transport mechanisms of nanofluids.Understanding the dynamic behavior of molecules in two-dimensional(2D)confined channels is of great importance in the areas of sensing,catalysis and energy storage.As a popular candidate for a new type of gas sensing material,MXenes have the problem of nonselectivity towards polar gases with slow responses,which severely limits their applications.Here,we report a study on regulating the confinement effect of 2D channels between MXene layers through annealing treatment and ion(Na^(+))intercalation for high-performance ammonia(NH_(3))sensing.Firstly,the annealing treatment accurately modulates the size of the 2D channels to effectively block the entry of large-size gas molecules and improve the selectivity for NH_(3).Ab initio molecular dynamics(AIMD)also confirms that the modulated channel size has a special"nano-pumping effect",which can accelerate the dynamic behavior of NH_(3) molecules in the 2D confined space.Moreover,the intercalation of Na+ions increases the adsorption capacity of NH_(3).Therefore,the"nano-pumping effect"and theintercalation of Na+ions effectively enhance the response speed and sensitivity of MXene to NH_(3),respectively.The experimental results show that the modified Ti_(3)C_(2) exhibits high sensitivity(0.17),rapid response(181 s),excellent selectivity and stability towards NH_(3).
文摘Bone regeneration for non-load-bearing defects remains a significant clinical challenge requiring advanced biomaterials and cellular strategies.Adiposederived mesenchymal stem cells(AD-MSCs)have garnered significant interest in bone tissue engineering(BTE)because of their abundant availability,minimally invasive harvesting procedures,and robust differentiation potential into osteogenic lineages.Unlike bone marrow-derived mesenchymal stem cells,AD-MSCs can be easily obtained in large quantities,making them appealing alternatives for therapeutic applications.This review explores hydrogels containing polymers,such as chitosan,collagen,gelatin,and hyaluronic acid,and their composites,tailored for BTE,and emphasizes the importance of these hydrogels as scaffolds for the delivery of AD-MSCs.Various hydrogel fabrication techniques and biocompatibility assessments are discussed,along with innovative modifications to enhance osteogenesis.This review also briefly outlines AD-MSC isolation methods and advanced embedding techniques for precise cell placement,such as direct encapsulation and three-dimensional bioprinting.We discuss the mechanisms of bone regeneration in the AD-MSC-laden hydrogels,including osteoinduction,vascularization,and extracellular matrix remodeling.We also review the preclinical and clinical applications of AD-MSC-hydrogel systems,emphasizing their success and limitations.In this review,we provide a comprehensive overview of AD-MSC-based hydrogel systems to guide the development of effective therapies for bone regeneration.
基金the financial support from the National Natural Science Foundation of China(52203123 and 52473248)State Key Laboratory of Polymer Materials Engineering(sklpme2024-2-04)+1 种基金the Fundamental Research Funds for the Central Universitiessponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.
基金the National Natural Science Foundation of China(Nos.51873039 and 51673042)the Young Elite Scientist Sponsorship Program by CAST(No.2017QNRC001)the fund for post-doctoral program of Henan University to Z.H.C.(No.FJ3050A0670001).
文摘As a promising graphene analogue,two-dimensional(2D)polymer nanosheets with unique 2D features,diversified topological structures and as well as tunable electronic properties,have received extensive attention in recent years.Here in this review,we summarized the recent research progress in the preparation methods of 2D polymer nanosheets,mainly including interfacial polymerization and solution polymerization.We also discussed the recent research advancements of 2D polymer nanosheets in the fields of energy storage and conversion applications,such as batteries,supercapacitors,electrocatalysis and photocatalysis.Finally,on the basis of their current development,we put forward the existing challenges and some personal perspectives.
基金financially supported by the National Natural Science Foundation of China (Nos. 21472225, 21725404)the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDAB20000000)
文摘Two-dimensional(2D) materials have been demonstrated to exhibit unique properties originating from its 2D nature. In recent years, the construction of 2D materials has become a topic of great interest. This article summarizes the recent advance of 2D supramolecular organic frameworks(SOFs) which are homogeneously constructed in solution phase through self-assembly of rationally designed building blocks. These 2D SOFs are soluble and still maintain stable network structures in solutions, which exhibit uniqueness not only in structures but also in properties. In this concise review, the SOFs-related background is briefly introduced firstly, followed by outlining the research progress of soluble 2D SOFs from the perspective of monomer design, assembly, and structural characterization.The article ends with a personal outlook on the future development of this new class of supramolecular polymers.
基金financially supported by the National Natural Science Foundation of China(Nos.21274030,51473038 and 21604024)the Natural Science Foundation of Shanghai(No.17ZR1440400)+1 种基金the Open Project of State Key Laboratory of Chemical Engineering(No.SKL-Ch E-16C02)“Chenguang Plan”
文摘Generalized two-dimensional correlation spectroscopy （2DCOS） and its derivate technique, perturbation correlation moving window （PCMW）, have found great potential in studying a series of physico-chemical phenomena in stimuli-responsive polymeric systems. By spreading peaks along a second dimension, 2DCOS can significantly enhance spectral resolution and discern the sequence of group dynamics applicable to various external perturbation-induced spectroscopic changes, especially in infrared （IR）, near-infrared （NIR） and Raman spectroscopy. On the basis of 2DCOS synchronous power spectra changing, PCMW proves to be a powerful tool to monitor complicated spectral variations and to find transition points and ranges. This article reviews the recent work of our research group in the application of 2DCOS and PCMW in thermoresponsive polymers, mainly focused on liquid crystalline polymers and lower critical solution temperature （LCST）-type polymers. Details of group motions and chain conformational changes upon temperature perturbation can thus be elucidated at the molecular level, which contribute to the understanding of their phase transition nature.
基金supported by the Science and Technology Research Projects of the Education Department of Jilin Province (No. 2012.479)
文摘A metal-organic coordination polymer [Cd（tdc）（bimb）（μ2-H2O）]n （H2tdc = thiophe-ne-2,5-dicarboxylic acid, bimb = 1,4-bis（imidazol-l-yl）-butane） 1 has been hydrothermally synthe- sized and characterized by elemental analysis, IR, TG, luminescence spectrum and single-crystal X-ray diffraction. Colorless crystals crystallize in the triclinic system, space group P^-1 with a = 5.8945（3）, b = 10.3129（5）, c = 11.2226（5） A, a = 95.1430（10）,β = 97.9020（10）, γ = 90.5910（10）°, V = 672.84（6） A^3, C11H11CdN2O5S, Mr= 395.68, De = 1.953 g/cm^3, μ（MoKa） = 1.797 mm^-1, F（000） = 390, Z = 2, the final R = 0.0209 and wR = 0.0508 for 2514 observed reflections （I 〉 2σ（I））. The structure of 1 exhibits a two-dimensional layer-like structure.
基金Supported by the Institute Foundation of Siping City (No.2009011)
文摘A new coordination polymer, [Mn（L）（1,4-bdc）] （L = 11-fluoro-dipyrido[3,2- a：2＂,3 ＂- c]phenazine, 1,4-bdc - benzene-1,4-dicarboxylate）, has been synthesized through the hydrothermal method and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.7544（9）, b = 10.8254（10）, c = 11.5288（10） A, a = 114.1300（10）, β = 96.6110（10）, y = 105.0390（10）°, V= 1038.62（16）/k3, Z= 2, C26H13FMnN404, Mr = 519.34, Dc = 1.661 g/cm3, F（000） = 526, ,u（MoKa） = 0.691 mm^-, R = 0.0405 and wR = 0.0977. The 1,4-bdc dianions link the neighboring Mn（II） atoms to yield a two-dimensional layer structure. The L ligands are attached on both sides of the layer. The π-π interactions between the L ligands of neighboring layers result in a three-dimensional supramolecular architecture.
基金the support from National Program for Thousand Young Talents of Chinathe National Natural Science Foundation of China(No.21544001)Fudan University
文摘In recent years,as a new class of two-dimensional polymer,covalent organic frameworks（COFs） have attracted intensive attention and developed rapidly.This review provides an overview of a type of COFs which can be utilized as organic semiconductors.Carefully choosing monomers as the building blocks will bestow different types of semiconducting character on COFs.We summarize the p-type,n-type and ambipolar semiconducting COFs and highlight the effects of π-functional building blocks on the photoconductive behaviors of the semiconducting COFs.
基金supported by National Program for Thousand Young Talents of China,the National Natural Science Foundation of China(Nos.51773041,21544001,21603038)Shanghai Committee of Science and Technology in China(No.18ZR1404900)Fudan University
文摘Self-healing materials have been developed over the past decade with the recovery ability after damage.However,most researches focused on the self-healing process at three-dimension.Herein,we prepare monolayer self-healing hydrogen-bond-based supramolecular polymer film and explore the self-healing process at the two-dimensional limit.The healing process,which can be reversibly repeated for at least three times,is influenced by the temperature,the molecule-substrate interaction and the substrate roughness.In the application,the monolayer self-healing polymer film can be used to modify the SiO2 dielectric for copper phthalocyanine field effect transistor with improved mobility.This work will be valuable for developing two-dimensional functional self-healing materials in the future.
