In 2022,The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results.First,a series of well-defined dinuclear organoboron catalysts were develo...In 2022,The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results.First,a series of well-defined dinuclear organoboron catalysts were developed to precisely control the enchainment of ether and carbonate segments during the copolymerization of CO_(2)and epoxides.Second,polyester had been synthesized through cationic copolymerization of cyclic anhydride.Third,ring-opening polymerization of carbon dioxide based valerolactone had been achieved,revealing the prospect of 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one(EVL)in utilizing CO_(2)and synthesizing functional polymers.Fourth,machine learning methods have been applied to biomaterial research,enabling high-throughput screening of functional biomaterial surfaces for implantable devices,and searching for potent antimicrobial peptides in whole combinatorial peptide libraries.Fifth,methods of characterization of biomacromolecule RNA transcription and manipulation of nucleoside modification were developed.Sixth,artificial enzymes-armed Bifidobacterium Longum probiotics were established to tune down gut inflammation.Seventh,three-dimensional(3D)printing technologies were used to engineer tough supramolecular hydrogels.Eighth,hydroplastic foaming graphene frameworks for acoustic and conductive polymer composites were provided for application.Ninth,aggregate photophysics about the nature of through-space interactions(TSIs)and manipulating their strength in small molecules with non-conjugated structure had been elucidated.Tenth,the forming mechanism of a newfound nested texture in poly(L-lactic acid)(PLLA)spherulitic films had been revealed.Finally,the isotropically dyeing mechanism of KDP single crystals grown from hydrogels have been explored.The related works are reviewed in this paper.展开更多
In 2021,The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results.First,a series of versatile organoboron catalysts were synthesized for rin...In 2021,The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results.First,a series of versatile organoboron catalysts were synthesized for ring-opening(co)polymerizations.Second,a catalyst-free polycondensation mechanism was proposed for the production of polyesters with high molecular weights.Third,a co-assembly method that can fabricate films and coatings with controllable structures and properties on various substrates was demonstrated,providing a platform for the construction of novel surface coatings.Forth,facile methods for producing high-productivity poly(propylene carbonate)and semicrystalline polyester have been discovered.And linear non-conjugated polyesters exhibiting yellow-green clusteroluminescence were developed for the first time.Fifth,a supramolecular prodrug nano-assembly strategy has been developed for reactive nitrogen species potentiated chemotherapy.Sixth,a series of tough and stiff supramolecular hydrogels with shape memory properties have been used for information encryption.Seventh,reversible fusion and fission of wet-spun graphene oxide fibers has been successfully achieved.Eighth,three non-conjugated polypeptides were synthesized and the mechanism of clusteroluminescence was studied.Ninth,a series of conducting covalent organic frameworks with high electrical conductivity and carrier mobility have been used as high-performance chemiresistor,electrocatalyst,and organic field-effect transistor.Tenth,the exploration of non-fused electron acceptors,and their photostable mechanism are exemplified for developing high-performance,low-cost and eco-friendly polymer solar cells.Finally,gel-grown long-range ordering bulk-heterojunctions has achieved improved X-ray detector performance.展开更多
In 2020, the MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had made progresses in several aspects. First, a series of metal-free organoboron catalysts had been designed an...In 2020, the MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had made progresses in several aspects. First, a series of metal-free organoboron catalysts had been designed and synthesized facilely, exhibiting outstanding reactivity, thermalstability and productivity in different kinds of polymerization and cycloaddition reactions. Second, a variety of chalcogen(O, S, Se)-rich polymers had been synthesized via organocatalysis and fabricated to be the ionic conductive and photoluminescent materials. Third, diverse microenvironment-sensitive nanoparticles had been designed,and novel strategies had been realized, to enhance the therapeutic efficacy in cancer as well as biofilmassociated infections. Fourth, m6 A modification on cellular transcriptome-wide messenger RNA had been successfully mapped at single base resolution using a metabolic labeling method. Fifth, a hydrogel-based robot had been developed, showing swift locomotion as a response to dynamic light stimulations. Sixth,the conformation-size scaling law and the conformation evolution map of 2 D macromolecules in solution had been elucidated experimentally, in the single-layer graphene oxide model. Seventh, semitransparent polymer solar cells, promising as building-integrated photovoltaics, have been developed with the fine balance among power conversion efficiency, visible light transparency and infrared photon radiation rejection. Finally, long-range ordered bulk-heterojunctions of organic semiconductors had been achieved,and their superior optoelectronic properties and potential application in photoelectric conversion had been revealed. The related work progresses are reviewed in this paper.展开更多
Following the conventional carbon allotropes of diamond and graphite,fullerene,carbon nanotubes(CNTs) and graphene as 0D,1D and 2D graphitic macromolecules have been discovered recently in succession,declaring the unl...Following the conventional carbon allotropes of diamond and graphite,fullerene,carbon nanotubes(CNTs) and graphene as 0D,1D and 2D graphitic macromolecules have been discovered recently in succession,declaring the unlimited potential of carbon-based nanomaterials and nanotechnology.Although CNTs exhibit significant potential applications in advanced materials and other fields due to their extraordinary mechanical strength and electrical/thermal conductivity properties,their low solubility,poor wettability and bad dispersibility in common solvents and solid matrices have limited their processing and applications.Thus,the attempt to achieve wettable/processable CNTs by functionalization has attracted increasing attention in both scientific and industrial communities.In recent years,azide chemistry has been demonstrated as a powerful means to covalently modify CNTs.It consists of two major approaches:click chemistry and nitrene chemistry,which both involve the usage of various azide compounds.The former one is based on highly reactive and stereospecifical Cu(I) catalyzed azide-alkyne cycloaddition reaction;the latter one is based on the electrophilic attack to unsaturated bonds of CNTs with nitrenes as reactive intermediates formed from thermolysis or photolysis of azides.In this mini-review paper,the azide chemistry to functionalize CNTs is highlighted and the corresponding functionalization routes to build CNT-based complex structures are also discussed.Besides,covalent functionalizations of other graphitic nanomaterials such as fullerence and graphene,via azide chemistry,are commented briefly.展开更多
Pre-polymerized vinyl trimethoxy silane(PVTMS)@MWCNT nano-aerogel system was constructed via radical polymerization,sol-gel transition and supercritical CO_(2)drying.The fabricated organic-inorganic hybrid PVTMS@MWCNT...Pre-polymerized vinyl trimethoxy silane(PVTMS)@MWCNT nano-aerogel system was constructed via radical polymerization,sol-gel transition and supercritical CO_(2)drying.The fabricated organic-inorganic hybrid PVTMS@MWCNT aerogel structure shows nano-pore size(30-40 nm),high specific surface area(559 m^(2)g^(−1)),high void fraction(91.7%)and enhanced mechanical property:(1)the nano-pore size is beneficial for efficiently blocking thermal conduction and thermal convection via Knudsen effect(beneficial for infrared(IR)stealth);(2)the heterogeneous interface was beneficial for IR reflection(beneficial for IR stealth)and MWCNT polarization loss(beneficial for electromagnetic wave(EMW)attenuation);(3)the high void fraction was beneficial for enhancing thermal insulation(beneficial for IR stealth)and EMW impedance match(beneficial for EMW attenuation).Guided by the above theoretical design strategy,PVTMS@MWCNT nano-aerogel shows superior EMW absorption property(cover all Ku-band)and thermal IR stealth property(ΔT reached 60.7℃).Followed by a facial combination of the above nano-aerogel with graphene film of high electrical conductivity,an extremely high electromagnetic interference shielding material(66.5 dB,2.06 mm thickness)with superior absorption performance of an average absorption-to-reflection(A/R)coefficient ratio of 25.4 and a low reflection bandwidth of 4.1 GHz(A/R ratio more than 10)was experimentally obtained in this work.展开更多
Highly thermally conductive graphitic film(GF)materials have become a competitive solution for the thermal management of high-power electronic devices.However,their catastrophic structural failure under extreme altern...Highly thermally conductive graphitic film(GF)materials have become a competitive solution for the thermal management of high-power electronic devices.However,their catastrophic structural failure under extreme alternating thermal/cold shock poses a significant challenge to reliability and safety.Here,we present the first investigation into the structural failure mechanism of GF during cyclic liquid nitrogen shocks(LNS),which reveals a bubbling process characterized by“permeation-diffusion-deformation”phenomenon.To overcome this long-standing structural weakness,a novel metal-nanoarmor strategy is proposed to construct a Cu-modified graphitic film(GF@Cu)with seamless heterointerface.This well-designed interface ensures superior structural stability for GF@Cu after hundreds of LNS cycles from 77 to 300 K.Moreover,GF@Cu maintains high thermal conductivity up to 1088 W m^(−1)K^(−1)with degradation of less than 5%even after 150 LNS cycles,superior to that of pure GF(50%degradation).Our work not only offers an opportunity to improve the robustness of graphitic films by the rational structural design but also facilitates the applications of thermally conductive carbon-based materials for future extreme thermal management in complex aerospace electronics.展开更多
LiBH_(4)with high hydrogen storage density,is regarded as one of the most promising hydrogen storage materials.Nevertheless,it suffers from high dehydrogenation temperature and poor reversibility for practical use.Nan...LiBH_(4)with high hydrogen storage density,is regarded as one of the most promising hydrogen storage materials.Nevertheless,it suffers from high dehydrogenation temperature and poor reversibility for practical use.Nanoconfinement is effective in achieving low dehydrogenation temperature and favorable reversibility.Besides,graphene can serve as supporting materials for LiBH_(4)catalysts and also destabilize LiBH_(4)via interfacial reaction.However,graphene has never been used alone as a frame material for nanoconfining LiBH_(4).In this study,graphene microflowers with large pore volumes were prepared and used as nanoconfinement framework material for LiBH_(4),and the nanoconfinement effect of graphene was revealed.After loading 70 wt%of LiBH_(4) and mechanically compressed at 350 MPa,8.0 wt% of H2 can be released within 100 min at 320C,corresponding to the highest volumetric hydrogen storage density of 94.9 g H2 L^(-1)ever reported.Thanks to the nanoconfinement of graphene,the rate-limiting step of dehydrogenation of nanoconfined LiBH_(4) was changed and its apparent activation energy of the dehydrogenation(107.3 kJ mol^(-1))was 42%lower than that of pure LiBH_(4).Moreover,the formation of the intermediate Li_(2)B_(12)H_(12) was effectively inhibited,and the stable nanoconfined structure enhanced the reversibility of LiBH_(4).This work widens the understanding of graphene's nanoconfinement effect and provides new insights for developing high-density hydrogen storage materials.展开更多
Bulk graphene nanofilms feature fast electronic and phonon transport in combination with strong light-matter interaction and thus have great potential for versatile applications,spanning from photonic,electronic,and o...Bulk graphene nanofilms feature fast electronic and phonon transport in combination with strong light-matter interaction and thus have great potential for versatile applications,spanning from photonic,electronic,and optoelectronic devices to charge-stripping and electromagnetic shielding,etc.However,large-area flexible close-stacked graphene nanofilms with a wide thickness range have yet to be reported.Here,we report a polyacrylonitrile-assisted’substrate replacement’strategy to fabricate large-area free-standing graphene oxide/polyacrylonitrile nanofilms(lateral size~20 cm).Linear polyacrylonitrile chains-derived nanochannels promote the escape of gases and enable macro-assembled graphene nanofilms(nMAGs)of 50-600 nm thickness following heat treatment at 3,000℃.The uniform nMAGs exhibit 802-1,540 cm^(2)V-1s-1carrier mobility,4.3-4.7 ps carrier lifetime,and>1,581 W m^(-1)K^(-1)thermal conductivity(n MAG-assembled 10μm-thick films,mMAGs).nMAGs are highly flexible and show no structure damage even after 1.0×10^(5)cycles of folding-unfolding.Furthermore,n MAGs broaden the detection region of graphene/silicon heterojunction from near-infrared to mid-infrared and demonstrate higher absolute electromagnetic interference(EMI)shielding effectiveness than state-of-the-art EMI materials of the same thickness.These results are expected to lead to the broad applications of such bulk nanofilms,especially as micro/nanoelectronic and optoelectronic platforms.展开更多
In this article Florian Puchtler at affiliation‘University of Bayreuth’,Josef Breu at affiliation‘University of Bayreuth’,and Ziliang Wu at affiliation‘Zhejiang University’was missing from the author Min Cao,Sen...In this article Florian Puchtler at affiliation‘University of Bayreuth’,Josef Breu at affiliation‘University of Bayreuth’,and Ziliang Wu at affiliation‘Zhejiang University’was missing from the author Min Cao,Senping Liu,Qingli Zhu,Ya Wang,Jingyu Ma,Zeshen Li,Dan Chang,Enhui Zhu,Xin Ming,Florian Puchtler,Josef Breu,Ziliang Wu,Yingjun Liu,Yanqiu Jiang,Zhen Xu,Chao Gao list.展开更多
Neurological disorders have always been a threat to human physical and mental health nowadays,which are closely related to the nonregeneration of neurons in the nervous system(NS).The damage to the NS is currently dif...Neurological disorders have always been a threat to human physical and mental health nowadays,which are closely related to the nonregeneration of neurons in the nervous system(NS).The damage to the NS is currently difficult to repair using conventional therapies,such as surgery and medication.Therefore,repairing the damaged NS has always been a vast challenge in the area of neurology.Tissue engineering(TE),which integrates the cell biology and materials science to reconstruct or repair organs and tissues,has widespread applications in bone,periodontal tissue defects,skin repairs,and corneal transplantation.Recently,tremendous advances have been made in TE regarding neuroscience.In this review,we summarize TE’s recent progress in neuroscience,including pathological mechanisms of various neurological disorders,the concepts and classification of TE,and the most recent development of TE in neuroscience.Lastly,we prospect the future directions and unresolved problems of TE in neuroscience.展开更多
Graphene has shown great potential in microwave absorption(MA) owing to its high surface area, low density,tunable electrical conductivity and good chemical stability.To fully realize graphenes& MA ability, the mi...Graphene has shown great potential in microwave absorption(MA) owing to its high surface area, low density,tunable electrical conductivity and good chemical stability.To fully realize graphenes& MA ability, the microstructure of graphene should be carefully addressed. Here we prepared graphene microflowers(Gmfs) with highly porous structure for high-performance MA filler material. The efficient absorption bandwidth(reflection loss B-10 dB) reaches 5.59 GHz and the minimum reflection loss is up to -42.9 dB, showing significant increment compared with stacked graphene. Such performance is higher than most graphene-based materials in the literature. Besides, the low filling content(10 wt%) and low density(40–50 mg cm^(-3))are beneficial for the practical applications. Without compounding with magnetic materials or conductive polymers,Gmfs show outstanding MA performance with the aid of rational microstructure design. Furthermore, Gmfs exhibit advantages in facile processibility and large-scale production compared with other porous graphene materials including aerogels and foams.展开更多
A facile "click chemistry" approach to functionalize 2D macromolecules of graphene oxide nanosheets with poly(ethylene glycol) of different molecular weights,polystyrene,palmitic acid and various amino acids...A facile "click chemistry" approach to functionalize 2D macromolecules of graphene oxide nanosheets with poly(ethylene glycol) of different molecular weights,polystyrene,palmitic acid and various amino acids was presented.FTIR,TGA,Raman spectroscopy,XPS,XRD,TEM,AFM and SEM were utilized to characterize the products.High degree of functionalization was achieved on the flat surfaces of graphene oxide,affording polymer-grafted 2D brushes and amino acids-immobilized nanosheets,which show improved solubility in organic solvents.The click chemistry strategy reported herein provides a facile and general method for functionalization of graphene oxide with macromolecules and desired biomolecules.展开更多
Nanocarbon-based materials, such as carbon nanotubes(CNTs) and graphene have been attached much attention by scientific and industrial community. As two representative nanocarbon materials, one-dimensional CNTs and tw...Nanocarbon-based materials, such as carbon nanotubes(CNTs) and graphene have been attached much attention by scientific and industrial community. As two representative nanocarbon materials, one-dimensional CNTs and twodimensional graphene both possess remarkable mechanical properties. In the past years, a large amount of work have been done by using CNTs or graphene as building blocks for constructing novel, macroscopic, mechanically strong fibrous materials. In this review, we summarize the assembly approaches of CNT-based fibers and graphene-based fibers in chronological order, respectively. The mechanical performances of these fibrous materials are compared, and the critical influences on the mechanical properties are discussed. Personal perspectives on the fabrication methods of CNT-and graphene-based fibers are further presented.展开更多
Recovering alcohols from dilute fermentation broth is an emergent task in bio-fuel production process. Since they are primary planned for fuels, energy required to separate these alcohols should be considered in evalu...Recovering alcohols from dilute fermentation broth is an emergent task in bio-fuel production process. Since they are primary planned for fuels, energy required to separate these alcohols should be considered in evaluating the potential of a separation technology. A membrane-based process, pervaporation, is of special interest because of its environmental friendliness and easy integrating character. This review probes into the fundamentals of pervaporation especially in terms of the heat required for evaporation. Meanwhile, the separation data of the most representative alcohol-selective pervaporation membranes reported in the literatures are collected and compared with the vapor–liquid equilibrium curve, which represents the distillation selectivity. They include:inorganic membranes, silicon rubber based membranes, Mixed Matrix Membranes and some other special materials. By doing so, the status of alcohol recovery via pervaporation would be more clear for researchers.For ethanol recovery, it is selectivity rather than flux that is in urgent need of solution. While for butanol recovery,membranes with satisfactory selectivity have been developed, increasing the separation capacity would be more pressing.展开更多
In this work, polypropylene (PP)/polystyrene (PS) blends with different organoclay concentrations were prepared via melt compounding. Differing from the results of previous reports, the organoclay platelets are mostly...In this work, polypropylene (PP)/polystyrene (PS) blends with different organoclay concentrations were prepared via melt compounding. Differing from the results of previous reports, the organoclay platelets are mostly located in the dispersed PS phase instead of the interface. The dimensions of the dispersed PS droplets are greatly reduced and apparent compatibilization effect still exists, which cannot be explained by the traditional compatibilization mechanism. A novel compatibilization mecha- nism, "cutting" to apparently compatibilize the immiscible PP/PS blends was proposed. The organoclay platelets tend to form a special "knife-like structure" in the PS domain under the shear stress of the continuous PP phase during compounding. The "clay knife" can split the dispersed PS domain apart and lead to the dramatic reduction of the dispersed domain size.展开更多
Modern wearable electronics are thirsty for flexible, lightweight energy storage and supply devices. Flexible fiber-shaped supercapacitors, possess good flexibility, high power density, fast charging capability and lo...Modern wearable electronics are thirsty for flexible, lightweight energy storage and supply devices. Flexible fiber-shaped supercapacitors, possess good flexibility, high power density, fast charging capability and long cycle life, becoming a promising option for wearable devices. The past decade has witnessed the emergence of graphene fiber based supercapacitors(GFSCs) as one of the most active vicinity in fiber-supercapactiors, for their excellent properties including high surface area, chemical stability, excellent electrical conductivity, lightweight and mechanical properties. In this perspective, we introduced the basic energy storage mechanisms of GFSCs, followed by the analysis in improving their overall performances, recent advances, and a conclusive discussion on the challenges and opportunities.展开更多
Eliminating topological defects to achieve monodomain liquid crystals is highly significant for the fundamental studies of soft matter and building long-range ordered materials.However,liquid crystals are metastable a...Eliminating topological defects to achieve monodomain liquid crystals is highly significant for the fundamental studies of soft matter and building long-range ordered materials.However,liquid crystals are metastable and sensitive to external stimuli,such as flow,confinement,and electromagnetic fields,which cause their intrinsic polycrystallinity and topological defects.Here,we achieve the monodomain liquid crystals of graphene oxide over 30 cm through boundary-free sheargraphy.The obtained monodomain liquid crystals exhibit large-area uniform alignment of sheets,which has the same optical polarized angle and intensity.The monodomain liquid crystals provide bidirectionally ordered skeletons,which can be applied as lightweight thermal management materials with bidirectionally high thermal and electrical conductivity.Furthermore,we extend the controllable topology of two-dimensional colloids by introducing singularities and disclinations in monodomain liquid crystals.Topological structures with defect strength from−2 to+2 were realized.This work provides a facile methodology to study the structural order of soft matter at a macroscopic level,facilitating the fabrication of metamaterials with tunable and highly anisotropic architectures.展开更多
The processing capability is vital for the wide applications of materials to forge structures as-demand.Graphene-based macroscopic materials have shown excellent mechanical and functional properties.However,different ...The processing capability is vital for the wide applications of materials to forge structures as-demand.Graphene-based macroscopic materials have shown excellent mechanical and functional properties.However,different from usual polymers and metals,graphene solids exhibit limited deformability and processibility for precise forming.Here,we present a precise thermoplastic forming of graphene materials by polymer intercalation from graphene oxide(GO)precursor.The intercalated polymer enables the thermoplasticity of GO solids by thermally activated motion of polymer chains.We detect a critical minimum containing of intercalated polymer that can expand the interlayer spacing exceeding 1.4 nm to activate thermoplasticity,which becomes the criteria for thermal plastic forming of GO solids.By thermoplastic forming,the flat GO-composite films are forged to Gaussian curved shapes and imprinted to have surface relief patterns with size precision down to 360 nm.The plastic-formed structures maintain the structural integration with outstanding electrical(3.07×10^(5) S m^(−1))and thermal conductivity(745.65 W m^(−1) K^(−1))after removal of polymers.The thermoplastic strategy greatly extends the forming capability of GO materials and other layered materials and promises versatile structural designs for more broad applications.展开更多
The performance of ion-exchange resin catalysts during isobutene (IB) dimerization was investigated under different IB contents,temperatures and liquid-volume hourly space velocity (LHSV) using a plug flow reactor in ...The performance of ion-exchange resin catalysts during isobutene (IB) dimerization was investigated under different IB contents,temperatures and liquid-volume hourly space velocity (LHSV) using a plug flow reactor in the absence of any selectivity enhancing component.High IB content and temperature resulted in a high conversion and C12 selectivity bu low C8 selectivity.The influence of LHSV was related with the IB content:LHSV had great effect at high IB content,while the performance of ion-exchange resin changed little with LHSV if IB content was low.The effect of water on the stability of resins was also studied.Desulfonation was observed during the C4 dimerization reaction when water was added to the feed.Chlorinated resin was more stable than conventional polystyrene-based resins during the test.展开更多
基金the support from the SCI-TECH Academy of Zhejiang University。
文摘In 2022,The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results.First,a series of well-defined dinuclear organoboron catalysts were developed to precisely control the enchainment of ether and carbonate segments during the copolymerization of CO_(2)and epoxides.Second,polyester had been synthesized through cationic copolymerization of cyclic anhydride.Third,ring-opening polymerization of carbon dioxide based valerolactone had been achieved,revealing the prospect of 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one(EVL)in utilizing CO_(2)and synthesizing functional polymers.Fourth,machine learning methods have been applied to biomaterial research,enabling high-throughput screening of functional biomaterial surfaces for implantable devices,and searching for potent antimicrobial peptides in whole combinatorial peptide libraries.Fifth,methods of characterization of biomacromolecule RNA transcription and manipulation of nucleoside modification were developed.Sixth,artificial enzymes-armed Bifidobacterium Longum probiotics were established to tune down gut inflammation.Seventh,three-dimensional(3D)printing technologies were used to engineer tough supramolecular hydrogels.Eighth,hydroplastic foaming graphene frameworks for acoustic and conductive polymer composites were provided for application.Ninth,aggregate photophysics about the nature of through-space interactions(TSIs)and manipulating their strength in small molecules with non-conjugated structure had been elucidated.Tenth,the forming mechanism of a newfound nested texture in poly(L-lactic acid)(PLLA)spherulitic films had been revealed.Finally,the isotropically dyeing mechanism of KDP single crystals grown from hydrogels have been explored.The related works are reviewed in this paper.
基金the support from the SCI-TECH Academy of Zhejiang University。
文摘In 2021,The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results.First,a series of versatile organoboron catalysts were synthesized for ring-opening(co)polymerizations.Second,a catalyst-free polycondensation mechanism was proposed for the production of polyesters with high molecular weights.Third,a co-assembly method that can fabricate films and coatings with controllable structures and properties on various substrates was demonstrated,providing a platform for the construction of novel surface coatings.Forth,facile methods for producing high-productivity poly(propylene carbonate)and semicrystalline polyester have been discovered.And linear non-conjugated polyesters exhibiting yellow-green clusteroluminescence were developed for the first time.Fifth,a supramolecular prodrug nano-assembly strategy has been developed for reactive nitrogen species potentiated chemotherapy.Sixth,a series of tough and stiff supramolecular hydrogels with shape memory properties have been used for information encryption.Seventh,reversible fusion and fission of wet-spun graphene oxide fibers has been successfully achieved.Eighth,three non-conjugated polypeptides were synthesized and the mechanism of clusteroluminescence was studied.Ninth,a series of conducting covalent organic frameworks with high electrical conductivity and carrier mobility have been used as high-performance chemiresistor,electrocatalyst,and organic field-effect transistor.Tenth,the exploration of non-fused electron acceptors,and their photostable mechanism are exemplified for developing high-performance,low-cost and eco-friendly polymer solar cells.Finally,gel-grown long-range ordering bulk-heterojunctions has achieved improved X-ray detector performance.
基金support from the SCI-TECH Academy of Zhejiang University。
文摘In 2020, the MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had made progresses in several aspects. First, a series of metal-free organoboron catalysts had been designed and synthesized facilely, exhibiting outstanding reactivity, thermalstability and productivity in different kinds of polymerization and cycloaddition reactions. Second, a variety of chalcogen(O, S, Se)-rich polymers had been synthesized via organocatalysis and fabricated to be the ionic conductive and photoluminescent materials. Third, diverse microenvironment-sensitive nanoparticles had been designed,and novel strategies had been realized, to enhance the therapeutic efficacy in cancer as well as biofilmassociated infections. Fourth, m6 A modification on cellular transcriptome-wide messenger RNA had been successfully mapped at single base resolution using a metabolic labeling method. Fifth, a hydrogel-based robot had been developed, showing swift locomotion as a response to dynamic light stimulations. Sixth,the conformation-size scaling law and the conformation evolution map of 2 D macromolecules in solution had been elucidated experimentally, in the single-layer graphene oxide model. Seventh, semitransparent polymer solar cells, promising as building-integrated photovoltaics, have been developed with the fine balance among power conversion efficiency, visible light transparency and infrared photon radiation rejection. Finally, long-range ordered bulk-heterojunctions of organic semiconductors had been achieved,and their superior optoelectronic properties and potential application in photoelectric conversion had been revealed. The related work progresses are reviewed in this paper.
基金financially supported by the National Natural Science Foundation of China (No.50773038,and No.20974093)National Basic Research Program of China (973 Program) (No.2007CB936000)+3 种基金the Fundamental Research Funds for the Central Universities (2009QNA4040)Qianjiang Talent Foundation of Zhejiang Province (2010R10021)the Foundation for the Author of National Excellent Doctoral Disser-tation of China (No.200527)China Postdoctoral Science Foundation (No.20100471707)
文摘Following the conventional carbon allotropes of diamond and graphite,fullerene,carbon nanotubes(CNTs) and graphene as 0D,1D and 2D graphitic macromolecules have been discovered recently in succession,declaring the unlimited potential of carbon-based nanomaterials and nanotechnology.Although CNTs exhibit significant potential applications in advanced materials and other fields due to their extraordinary mechanical strength and electrical/thermal conductivity properties,their low solubility,poor wettability and bad dispersibility in common solvents and solid matrices have limited their processing and applications.Thus,the attempt to achieve wettable/processable CNTs by functionalization has attracted increasing attention in both scientific and industrial communities.In recent years,azide chemistry has been demonstrated as a powerful means to covalently modify CNTs.It consists of two major approaches:click chemistry and nitrene chemistry,which both involve the usage of various azide compounds.The former one is based on highly reactive and stereospecifical Cu(I) catalyzed azide-alkyne cycloaddition reaction;the latter one is based on the electrophilic attack to unsaturated bonds of CNTs with nitrenes as reactive intermediates formed from thermolysis or photolysis of azides.In this mini-review paper,the azide chemistry to functionalize CNTs is highlighted and the corresponding functionalization routes to build CNT-based complex structures are also discussed.Besides,covalent functionalizations of other graphitic nanomaterials such as fullerence and graphene,via azide chemistry,are commented briefly.
基金the National Natural Science Foundation(No.52073187)NSAF Foundation(No.U2230202)for their financial support of this project+3 种基金National Natural Science Foundation(No.51721091)Programme of Introducing Talents of Discipline to Universities(No.B13040)State Key Laboratory of Polymer Materials Engineering(No.sklpme2022-2-03)support of China Scholarship Council
文摘Pre-polymerized vinyl trimethoxy silane(PVTMS)@MWCNT nano-aerogel system was constructed via radical polymerization,sol-gel transition and supercritical CO_(2)drying.The fabricated organic-inorganic hybrid PVTMS@MWCNT aerogel structure shows nano-pore size(30-40 nm),high specific surface area(559 m^(2)g^(−1)),high void fraction(91.7%)and enhanced mechanical property:(1)the nano-pore size is beneficial for efficiently blocking thermal conduction and thermal convection via Knudsen effect(beneficial for infrared(IR)stealth);(2)the heterogeneous interface was beneficial for IR reflection(beneficial for IR stealth)and MWCNT polarization loss(beneficial for electromagnetic wave(EMW)attenuation);(3)the high void fraction was beneficial for enhancing thermal insulation(beneficial for IR stealth)and EMW impedance match(beneficial for EMW attenuation).Guided by the above theoretical design strategy,PVTMS@MWCNT nano-aerogel shows superior EMW absorption property(cover all Ku-band)and thermal IR stealth property(ΔT reached 60.7℃).Followed by a facial combination of the above nano-aerogel with graphene film of high electrical conductivity,an extremely high electromagnetic interference shielding material(66.5 dB,2.06 mm thickness)with superior absorption performance of an average absorption-to-reflection(A/R)coefficient ratio of 25.4 and a low reflection bandwidth of 4.1 GHz(A/R ratio more than 10)was experimentally obtained in this work.
基金the National Natural Science Foundation of China(Nos.52272046,52090030,52090031,52122301,51973191)the Natural Science Foundation of Zhejiang Province(LR23E020003)+4 种基金Shanxi-Zheda Institute of New Materials and Chemical Engineering(2021SZ-FR004,2022SZ-TD011,2022SZ-TD012,2022SZ-TD014)Hundred Talents Program of Zhejiang University(188020*194231701/113,112300+1944223R3/003,112300+1944223R3/004)the Fundamental Research Funds for the Central Universities(Nos.226-2023-00023,226-2023-00082,2021FZZX001-17,K20200060)National Key R&D Program of China(NO.2022YFA1205300,NO.2022YFA1205301,NO.2020YFF0204400,NO.2022YFF0609801)“Pioneer”and“Leading Goose”R&D Program of Zhejiang 2023C01190.
文摘Highly thermally conductive graphitic film(GF)materials have become a competitive solution for the thermal management of high-power electronic devices.However,their catastrophic structural failure under extreme alternating thermal/cold shock poses a significant challenge to reliability and safety.Here,we present the first investigation into the structural failure mechanism of GF during cyclic liquid nitrogen shocks(LNS),which reveals a bubbling process characterized by“permeation-diffusion-deformation”phenomenon.To overcome this long-standing structural weakness,a novel metal-nanoarmor strategy is proposed to construct a Cu-modified graphitic film(GF@Cu)with seamless heterointerface.This well-designed interface ensures superior structural stability for GF@Cu after hundreds of LNS cycles from 77 to 300 K.Moreover,GF@Cu maintains high thermal conductivity up to 1088 W m^(−1)K^(−1)with degradation of less than 5%even after 150 LNS cycles,superior to that of pure GF(50%degradation).Our work not only offers an opportunity to improve the robustness of graphitic films by the rational structural design but also facilitates the applications of thermally conductive carbon-based materials for future extreme thermal management in complex aerospace electronics.
基金supported by National Key Research and Development Program of China(2021YFB4000602)National Natural Science Foundation of PR China(Nos.52071287,52072342,52271227)+3 种基金National Outstanding Youth Foundation of China(No.52125104)Natural Science Foundation of Zhejiang Province,PR China(No.LZ23E010002)Young Talent Fund of Association for Science and Technology in Shaanxi,China(No.20220456)Young Star Project of Science and Technology of Shaanxi Province(2022KJXX-43).
文摘LiBH_(4)with high hydrogen storage density,is regarded as one of the most promising hydrogen storage materials.Nevertheless,it suffers from high dehydrogenation temperature and poor reversibility for practical use.Nanoconfinement is effective in achieving low dehydrogenation temperature and favorable reversibility.Besides,graphene can serve as supporting materials for LiBH_(4)catalysts and also destabilize LiBH_(4)via interfacial reaction.However,graphene has never been used alone as a frame material for nanoconfining LiBH_(4).In this study,graphene microflowers with large pore volumes were prepared and used as nanoconfinement framework material for LiBH_(4),and the nanoconfinement effect of graphene was revealed.After loading 70 wt%of LiBH_(4) and mechanically compressed at 350 MPa,8.0 wt% of H2 can be released within 100 min at 320C,corresponding to the highest volumetric hydrogen storage density of 94.9 g H2 L^(-1)ever reported.Thanks to the nanoconfinement of graphene,the rate-limiting step of dehydrogenation of nanoconfined LiBH_(4) was changed and its apparent activation energy of the dehydrogenation(107.3 kJ mol^(-1))was 42%lower than that of pure LiBH_(4).Moreover,the formation of the intermediate Li_(2)B_(12)H_(12) was effectively inhibited,and the stable nanoconfined structure enhanced the reversibility of LiBH_(4).This work widens the understanding of graphene's nanoconfinement effect and provides new insights for developing high-density hydrogen storage materials.
基金supported by the National Natural Science Foundation of China(No.52090030)the China Postdoctoral Science Foundation(2022T150558,2020M681819)+1 种基金the Fundamental Research Funds for the Central Universities(No.2021FZZX001-17)the Postdoctoral Research Program of Zhejiang Province(ZJ2021145).
文摘Bulk graphene nanofilms feature fast electronic and phonon transport in combination with strong light-matter interaction and thus have great potential for versatile applications,spanning from photonic,electronic,and optoelectronic devices to charge-stripping and electromagnetic shielding,etc.However,large-area flexible close-stacked graphene nanofilms with a wide thickness range have yet to be reported.Here,we report a polyacrylonitrile-assisted’substrate replacement’strategy to fabricate large-area free-standing graphene oxide/polyacrylonitrile nanofilms(lateral size~20 cm).Linear polyacrylonitrile chains-derived nanochannels promote the escape of gases and enable macro-assembled graphene nanofilms(nMAGs)of 50-600 nm thickness following heat treatment at 3,000℃.The uniform nMAGs exhibit 802-1,540 cm^(2)V-1s-1carrier mobility,4.3-4.7 ps carrier lifetime,and>1,581 W m^(-1)K^(-1)thermal conductivity(n MAG-assembled 10μm-thick films,mMAGs).nMAGs are highly flexible and show no structure damage even after 1.0×10^(5)cycles of folding-unfolding.Furthermore,n MAGs broaden the detection region of graphene/silicon heterojunction from near-infrared to mid-infrared and demonstrate higher absolute electromagnetic interference(EMI)shielding effectiveness than state-of-the-art EMI materials of the same thickness.These results are expected to lead to the broad applications of such bulk nanofilms,especially as micro/nanoelectronic and optoelectronic platforms.
文摘In this article Florian Puchtler at affiliation‘University of Bayreuth’,Josef Breu at affiliation‘University of Bayreuth’,and Ziliang Wu at affiliation‘Zhejiang University’was missing from the author Min Cao,Senping Liu,Qingli Zhu,Ya Wang,Jingyu Ma,Zeshen Li,Dan Chang,Enhui Zhu,Xin Ming,Florian Puchtler,Josef Breu,Ziliang Wu,Yingjun Liu,Yanqiu Jiang,Zhen Xu,Chao Gao list.
基金This work was supported by grants from the National Key R&D Program of China(2021YFA0909900)Zhejiang Province“Kunpeng Action”Plan to Z.G.,the National Natural Science Foundation of China(52173142)+1 种基金the Startup Packages of Zhejiang University to Z.G.Competing interes ts:Z.G.is the cofounder of Zenomics Inc.,Zencapsule Inc.,Lizen Inc.,Wskin Inc.,ZCapsule Inc.All other authors declare that they have no competing interests.
文摘Neurological disorders have always been a threat to human physical and mental health nowadays,which are closely related to the nonregeneration of neurons in the nervous system(NS).The damage to the NS is currently difficult to repair using conventional therapies,such as surgery and medication.Therefore,repairing the damaged NS has always been a vast challenge in the area of neurology.Tissue engineering(TE),which integrates the cell biology and materials science to reconstruct or repair organs and tissues,has widespread applications in bone,periodontal tissue defects,skin repairs,and corneal transplantation.Recently,tremendous advances have been made in TE regarding neuroscience.In this review,we summarize TE’s recent progress in neuroscience,including pathological mechanisms of various neurological disorders,the concepts and classification of TE,and the most recent development of TE in neuroscience.Lastly,we prospect the future directions and unresolved problems of TE in neuroscience.
基金supported by the National Natural Science Foundation of China (Nos. 21325417 and 51533008)National Key R&D Program of China (No. 2016YFA0200200)Fundamental Research Funds for the Central Universities (2017XZZX008-06)
文摘Graphene has shown great potential in microwave absorption(MA) owing to its high surface area, low density,tunable electrical conductivity and good chemical stability.To fully realize graphenes& MA ability, the microstructure of graphene should be carefully addressed. Here we prepared graphene microflowers(Gmfs) with highly porous structure for high-performance MA filler material. The efficient absorption bandwidth(reflection loss B-10 dB) reaches 5.59 GHz and the minimum reflection loss is up to -42.9 dB, showing significant increment compared with stacked graphene. Such performance is higher than most graphene-based materials in the literature. Besides, the low filling content(10 wt%) and low density(40–50 mg cm^(-3))are beneficial for the practical applications. Without compounding with magnetic materials or conductive polymers,Gmfs show outstanding MA performance with the aid of rational microstructure design. Furthermore, Gmfs exhibit advantages in facile processibility and large-scale production compared with other porous graphene materials including aerogels and foams.
基金financially supported by the National Natural Science Foundation of China (No.50773038,and No.20974093)National Basic Research Program of China (973 Program) (No.2007CB936000)+2 种基金Qianjiang Talent Foundation of Zhejiang Province (2010R10021)the Fundamental Research Funds for the Central Universities (2009QNA4040)the Foundation for the Author of National Excellent Doctoral Dissertation of China (No.200527)
文摘A facile "click chemistry" approach to functionalize 2D macromolecules of graphene oxide nanosheets with poly(ethylene glycol) of different molecular weights,polystyrene,palmitic acid and various amino acids was presented.FTIR,TGA,Raman spectroscopy,XPS,XRD,TEM,AFM and SEM were utilized to characterize the products.High degree of functionalization was achieved on the flat surfaces of graphene oxide,affording polymer-grafted 2D brushes and amino acids-immobilized nanosheets,which show improved solubility in organic solvents.The click chemistry strategy reported herein provides a facile and general method for functionalization of graphene oxide with macromolecules and desired biomolecules.
基金supported by the National Natural Science Foundation of China (Nos. 21325417, 51533008)the MOST National Key Research and Development Plan (2016YFA0200200)+1 种基金the National Postdoctoral Program for Innovative Talents (No. BX201700209)the State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University (No. LK1403)
文摘Nanocarbon-based materials, such as carbon nanotubes(CNTs) and graphene have been attached much attention by scientific and industrial community. As two representative nanocarbon materials, one-dimensional CNTs and twodimensional graphene both possess remarkable mechanical properties. In the past years, a large amount of work have been done by using CNTs or graphene as building blocks for constructing novel, macroscopic, mechanically strong fibrous materials. In this review, we summarize the assembly approaches of CNT-based fibers and graphene-based fibers in chronological order, respectively. The mechanical performances of these fibrous materials are compared, and the critical influences on the mechanical properties are discussed. Personal perspectives on the fabrication methods of CNT-and graphene-based fibers are further presented.
基金Supported by the National Natural Science Foundation of China(No.21706003)The Importation and Development of High-Caliber Talents Project of Beijing Municipal Institutions(CIT&TCD20170305)
文摘Recovering alcohols from dilute fermentation broth is an emergent task in bio-fuel production process. Since they are primary planned for fuels, energy required to separate these alcohols should be considered in evaluating the potential of a separation technology. A membrane-based process, pervaporation, is of special interest because of its environmental friendliness and easy integrating character. This review probes into the fundamentals of pervaporation especially in terms of the heat required for evaporation. Meanwhile, the separation data of the most representative alcohol-selective pervaporation membranes reported in the literatures are collected and compared with the vapor–liquid equilibrium curve, which represents the distillation selectivity. They include:inorganic membranes, silicon rubber based membranes, Mixed Matrix Membranes and some other special materials. By doing so, the status of alcohol recovery via pervaporation would be more clear for researchers.For ethanol recovery, it is selectivity rather than flux that is in urgent need of solution. While for butanol recovery,membranes with satisfactory selectivity have been developed, increasing the separation capacity would be more pressing.
文摘In this work, polypropylene (PP)/polystyrene (PS) blends with different organoclay concentrations were prepared via melt compounding. Differing from the results of previous reports, the organoclay platelets are mostly located in the dispersed PS phase instead of the interface. The dimensions of the dispersed PS droplets are greatly reduced and apparent compatibilization effect still exists, which cannot be explained by the traditional compatibilization mechanism. A novel compatibilization mecha- nism, "cutting" to apparently compatibilize the immiscible PP/PS blends was proposed. The organoclay platelets tend to form a special "knife-like structure" in the PS domain under the shear stress of the continuous PP phase during compounding. The "clay knife" can split the dispersed PS domain apart and lead to the dramatic reduction of the dispersed domain size.
基金supported by the National Natural Science Foundation of China(Nos.21325417 and 51533008)National Key R&D Program of China(No.2016YFA0200200)+1 种基金Fundamental Research Funds for the Central Universities(No.2017XZZX008-06)the China Postdoctoral Science Foundation(No.2017M621927)
文摘Modern wearable electronics are thirsty for flexible, lightweight energy storage and supply devices. Flexible fiber-shaped supercapacitors, possess good flexibility, high power density, fast charging capability and long cycle life, becoming a promising option for wearable devices. The past decade has witnessed the emergence of graphene fiber based supercapacitors(GFSCs) as one of the most active vicinity in fiber-supercapactiors, for their excellent properties including high surface area, chemical stability, excellent electrical conductivity, lightweight and mechanical properties. In this perspective, we introduced the basic energy storage mechanisms of GFSCs, followed by the analysis in improving their overall performances, recent advances, and a conclusive discussion on the challenges and opportunities.
基金The authors gratefully acknowledge the support of National Key Research and Development Program of China(2020YFE0204400)National Natural Science Foundation of China(Nos.52090030,52122301,51973191)+3 种基金Shanxi-Zheda Institute of New Materials and Chemical Engineering(2012SZ-FR004)Hundred Talents Program of Zhejiang University(188020*194231701/113)China Postdoctoral Science Foundation(2021M692772)supported by the Fundamental Research Funds for the Central Universities(Nos.2021FZZX001-17).
文摘Eliminating topological defects to achieve monodomain liquid crystals is highly significant for the fundamental studies of soft matter and building long-range ordered materials.However,liquid crystals are metastable and sensitive to external stimuli,such as flow,confinement,and electromagnetic fields,which cause their intrinsic polycrystallinity and topological defects.Here,we achieve the monodomain liquid crystals of graphene oxide over 30 cm through boundary-free sheargraphy.The obtained monodomain liquid crystals exhibit large-area uniform alignment of sheets,which has the same optical polarized angle and intensity.The monodomain liquid crystals provide bidirectionally ordered skeletons,which can be applied as lightweight thermal management materials with bidirectionally high thermal and electrical conductivity.Furthermore,we extend the controllable topology of two-dimensional colloids by introducing singularities and disclinations in monodomain liquid crystals.Topological structures with defect strength from−2 to+2 were realized.This work provides a facile methodology to study the structural order of soft matter at a macroscopic level,facilitating the fabrication of metamaterials with tunable and highly anisotropic architectures.
基金the support of the National Natural Science Foundation of China(Nos.51803177,51973191,51533008,and 51636002)National Key R&D Program of China(No.2016YFA0200200)+5 种基金the China Postdoctoral Science Foundation(No.2021M690134)Hundred Talents Program of Zhejiang University(188020*194231701/113)Key Research and Development Plan of Zhejiang Province(2018C01049)the National Postdoctoral Program for Innovative Talents(No.BX201700209)the Fundamental Research Funds for the Central Universities(2021FZZX001-17),the Natural Science Foundation of Jiangsu Province(BK20210353)the Fundamental Research Funds for the Central Universities(No.30920041106).
文摘The processing capability is vital for the wide applications of materials to forge structures as-demand.Graphene-based macroscopic materials have shown excellent mechanical and functional properties.However,different from usual polymers and metals,graphene solids exhibit limited deformability and processibility for precise forming.Here,we present a precise thermoplastic forming of graphene materials by polymer intercalation from graphene oxide(GO)precursor.The intercalated polymer enables the thermoplasticity of GO solids by thermally activated motion of polymer chains.We detect a critical minimum containing of intercalated polymer that can expand the interlayer spacing exceeding 1.4 nm to activate thermoplasticity,which becomes the criteria for thermal plastic forming of GO solids.By thermoplastic forming,the flat GO-composite films are forged to Gaussian curved shapes and imprinted to have surface relief patterns with size precision down to 360 nm.The plastic-formed structures maintain the structural integration with outstanding electrical(3.07×10^(5) S m^(−1))and thermal conductivity(745.65 W m^(−1) K^(−1))after removal of polymers.The thermoplastic strategy greatly extends the forming capability of GO materials and other layered materials and promises versatile structural designs for more broad applications.
基金supported financially by the Purolite Company and the Chinese National Natural Science Foundation (20674069)
文摘The performance of ion-exchange resin catalysts during isobutene (IB) dimerization was investigated under different IB contents,temperatures and liquid-volume hourly space velocity (LHSV) using a plug flow reactor in the absence of any selectivity enhancing component.High IB content and temperature resulted in a high conversion and C12 selectivity bu low C8 selectivity.The influence of LHSV was related with the IB content:LHSV had great effect at high IB content,while the performance of ion-exchange resin changed little with LHSV if IB content was low.The effect of water on the stability of resins was also studied.Desulfonation was observed during the C4 dimerization reaction when water was added to the feed.Chlorinated resin was more stable than conventional polystyrene-based resins during the test.
