Solid-state batteries(SSBs) with high safety are promising for the energy fields,but the development has long been limited by machinability and interfacial problems.Hence,self-supporting,flexible Nano LLZO CSEs are pr...Solid-state batteries(SSBs) with high safety are promising for the energy fields,but the development has long been limited by machinability and interfacial problems.Hence,self-supporting,flexible Nano LLZO CSEs are prepared with a solvent-free method at 25℃.The 99.8 wt% contents of Nano LLZO particles enable the Nano LLZO CSEs to maintain good thermal stability while exhibiting a wide electrochemical window of 5.0 V and a high Li~+ transfer number of 0.8.The mean modulus reaches 4376 MPa.Benefiting from the interfacial modulation,the Li|Li symmetric batteries based on the Nano LLZO CSEs show benign stability with lithium at the current densities of 0.1 mA cm^(-2),0.2 mA cm^(-2),and 0.5 mA cm^(-2).In addition,the Li|LiFePO_(4)(LFP) SSBs achieve favorable cycling performance:the specific capacity reaches128.1 mAh g^(-1) at 0.5 C rate,with a capacity retention of about 80% after 600 cycles.In the further tests of the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811) cathodes with higher energy density,the Nano LLZO CSEs also demonstrate good compatibility:the specific capacities of NCM811-based SSBs reach 177.9 mAh g^(-1) at 0.5 C rate,while the capacity retention is over 96% after 150 cycles.Furthermore,the Li|LFP soft-pack SSBs verify the safety characteristics and the potential for application,which have a desirable prospect.展开更多
Rapid developments in lithium-ion battery(LIB)technology have been fueled by the expanding market for electric vehicles and increased demands for energy storage.Recently,thick electrode fabrication by solvent-free met...Rapid developments in lithium-ion battery(LIB)technology have been fueled by the expanding market for electric vehicles and increased demands for energy storage.Recently,thick electrode fabrication by solvent-free methods has emerged as a promising strategy for enhancing the energy density of LIBs.However,as electrode thickness increases,the tortuosity of lithium-ion transport also increases,resulting in severe polarization and poor electrochemical performance.Here,we investigate the effect of conductive agent morphology on the structural and electrochemical properties of 250μm thick lithium iron phosphate(LFP)/conductive agent/polytetrafluoroethylene(PTFE)-based electrodes.Three commercially available conductive additives,namely 0D Super P,1D multi-walled carbon nanotubes(MWCNTs),and 2D graphene nanoplatelets(GNPs),were incorporated into LFP-based electrodes.The MWCNT-incorporated electrode with a high loading mass(42 mg cm^(-2))exhibited a high porosity(ε=51%)and low tortuosity(τ=4.02)owing to its highly interconnected fibrous network of MWCNTs.Due to the fast lithium-ion transport kinetics in the MWCNT-incorporated electrode,the electrochemical performances exhibited a high specific capacity of 157 mAh g^(-1)at 0.1 C and an areal capacity of 7.16 mAh cm^(-2)at 0.1 C with a high-rate capability and excellent cycling stability over 300 cycles at 0.1 C.This study provides a guidance for utilizing conductive agents to apply in the low tortuous thick electrode fabricated by a solvent-free process.Additionally,this work paves the way to achieve scalable and sustainable dry processing techniques for developing next-generation energy storage technologies.展开更多
Designing efficient adsorbents for the deep removal of refractory dibenzothiophene(DBT)from fuel oil is vital for addressing environmental issues such as acid rain.Herein,zinc gluconate and urea-derived porous carbons...Designing efficient adsorbents for the deep removal of refractory dibenzothiophene(DBT)from fuel oil is vital for addressing environmental issues such as acid rain.Herein,zinc gluconate and urea-derived porous carbons SF-ZnNC-T(T represents the carbonization temperature)were synthesized without solvents.Through a temperature-controlled process of“melting the zinc gluconate and urea mixture,forming H-bonded polymers,and carbonizing the polymers,”the optimal carbon,SF-ZnNC-900,was obtained with a large surface area(2280 m^(2)g^(-1),highly dispersed Zn sites,and hierarchical pore structures.Consequently,SF-ZnNC-900 demonstrated significantly higher DBT adsorption capacity of43.2 mg S g^(-1),compared to just 4.3 mg S g^(-1)for the precursor.It also demonstrated good reusability,fast adsorption rate,and the ability for ultra-deep desulfurization.The superior DBT adsorption performance resulted from the evaporation of residual zinc species,which generated abundant mesopores that facilitated DBT transformation,as well as the formation of Zn-N_(x) sites that strengthened the host-vip interaction(ΔE=-1.466 e V).The solvent-free synthesized highly dispersed Zn-doped carbon shows great potential for producing sulfur-free fuel oil and for designing metal-loaded carbon adsorbents.展开更多
Bioinspired active pillar structures,known for their large surface area,mechanical compliance,and diverse deformation modes,have garnered extensive research interest.Among various active pillar structures,liquid cryst...Bioinspired active pillar structures,known for their large surface area,mechanical compliance,and diverse deformation modes,have garnered extensive research interest.Among various active pillar structures,liquid crystal elastomer(LCE)pillar arrays are capable of exhibiting significant and reversible anisotropic deformation under cyclic heating and cooling,showing great potential in tunable adhesion,soft robots,and biomedical devices.However,scaling up LCE pillar manufacturing remains challenging,limiting its practical applications.In this work,a solventfree LCE resin is developed with unique features including simple operating procedure,short fabrication time,and tunable responsive temperature,enabling rapid and large-scale production of LCE pillar arrays.The LCE resin allows for the preparation of complex 3D shapes in addition to film or specimen.The fabrication time can be as short as 4 h,without the need to evaporate solvent.Moreover,the LCE resins can be adjusted with a variable phase transition temperature range from 49.4℃ to 97.7℃ by incorporating non-liquid crystal acrylate chains.The resulting active pillar array structure can undertake sequential actuation upon heating with the tunable actuation temperature.Finally,the application of these pillar arrays in multi-level information encryption is demonstrated.The LCE pillar structure introduced here offers a new strategy for constructing advanced active LCE structures with tunable responsive behavior.展开更多
The imperative pursuit of elevated energy density in lithium primary coin cells(LPCCs)necessitates strategic architectural optimization to align with evolving market demands.A predominant approach involves the systema...The imperative pursuit of elevated energy density in lithium primary coin cells(LPCCs)necessitates strategic architectural optimization to align with evolving market demands.A predominant approach involves the systematic replacement of metallic structural support components(MSSCs)to minimize non-active constituent ratios,contingent upon maintaining robust interfacial contact integrity among electrodes,separators,and battery shells.Herein,we present a novel LPCC configuration employing solvent-free processed ultra-thick fluorinated carbon cathode(UCFxC)to achieve complete MSSCs elimination.The engineered UCFxC demonstrates exceptional areal capacity metrics(249.45 mg cm^(-2),215.77 m Ah cm^(-2)),enabling a 27.8% mass reduction compared with conventional laboratoryassembled coin cell while achieving 941.5% energy density enhancement through optimized electrode conductivity.Notably,single-walled carbon nanotube(SWCNT)-modified UCFxC architectures exhibited superior performance with energy exceeding 1.0 Wh at 50℃.This architectural paradigm provides valuable insights for developing next-generation high-energy-density LPCC systems,with practical implications for advancing miniaturized power source technologies.展开更多
γ-MnO2 nanorobs and Au/γ-MnO2 catalysts were synthesized and characterized by the X-ray powder diffraction XRD the scanning electron microscope SEM and transmission electron microscope TEM . The characterizations sh...γ-MnO2 nanorobs and Au/γ-MnO2 catalysts were synthesized and characterized by the X-ray powder diffraction XRD the scanning electron microscope SEM and transmission electron microscope TEM . The characterizations show that Au particles are well dispersed on the surface of γ-MnO2 nanorobs with a particle size of about 10 nm.The catalytic performance is evaluated in solvent-free toluene oxidation with oxygen. The influences of several process parameters such as reaction time reaction temperature initial oxygen pressure and catalyst amounts on the catalytic performance are studied.Catalytic results reveal that Au/γ-MnO2 catalyst has a unique selectivity to benzaldehyde and all these factors greatly influence the conversion of toluene and selectivity of bezaldehyde benzoic acid and benzyl benzoate.However these factors have slight influence on the selectivity of benzyl alcohol.展开更多
The effects of calcination temperature on the physicochemical properties of manganese oxide catalysts prepared by a precipitation method were assessed by X-ray diffraction,N2 adsorption-desorption,X-ray photoelectron ...The effects of calcination temperature on the physicochemical properties of manganese oxide catalysts prepared by a precipitation method were assessed by X-ray diffraction,N2 adsorption-desorption,X-ray photoelectron spectroscopy,H2 temperature-programmed reduction,O2 temperature-programmed desorption,and thermogravimetry-differential analysis.The catalytic performance of each of these materials during the selective oxidation of cyclohexane with oxygen in a solvent-free system was subsequently examined.It was found that the MnOx-500 catalyst,calcined at 500 °C,consisted of a Mn2O3 phase in addition to Mn5O8 and Mn3O4 phases and possessed a low surface area.Unlike MnOx-500,the MnOx-400 catalyst prepared at 400 °C was composed solely of Mn3O4 and Mn5O8 and had a higher surface area.The pronounced catalytic activity of this latter material for the oxidation of cyclohexene was determined to result from numerous factors,including a higher concentration of surface adsorbed oxygen,greater quantities of the surface Mn4＋ ions that promote oxygen mobility and the extent of O2 adsorption and reducibility on the catalyst.The effects of various reaction conditions on the activity of the MnOx-400 during the oxidation of cyclohexane were also evaluated,such as the reaction temperature,reaction time,and initial oxygen pressure.Following a 4 h reaction at an initial O2 pressure of 0.5 MPa and 140 °C,an 8.0% cyclohexane conversion and 5.0% yield of cyclohexanol and cyclohexanone were achieved over the MnOx-400 catalyst.In contrast,employing MnOx-500 resulted in a 6.1% conversion of cyclohexane and 75% selectivity for cyclohexanol and cyclohexanone.After being recycled through 10 replicate uses,the catalytic activity of the MnOx-400 catalyst was unchanged,demonstrating its good stability.展开更多
Silica gel-supported polyphosphoric acid （PPA-SiO2） was found to be an efficient catalyst for the one-pot four-component Hantzsch condensation reaction of aryl aldehydes, dimedone, ethyl acetoacetate and ammonium ac...Silica gel-supported polyphosphoric acid （PPA-SiO2） was found to be an efficient catalyst for the one-pot four-component Hantzsch condensation reaction of aryl aldehydes, dimedone, ethyl acetoacetate and ammonium acetate to afford the corresponding polyhydroquinoline derivatives in high yields. The main advantages of the present approach are short reaction times, clean reaction profiles, simple experimental and workup procedures.展开更多
β-Amino esters were synthesized via ZnCl2-catalyzed Mannich-type reaction of imines and malonate esters under solvent-free conditions in 6 min. The β-amino ester was converted into the corresponding aspartic acid de...β-Amino esters were synthesized via ZnCl2-catalyzed Mannich-type reaction of imines and malonate esters under solvent-free conditions in 6 min. The β-amino ester was converted into the corresponding aspartic acid derivatives.展开更多
Carbides/carbon composites are emerging as a new kind of binary dielectric systems with good microwave absorption performance.Herein,we obtain a series of tungsten carbide/carbon composites through a simple solvent-fr...Carbides/carbon composites are emerging as a new kind of binary dielectric systems with good microwave absorption performance.Herein,we obtain a series of tungsten carbide/carbon composites through a simple solvent-free strategy,where the solid mixture of dicyandiamide(DCA)and ammonium metatungstate(AM)is employed as the precursor.Ultrafine cubic WC1-x nanoparticles(3-4 nm)are in situ generated and uniformly dispersed on carbon nanosheets.This configuration overcomes some disadvantages of conventional carbides/carbon composites and is greatly helpful for electromagnetic dissipation.It is found that the weight ratio of DCA to AM can regulate chemical composition of these composites,while less impact on the average size of WC1-x nanoparticles.With the increase in carbon nanosheets,the relative complex permittivity and dielectric loss ability are constantly enhanced through conductive loss and polarization relaxation.The different dielectric properties endow these composites with distinguishable attenuation ability and impedance matching.When DCA/AM weight ratio is 6.0,the optimized composite can produce good microwave absorption performance,whose strongest reflection loss intensity reaches up to-55.6 dB at 17.5 GHz and qualified absorption bandwidth covers 3.6-18.0 GHz by manipulating the thickness from 1.0 to 5.0 mm.Such a performance is superior to many conventional carbides/carbon composites.展开更多
A series of Co-imbedded zeolite-based catalysts were synthesized following a facile solvent-free grinding route.The catalytic performance for direct syngas conversion to gasoline range hydrocarbons was compared with t...A series of Co-imbedded zeolite-based catalysts were synthesized following a facile solvent-free grinding route.The catalytic performance for direct syngas conversion to gasoline range hydrocarbons was compared with their counterpart Co-impregnated zeolite-based catalysts.Successful transformation of solid raw materials to targeted zeolite was confirmed by XRD,SEM,STEM,and N2 physisorption analysis.An in-depth study of acidic strength and acidic site distribution was conducted by NH3-TPD and Py-IR spectroscopy.Acidic strength showed a pivotal role in defining product range.Co@S1,with the weakest acidic strength of silicalite-1 among three types of zeolites,evaded over-cracking of product and exhibited the highest gasoline and isoparaffin selectivity(≈70%and 30.7%,respectively).Moreover,the solvent-free raw material grinding route for zeolite synthesis accompanies several advantages like the elimination of production of wastewater,high product yield within confined crystallization space,and elimination of safety concerns regarding high pressure due to the absence of the solvent.Facileness and easiness of the solvent-free synthesis route together with promising catalytic performance strongly support its application on the industrial scale.展开更多
Six new asymmetric thiocarbonohydrazones 3a-3f were synthesized from following steps： firstly hydrazine hydrate reacted with carbon disulfide to form thiocarbonohydrazide （1） under microwave irradiation. Then compo...Six new asymmetric thiocarbonohydrazones 3a-3f were synthesized from following steps： firstly hydrazine hydrate reacted with carbon disulfide to form thiocarbonohydrazide （1） under microwave irradiation. Then compound （1） reacted with ketone and different aldehydes step by step to give 3a-3f with excellent yields under solvent-free conditions using microwave irradiation. Their structures have been determined by elemental analysis, IR, MS and ^1H NMR data. 2009 Qing Han Li. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
Benzyltriphenylphosphonium tribromide（BTPTB） has been applied as an efficient catalyst for the preparation of bis（indolyl）-methanes （BIMs） via electrophilic substitution of indoles with aldehydes in the absence ...Benzyltriphenylphosphonium tribromide（BTPTB） has been applied as an efficient catalyst for the preparation of bis（indolyl）-methanes （BIMs） via electrophilic substitution of indoles with aldehydes in the absence of solvent.展开更多
Oxalic acid was found to be an efficient catalyst for Pechmann condensation, which includes the reaction between phenols and β-keto esters leading to formation of coumarin derivatives. The advantages of present metho...Oxalic acid was found to be an efficient catalyst for Pechmann condensation, which includes the reaction between phenols and β-keto esters leading to formation of coumarin derivatives. The advantages of present methods are the use of cheap and easy available catalyst, solvent-free reaction conditions, better yields and shorter reaction time.展开更多
Conventional synthesis of monolith-supported zeolite catalysts is based on a hydrothermal strategy.Here,we report a solvent-free crystallization process to coat ZSM-5 zeolite crystals on a monolithic SiC foam with a h...Conventional synthesis of monolith-supported zeolite catalysts is based on a hydrothermal strategy.Here,we report a solvent-free crystallization process to coat ZSM-5 zeolite crystals on a monolithic SiC foam with a honeycomb structure(ZSM-5/SiC).Characterizations of the ZSM-5/SiC by scanning electron microscopy,N2 sorption,and X-ray diffraction indicate that the zeolite sheath has been ideally coated on the surface of the SiC foam with high purity and crystallinity.Fixing Pd nanoparticles within the ZSM-5 zeolite crystals delivers a bifunctional Pd@ZSM-5/SiC catalyst,which exhibits high activity and selectivity toward diesel range paraffins in the hydrodeoxygenation of methyl oleate,a model molecule for biofuel.In comparison to the powder Pd@ZSM-5,the Pd@ZSM-5/SiC monolith catalyst shows more efficiency,which is attributed to the fast mass transfer and high heat conductivity on the honeycomb SiC structure.The durability test indicates that the Pd@ZSM-5/SiC catalyst is stable under the reaction and high-temperature regeneration conditions.展开更多
Six new N4-[bi-（4-fluorophenyl）-methyl]-piperazine thiosemicarbazones 3a-f have been prepared starting from [bi-（4-fluorophenyl）-methyl]-piperazine in solvent-free condition under microwave irradiation with excell...Six new N4-[bi-（4-fluorophenyl）-methyl]-piperazine thiosemicarbazones 3a-f have been prepared starting from [bi-（4-fluorophenyl）-methyl]-piperazine in solvent-free condition under microwave irradiation with excellent yields. Their structures have been determined by elemental analysis, IR, MS and 1H NMR data.展开更多
In this study, 1,3-disulfonic acid imidazolium hydrogen sulfate （DSIMHS） is used as an efficient and reusable ionic liquid for the green, mild, and efficient synthesis of xanthenes under solvent-free conditions. Sim...In this study, 1,3-disulfonic acid imidazolium hydrogen sulfate （DSIMHS） is used as an efficient and reusable ionic liquid for the green, mild, and efficient synthesis of xanthenes under solvent-free conditions. Simple and easy work-up, low cost, green process, short reaction times and excellent yields of the products are the advantages of this procedure. Further, the catalyst can be recycled and reused at least for four times without a noticeably decrease in its catalytic activity.展开更多
It is essential to design economic and efficient tougheners to prepare high-performance epoxy resin;however,this has remained a huge challenge.Herein,an eco-friendly,low-cost,and facile-fabricated bio-based hyperbranc...It is essential to design economic and efficient tougheners to prepare high-performance epoxy resin;however,this has remained a huge challenge.Herein,an eco-friendly,low-cost,and facile-fabricated bio-based hyperbranched toughener,carboxylic acid-functionalized tannic acid(CATA),was successfully prepared and applicated to the preparation of solvent-free epoxy resins.The mechanical performance,morphology,structural characterization,and thermal characterization of toughened epoxy resin system were studied.The toughened epoxy resin system with only 1.0wt%CATA reached the highest impact strength,111%higher than the neat epoxy resin system.Notably,the tensile strength and elongation at break of toughened epoxy resin systems increased moderately with increasing CATA loading.Nonphase-separated hybrids with significant toughening effect were obtained.Additionally,the thermal stabilities of toughened epoxy resin systems decreased with increasing CATA loading.This study provides an eco-friendly,cost-effective,and facile approach for the preparation of high-performance,solvent-free epoxy resins with potential for practical applications in sealing integrated circuits and electrical devices fields.展开更多
A convenient and effective Paal-Knorr condensations of 2,5-hexanedione with most amines have been carried out at room temperature under solvent-free condition.Macroporous strongly acidic styrol resin(D001) as a novel,...A convenient and effective Paal-Knorr condensations of 2,5-hexanedione with most amines have been carried out at room temperature under solvent-free condition.Macroporous strongly acidic styrol resin(D001) as a novel,efficient,cost-effective,and reusable solid acid catalyst for the synthesis of pyrroles under the same conditions.The pyrroles were obtained in high yields in short reaction times.展开更多
An efficient synthesis of 3,4-dihydropyrimidin-2(1H)-one derivatives using formic acid as catalyst, from aldehydes, β-ketoester and urea(thiourea) without solvent under the irradiation of microwave is described. Comp...An efficient synthesis of 3,4-dihydropyrimidin-2(1H)-one derivatives using formic acid as catalyst, from aldehydes, β-ketoester and urea(thiourea) without solvent under the irradiation of microwave is described. Compared with the classical Biginelli reaction, this new method has the advantage of good yields (77–94% for aromatic aldehydes) and short reaction time (3–8 min).展开更多
基金supported by Science and Technology Project of China Southern Power Grid (SZKJXM20230049/090000KC23010038)。
文摘Solid-state batteries(SSBs) with high safety are promising for the energy fields,but the development has long been limited by machinability and interfacial problems.Hence,self-supporting,flexible Nano LLZO CSEs are prepared with a solvent-free method at 25℃.The 99.8 wt% contents of Nano LLZO particles enable the Nano LLZO CSEs to maintain good thermal stability while exhibiting a wide electrochemical window of 5.0 V and a high Li~+ transfer number of 0.8.The mean modulus reaches 4376 MPa.Benefiting from the interfacial modulation,the Li|Li symmetric batteries based on the Nano LLZO CSEs show benign stability with lithium at the current densities of 0.1 mA cm^(-2),0.2 mA cm^(-2),and 0.5 mA cm^(-2).In addition,the Li|LiFePO_(4)(LFP) SSBs achieve favorable cycling performance:the specific capacity reaches128.1 mAh g^(-1) at 0.5 C rate,with a capacity retention of about 80% after 600 cycles.In the further tests of the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811) cathodes with higher energy density,the Nano LLZO CSEs also demonstrate good compatibility:the specific capacities of NCM811-based SSBs reach 177.9 mAh g^(-1) at 0.5 C rate,while the capacity retention is over 96% after 150 cycles.Furthermore,the Li|LFP soft-pack SSBs verify the safety characteristics and the potential for application,which have a desirable prospect.
基金supported by the Materials/Parts Technology Development Programs(RS-2024-00466920,RS-2024-00432627,and RS-2024-00421058)funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea).
文摘Rapid developments in lithium-ion battery(LIB)technology have been fueled by the expanding market for electric vehicles and increased demands for energy storage.Recently,thick electrode fabrication by solvent-free methods has emerged as a promising strategy for enhancing the energy density of LIBs.However,as electrode thickness increases,the tortuosity of lithium-ion transport also increases,resulting in severe polarization and poor electrochemical performance.Here,we investigate the effect of conductive agent morphology on the structural and electrochemical properties of 250μm thick lithium iron phosphate(LFP)/conductive agent/polytetrafluoroethylene(PTFE)-based electrodes.Three commercially available conductive additives,namely 0D Super P,1D multi-walled carbon nanotubes(MWCNTs),and 2D graphene nanoplatelets(GNPs),were incorporated into LFP-based electrodes.The MWCNT-incorporated electrode with a high loading mass(42 mg cm^(-2))exhibited a high porosity(ε=51%)and low tortuosity(τ=4.02)owing to its highly interconnected fibrous network of MWCNTs.Due to the fast lithium-ion transport kinetics in the MWCNT-incorporated electrode,the electrochemical performances exhibited a high specific capacity of 157 mAh g^(-1)at 0.1 C and an areal capacity of 7.16 mAh cm^(-2)at 0.1 C with a high-rate capability and excellent cycling stability over 300 cycles at 0.1 C.This study provides a guidance for utilizing conductive agents to apply in the low tortuous thick electrode fabricated by a solvent-free process.Additionally,this work paves the way to achieve scalable and sustainable dry processing techniques for developing next-generation energy storage technologies.
基金supported by the National Natural Science Foundation of China(Grant No.22378065,22278077,22278076)。
文摘Designing efficient adsorbents for the deep removal of refractory dibenzothiophene(DBT)from fuel oil is vital for addressing environmental issues such as acid rain.Herein,zinc gluconate and urea-derived porous carbons SF-ZnNC-T(T represents the carbonization temperature)were synthesized without solvents.Through a temperature-controlled process of“melting the zinc gluconate and urea mixture,forming H-bonded polymers,and carbonizing the polymers,”the optimal carbon,SF-ZnNC-900,was obtained with a large surface area(2280 m^(2)g^(-1),highly dispersed Zn sites,and hierarchical pore structures.Consequently,SF-ZnNC-900 demonstrated significantly higher DBT adsorption capacity of43.2 mg S g^(-1),compared to just 4.3 mg S g^(-1)for the precursor.It also demonstrated good reusability,fast adsorption rate,and the ability for ultra-deep desulfurization.The superior DBT adsorption performance resulted from the evaporation of residual zinc species,which generated abundant mesopores that facilitated DBT transformation,as well as the formation of Zn-N_(x) sites that strengthened the host-vip interaction(ΔE=-1.466 e V).The solvent-free synthesized highly dispersed Zn-doped carbon shows great potential for producing sulfur-free fuel oil and for designing metal-loaded carbon adsorbents.
基金financially supported by the National Key Research and Development Program of China(No.2023YFB3812500)the National Natural Science Foundation of China(No.52105003)the Beijing Municipal Natural Science Foundation(No.2222058)。
文摘Bioinspired active pillar structures,known for their large surface area,mechanical compliance,and diverse deformation modes,have garnered extensive research interest.Among various active pillar structures,liquid crystal elastomer(LCE)pillar arrays are capable of exhibiting significant and reversible anisotropic deformation under cyclic heating and cooling,showing great potential in tunable adhesion,soft robots,and biomedical devices.However,scaling up LCE pillar manufacturing remains challenging,limiting its practical applications.In this work,a solventfree LCE resin is developed with unique features including simple operating procedure,short fabrication time,and tunable responsive temperature,enabling rapid and large-scale production of LCE pillar arrays.The LCE resin allows for the preparation of complex 3D shapes in addition to film or specimen.The fabrication time can be as short as 4 h,without the need to evaporate solvent.Moreover,the LCE resins can be adjusted with a variable phase transition temperature range from 49.4℃ to 97.7℃ by incorporating non-liquid crystal acrylate chains.The resulting active pillar array structure can undertake sequential actuation upon heating with the tunable actuation temperature.Finally,the application of these pillar arrays in multi-level information encryption is demonstrated.The LCE pillar structure introduced here offers a new strategy for constructing advanced active LCE structures with tunable responsive behavior.
基金the financial support from the National Natural Science Foundation of China,Grant Nos.52307249the Natural Science Foundation of Shanghai Province,Nos.23ZR1465900+2 种基金the Chenguang Program of Shanghai Education Development Foundation and Shanghai Municipal Education Commission,Nos.23CGA25the Fundamental Research Funds for the Central Universities at Tongji University,Nos.PA2022000668/22120220426the Nanchang Automotive Institute of Intelligence&New Energy of Tongji University,Nos.TPD-TC202211-02。
文摘The imperative pursuit of elevated energy density in lithium primary coin cells(LPCCs)necessitates strategic architectural optimization to align with evolving market demands.A predominant approach involves the systematic replacement of metallic structural support components(MSSCs)to minimize non-active constituent ratios,contingent upon maintaining robust interfacial contact integrity among electrodes,separators,and battery shells.Herein,we present a novel LPCC configuration employing solvent-free processed ultra-thick fluorinated carbon cathode(UCFxC)to achieve complete MSSCs elimination.The engineered UCFxC demonstrates exceptional areal capacity metrics(249.45 mg cm^(-2),215.77 m Ah cm^(-2)),enabling a 27.8% mass reduction compared with conventional laboratoryassembled coin cell while achieving 941.5% energy density enhancement through optimized electrode conductivity.Notably,single-walled carbon nanotube(SWCNT)-modified UCFxC architectures exhibited superior performance with energy exceeding 1.0 Wh at 50℃.This architectural paradigm provides valuable insights for developing next-generation high-energy-density LPCC systems,with practical implications for advancing miniaturized power source technologies.
基金The National Natural Science Foundation of China(No.21276050)the Scientific Research Foundation of Graduate School of Southeast University(No.YBJJ1341)
文摘γ-MnO2 nanorobs and Au/γ-MnO2 catalysts were synthesized and characterized by the X-ray powder diffraction XRD the scanning electron microscope SEM and transmission electron microscope TEM . The characterizations show that Au particles are well dispersed on the surface of γ-MnO2 nanorobs with a particle size of about 10 nm.The catalytic performance is evaluated in solvent-free toluene oxidation with oxygen. The influences of several process parameters such as reaction time reaction temperature initial oxygen pressure and catalyst amounts on the catalytic performance are studied.Catalytic results reveal that Au/γ-MnO2 catalyst has a unique selectivity to benzaldehyde and all these factors greatly influence the conversion of toluene and selectivity of bezaldehyde benzoic acid and benzyl benzoate.However these factors have slight influence on the selectivity of benzyl alcohol.
基金supported by the National Basic Research Program of China(973 Program,2010CB732300)the National Natural Science Foundation of China(21103048)~~
文摘The effects of calcination temperature on the physicochemical properties of manganese oxide catalysts prepared by a precipitation method were assessed by X-ray diffraction,N2 adsorption-desorption,X-ray photoelectron spectroscopy,H2 temperature-programmed reduction,O2 temperature-programmed desorption,and thermogravimetry-differential analysis.The catalytic performance of each of these materials during the selective oxidation of cyclohexane with oxygen in a solvent-free system was subsequently examined.It was found that the MnOx-500 catalyst,calcined at 500 °C,consisted of a Mn2O3 phase in addition to Mn5O8 and Mn3O4 phases and possessed a low surface area.Unlike MnOx-500,the MnOx-400 catalyst prepared at 400 °C was composed solely of Mn3O4 and Mn5O8 and had a higher surface area.The pronounced catalytic activity of this latter material for the oxidation of cyclohexene was determined to result from numerous factors,including a higher concentration of surface adsorbed oxygen,greater quantities of the surface Mn4＋ ions that promote oxygen mobility and the extent of O2 adsorption and reducibility on the catalyst.The effects of various reaction conditions on the activity of the MnOx-400 during the oxidation of cyclohexane were also evaluated,such as the reaction temperature,reaction time,and initial oxygen pressure.Following a 4 h reaction at an initial O2 pressure of 0.5 MPa and 140 °C,an 8.0% cyclohexane conversion and 5.0% yield of cyclohexanol and cyclohexanone were achieved over the MnOx-400 catalyst.In contrast,employing MnOx-500 resulted in a 6.1% conversion of cyclohexane and 75% selectivity for cyclohexanol and cyclohexanone.After being recycled through 10 replicate uses,the catalytic activity of the MnOx-400 catalyst was unchanged,demonstrating its good stability.
文摘Silica gel-supported polyphosphoric acid （PPA-SiO2） was found to be an efficient catalyst for the one-pot four-component Hantzsch condensation reaction of aryl aldehydes, dimedone, ethyl acetoacetate and ammonium acetate to afford the corresponding polyhydroquinoline derivatives in high yields. The main advantages of the present approach are short reaction times, clean reaction profiles, simple experimental and workup procedures.
基金the financial support form National Natural Science Foundation of China(No.20472116).
文摘β-Amino esters were synthesized via ZnCl2-catalyzed Mannich-type reaction of imines and malonate esters under solvent-free conditions in 6 min. The β-amino ester was converted into the corresponding aspartic acid derivatives.
基金supported by National Natural Science Foundation of China(21676065 and 21776053)。
文摘Carbides/carbon composites are emerging as a new kind of binary dielectric systems with good microwave absorption performance.Herein,we obtain a series of tungsten carbide/carbon composites through a simple solvent-free strategy,where the solid mixture of dicyandiamide(DCA)and ammonium metatungstate(AM)is employed as the precursor.Ultrafine cubic WC1-x nanoparticles(3-4 nm)are in situ generated and uniformly dispersed on carbon nanosheets.This configuration overcomes some disadvantages of conventional carbides/carbon composites and is greatly helpful for electromagnetic dissipation.It is found that the weight ratio of DCA to AM can regulate chemical composition of these composites,while less impact on the average size of WC1-x nanoparticles.With the increase in carbon nanosheets,the relative complex permittivity and dielectric loss ability are constantly enhanced through conductive loss and polarization relaxation.The different dielectric properties endow these composites with distinguishable attenuation ability and impedance matching.When DCA/AM weight ratio is 6.0,the optimized composite can produce good microwave absorption performance,whose strongest reflection loss intensity reaches up to-55.6 dB at 17.5 GHz and qualified absorption bandwidth covers 3.6-18.0 GHz by manipulating the thickness from 1.0 to 5.0 mm.Such a performance is superior to many conventional carbides/carbon composites.
基金the financial support from the Zhejiang Province Natural Science Foundation(LY19B060001)the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(2018-K25)the Foundation of Zhejiang University of Science and Technology(2019QN18,2019QN23)~~
文摘A series of Co-imbedded zeolite-based catalysts were synthesized following a facile solvent-free grinding route.The catalytic performance for direct syngas conversion to gasoline range hydrocarbons was compared with their counterpart Co-impregnated zeolite-based catalysts.Successful transformation of solid raw materials to targeted zeolite was confirmed by XRD,SEM,STEM,and N2 physisorption analysis.An in-depth study of acidic strength and acidic site distribution was conducted by NH3-TPD and Py-IR spectroscopy.Acidic strength showed a pivotal role in defining product range.Co@S1,with the weakest acidic strength of silicalite-1 among three types of zeolites,evaded over-cracking of product and exhibited the highest gasoline and isoparaffin selectivity(≈70%and 30.7%,respectively).Moreover,the solvent-free raw material grinding route for zeolite synthesis accompanies several advantages like the elimination of production of wastewater,high product yield within confined crystallization space,and elimination of safety concerns regarding high pressure due to the absence of the solvent.Facileness and easiness of the solvent-free synthesis route together with promising catalytic performance strongly support its application on the industrial scale.
基金the Natural Science Foundation of Southwest University for Nationalities (No.08NQZ002) for financial support.
文摘Six new asymmetric thiocarbonohydrazones 3a-3f were synthesized from following steps： firstly hydrazine hydrate reacted with carbon disulfide to form thiocarbonohydrazide （1） under microwave irradiation. Then compound （1） reacted with ketone and different aldehydes step by step to give 3a-3f with excellent yields under solvent-free conditions using microwave irradiation. Their structures have been determined by elemental analysis, IR, MS and ^1H NMR data. 2009 Qing Han Li. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
文摘Benzyltriphenylphosphonium tribromide（BTPTB） has been applied as an efficient catalyst for the preparation of bis（indolyl）-methanes （BIMs） via electrophilic substitution of indoles with aldehydes in the absence of solvent.
文摘Oxalic acid was found to be an efficient catalyst for Pechmann condensation, which includes the reaction between phenols and β-keto esters leading to formation of coumarin derivatives. The advantages of present methods are the use of cheap and easy available catalyst, solvent-free reaction conditions, better yields and shorter reaction time.
文摘Conventional synthesis of monolith-supported zeolite catalysts is based on a hydrothermal strategy.Here,we report a solvent-free crystallization process to coat ZSM-5 zeolite crystals on a monolithic SiC foam with a honeycomb structure(ZSM-5/SiC).Characterizations of the ZSM-5/SiC by scanning electron microscopy,N2 sorption,and X-ray diffraction indicate that the zeolite sheath has been ideally coated on the surface of the SiC foam with high purity and crystallinity.Fixing Pd nanoparticles within the ZSM-5 zeolite crystals delivers a bifunctional Pd@ZSM-5/SiC catalyst,which exhibits high activity and selectivity toward diesel range paraffins in the hydrodeoxygenation of methyl oleate,a model molecule for biofuel.In comparison to the powder Pd@ZSM-5,the Pd@ZSM-5/SiC monolith catalyst shows more efficiency,which is attributed to the fast mass transfer and high heat conductivity on the honeycomb SiC structure.The durability test indicates that the Pd@ZSM-5/SiC catalyst is stable under the reaction and high-temperature regeneration conditions.
基金Natural Foundation of Southwest University for Nationalities(No.234688).
文摘Six new N4-[bi-（4-fluorophenyl）-methyl]-piperazine thiosemicarbazones 3a-f have been prepared starting from [bi-（4-fluorophenyl）-methyl]-piperazine in solvent-free condition under microwave irradiation with excellent yields. Their structures have been determined by elemental analysis, IR, MS and 1H NMR data.
基金the University of Guilan Research Council for the partial support
文摘In this study, 1,3-disulfonic acid imidazolium hydrogen sulfate （DSIMHS） is used as an efficient and reusable ionic liquid for the green, mild, and efficient synthesis of xanthenes under solvent-free conditions. Simple and easy work-up, low cost, green process, short reaction times and excellent yields of the products are the advantages of this procedure. Further, the catalyst can be recycled and reused at least for four times without a noticeably decrease in its catalytic activity.
基金from the Special Fund for the Program for Zhejiang Provincial Natural Science Foundation of China(LZ16C160001)National Key Research and Development Program(2017YFD0601105),the National Natural Science Foundation of China(Grant No.21806142)the Zhejiang Provincial Natural Science Foundation of China(Grant No.LY20B070002).
文摘It is essential to design economic and efficient tougheners to prepare high-performance epoxy resin;however,this has remained a huge challenge.Herein,an eco-friendly,low-cost,and facile-fabricated bio-based hyperbranched toughener,carboxylic acid-functionalized tannic acid(CATA),was successfully prepared and applicated to the preparation of solvent-free epoxy resins.The mechanical performance,morphology,structural characterization,and thermal characterization of toughened epoxy resin system were studied.The toughened epoxy resin system with only 1.0wt%CATA reached the highest impact strength,111%higher than the neat epoxy resin system.Notably,the tensile strength and elongation at break of toughened epoxy resin systems increased moderately with increasing CATA loading.Nonphase-separated hybrids with significant toughening effect were obtained.Additionally,the thermal stabilities of toughened epoxy resin systems decreased with increasing CATA loading.This study provides an eco-friendly,cost-effective,and facile approach for the preparation of high-performance,solvent-free epoxy resins with potential for practical applications in sealing integrated circuits and electrical devices fields.
文摘A convenient and effective Paal-Knorr condensations of 2,5-hexanedione with most amines have been carried out at room temperature under solvent-free condition.Macroporous strongly acidic styrol resin(D001) as a novel,efficient,cost-effective,and reusable solid acid catalyst for the synthesis of pyrroles under the same conditions.The pyrroles were obtained in high yields in short reaction times.
文摘An efficient synthesis of 3,4-dihydropyrimidin-2(1H)-one derivatives using formic acid as catalyst, from aldehydes, β-ketoester and urea(thiourea) without solvent under the irradiation of microwave is described. Compared with the classical Biginelli reaction, this new method has the advantage of good yields (77–94% for aromatic aldehydes) and short reaction time (3–8 min).
