The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with th...The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.展开更多
Appropriate drying process with optimized controlling of drying parameters plays a vital role in the improvement of the quality and performance of propellant products.However,few research on solvent transport dynamics...Appropriate drying process with optimized controlling of drying parameters plays a vital role in the improvement of the quality and performance of propellant products.However,few research on solvent transport dynamics within NC-based propellants was reported,and its effect on the evolution of mechanical properties was not interpreted yet.This study is conducted to gain a comprehensive understanding of hot-air drying for NC-based propellants and clarify the effect of temperature on solvent transport behavior and further the change of mechanical properties during drying.The drying kinetic curves show the drying time required is decreased but the steady solvent content is increased and the drying rate is obviously increased with the increase of hot-air temperatures,indicating hot-air temperatures have a significant effect on drying kinetics.A modified drying model was established,and results show it is more appropriate to describe solvent transport behavior within NC-based propellants.Moreover,two linear equations were established to exhibit the relationship between solvent content and its effect on the change of tensile properties,and the decrease of residual solvent content causes an obvious increase of tensile strength and tensile modulus of propellant products,indicating its mechanical properties can be partly improved by adjustment of residual solvent content.The outcomes can be used to clarify solvent transport mechanisms and optimize drying process parameters of double-based gun propellants.展开更多
Sustainable energy is the key issue for the environment protection,human activity and economic development.Ionic liquids(ILs)and deep eutectic solvents(DESs)are dogmatically regarded as green and sustainable electroly...Sustainable energy is the key issue for the environment protection,human activity and economic development.Ionic liquids(ILs)and deep eutectic solvents(DESs)are dogmatically regarded as green and sustainable electrolytes in lithium-ion,lithium-metal(e.g.,lithium-sulphur,lithium-oxygen)and post-lithium-ion(e.g.,sodium-ion,magnesium-ion,and aluminum-ion)batteries.High electrochemical stability of ILs/DESs is one of the prerequisites for green,sustainable and safe energy;while easy electrochemical decomposition of ILs/DESs would be contradictory to the concept of green chemistry by adding the cost,releasing volatile/hazardous by-products and hindering the recyclability.However,(1)are ILs/DESs-based electrolytes really electrochemically stable when they are not used in batteries?(2)are ILs/DESs-based electrolytes really electrochemically stable in real batteries?(3)how to design ILs/DESs-based electrolytes with high electrochemical stability for batteries to achieve sustainability and green development?Up to now,there is no summary on this topic,to the best of our knowledge.Here,we review the effect of chemical structure and non-structural factors on the electrochemical stability of ILs/DESs in simulated conditions.More importantly,electrochemical stability of ILs/DESs in real lithium-ion,lithium-metal and post-lithium-ion batteries is concluded and compared.Finally,the strategies to improve the electrochemical stability of ILs/DESs in lithium-ion,lithium-metal and post-lithium-ion batteries are proposed.This review would provide a guide to design ILs/DESs with high electrochemical stability for lithium-ion,lithium-metal and postlithium-ion batteries to achieve sustainable and green energy.展开更多
The isolation of minor components from complex natural product matrices presents a significant challenge in the field of purification science due to their low concentrations and the presence of structurally similar co...The isolation of minor components from complex natural product matrices presents a significant challenge in the field of purification science due to their low concentrations and the presence of structurally similar compounds.This study introduces an optimized twin-column recycling chromatography method for the efficient and simultaneous purification of these elusive constituents.By introducing water at a small flowing rate between the twin columns,a step solvent gradient is created,by which the leading edge of concentration band would migrate at a slower rate than the trailing edge as it flowing from the upstream to downstream column.Hence,the band broadening is counterbalanced,resulting in an enrichment effect for those minor components in separation process.Herein,two target substances,which showed similar peak position in high performance liquid chromatography(HPLC)and did not exceed 1.8%in crude paclitaxel were selected as target compounds for separation.By using the twin-column recycling chromatography with a step solvent gradient,a successful purification was achieved in getting the two with the purity almost 100%.We suggest this method is suitable for the separation of most components in natural produces,which shows higher precision and recovery rate compared with the common lab-operated separation ways for natural products(thin-layer chromatography and prep-HPLC).展开更多
Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in che...Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in chemical engineering.Deep eutectic solvents (DESs) as a sustainable green separation solvent have been proposed for the separation of carbazole from model anthracene oil.In this research,three quaternary ammonium-based DESs were prepared using ethylene glycol (EG) as hydrogen bond donor and tetrabutylammonium chloride (TBAC),tetrabutylammonium bromide or choline chloride as hydrogen bond acceptors.To explore their extraction performance of carbazole,the conductor-like screening model for real solvents (COSMO-RS) model was used to predict the activity coefficient at infinite dilution (γ^(∞)) of carbazole in DESs,and the result indicated TBAC:EG (1:2) had the stronger extraction ability for carbazole due to the higher capacity at infinite dilution (C^(∞)) value.Then,the separation performance of these three DESs was evaluated by experiments,and the experimental results were in good agreement with the COSMO-RS prediction results.The TBAC:EG (1:2) was determined as the most promising solvent.Additionally,the extraction conditions of TBAC:EG (1:2) were optimized,and the extraction efficiency,distribution coefficient and selectivity of carbazole could reach up to 85.74%,30.18 and 66.10%,respectively.Moreover,the TBAC:EG (1:2) could be recycled by using environmentally friendly water as antisolvent.In addition,the separation performance of TBAC:EG (1:2) was also evaluated by real crude anthracene,the carbazole was obtained with purity and yield of 85.32%,60.27%,respectively.Lastly,the extraction mechanism was elucidated byσ-profiles and interaction energy analysis.Theoretical calculation results showed that the main driving force for the extraction process was the hydrogen bonding ((N–H...Cl) and van der Waals interactions (C–H...O and C–H...π),which corresponding to the blue and green isosurfaces in IGMH analysis.This work presented a novel method for separating carbazole from crude anthracene oil,and will provide an important reference for the separation of other high value-added products from coal tar.展开更多
The efficient separation and collection of ammonia(NH_(3))during NH_(3) synthesis process is essential to improve the economic efficiency and protect the environment.In this work,ethanolammonium hydrochloride(EtOHACl)...The efficient separation and collection of ammonia(NH_(3))during NH_(3) synthesis process is essential to improve the economic efficiency and protect the environment.In this work,ethanolammonium hydrochloride(EtOHACl)and phenol(PhOH)were used to prepare a novel class of deep eutectic solvents(DESs)with multiple active sites and low viscosities.The NH_(3) separation performance of EtOHACl+PhOH DESs was analyzed completely.It is figured out that the NH_(3) absorption rates in EtOHACl+PhOH DESs are very fast.The NH_(3) absorption capacities are very high and reach up to 5.52 and 10.74 mol·kg1 at 11.2 and 100.4 kPa under 298.2 K,respectively.In addition,the EtOHACl+PhOH DESs present highly selective absorption of NH_(3) over N_(2) and H_(2) and good regenerative properties after seven cycles of absorption/desorption.The intrinsic separation mechanism of NH_(3) by EtOHACl+PhOH DESs was further revealed by spectroscopic analysis and quantum chemistry calculations.展开更多
Chemical solvents instead of pure water being as hydraulic fracturing fluid could effectively increase permeability and improve clean methane extraction efficiency.However,pore-fracture variation features of lean coal...Chemical solvents instead of pure water being as hydraulic fracturing fluid could effectively increase permeability and improve clean methane extraction efficiency.However,pore-fracture variation features of lean coal synergistically affected by solvents have not been fully understood.Ultrasonic testing,nuclear magnetic resonance analysis,liquid phase mass spectrometry was adopted to comprehensively analyze pore-fracture change characteristics of lean coal treated by combined solvent(NMP and CS_(2)).Meanwhile,quantitative characterization of above changing properties was conducted using geometric fractal theory.Relationship model between permeability,fractal dimension and porosity were established.Results indicate that the end face fractures of coal are well developed after CS2and combined solvent treatments,of which,end face box-counting fractal dimensions range from 1.1227 to 1.4767.Maximum decreases in ultrasonic longitudinal wave velocity of coal affected by NMP,CS_(2)and combined solvent are 2.700%,20.521%,22.454%,respectively.Solvent treatments could lead to increasing amount of both mesopores and macropores.Decrease ratio of fractal dimension Dsis 0.259%–2.159%,while permeability increases ratio of NMR ranges from 0.1904 to 6.4486.Meanwhile,combined solvent could dissolve coal polar and non-polar small molecules and expand flow space.Results could provide reference for solvent selection and parameter optimization of permeability-enhancement technology.展开更多
For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of sol...For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of solvent on the mechanism and kinetics of LAP was revealed through a strategy combining density functional theory(DFT)calculations and kinetic modeling.In terms of mechanism,it is found that the stronger the solvent polarity,the more electrons transfer from initiator to solvent through detailed energy decomposition analysis of electrostatic interactions between initiator and solvent molecules.Furthermore,we also found that the stronger the solvent polarity,the higher the monomer initiation energy barrier and the smaller the initiation rate coefficient.Counterintuitively,initiation is more favorable at lower temperatures based on the calculated results ofΔG_(TS).Finally,the kinetic characteristics in different solvents were further examined by kinetic modeling.It is found that in benzene and n-pentane,the polymerization rate exhibits first-order kinetics.While,slow initiation and fast propagation were observed in tetrahydrofuran(THF)due to the slow free ion formation rate,leading to a deviation from first-order kinetics.展开更多
Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However...Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.展开更多
Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it ...Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it to achieve its theory.In this study,we design a new electrolyte,namely 1 M LiBF_(4)DMSO:DOL(1:9 vol.),achieving a high energy density in Li/CF_xprimary cells.The DMSO with a small molecular size and high donor number successfully solvates Li^(+)into a defined Li^(+)-solvation structure.Such solvated Li^(+)can intercalate into the large-spacing carbon layers and achieve an improved capacity.Consequently,when discharged to 1.0 V,the CF_(1.12)cathode demonstrates a specific capacity of 1944 m A h g^(-1)with a specific energy density of 3793 W h kg^(-1).This strategy demonstrates that designing the electrolyte is powerful in improving the electrochemical performance of CF_(x) cathode.展开更多
Biocatalysis in organic solvents(OSs)has numerous important applications,but native enzymes in OSs often exhibit limited catalytic performance.Herein,we proposed a computation-aided surface charge engineering strategy...Biocatalysis in organic solvents(OSs)has numerous important applications,but native enzymes in OSs often exhibit limited catalytic performance.Herein,we proposed a computation-aided surface charge engineering strategy to improve the catalytic performance of haloalkane dehalogenase DhaA in OSs based on the energetic analysis of substrate binding to the DhaA surface.Several variants with enhanced OS resistance were obtained by replacing negative charged residues on the surface with positive charged residue(Arg).Particularly,a four-substitution variant E16R/E93R/E121R/E257R exhibited the best catalytic performance(five-fold improvement in OS resistance and seven-fold half-life increase in 40%(vol)dimethylsulfoxide).As a result,the overall catalytic performance of the variant could be at least 26 times higher than the wild-type DhaA.Fluorescence spectroscopy and molecular dynamics simulation studies revealed that the residue substitution mainly enhanced OS resistance from four aspects:(a)improved the overall structural stability,(b)increased the hydrophobicity of the local microenvironment around the catalytic triad,(c)enriched the hydrophobic substrate around the enzyme molecule,and(d)lowered the contact frequency between OS molecules and the catalytic triad.Our findings validate that computationaided surface charge engineering is an effective and ingenious rational strategy for tailoring enzyme performance in OSs.展开更多
Corn as one of the world's major food crops,its by-product corn cob is also rich in resources.However,the unreasonable utilization of corn cob often causes the environmental pollution,waste of resources and other ...Corn as one of the world's major food crops,its by-product corn cob is also rich in resources.However,the unreasonable utilization of corn cob often causes the environmental pollution,waste of resources and other problems.As one of the most abundant polymers in nature,xylan is widely used in food,medicine,materials and other fields.Corn cob is rich in xylan,which is an ideal raw material for extracting xylan.However,the intractable lignin is covalently linked to xylan,which increases the difficulty of xylan extraction.It has been reported that the deep eutectic solvent(DES)could preferentially dissolve lignin in biomass,thereby dissolving the xylan.Then,the xylan in the extract was separated by ethanol precipitation method.The xylan precipitate was obtained after centrifugation,while the supernatant was retained.The components of the supernatant after ethanol precipitation were separated by the rotary evaporator.The ethanol,water and DES were collected for the subsequent extraction of corn cob xylan.In this study,a novel way was provided for the green production of corn cob xylan.The DES was used to extract xylan from corn cob which was used as the raw material.The effects of solid-liquid ratio,reaction time,reaction temperature and water content of DES on the extraction rate of corn cob xylan were investigated by the single factor test.Furthermore,the orthogonal test was designed to optimize the xylan extraction process.The structure of corn cob xylan was analyzed and verified.The results showed that the optimum extraction conditions of corn cob xylan were as follows:the ratio of corn cob to DES was 1:15(g:mL),the extraction time was 3 h,the extraction temperature was 60℃,and the water content of DES was 70%.Under these conditions,the extraction rate of xylan was 16.46%.The extracted corn cob xylan was distinctive triple helix of polysaccharide,which was similar to the structure of commercially available xylan.Xylan was effectively and workably extracted from corn cob by the DES method.This study provided a new approach for high value conversion of corn cob and the clean production of xylan.展开更多
A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80 °C to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs w...A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80 °C to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were characterized byFourier transform infrared spectrophotometry (FT-IR), thermogravimetry/differential thermogravimetry (TG/DTG), andelectron spray ionization mass spectrometry (ESI-MS). The DESs were used as both extractants and catalysts to removedibenzothiophene from fuels via oxidative desulfurization (ODS). Experiments were performed to investigated the influenceof factors such as composition of DES, temperature, oxidant dosage (molar ratio of O:S), DES dosage (volume ratio ofDES:oil), and number of cycles on desulfurization rate. The results indicated that the removal rate of dibenzothiophene (DBT)was affected by the Lewis acidic DESs, with that of H_(3)PO_(4)/0.25∙ZnCl_(2) reaching 96.4% under optimal conditions (Voil=5 mL,VDES=1 mL, an oxidant dosage of 6, T=50 ℃). After six cycles, the desulfurization rate of H_(3)PO_(4)/0.25∙ZnCl_(2) remained above94.1%. The apparent activation energy of dibenzothiophene (DBT) removal reaction was determined by a pseudo-first orderkinetic equation according to the Arrhenius equation to be 32.34 kJ/mol, as estimated. A reaction mechanism is proposedbased on the experimental data and characterization results.展开更多
As a new type of green solvents,deep eutectic solvents(DESs)have the advantages of strong extraction ability,designability,simple preparation,low price,recoverability and biodegradation,and show great application pote...As a new type of green solvents,deep eutectic solvents(DESs)have the advantages of strong extraction ability,designability,simple preparation,low price,recoverability and biodegradation,and show great application potential in the field of plant flavonoid extraction.In this paper,the definition,classification and preparation methods of DESs were introduced.The effects of DES composition,molar ratio of DES components,water content of DES systems,liquid-material ratio,extraction temperature,extraction time and extraction auxiliary techniques on the extraction yield of plant flavonoids were expounded.The recycling methods of DESs were summarized.Existing problems of DESs in the field of plant flavonoids extraction were pointed out,and further research direction and trend were analyzed and prospected.展开更多
As the demand for sustainable energy sources continues to rise,the need for efficient and reliable energy storage systems becomes crucial.In order to effectively store and distribute renewable energy,new and innovativ...As the demand for sustainable energy sources continues to rise,the need for efficient and reliable energy storage systems becomes crucial.In order to effectively store and distribute renewable energy,new and innovative solutions must be explored.This review examines the deep eutectic solvents(DESs)as a green,safe,and affordable solution for the electrochemical energy storage and conversion field,offering tremendous opportunities and a promising future.DESs are a class of environment-friendly solvents known for their low toxicity and unique properties,such as their good conductivity,high thermal stability,and nonflammability.This review explores the fundamentals,preparations,and various interactions that often predominate in the formation of DESs,the properties of DESs,and how DESs are better than traditional solvents involving cost-ineffective and unsafe organic electrolytes and ionic liquids as well as inefficient aqueous systems due to low energy density for electrochemical energy storage applications.Then,a particular focus is placed on the various electrochemical applications of DESs,including their role in the electrolytes in batteries/supercapacitors,electropolishing and electrodeposition of metals,synthesis of electrode materials,recycling of electrodes,and their potential for use in CO_(2)capture.The review concludes by exploring the challenges,research gaps,and future potential of DESs in electrochemical applications,providing a comprehensive overview,and highlighting key considerations for their design and use.展开更多
Sinomenine is the main bio-active ingredient of Sinomenii Caulis and usually produced by solventextraction techniques. However, the extraction of sinomenine suffers from the lack of highly efficient and environmentall...Sinomenine is the main bio-active ingredient of Sinomenii Caulis and usually produced by solventextraction techniques. However, the extraction of sinomenine suffers from the lack of highly efficient and environmentally-benign solvents. In this work, deep eutectic solvents(DESs) based on fragrances were synthesized, hydrogen-bond donors(HBDs) and hydrogen-bond acceptors(HBAs) components of DESs were identified and their extraction ability for sinomenine was evaluated and the extraction conditions were optimized by single-factor and orthogonal design experiments. It was found that the hydrogen-bonding interaction between sinomenine and DESs was the main extraction driving force and there was no explicit relationship between the extraction ability and the hydrophobicity of the DESs. The DESs could be recycled and sinomenine could be recovered quantitatively via backextraction. High-purity sinomenine((95.0 ± 2.3)%) could be produced. These findings suggest that DESs are highly-effective solvents for the isolation of sinomenine and exhibit great potential for the extraction of other bio-active compounds.展开更多
Over the last decade,remarkable progress has been made in metal halide perovskite solar cells(PSCs),which have been a focus of emerging photovoltaic techniques and show great potential for commercialization.However,th...Over the last decade,remarkable progress has been made in metal halide perovskite solar cells(PSCs),which have been a focus of emerging photovoltaic techniques and show great potential for commercialization.However,the upscaling of small-area PSCs to large-area solar modules to meet the demands of practical applications remains a significant challenge.The scalable production of high-quality perovskite films by a simple,reproducible process is crucial for resolving this issue.Furthermore,the crystallization behavior in the solution-processed fabrication of perovskite films can be strongly influenced by the physicochemical properties of the precursor inks,which are significantly affected by the employed solvents and their interactions with the solutes.Thus,a comprehensive understanding of solvent engineering for fabricating perovskite films over large areas is urgently required.In this paper,we first analyze the role of solvents in the solution-processed fabrication of large-area perovskite films based on the classical crystal nucleation and growth mechanism.Recent efforts in solvent engineering to improve the quality of perovskite films for solar modules are discussed.Finally,the basic principles and future challenges of solvent system design for scalable fabrication of high-quality perovskite films for efficient solar modules are proposed.展开更多
Lubricating oils are usually produced by solvent extraction to separate aromatics in order to achieve the desired specifications and better quality products.Among the different properties of lubricating oils,density a...Lubricating oils are usually produced by solvent extraction to separate aromatics in order to achieve the desired specifications and better quality products.Among the different properties of lubricating oils,density and refractive index are some of the most important properties which can both be used for petroleum fluid characterization.Predictions of density and refractive index for naphthenic oils during solvent extraction by DMSO obtained by the pseudo-component approach and the quadratic correlation were both examined.The pseudo-component approach is a method to predict density and refractive index from composition while the latter merely relates density to refractive index.Results indicated that the predictions yielded by the pseudo-component method were in good agreement with experimental data for naphthenic oils.And the use of a function of refractive index(FRI_(20))as a pseudo-component property remarkably improved n_(20)predictions for the naphthenic mixtures.However,the density and refractive index predictions obtained by the quadratic correlation exhibited significantly higher de-viations for naphthenic oils than those for paraffinic oils.Thus a new modified correlation of the same functional form was proposed for naphthenic oils.The modification significantly improved predictions for naphthenic oils,which presented similar accuracy as the pseudo-component approach.And the previous correlation was still used for paraffinic oils.Additionally,effect of temperature on density and refractive index of naphthenic oils was examined.Results showed that the modified quadratic correlation was accurate for describing the relationship between density and refractive index of naphthenic oils at 20-90℃.The temperature dependence of density and refractive index for the raffinates and the extracts could be accurately described by the thermal coefficients for saturates and aromatics,respectively.Regarding the refractive index variation of the extracts with temperature,the empirical equation was proved to be a better option compared with the method using the thermal coefficient for aromatics.展开更多
Drying is a complicated physical process which involves simultaneous heat and mass transfer in the removal of solvents inside propellants.Inappropriate drying techniques may result in the formation of a hard skin laye...Drying is a complicated physical process which involves simultaneous heat and mass transfer in the removal of solvents inside propellants.Inappropriate drying techniques may result in the formation of a hard skin layer near the surface to block the free access of most solvent through for long stick propellants with large web thickness,which lead to lower drying efficiency and worse drying quality.This study aims to gain a comprehensive understanding of drying process and clarify the mechanism of the blocked layer near the propellant surface.A new three-dimensional coupled heat and mass transfer(3D-CHMT)model was successfully developed under transient conditions.The drying experiment results show that the 3DCHMT model could be applied to describe the drying process well since the relative error of the content of solvent between simulation and experiment values is only 5.5%.The solvent behavior simulation demonstrates that the mass transfer process can be divided into super-fast(SF)and subsequent minorfast(MF)stages,and the SF stage is vital to the prevention of the blocked layer against the free access for solvent molecules inside propellant grains.The effective solvent diffusion coefficient(Deff)of the propellant surface initially increases from 3.4×10^(-6)to 5.3×10^(-6)m^(2)/s as the temperature increases,and then decreases to 4.1×10^(-8)m^(2)/s at 60-100 min.The value of Deffof surface between 0-1.4 mm has a unique trend of change compared with other regions,and it is much lower than that of the internal at100 min under simulation conditions.Meanwhile,the temperature of the propellant surface increases rapidly at the SF stage(0-100 min)and then very slowly thereafter.Both the evolution of Deffand temperature distribution demonstrate that the blocked layer near the propellant surface has been formed in the time period of approximately 0-100 min and its thickness is about 1.4 mm.To mitigate the formation of blocked layer and improve its drying quality of finial propellant products effectively,it should be initially dried at lower drying temperature(30-40℃)in 0-100 min and then dried at higher drying temperature(50-60℃)to reduce drying time for later drying process in double base gun propellants.The present results can provide theoretical guidance for drying process and optimization of drying parameters for long stick propellants with large web thickness.展开更多
Power-conversion-efficiencies(PCEs)of organic solar cells(OSCs)in laboratory,normally processed by spin-coating technology with toxic halogenated solvents,have reached over 19%.However,there is usually a marked PCE dr...Power-conversion-efficiencies(PCEs)of organic solar cells(OSCs)in laboratory,normally processed by spin-coating technology with toxic halogenated solvents,have reached over 19%.However,there is usually a marked PCE drop when the bladecoating and/or green-solvents toward large-scale printing are used instead,which hampers the practical development of OSCs.Here,a new series of N-alkyl-tailored small molecule acceptors named YR-SeNF with a same molecular main backbone are developed by combining selenium-fused central-core and naphthalene-fused endgroup.Thanks to the N-alkyl engineering,NIR-absorbing YR-SeNF series show different crystallinity,packing patterns,and miscibility with polymeric donor.The studies exhibit that the molecular packing,crystallinity,and vertical distribution of active layer morphologies are well optimized by introducing newly designed guest acceptor associated with tailored N-alkyl chains,providing the improved charge transfer dynamics and stability for the PM6:L8-BO:YRSeNF-based OSCs.As a result,a record-high PCE approaching 19%is achieved in the blade-coating OSCs fabricated from a greensolvent o-xylene with high-boiling point.Notably,ternary OSCs offer robust operating stability under maximum-power-point tracking and well-keep>80%of the initial PCEs for even over 400 h.Our alkyl-tailored guest acceptor strategy provides a unique approach to develop green-solvent and blade-coating processed high-efficiency and operating stable OSCs,which paves a way for industrial development.展开更多
基金supported by the National Natural Science Foundation of China(22078211)the China Postdoctoral Science Foundation(2022M721115).
文摘The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.
基金the National Natural Science Foundation of China(Grant No.22075146).
文摘Appropriate drying process with optimized controlling of drying parameters plays a vital role in the improvement of the quality and performance of propellant products.However,few research on solvent transport dynamics within NC-based propellants was reported,and its effect on the evolution of mechanical properties was not interpreted yet.This study is conducted to gain a comprehensive understanding of hot-air drying for NC-based propellants and clarify the effect of temperature on solvent transport behavior and further the change of mechanical properties during drying.The drying kinetic curves show the drying time required is decreased but the steady solvent content is increased and the drying rate is obviously increased with the increase of hot-air temperatures,indicating hot-air temperatures have a significant effect on drying kinetics.A modified drying model was established,and results show it is more appropriate to describe solvent transport behavior within NC-based propellants.Moreover,two linear equations were established to exhibit the relationship between solvent content and its effect on the change of tensile properties,and the decrease of residual solvent content causes an obvious increase of tensile strength and tensile modulus of propellant products,indicating its mechanical properties can be partly improved by adjustment of residual solvent content.The outcomes can be used to clarify solvent transport mechanisms and optimize drying process parameters of double-based gun propellants.
基金supported by National Natural Science Foundation of China(22103030,22073112)Youth Topnotch Talent Program of Hebei Institution of Higher Learning(BJ2021057)for financial support.
文摘Sustainable energy is the key issue for the environment protection,human activity and economic development.Ionic liquids(ILs)and deep eutectic solvents(DESs)are dogmatically regarded as green and sustainable electrolytes in lithium-ion,lithium-metal(e.g.,lithium-sulphur,lithium-oxygen)and post-lithium-ion(e.g.,sodium-ion,magnesium-ion,and aluminum-ion)batteries.High electrochemical stability of ILs/DESs is one of the prerequisites for green,sustainable and safe energy;while easy electrochemical decomposition of ILs/DESs would be contradictory to the concept of green chemistry by adding the cost,releasing volatile/hazardous by-products and hindering the recyclability.However,(1)are ILs/DESs-based electrolytes really electrochemically stable when they are not used in batteries?(2)are ILs/DESs-based electrolytes really electrochemically stable in real batteries?(3)how to design ILs/DESs-based electrolytes with high electrochemical stability for batteries to achieve sustainability and green development?Up to now,there is no summary on this topic,to the best of our knowledge.Here,we review the effect of chemical structure and non-structural factors on the electrochemical stability of ILs/DESs in simulated conditions.More importantly,electrochemical stability of ILs/DESs in real lithium-ion,lithium-metal and post-lithium-ion batteries is concluded and compared.Finally,the strategies to improve the electrochemical stability of ILs/DESs in lithium-ion,lithium-metal and post-lithium-ion batteries are proposed.This review would provide a guide to design ILs/DESs with high electrochemical stability for lithium-ion,lithium-metal and postlithium-ion batteries to achieve sustainable and green energy.
基金supported by the National Natural Science Foundation of China(22078281)。
文摘The isolation of minor components from complex natural product matrices presents a significant challenge in the field of purification science due to their low concentrations and the presence of structurally similar compounds.This study introduces an optimized twin-column recycling chromatography method for the efficient and simultaneous purification of these elusive constituents.By introducing water at a small flowing rate between the twin columns,a step solvent gradient is created,by which the leading edge of concentration band would migrate at a slower rate than the trailing edge as it flowing from the upstream to downstream column.Hence,the band broadening is counterbalanced,resulting in an enrichment effect for those minor components in separation process.Herein,two target substances,which showed similar peak position in high performance liquid chromatography(HPLC)and did not exceed 1.8%in crude paclitaxel were selected as target compounds for separation.By using the twin-column recycling chromatography with a step solvent gradient,a successful purification was achieved in getting the two with the purity almost 100%.We suggest this method is suitable for the separation of most components in natural produces,which shows higher precision and recovery rate compared with the common lab-operated separation ways for natural products(thin-layer chromatography and prep-HPLC).
基金financially supported by Shanxi Province Natural Science Foundation of China(20210302123167)NSFC-Shanxi joint fund for coal-based low carbon(U1610223)Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2021SX-TD006).
文摘Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in chemical engineering.Deep eutectic solvents (DESs) as a sustainable green separation solvent have been proposed for the separation of carbazole from model anthracene oil.In this research,three quaternary ammonium-based DESs were prepared using ethylene glycol (EG) as hydrogen bond donor and tetrabutylammonium chloride (TBAC),tetrabutylammonium bromide or choline chloride as hydrogen bond acceptors.To explore their extraction performance of carbazole,the conductor-like screening model for real solvents (COSMO-RS) model was used to predict the activity coefficient at infinite dilution (γ^(∞)) of carbazole in DESs,and the result indicated TBAC:EG (1:2) had the stronger extraction ability for carbazole due to the higher capacity at infinite dilution (C^(∞)) value.Then,the separation performance of these three DESs was evaluated by experiments,and the experimental results were in good agreement with the COSMO-RS prediction results.The TBAC:EG (1:2) was determined as the most promising solvent.Additionally,the extraction conditions of TBAC:EG (1:2) were optimized,and the extraction efficiency,distribution coefficient and selectivity of carbazole could reach up to 85.74%,30.18 and 66.10%,respectively.Moreover,the TBAC:EG (1:2) could be recycled by using environmentally friendly water as antisolvent.In addition,the separation performance of TBAC:EG (1:2) was also evaluated by real crude anthracene,the carbazole was obtained with purity and yield of 85.32%,60.27%,respectively.Lastly,the extraction mechanism was elucidated byσ-profiles and interaction energy analysis.Theoretical calculation results showed that the main driving force for the extraction process was the hydrogen bonding ((N–H...Cl) and van der Waals interactions (C–H...O and C–H...π),which corresponding to the blue and green isosurfaces in IGMH analysis.This work presented a novel method for separating carbazole from crude anthracene oil,and will provide an important reference for the separation of other high value-added products from coal tar.
基金supported by the National Natural Science Foundation of China(22221005 and 22008033).
文摘The efficient separation and collection of ammonia(NH_(3))during NH_(3) synthesis process is essential to improve the economic efficiency and protect the environment.In this work,ethanolammonium hydrochloride(EtOHACl)and phenol(PhOH)were used to prepare a novel class of deep eutectic solvents(DESs)with multiple active sites and low viscosities.The NH_(3) separation performance of EtOHACl+PhOH DESs was analyzed completely.It is figured out that the NH_(3) absorption rates in EtOHACl+PhOH DESs are very fast.The NH_(3) absorption capacities are very high and reach up to 5.52 and 10.74 mol·kg1 at 11.2 and 100.4 kPa under 298.2 K,respectively.In addition,the EtOHACl+PhOH DESs present highly selective absorption of NH_(3) over N_(2) and H_(2) and good regenerative properties after seven cycles of absorption/desorption.The intrinsic separation mechanism of NH_(3) by EtOHACl+PhOH DESs was further revealed by spectroscopic analysis and quantum chemistry calculations.
基金financially supported by National Natural Science Foundation of China(No.52274171)Joint National-Local Engineering Research Centre for Safe and Precise Coal Mining Fund(No.EC2023015)+1 种基金Excellent Youth Project of Universities in Anhui Province(No.2023AH030042)Unveiled List of Bidding Projects of Shanxi Province(No.20201101001)。
文摘Chemical solvents instead of pure water being as hydraulic fracturing fluid could effectively increase permeability and improve clean methane extraction efficiency.However,pore-fracture variation features of lean coal synergistically affected by solvents have not been fully understood.Ultrasonic testing,nuclear magnetic resonance analysis,liquid phase mass spectrometry was adopted to comprehensively analyze pore-fracture change characteristics of lean coal treated by combined solvent(NMP and CS_(2)).Meanwhile,quantitative characterization of above changing properties was conducted using geometric fractal theory.Relationship model between permeability,fractal dimension and porosity were established.Results indicate that the end face fractures of coal are well developed after CS2and combined solvent treatments,of which,end face box-counting fractal dimensions range from 1.1227 to 1.4767.Maximum decreases in ultrasonic longitudinal wave velocity of coal affected by NMP,CS_(2)and combined solvent are 2.700%,20.521%,22.454%,respectively.Solvent treatments could lead to increasing amount of both mesopores and macropores.Decrease ratio of fractal dimension Dsis 0.259%–2.159%,while permeability increases ratio of NMR ranges from 0.1904 to 6.4486.Meanwhile,combined solvent could dissolve coal polar and non-polar small molecules and expand flow space.Results could provide reference for solvent selection and parameter optimization of permeability-enhancement technology.
基金financially supported by the National Natural Science Foundation of China(U21A20313,22222807)。
文摘For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of solvent on the mechanism and kinetics of LAP was revealed through a strategy combining density functional theory(DFT)calculations and kinetic modeling.In terms of mechanism,it is found that the stronger the solvent polarity,the more electrons transfer from initiator to solvent through detailed energy decomposition analysis of electrostatic interactions between initiator and solvent molecules.Furthermore,we also found that the stronger the solvent polarity,the higher the monomer initiation energy barrier and the smaller the initiation rate coefficient.Counterintuitively,initiation is more favorable at lower temperatures based on the calculated results ofΔG_(TS).Finally,the kinetic characteristics in different solvents were further examined by kinetic modeling.It is found that in benzene and n-pentane,the polymerization rate exhibits first-order kinetics.While,slow initiation and fast propagation were observed in tetrahydrofuran(THF)due to the slow free ion formation rate,leading to a deviation from first-order kinetics.
基金supported by the National Natural Science Foundation of China(22168002,22108070,21878078)the Natural Science Foundation of Guangxi Province(2020GXNSFAA159119)+2 种基金the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2021Z012)the Open Fund of the State Key Laboratory of Molecular Reaction Dynamics in DICP(SKLMRD-K202106)the Young Elite Scientists Sponsorship Program by CAST(2022QNRC001)。
文摘Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.
基金supported by the National Natural Science Foundation of China(Nos.52072061,22322903,12174162)the Natural Science Foundation of Sichuan,China(No.2023NSFSC1914)21C Innovation Laboratory,Contemporary Amperex Technology Ltd.by project No.21C-OP-202103。
文摘Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it to achieve its theory.In this study,we design a new electrolyte,namely 1 M LiBF_(4)DMSO:DOL(1:9 vol.),achieving a high energy density in Li/CF_xprimary cells.The DMSO with a small molecular size and high donor number successfully solvates Li^(+)into a defined Li^(+)-solvation structure.Such solvated Li^(+)can intercalate into the large-spacing carbon layers and achieve an improved capacity.Consequently,when discharged to 1.0 V,the CF_(1.12)cathode demonstrates a specific capacity of 1944 m A h g^(-1)with a specific energy density of 3793 W h kg^(-1).This strategy demonstrates that designing the electrolyte is powerful in improving the electrochemical performance of CF_(x) cathode.
基金funded by the National Key Research and Development Program of China(2018YFA0900702).
文摘Biocatalysis in organic solvents(OSs)has numerous important applications,but native enzymes in OSs often exhibit limited catalytic performance.Herein,we proposed a computation-aided surface charge engineering strategy to improve the catalytic performance of haloalkane dehalogenase DhaA in OSs based on the energetic analysis of substrate binding to the DhaA surface.Several variants with enhanced OS resistance were obtained by replacing negative charged residues on the surface with positive charged residue(Arg).Particularly,a four-substitution variant E16R/E93R/E121R/E257R exhibited the best catalytic performance(five-fold improvement in OS resistance and seven-fold half-life increase in 40%(vol)dimethylsulfoxide).As a result,the overall catalytic performance of the variant could be at least 26 times higher than the wild-type DhaA.Fluorescence spectroscopy and molecular dynamics simulation studies revealed that the residue substitution mainly enhanced OS resistance from four aspects:(a)improved the overall structural stability,(b)increased the hydrophobicity of the local microenvironment around the catalytic triad,(c)enriched the hydrophobic substrate around the enzyme molecule,and(d)lowered the contact frequency between OS molecules and the catalytic triad.Our findings validate that computationaided surface charge engineering is an effective and ingenious rational strategy for tailoring enzyme performance in OSs.
基金This work was supported by the National Natural Science Foundation of China[21978070]Natural Science Foundation of Henan[212300410032,232103810065]+2 种基金Key Research and Development Projects of Henan Province[221111320500]Program for Science&Technology Innovation Talents in Universities of Henan Province[20HASTIT034]Henan Province“Double First-Class”Project-Food Science and Technology.
文摘Corn as one of the world's major food crops,its by-product corn cob is also rich in resources.However,the unreasonable utilization of corn cob often causes the environmental pollution,waste of resources and other problems.As one of the most abundant polymers in nature,xylan is widely used in food,medicine,materials and other fields.Corn cob is rich in xylan,which is an ideal raw material for extracting xylan.However,the intractable lignin is covalently linked to xylan,which increases the difficulty of xylan extraction.It has been reported that the deep eutectic solvent(DES)could preferentially dissolve lignin in biomass,thereby dissolving the xylan.Then,the xylan in the extract was separated by ethanol precipitation method.The xylan precipitate was obtained after centrifugation,while the supernatant was retained.The components of the supernatant after ethanol precipitation were separated by the rotary evaporator.The ethanol,water and DES were collected for the subsequent extraction of corn cob xylan.In this study,a novel way was provided for the green production of corn cob xylan.The DES was used to extract xylan from corn cob which was used as the raw material.The effects of solid-liquid ratio,reaction time,reaction temperature and water content of DES on the extraction rate of corn cob xylan were investigated by the single factor test.Furthermore,the orthogonal test was designed to optimize the xylan extraction process.The structure of corn cob xylan was analyzed and verified.The results showed that the optimum extraction conditions of corn cob xylan were as follows:the ratio of corn cob to DES was 1:15(g:mL),the extraction time was 3 h,the extraction temperature was 60℃,and the water content of DES was 70%.Under these conditions,the extraction rate of xylan was 16.46%.The extracted corn cob xylan was distinctive triple helix of polysaccharide,which was similar to the structure of commercially available xylan.Xylan was effectively and workably extracted from corn cob by the DES method.This study provided a new approach for high value conversion of corn cob and the clean production of xylan.
基金the College Student Innovation and Entrepreneurship Training Program Project of Liaoning Province(202310148016)Doctoral Fund of Liaoning Province(201501105).
文摘A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80 °C to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were characterized byFourier transform infrared spectrophotometry (FT-IR), thermogravimetry/differential thermogravimetry (TG/DTG), andelectron spray ionization mass spectrometry (ESI-MS). The DESs were used as both extractants and catalysts to removedibenzothiophene from fuels via oxidative desulfurization (ODS). Experiments were performed to investigated the influenceof factors such as composition of DES, temperature, oxidant dosage (molar ratio of O:S), DES dosage (volume ratio ofDES:oil), and number of cycles on desulfurization rate. The results indicated that the removal rate of dibenzothiophene (DBT)was affected by the Lewis acidic DESs, with that of H_(3)PO_(4)/0.25∙ZnCl_(2) reaching 96.4% under optimal conditions (Voil=5 mL,VDES=1 mL, an oxidant dosage of 6, T=50 ℃). After six cycles, the desulfurization rate of H_(3)PO_(4)/0.25∙ZnCl_(2) remained above94.1%. The apparent activation energy of dibenzothiophene (DBT) removal reaction was determined by a pseudo-first orderkinetic equation according to the Arrhenius equation to be 32.34 kJ/mol, as estimated. A reaction mechanism is proposedbased on the experimental data and characterization results.
基金Supported by Project of The Education Department of Fujian Province(JAT201227).
文摘As a new type of green solvents,deep eutectic solvents(DESs)have the advantages of strong extraction ability,designability,simple preparation,low price,recoverability and biodegradation,and show great application potential in the field of plant flavonoid extraction.In this paper,the definition,classification and preparation methods of DESs were introduced.The effects of DES composition,molar ratio of DES components,water content of DES systems,liquid-material ratio,extraction temperature,extraction time and extraction auxiliary techniques on the extraction yield of plant flavonoids were expounded.The recycling methods of DESs were summarized.Existing problems of DESs in the field of plant flavonoids extraction were pointed out,and further research direction and trend were analyzed and prospected.
文摘As the demand for sustainable energy sources continues to rise,the need for efficient and reliable energy storage systems becomes crucial.In order to effectively store and distribute renewable energy,new and innovative solutions must be explored.This review examines the deep eutectic solvents(DESs)as a green,safe,and affordable solution for the electrochemical energy storage and conversion field,offering tremendous opportunities and a promising future.DESs are a class of environment-friendly solvents known for their low toxicity and unique properties,such as their good conductivity,high thermal stability,and nonflammability.This review explores the fundamentals,preparations,and various interactions that often predominate in the formation of DESs,the properties of DESs,and how DESs are better than traditional solvents involving cost-ineffective and unsafe organic electrolytes and ionic liquids as well as inefficient aqueous systems due to low energy density for electrochemical energy storage applications.Then,a particular focus is placed on the various electrochemical applications of DESs,including their role in the electrolytes in batteries/supercapacitors,electropolishing and electrodeposition of metals,synthesis of electrode materials,recycling of electrodes,and their potential for use in CO_(2)capture.The review concludes by exploring the challenges,research gaps,and future potential of DESs in electrochemical applications,providing a comprehensive overview,and highlighting key considerations for their design and use.
基金financially supported by the National Natural Science Foundation of China ( 21307028)Foundation of Henan province (202102310614)+1 种基金the Fundamental Research Funds for the Universities of Henan Province (NSFRF210428)the Foundation of Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University (KJS2016)。
文摘Sinomenine is the main bio-active ingredient of Sinomenii Caulis and usually produced by solventextraction techniques. However, the extraction of sinomenine suffers from the lack of highly efficient and environmentally-benign solvents. In this work, deep eutectic solvents(DESs) based on fragrances were synthesized, hydrogen-bond donors(HBDs) and hydrogen-bond acceptors(HBAs) components of DESs were identified and their extraction ability for sinomenine was evaluated and the extraction conditions were optimized by single-factor and orthogonal design experiments. It was found that the hydrogen-bonding interaction between sinomenine and DESs was the main extraction driving force and there was no explicit relationship between the extraction ability and the hydrophobicity of the DESs. The DESs could be recycled and sinomenine could be recovered quantitatively via backextraction. High-purity sinomenine((95.0 ± 2.3)%) could be produced. These findings suggest that DESs are highly-effective solvents for the isolation of sinomenine and exhibit great potential for the extraction of other bio-active compounds.
基金financially supported by the National Key Research and Development Project funding from the Ministry of Science and Technology of China(2021YFB3800104)the National Natural Science Foundation of China(51822203,52002140,U20A20252,51861145404,62105293,62205187)+4 种基金the Young Elite Scientists Sponsorship Program by CAST,the Self-determined and Innovative Research Funds of HUST(2020KFYXJJS008)the Natural Science Foundation of Hubei Province(ZRJQ2022000408)the Shenzhen Science and Technology Innovation Committee(JCYJ20180507182257563)Fundamental Research Program of Shanxi Province(202103021223032)the Innovation Project of Optics Valley Laboratory of China(OVL2021BG008)。
文摘Over the last decade,remarkable progress has been made in metal halide perovskite solar cells(PSCs),which have been a focus of emerging photovoltaic techniques and show great potential for commercialization.However,the upscaling of small-area PSCs to large-area solar modules to meet the demands of practical applications remains a significant challenge.The scalable production of high-quality perovskite films by a simple,reproducible process is crucial for resolving this issue.Furthermore,the crystallization behavior in the solution-processed fabrication of perovskite films can be strongly influenced by the physicochemical properties of the precursor inks,which are significantly affected by the employed solvents and their interactions with the solutes.Thus,a comprehensive understanding of solvent engineering for fabricating perovskite films over large areas is urgently required.In this paper,we first analyze the role of solvents in the solution-processed fabrication of large-area perovskite films based on the classical crystal nucleation and growth mechanism.Recent efforts in solvent engineering to improve the quality of perovskite films for solar modules are discussed.Finally,the basic principles and future challenges of solvent system design for scalable fabrication of high-quality perovskite films for efficient solar modules are proposed.
基金sponsored by the Natural Science Foundation of Xinjiang Uygur Autonomous Region(No.2022D01F37).
文摘Lubricating oils are usually produced by solvent extraction to separate aromatics in order to achieve the desired specifications and better quality products.Among the different properties of lubricating oils,density and refractive index are some of the most important properties which can both be used for petroleum fluid characterization.Predictions of density and refractive index for naphthenic oils during solvent extraction by DMSO obtained by the pseudo-component approach and the quadratic correlation were both examined.The pseudo-component approach is a method to predict density and refractive index from composition while the latter merely relates density to refractive index.Results indicated that the predictions yielded by the pseudo-component method were in good agreement with experimental data for naphthenic oils.And the use of a function of refractive index(FRI_(20))as a pseudo-component property remarkably improved n_(20)predictions for the naphthenic mixtures.However,the density and refractive index predictions obtained by the quadratic correlation exhibited significantly higher de-viations for naphthenic oils than those for paraffinic oils.Thus a new modified correlation of the same functional form was proposed for naphthenic oils.The modification significantly improved predictions for naphthenic oils,which presented similar accuracy as the pseudo-component approach.And the previous correlation was still used for paraffinic oils.Additionally,effect of temperature on density and refractive index of naphthenic oils was examined.Results showed that the modified quadratic correlation was accurate for describing the relationship between density and refractive index of naphthenic oils at 20-90℃.The temperature dependence of density and refractive index for the raffinates and the extracts could be accurately described by the thermal coefficients for saturates and aromatics,respectively.Regarding the refractive index variation of the extracts with temperature,the empirical equation was proved to be a better option compared with the method using the thermal coefficient for aromatics.
基金supported by the National Natural Science Foundation of China(Grant No.22075146)。
文摘Drying is a complicated physical process which involves simultaneous heat and mass transfer in the removal of solvents inside propellants.Inappropriate drying techniques may result in the formation of a hard skin layer near the surface to block the free access of most solvent through for long stick propellants with large web thickness,which lead to lower drying efficiency and worse drying quality.This study aims to gain a comprehensive understanding of drying process and clarify the mechanism of the blocked layer near the propellant surface.A new three-dimensional coupled heat and mass transfer(3D-CHMT)model was successfully developed under transient conditions.The drying experiment results show that the 3DCHMT model could be applied to describe the drying process well since the relative error of the content of solvent between simulation and experiment values is only 5.5%.The solvent behavior simulation demonstrates that the mass transfer process can be divided into super-fast(SF)and subsequent minorfast(MF)stages,and the SF stage is vital to the prevention of the blocked layer against the free access for solvent molecules inside propellant grains.The effective solvent diffusion coefficient(Deff)of the propellant surface initially increases from 3.4×10^(-6)to 5.3×10^(-6)m^(2)/s as the temperature increases,and then decreases to 4.1×10^(-8)m^(2)/s at 60-100 min.The value of Deffof surface between 0-1.4 mm has a unique trend of change compared with other regions,and it is much lower than that of the internal at100 min under simulation conditions.Meanwhile,the temperature of the propellant surface increases rapidly at the SF stage(0-100 min)and then very slowly thereafter.Both the evolution of Deffand temperature distribution demonstrate that the blocked layer near the propellant surface has been formed in the time period of approximately 0-100 min and its thickness is about 1.4 mm.To mitigate the formation of blocked layer and improve its drying quality of finial propellant products effectively,it should be initially dried at lower drying temperature(30-40℃)in 0-100 min and then dried at higher drying temperature(50-60℃)to reduce drying time for later drying process in double base gun propellants.The present results can provide theoretical guidance for drying process and optimization of drying parameters for long stick propellants with large web thickness.
基金the support from the NSFC (22209131, 22005121, 21875182, and 52173023)National Key Research and Development Program of China (2022YFE0132400)+4 种基金Key Scientific and Technological Innovation Team Project of Shaanxi Province (2020TD-002)111 project 2.0 (BP0618008)Open Fund of Jiangsu Engineering Laboratory of Light-Electricity-Heat Energy-Converting Materials and Applications (Changzhou University, GDRGCS2022002)Open Fund of Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education (Jiangxi Normal University, KFSEMC-202201)acquired at beamlines 7.3.3 and 11.0.1.2 at the Advanced Light Source, which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC0205CH11231
文摘Power-conversion-efficiencies(PCEs)of organic solar cells(OSCs)in laboratory,normally processed by spin-coating technology with toxic halogenated solvents,have reached over 19%.However,there is usually a marked PCE drop when the bladecoating and/or green-solvents toward large-scale printing are used instead,which hampers the practical development of OSCs.Here,a new series of N-alkyl-tailored small molecule acceptors named YR-SeNF with a same molecular main backbone are developed by combining selenium-fused central-core and naphthalene-fused endgroup.Thanks to the N-alkyl engineering,NIR-absorbing YR-SeNF series show different crystallinity,packing patterns,and miscibility with polymeric donor.The studies exhibit that the molecular packing,crystallinity,and vertical distribution of active layer morphologies are well optimized by introducing newly designed guest acceptor associated with tailored N-alkyl chains,providing the improved charge transfer dynamics and stability for the PM6:L8-BO:YRSeNF-based OSCs.As a result,a record-high PCE approaching 19%is achieved in the blade-coating OSCs fabricated from a greensolvent o-xylene with high-boiling point.Notably,ternary OSCs offer robust operating stability under maximum-power-point tracking and well-keep>80%of the initial PCEs for even over 400 h.Our alkyl-tailored guest acceptor strategy provides a unique approach to develop green-solvent and blade-coating processed high-efficiency and operating stable OSCs,which paves a way for industrial development.