We prepared and characterized a form-stable composite phase change material （PCM） with higher thermal conductivity. Capric acid（CA）-myristic acid（MA） eutectic as core, poly-methyl methacrylate （PMMA） as suppor...We prepared and characterized a form-stable composite phase change material （PCM） with higher thermal conductivity. Capric acid（CA）-myristic acid（MA） eutectic as core, poly-methyl methacrylate （PMMA） as supportive matrix and modified graphite （MG） powders serving as the thermal conductance improver were blended by bulk- polymerization method. The composite PCMs with different MG mass fraction （2%, 5%, 7%, 10% and 15%） were characterized by FT-IR, SEM, DSC technique and mechanical tests. Thermal conductivities of the composites were measured by transient hot-wire method. The results indicate that MG powders have been successfully inserted into the CA-MA/PMMA matrix without any chemical reaction with each other. The MG/CA-MA/PMMA composites maintain good thermal storage performance while the thermal conductivity has been enhanced significantly. The composite PCM added with 15 wt% MG powders increases approximately as 195.9% in thermal conductivity. Moreover, the thermal conductivity improvement of the composite PCMs is also verified by the melting-freezing experiment, which is profitable for the heat transfer efficiency in latent heat thermal energy storage system.展开更多
This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified...This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified, the synthesis methods are described, and the physicochemical properties including freezing point, acidity, density, viscosity and conductivity are presented. Furthermore, the applications of Br?nsted acidic deep eutectic solvents(BADES) and Lewis acidic deep eutectic solvents(LADES) are overviewed, respectively, covering the fields in dissolution, extraction, organic reaction and metal electrodeposition. It is expected that the ADES has great potential to replace the pollutional mineral acid, expensive and unstable solid acid, and costly ionic liquid in many acid-employed chemical processes, thus meeting the demands of green chemistry.展开更多
Stearic acid (67.83℃) and myristic acid (52.32℃) have high melting temperatures that can limit their use as phase change material (PCM) in low temperature solar heating applications such as solar space and greenhous...Stearic acid (67.83℃) and myristic acid (52.32℃) have high melting temperatures that can limit their use as phase change material (PCM) in low temperature solar heating applications such as solar space and greenhouse heating in regard to climatic requirements. However, their melting temperatures can be adjusted to a suitable value by preparing a eutectic mixture of the myristic acid (MA) and the stearic acid (SA). In the present study, the thermal analysis based on differential scanning calorimetry (DSC) technique shows that the mixture of myristic acid (MA) and stearic acid (SA) in the respective composition (by mass) of 64% and 36% forms a eutectic mixture having melting temperature of 44.13℃ and the latent heat of fusion of 182.4J·g-1. The thermal energy storage characteristics of the MA-SA eutectic mixture filled in the annulus of two concentric pipes were also experimentally established. The heat recovery rate and heat charging/discharging fractions were determined with respect to the change in the mass flow rate and the inlet temperature of heat transfer fluid. Based on the results obtained by DSC analysis and by the heat charg- ing/discharging processes of the PCM, it can be concluded that the MA-SA eutectic mixture is a potential material for low temperature thermal energy storage applications in terms of its thermo-physical and thermal characteristics.展开更多
Lignin is an abundant renewable macromolecular material in nature,and degradation of lignin to improve its hydroxyl content is the key to its efficient use.Alkali lignin(AL)was treated with Brønsted acidic deep e...Lignin is an abundant renewable macromolecular material in nature,and degradation of lignin to improve its hydroxyl content is the key to its efficient use.Alkali lignin(AL)was treated with Brønsted acidic deep eutectic solvent(DES)based on choline chloride and p-toluenesulfonic acid at mild reaction temperature,the structure of the lignin before and after degradation,as well as the composition of small molecules of lignin were analyzed in order to investigate the chemical structure changes of lignin with DES treatment,and the degradation mechanism of lignin in this acidic DES was elucidated in this work.FTIR and NMR analyses demonstrated the selective cleavage of the lignin ether linkages in the degradation process,which was in line with the increased content of phenolic hydroxyl species.XPS revealed that the O/C atomic ratio of the regenerated lignin was lower than that of the AL sample,revealing that the lignin underwent decarbonylation during the DES treatment.Regenerated lignin with low molecular weight and narrow polydispersity index was obtained,and the average molecular weight(Mw)decreased from 17680 g/mol to 2792 g/mol(130°C,3 h)according to GPC analysis.The lignin-degraded products were mainly G-type phenolics and ketones,and small number of aldehydes were also generated,the possible degradation pathway of lignin in this acidic DES was proposed.展开更多
Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or a...Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.展开更多
Natural long-chain alkanol and alkyl carboxylic acid were used to prepare novel hydrophobic deep eutectic solvents(HDESs).These HDESs are liquid at room temperature and have low viscosity(<12.26 mPa·s),low pol...Natural long-chain alkanol and alkyl carboxylic acid were used to prepare novel hydrophobic deep eutectic solvents(HDESs).These HDESs are liquid at room temperature and have low viscosity(<12.26 mPa·s),low polarity(lower than that of methanol,ChCl-based deep eutectic solvents and other reported HDESs),and low density(<0.928 g/mL).A simple one-pot method based on a novel HDES-water two-phase extraction system was constructed for the extraction of weak-polarity bioactive components,anthraquinones,from Rhei Radix et Rhizoma.This HDES-based new extraction method does not consume hazardous organic solvents and can obtain a total anthraquinone yield of 21.52 mg/g,which is close to that obtained by the Chinese pharmacopoeia method(21.22 mg/g)and considerably higher than those by other reported HDESs-based extraction methods(14.20-20.09 mg/g,p<0.01).The high extraction yield can be mainly attributed to the severe destruction of the RRR cell walls by the extraction system and the excellent dissolving ability of novel HDESs for anthraquinones.展开更多
Pyromellitic acid(PMA)and trimellitic acid(TMA)are significant chemical raw materials and intermediates.They simultaneously exist in the industry processes of synthesis and are difficult to be separated.In this work,s...Pyromellitic acid(PMA)and trimellitic acid(TMA)are significant chemical raw materials and intermediates.They simultaneously exist in the industry processes of synthesis and are difficult to be separated.In this work,several kinds of biodegradable compounds were chosen as hydrogen bond acceptors(HBAs)to separate PMA and TMA mixtures from acetone solutions via forming deep eutectic solvent(DES).It has been found that all these compounds can separate PMA and TMA mixtures to obtain pure PMA or TMA.However,the interaction between HBAs and PMA or TMA is quite different.Choline chloride cannot extract TMA but can form a DES with PMA in acetone.Hexamethylenetetramine(HA)and L-carnitine(L-car)can form DESs with both PMA and TMA in acetone solution.But when L-car or HA is added,the extraction rate of PMA is larger than that of TMA until the extraction rate of PMA reach 100%,and pure TMA is left in the acetone solution.The selective separation mechanism was explored by infrared spectroscopy combined with quantum chemistry calculation,and the strength and site of the interaction between extractants with PMA and TMA were calculated.展开更多
As the most favorable alternative to petroleum-based polymers,polylactic acid(PLA)which is the most promising degradable polymer has attracted increasing attention.However,the addition of cellulose to improve its stre...As the most favorable alternative to petroleum-based polymers,polylactic acid(PLA)which is the most promising degradable polymer has attracted increasing attention.However,the addition of cellulose to improve its strength often results in a reduction in its toughness.In this work,microscale cellulose is first prepared from pulp fibers by using a deep eutectic solvent,and then is used as the reinforcement of PLA.A microcrystalline cellulose(MCC)/PLA sheet with uniform texture is obtained by the solution mixing,melt blending,hot-pressing and cold-pressing process.The effects of MCC on the crystallization,thermal stability and mechanical properties of the PLA matrix were studied.Upon the addition of 1%cellulose fiber,the tensile strength of MCC/PLA composite sheet increased by 27%,and the elongation at break did not shown an evident decrease.The strength enhancement mechanism was elucidated using scanning electron microscopy,differential scanning calorimetry,and dynamic thermomechanical analysis.The energy dissipation during the deformation process and the compatibility of AMCC and rougher surface of MCC play important role in the strength enhancement.Additionally,UV spectroscopy showed that the composite material absorbed some ultraviolet light.Our results show that the combined use of a deep eutectic solvent and solution mixing is an effective approach for improving the strength of PLA while maintaining its toughness.展开更多
Seabuckthorn seed meal(SSM) is a waste of oil extraction industry that rich in protein. In order to seek suitable protein extraction method, three different deep eutectic solvents(DESs)(including choline chlorideglyce...Seabuckthorn seed meal(SSM) is a waste of oil extraction industry that rich in protein. In order to seek suitable protein extraction method, three different deep eutectic solvents(DESs)(including choline chlorideglycerol, choline chloride-oxalic acid and choline chloride-urea) were developed for extracting protein from SSM and compared with alkaline. Result indicated that alkaline could effectively extract 56.9% protein from SSM and its protein content was 73.1%, higher than DES at 31.0%-41.4% and 64.3%-67.5%, respectively. However, compared to alkali, DES led to a product with less β-sheet, more β-turn, more essential amino acids, higher total amino acid content, especially choline chloride-urea which extracted protein showing an integrated and similar protein weight distribution compared to SSM. Also, this protein extracted chloride-urea showed a highest digestibility in vitro(by pepsin)(54.2%). These results indicated that choline chloride-urea extraction is better than alkaline extraction for SSM.展开更多
A novel molten salt extraction process consisting of chlorination roasting and molten salt electrolysis was proposed to develop a more efficient and environmental friendly technology for recovering lead from spent lea...A novel molten salt extraction process consisting of chlorination roasting and molten salt electrolysis was proposed to develop a more efficient and environmental friendly technology for recovering lead from spent lead acid batteries(LABs).The feasibility of this process was firstly assessed based on thermodynamics fundamentals.The electrochemical behavior of Pb(II)on a tungsten electrode in the eutectic NaCl−KCl melts at 700℃ was then investigated in detail by transient electrochemical techniques.The results indicated that the reduction reaction of Pb(II)in NaCl−KCl melts was a one-step process exchanging two electrons,and it was determined to be a quasi-reversible diffusion-controlled process.Finally,potentiostatic electrolysis was carried out at−0.6 V(vs Ag/AgCl)in the NaCl−KCl−PbCl2 melts,and the obtained cathodic product was identified as pure Pb by X-ray diffraction analysis.This investigation demonstrated that it is practically feasible to produce pure Pb metal by electrochemical reduction of PbCl2 in eutectic NaCl−KCl melts,and has provided important fundamental for the further study on lead recovery from spent LABs via molten salt extraction process.展开更多
The eutectic ionic liquid （EIL） tetraethyl ammonium bromide-malonic acid （TEAB-Mal） was synthesized, with its structure characterized by the FT-IR spectroscopy and the 1H NMR spectrometry. The performance for remo...The eutectic ionic liquid （EIL） tetraethyl ammonium bromide-malonic acid （TEAB-Mal） was synthesized, with its structure characterized by the FT-IR spectroscopy and the 1H NMR spectrometry. The performance for removal of basic nitrogen compounds by EIL was studied using coker diesel as the feedstock. Experimental results showed that the EIL （TEAB-Mal） exhibited a good denitrogenation performance, leading to a 93.6% of basic N-removal efficiency under reaction conditions covering： a temperature of 30 ℃, an EIL to oil mass ratio of 1：1, an extraction time of 30 min, and a settling time of 120 min, while the basic nitrogen content in diesel dropped from 580 μg/g to 37 gg/g. In addition, the efficiency for extraction of basic N-compounds could still reach 62.9% at am EIL/oil mass ratio of 1：7 after four recycles of the EIL.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℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were ch...A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80℃ 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
This work mainly involved the preparation of a nano-scale form-stable phase change material（PCM） consisting of capric and myristic acid（CA-MA） binary eutectic acting as thermal absorbing material and nano silicon ...This work mainly involved the preparation of a nano-scale form-stable phase change material（PCM） consisting of capric and myristic acid（CA-MA） binary eutectic acting as thermal absorbing material and nano silicon dioxide（nano-SiO_2） serving as the supporting material. Industrial water glass for preparation of the nano silicon dioxide matrix and CA-MA eutectic mixture were compounded by single-step sol-gel method with the silane coupling agent. The morphology, chemical characterization and form stability property of the composite PCM were investigated by transmission electron microscopy（TEM）, scanning electron microscopy（SEM）, Fourier-transform infrared（FT-IR） spectroscopy and polarizing microscopy（POM）. It was indicated that the average diameter of the composite PCM particle ranged from 30-100 nm. The CA-MA eutectic was immobilized in the network pores constructed by the Si-O bonds so that the composite PCM was allowed no liquid leakage above the melting temperature of the CA-MA eutectic. Differential scanning calorimetry（DSC） and thermogravimetric analysis（TGA） measurement were conducted to investigate the thermal properties and stability of the composite PCM. From the measurement results, the mass fraction of the CA-MA eutectic in the composite PCM was about 40%. The phase change temperature and latent heat of the composite were determined to be 21.15 ℃ and 55.67 J/g, respectively. Meanwhile, thermal conductivity of the composite was measured to be 0.208 W·m^（-1）·K^（-1） by using the transient hot-wire method. The composite PCM was able to maintain the surrounding temperature close to its phase change temperature and behaved well in thermalregulated performance which was verified by the heat storage-release experiment. This kind of form-stable PCM was supposed to complete thermal insulation even temperature regulation by the dual effect of relatively low thermal conductivity and phase change thermal storage-release properties. So it can be formulated that the nanoscale CA-MA/SiO_2 composite PCM with the form-stable property, good thermal storage capacity and relatively low thermal conductivity can be applied for energy conservation as a kind of thermal functional material.展开更多
Developing efficient and durable non-noble-metal catalysts for the oxygen evolution reaction(OER)in acidic media remains a critical challenge for proton-exchange membrane water electrolysis.Here,we report a dual-phase...Developing efficient and durable non-noble-metal catalysts for the oxygen evolution reaction(OER)in acidic media remains a critical challenge for proton-exchange membrane water electrolysis.Here,we report a dual-phase Mn_(3)O_(4)-Co_(2)MnO_(4)hybrid oxide electrocatalyst synthesized via a sulfur-assisted coelectrodeposition strategy in a choline chloride/ethylene glycol-based deep eutectic solvent,followed by annealing.The incorporation of sulfur facilitates the formation of a cubic spinel Co_(2)MnO_(4)phase within the Mn_(3)O_(4)host,optimizing electronic conductivity and stabilizing the catalytic layer by strengthening Mn-O bonds.When supported on a corrosion-resistant Pt/Ti substrate,the composite electrode achieves a low overpotential of 317 mV at 10 mA cm^(-2)and sustains stable operation for over 100 h in 0.05 M H_(2)SO_(4)(pH=1),outperforming most MnO_(x)-based catalysts and approaching noble-metal benchmarks.Density functional theory calculations reveal that the Co_(2)MnO_(4)phase lowers the energy barrier for the rate-determining OOH^(*)→O_(2)step,while in-situ spectroscopic analyses confirm its structural integrity under acidic OER conditions.Furthermore,electrolyte dissociation kinetics significantly influences performance,with HClO_(4) exhibiting superior mass transfer due to its high proton conductivity.This work provides a rational design pathway for non-noble-metal acidic OER catalysts through phase engineering and electrolyte optimization,advancing sustainable hydrogen production technologies.展开更多
In order to improve the thermal storage capacity of expanded vermiculite（EV） based formstable composite PCM（FS-PCM） via organic modification of EV, first, EV was modified with a sodium stearate（Na St） as surface...In order to improve the thermal storage capacity of expanded vermiculite（EV） based formstable composite PCM（FS-PCM） via organic modification of EV, first, EV was modified with a sodium stearate（Na St） as surface modifier, and organic EV（OEV） with hydrophobicity and higher adsorption capacity for fatty acid was obtained. A novel capric-stearic acid eutectic（CA-SA）/OEV FS-PCM with high thermal storage capacity was then developed. OEV and CA-SA/OEV were characterized by scanning electron microscopy（SEM）, X-ray diffraction（XRD）, Fourier transform infrared spectroscopy（FTIR）, differential scanning calorimetry（DSC）, thermal gravimetry（TG）, and thermal cycling test. Results showed that OEV has obvious hydrophobicity and a higher adsorption capacity for fatty acid. Its adsorption ratio has increased by 48.71% compared with that of EV. CA-SA/OEV possesses high thermal storage density（112.52 J/g）, suitable melting temperature（20.49 ℃）, good chemical compatibility, excellent thermal stability and reliability, indicating great application potential for building energy efficiency. Moreover, organic modification of inorganic matrix may offer novel options for improving its adsorption capacity for organic PCMs and increasing heat storage capacity of corresponding FS-PCMs.展开更多
The production of industrial chemicals with renewable biomass feedstock holds potential to aid the world in pursuing a carbon-neutral society.Trimellitic and trimesic acids are important commodity chemicals in industr...The production of industrial chemicals with renewable biomass feedstock holds potential to aid the world in pursuing a carbon-neutral society.Trimellitic and trimesic acids are important commodity chemicals in industry that are prepared by the oxidation of petroleum-derived trimethylbenzene.To reduce the dependence on the limited oil source,we develop a potential sustainable alternative towards trimellitic and trimesic acids using biomass-based 2-methyl-2,4-pentandiol(MPD),acrylate and crotonaldehyde as starting materials.The process for trimellitic acid includes dehydration/D-A reaction of MPD and acrylate,flow aromatization over Pd/C catalyst,hydrolysis and catalytic aerobic oxidation(60%overall yield).The challenging regioselectivity issue of D-A reaction is tackled by a matched combination of temperature and deep eutectic solvent ChCl/HCO_(2)H.Crotonaldehyde can also participate in the reaction,followed by Pd/C-catalyzed decarbonylation/dehydrogenation and oxidation to provide trimesic acid in 54%overall yield.Life cycle assessment implies that compared to conventional fossil process,our biomass-based routes present a potential in reducing carbon emissions.展开更多
基金Founded by the National Mega-Project of Scientific&Technical Supporting Programs during the 11th Five-year Period(No.2006BAJ04A04)the Foundation of Liaoning EducationalCommittee(No.L2012225)
文摘We prepared and characterized a form-stable composite phase change material （PCM） with higher thermal conductivity. Capric acid（CA）-myristic acid（MA） eutectic as core, poly-methyl methacrylate （PMMA） as supportive matrix and modified graphite （MG） powders serving as the thermal conductance improver were blended by bulk- polymerization method. The composite PCMs with different MG mass fraction （2%, 5%, 7%, 10% and 15%） were characterized by FT-IR, SEM, DSC technique and mechanical tests. Thermal conductivities of the composites were measured by transient hot-wire method. The results indicate that MG powders have been successfully inserted into the CA-MA/PMMA matrix without any chemical reaction with each other. The MG/CA-MA/PMMA composites maintain good thermal storage performance while the thermal conductivity has been enhanced significantly. The composite PCM added with 15 wt% MG powders increases approximately as 195.9% in thermal conductivity. Moreover, the thermal conductivity improvement of the composite PCMs is also verified by the melting-freezing experiment, which is profitable for the heat transfer efficiency in latent heat thermal energy storage system.
基金The financial support from National Natural Science Foundation of China(21776074,21576081,and 2181101120)is greatly acknowledged
文摘This review divides the acidic deep eutectic solvents(ADES) into Br?nsted and Lewis DES according to their diversity of acidic character.The hydrogen bond donors and halide salts for formulating an ADES are classified, the synthesis methods are described, and the physicochemical properties including freezing point, acidity, density, viscosity and conductivity are presented. Furthermore, the applications of Br?nsted acidic deep eutectic solvents(BADES) and Lewis acidic deep eutectic solvents(LADES) are overviewed, respectively, covering the fields in dissolution, extraction, organic reaction and metal electrodeposition. It is expected that the ADES has great potential to replace the pollutional mineral acid, expensive and unstable solid acid, and costly ionic liquid in many acid-employed chemical processes, thus meeting the demands of green chemistry.
基金Supported by the Research Fund of Gaziosmanpasa University (No.2003/42).
文摘Stearic acid (67.83℃) and myristic acid (52.32℃) have high melting temperatures that can limit their use as phase change material (PCM) in low temperature solar heating applications such as solar space and greenhouse heating in regard to climatic requirements. However, their melting temperatures can be adjusted to a suitable value by preparing a eutectic mixture of the myristic acid (MA) and the stearic acid (SA). In the present study, the thermal analysis based on differential scanning calorimetry (DSC) technique shows that the mixture of myristic acid (MA) and stearic acid (SA) in the respective composition (by mass) of 64% and 36% forms a eutectic mixture having melting temperature of 44.13℃ and the latent heat of fusion of 182.4J·g-1. The thermal energy storage characteristics of the MA-SA eutectic mixture filled in the annulus of two concentric pipes were also experimentally established. The heat recovery rate and heat charging/discharging fractions were determined with respect to the change in the mass flow rate and the inlet temperature of heat transfer fluid. Based on the results obtained by DSC analysis and by the heat charg- ing/discharging processes of the PCM, it can be concluded that the MA-SA eutectic mixture is a potential material for low temperature thermal energy storage applications in terms of its thermo-physical and thermal characteristics.
基金This project was supported by the Forestry Department Foundation of Guizhou Province of China(No.[2018]13)Natural Science Foundation of Guizhou Province(Nos.Qiankehe[2020]1Y125,[2019]1170)+2 种基金the Scientific and Technological Research Project of Guizhou Province(Nos.Qiankehe NY[2019]2325,[2019]2308)Education Department Foundation of Guizhou Province of China(Nos.QianJiaoHe KY Zi[2017]003,[2017]136)the Science and Technology Plan of Guizhou Province(No.Qiankehe Platform Talent[2017]5788).
文摘Lignin is an abundant renewable macromolecular material in nature,and degradation of lignin to improve its hydroxyl content is the key to its efficient use.Alkali lignin(AL)was treated with Brønsted acidic deep eutectic solvent(DES)based on choline chloride and p-toluenesulfonic acid at mild reaction temperature,the structure of the lignin before and after degradation,as well as the composition of small molecules of lignin were analyzed in order to investigate the chemical structure changes of lignin with DES treatment,and the degradation mechanism of lignin in this acidic DES was elucidated in this work.FTIR and NMR analyses demonstrated the selective cleavage of the lignin ether linkages in the degradation process,which was in line with the increased content of phenolic hydroxyl species.XPS revealed that the O/C atomic ratio of the regenerated lignin was lower than that of the AL sample,revealing that the lignin underwent decarbonylation during the DES treatment.Regenerated lignin with low molecular weight and narrow polydispersity index was obtained,and the average molecular weight(Mw)decreased from 17680 g/mol to 2792 g/mol(130°C,3 h)according to GPC analysis.The lignin-degraded products were mainly G-type phenolics and ketones,and small number of aldehydes were also generated,the possible degradation pathway of lignin in this acidic DES was proposed.
基金supported by the Key Area Research&Development Program of Guangdong Province(2020B0101070001)the National Natural Science Foundation of China(21978053,51508547)。
文摘Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.
基金the National Natural Science Foundation of China(Grant Nos.:81673394 and 82073811)the Fundamental Research Funds for the Central Universities(Grant No.:2042020kf1010)the Large-scale Instrument and Equipment Sharing Foundation of Wuhan University(Grant No.:LF20170838)
文摘Natural long-chain alkanol and alkyl carboxylic acid were used to prepare novel hydrophobic deep eutectic solvents(HDESs).These HDESs are liquid at room temperature and have low viscosity(<12.26 mPa·s),low polarity(lower than that of methanol,ChCl-based deep eutectic solvents and other reported HDESs),and low density(<0.928 g/mL).A simple one-pot method based on a novel HDES-water two-phase extraction system was constructed for the extraction of weak-polarity bioactive components,anthraquinones,from Rhei Radix et Rhizoma.This HDES-based new extraction method does not consume hazardous organic solvents and can obtain a total anthraquinone yield of 21.52 mg/g,which is close to that obtained by the Chinese pharmacopoeia method(21.22 mg/g)and considerably higher than those by other reported HDESs-based extraction methods(14.20-20.09 mg/g,p<0.01).The high extraction yield can be mainly attributed to the severe destruction of the RRR cell walls by the extraction system and the excellent dissolving ability of novel HDESs for anthraquinones.
基金financially supported by the National Natural Science Foundation of China(21676019 and 21776199).
文摘Pyromellitic acid(PMA)and trimellitic acid(TMA)are significant chemical raw materials and intermediates.They simultaneously exist in the industry processes of synthesis and are difficult to be separated.In this work,several kinds of biodegradable compounds were chosen as hydrogen bond acceptors(HBAs)to separate PMA and TMA mixtures from acetone solutions via forming deep eutectic solvent(DES).It has been found that all these compounds can separate PMA and TMA mixtures to obtain pure PMA or TMA.However,the interaction between HBAs and PMA or TMA is quite different.Choline chloride cannot extract TMA but can form a DES with PMA in acetone.Hexamethylenetetramine(HA)and L-carnitine(L-car)can form DESs with both PMA and TMA in acetone solution.But when L-car or HA is added,the extraction rate of PMA is larger than that of TMA until the extraction rate of PMA reach 100%,and pure TMA is left in the acetone solution.The selective separation mechanism was explored by infrared spectroscopy combined with quantum chemistry calculation,and the strength and site of the interaction between extractants with PMA and TMA were calculated.
基金supported by the Natural Science Foundation of China(No.32071704).
文摘As the most favorable alternative to petroleum-based polymers,polylactic acid(PLA)which is the most promising degradable polymer has attracted increasing attention.However,the addition of cellulose to improve its strength often results in a reduction in its toughness.In this work,microscale cellulose is first prepared from pulp fibers by using a deep eutectic solvent,and then is used as the reinforcement of PLA.A microcrystalline cellulose(MCC)/PLA sheet with uniform texture is obtained by the solution mixing,melt blending,hot-pressing and cold-pressing process.The effects of MCC on the crystallization,thermal stability and mechanical properties of the PLA matrix were studied.Upon the addition of 1%cellulose fiber,the tensile strength of MCC/PLA composite sheet increased by 27%,and the elongation at break did not shown an evident decrease.The strength enhancement mechanism was elucidated using scanning electron microscopy,differential scanning calorimetry,and dynamic thermomechanical analysis.The energy dissipation during the deformation process and the compatibility of AMCC and rougher surface of MCC play important role in the strength enhancement.Additionally,UV spectroscopy showed that the composite material absorbed some ultraviolet light.Our results show that the combined use of a deep eutectic solvent and solution mixing is an effective approach for improving the strength of PLA while maintaining its toughness.
基金the financial support from the National Natural Science Foundation of China (No. 31201416)Science and Technology Research Program of Guangdong Province (No. 2017A01010502)。
文摘Seabuckthorn seed meal(SSM) is a waste of oil extraction industry that rich in protein. In order to seek suitable protein extraction method, three different deep eutectic solvents(DESs)(including choline chlorideglycerol, choline chloride-oxalic acid and choline chloride-urea) were developed for extracting protein from SSM and compared with alkaline. Result indicated that alkaline could effectively extract 56.9% protein from SSM and its protein content was 73.1%, higher than DES at 31.0%-41.4% and 64.3%-67.5%, respectively. However, compared to alkali, DES led to a product with less β-sheet, more β-turn, more essential amino acids, higher total amino acid content, especially choline chloride-urea which extracted protein showing an integrated and similar protein weight distribution compared to SSM. Also, this protein extracted chloride-urea showed a highest digestibility in vitro(by pepsin)(54.2%). These results indicated that choline chloride-urea extraction is better than alkaline extraction for SSM.
基金Project(gxyq2018012)supported by the Developing Program Foundation for the Excellent Youth Talents of Higher Education of Anhui Province,ChinaProject(SKF19-05)supported by Foundation of Anhui Province Key Laboratory of Metallurgical Engineering&Resources Recycling,ChinaProjects(51904003,U1703130)supported by the National Natural Science Foundation of China。
文摘A novel molten salt extraction process consisting of chlorination roasting and molten salt electrolysis was proposed to develop a more efficient and environmental friendly technology for recovering lead from spent lead acid batteries(LABs).The feasibility of this process was firstly assessed based on thermodynamics fundamentals.The electrochemical behavior of Pb(II)on a tungsten electrode in the eutectic NaCl−KCl melts at 700℃ was then investigated in detail by transient electrochemical techniques.The results indicated that the reduction reaction of Pb(II)in NaCl−KCl melts was a one-step process exchanging two electrons,and it was determined to be a quasi-reversible diffusion-controlled process.Finally,potentiostatic electrolysis was carried out at−0.6 V(vs Ag/AgCl)in the NaCl−KCl−PbCl2 melts,and the obtained cathodic product was identified as pure Pb by X-ray diffraction analysis.This investigation demonstrated that it is practically feasible to produce pure Pb metal by electrochemical reduction of PbCl2 in eutectic NaCl−KCl melts,and has provided important fundamental for the further study on lead recovery from spent LABs via molten salt extraction process.
基金the financial support from the Doctoral Funds of Liaoning Provincial Natural Science Foundation(201601323)
文摘The eutectic ionic liquid （EIL） tetraethyl ammonium bromide-malonic acid （TEAB-Mal） was synthesized, with its structure characterized by the FT-IR spectroscopy and the 1H NMR spectrometry. The performance for removal of basic nitrogen compounds by EIL was studied using coker diesel as the feedstock. Experimental results showed that the EIL （TEAB-Mal） exhibited a good denitrogenation performance, leading to a 93.6% of basic N-removal efficiency under reaction conditions covering： a temperature of 30 ℃, an EIL to oil mass ratio of 1：1, an extraction time of 30 min, and a settling time of 120 min, while the basic nitrogen content in diesel dropped from 580 μg/g to 37 gg/g. In addition, the efficiency for extraction of basic N-compounds could still reach 62.9% at am EIL/oil mass ratio of 1：7 after four recycles of the EIL.
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℃ 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Funded by the National Natural Science Foundation of China(No.51308275)Natural Science Foundation of Liaoning Province(No.SY2016004)the Colleges and Universities Excellent Talents Supporting Plan Program of Liaoning Province(No.LJQ2015049)
文摘This work mainly involved the preparation of a nano-scale form-stable phase change material（PCM） consisting of capric and myristic acid（CA-MA） binary eutectic acting as thermal absorbing material and nano silicon dioxide（nano-SiO_2） serving as the supporting material. Industrial water glass for preparation of the nano silicon dioxide matrix and CA-MA eutectic mixture were compounded by single-step sol-gel method with the silane coupling agent. The morphology, chemical characterization and form stability property of the composite PCM were investigated by transmission electron microscopy（TEM）, scanning electron microscopy（SEM）, Fourier-transform infrared（FT-IR） spectroscopy and polarizing microscopy（POM）. It was indicated that the average diameter of the composite PCM particle ranged from 30-100 nm. The CA-MA eutectic was immobilized in the network pores constructed by the Si-O bonds so that the composite PCM was allowed no liquid leakage above the melting temperature of the CA-MA eutectic. Differential scanning calorimetry（DSC） and thermogravimetric analysis（TGA） measurement were conducted to investigate the thermal properties and stability of the composite PCM. From the measurement results, the mass fraction of the CA-MA eutectic in the composite PCM was about 40%. The phase change temperature and latent heat of the composite were determined to be 21.15 ℃ and 55.67 J/g, respectively. Meanwhile, thermal conductivity of the composite was measured to be 0.208 W·m^（-1）·K^（-1） by using the transient hot-wire method. The composite PCM was able to maintain the surrounding temperature close to its phase change temperature and behaved well in thermalregulated performance which was verified by the heat storage-release experiment. This kind of form-stable PCM was supposed to complete thermal insulation even temperature regulation by the dual effect of relatively low thermal conductivity and phase change thermal storage-release properties. So it can be formulated that the nanoscale CA-MA/SiO_2 composite PCM with the form-stable property, good thermal storage capacity and relatively low thermal conductivity can be applied for energy conservation as a kind of thermal functional material.
基金financial support of the National Natural Science Foundation of China(52361039,21962008)Yunnan Ten Thousand Talents Plan Young&Elite Talents Project(YNWR-QN BJ-2018-346)。
文摘Developing efficient and durable non-noble-metal catalysts for the oxygen evolution reaction(OER)in acidic media remains a critical challenge for proton-exchange membrane water electrolysis.Here,we report a dual-phase Mn_(3)O_(4)-Co_(2)MnO_(4)hybrid oxide electrocatalyst synthesized via a sulfur-assisted coelectrodeposition strategy in a choline chloride/ethylene glycol-based deep eutectic solvent,followed by annealing.The incorporation of sulfur facilitates the formation of a cubic spinel Co_(2)MnO_(4)phase within the Mn_(3)O_(4)host,optimizing electronic conductivity and stabilizing the catalytic layer by strengthening Mn-O bonds.When supported on a corrosion-resistant Pt/Ti substrate,the composite electrode achieves a low overpotential of 317 mV at 10 mA cm^(-2)and sustains stable operation for over 100 h in 0.05 M H_(2)SO_(4)(pH=1),outperforming most MnO_(x)-based catalysts and approaching noble-metal benchmarks.Density functional theory calculations reveal that the Co_(2)MnO_(4)phase lowers the energy barrier for the rate-determining OOH^(*)→O_(2)step,while in-situ spectroscopic analyses confirm its structural integrity under acidic OER conditions.Furthermore,electrolyte dissociation kinetics significantly influences performance,with HClO_(4) exhibiting superior mass transfer due to its high proton conductivity.This work provides a rational design pathway for non-noble-metal acidic OER catalysts through phase engineering and electrolyte optimization,advancing sustainable hydrogen production technologies.
基金Funded by the Major State Research Development Program of China during the 13th Five-Year Plan Period(No.2016YFC0700904)the Science and Technology Support Program of Hubei Province(Nos.2014BAA134 and 2015BAA107)
文摘In order to improve the thermal storage capacity of expanded vermiculite（EV） based formstable composite PCM（FS-PCM） via organic modification of EV, first, EV was modified with a sodium stearate（Na St） as surface modifier, and organic EV（OEV） with hydrophobicity and higher adsorption capacity for fatty acid was obtained. A novel capric-stearic acid eutectic（CA-SA）/OEV FS-PCM with high thermal storage capacity was then developed. OEV and CA-SA/OEV were characterized by scanning electron microscopy（SEM）, X-ray diffraction（XRD）, Fourier transform infrared spectroscopy（FTIR）, differential scanning calorimetry（DSC）, thermal gravimetry（TG）, and thermal cycling test. Results showed that OEV has obvious hydrophobicity and a higher adsorption capacity for fatty acid. Its adsorption ratio has increased by 48.71% compared with that of EV. CA-SA/OEV possesses high thermal storage density（112.52 J/g）, suitable melting temperature（20.49 ℃）, good chemical compatibility, excellent thermal stability and reliability, indicating great application potential for building energy efficiency. Moreover, organic modification of inorganic matrix may offer novel options for improving its adsorption capacity for organic PCMs and increasing heat storage capacity of corresponding FS-PCMs.
基金supported by the National Key R&D Program of China(no.2022YFA1504902,2022YFB4201802)National Natural Science Foundation of China(no.21721004,21801239,22178335,22078318),DICP(Grant:DICP I201944)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(grant:YLU-DNL Fund 2021020).
文摘The production of industrial chemicals with renewable biomass feedstock holds potential to aid the world in pursuing a carbon-neutral society.Trimellitic and trimesic acids are important commodity chemicals in industry that are prepared by the oxidation of petroleum-derived trimethylbenzene.To reduce the dependence on the limited oil source,we develop a potential sustainable alternative towards trimellitic and trimesic acids using biomass-based 2-methyl-2,4-pentandiol(MPD),acrylate and crotonaldehyde as starting materials.The process for trimellitic acid includes dehydration/D-A reaction of MPD and acrylate,flow aromatization over Pd/C catalyst,hydrolysis and catalytic aerobic oxidation(60%overall yield).The challenging regioselectivity issue of D-A reaction is tackled by a matched combination of temperature and deep eutectic solvent ChCl/HCO_(2)H.Crotonaldehyde can also participate in the reaction,followed by Pd/C-catalyzed decarbonylation/dehydrogenation and oxidation to provide trimesic acid in 54%overall yield.Life cycle assessment implies that compared to conventional fossil process,our biomass-based routes present a potential in reducing carbon emissions.
