Highly toxic phosgene,diethyl chlorophosphate(DCP)and volatile acyl chlorides endanger our life and public security.To achieve facile sensing and discrimination of multiple target analytes,herein,we presented a single...Highly toxic phosgene,diethyl chlorophosphate(DCP)and volatile acyl chlorides endanger our life and public security.To achieve facile sensing and discrimination of multiple target analytes,herein,we presented a single fluorescent probe(BDP-CHD)for high-throughput screening of phosgene,DCP and volatile acyl chlorides.The probe underwent a covalent cascade reaction with phosgene to form boron dipyrromethene(BODIPY)with bright green fluorescence.By contrast,DCP,diphosgene and acyl chlorides can covalently assembled with the probe,giving rise to strong blue fluorescence.The probe has demonstrated high-throughput detection capability,high sensitivity,fast response(within 3 s)and parts per trillion(ppt)level detection limit.Furthermore,a portable platform based on BDP-CHD was constructed,which has achieved high-throughput discrimination of 16 analytes through linear discriminant analysis(LDA).Moreover,a smartphone adaptable RGB recognition pattern was established for the quantitative detection of multi-analytes.Therefore,this portable fluorescence sensing platform can serve as a versatile tool for rapid and high-throughput detection of toxic phosgene,DCP and volatile acyl chlorides.The proposed“one for more”strategy simplifies multi-target discrimination procedures and holds great promise for various sensing applications.展开更多
The catalytic performance of different acidic catalysts for diethyl oxalate synthesis from the one-step transesterification of dimethyl oxalate and ethanol was evaluated.The effects of different factors(e.g.,acidity,e...The catalytic performance of different acidic catalysts for diethyl oxalate synthesis from the one-step transesterification of dimethyl oxalate and ethanol was evaluated.The effects of different factors(e.g.,acidity,electron accepting capacity,cations type and crystalline water)on the catalytic activity of acidic catalysts were investigated respectively.It was proposed and confirmed that the transesterification reaction catalyzed by a Lewis acid(FeCl3)and a Bronsted acid(H2SO4)follows a first-order kinetic reaction process.In addition,the Lewis acid-catalyzed transesterification processes with different ester structures were used to further explore and understand the speculated reaction mechanism.This work enriches the theoretical understanding of acid-catalyzed transesterification reactions and is of great significance for the development of highly active catalysts for diethyl oxalate synthesis,diminishing the industrial production cost of diethyl oxalate,and developing downstream bulk or high-value-added industrial products.展开更多
Cu/SiO2 catalysts prepared by the ammonia evaporation method were applied to hydrogenation of diethyl malonate to 1,3‐propanediol. The calcination temperature played an important role in the structural evolution and ...Cu/SiO2 catalysts prepared by the ammonia evaporation method were applied to hydrogenation of diethyl malonate to 1,3‐propanediol. The calcination temperature played an important role in the structural evolution and catalytic performance of the Cu/SiO2 catalysts, which were systematically characterized by N2 adsorption‐desorption, inductively coupled plasma‐atomic emission spectros‐copy, N2O chemisorption, X‐ray diffraction, Fourier transform infrared spectroscopy, H2 tempera‐ture‐programmed reduction, transmission electron microscopy, and X‐ray photoelectron spectros‐copy. When the Cu/SiO2 catalyst was calcined at 723 K, 90.7%conversion of diethyl malonate and 32.3%selectivity of 1,3‐propanediol were achieved. Compared with Cu/SiO2 catalysts calcined at other temperatures, the enhanced catalytic performance of the Cu/SiO2 catalyst calcined at 723 K can be attributed to better dispersion of copper species, larger cupreous surface area and greater amount of copper phyllosilicate, which results in a higher ratio of Cu＋/Cu0. The synergetic effect of Cu0 and Cu＋is suggested to be responsible for the optimum activity.展开更多
Diethyl malonate being an initial raw material, processed with chlorination-replacement-desalination-vacuum rectification, is used to produce carbonyl diethyl malonate. An experiment for optimization determines that t...Diethyl malonate being an initial raw material, processed with chlorination-replacement-desalination-vacuum rectification, is used to produce carbonyl diethyl malonate. An experiment for optimization determines that the best reaction condition was： （1 reaction for 7 h at 10 ℃ with mole-ratio being 2.4 ＂ 1 between chloride and raw material （diethyl malonate）; （2 reaction for 4.5 h at 118 ℃ with mole-ratio being 1.2 ： 1 between the anhydrous sodium acetate and intermediate I. The final product carbonyl diethyl rnalonate recovery ratio reaches up to as high as 79.12% with a purity of 96.4%, which meets the market requirement. This synthesis technique has the advantages of simple process, moderate reaction conditions, high yield and low cost, being suitable for industrial scale production.展开更多
A gram negative bacterium,named JDC-16,which can grow well on the substrate of phthalic acid esters(PAEs) as the sole source of carbon and energy,was isolated from river sludge.Based on the morphology,physiological an...A gram negative bacterium,named JDC-16,which can grow well on the substrate of phthalic acid esters(PAEs) as the sole source of carbon and energy,was isolated from river sludge.Based on the morphology,physiological and biochemical properties and analysis of 16S rRNA gene sequence,it was preliminarily identified belonging to the genus Acinetobacter.The result of substrates utilization range indicates that strain JDC-16 can utilize a variety of phthalates except for diisononyl phthalate(DINP) .The degradation tests using diethyl phthalate(DEP) as the model compound show that the optimal pH and temperature for DEP degradation by Acinetobacter sp.JDC-16 is 8.0 and 35℃,respectively.Meanwhile,degradation kinetics under various initial concentrations of DEP reveals that substrate depletion curves fit well with the modified Gompertz model with high correlation coefficient(R 2 >0.99) .Furthermore,the substrate induction test indicates that DEP-induction can apparently shorten the lag phase and enhance the degradation rate.This work highlights the potential of this isolate for bioremediation of phthalates-contaminated environments.展开更多
This paper presents experimental observations on the adsorption of individual solutes by a simple thermodynamic framework, and the equilibrium adsorption of ethyl benzoate and diethyl phthalate on phenolic resin adsor...This paper presents experimental observations on the adsorption of individual solutes by a simple thermodynamic framework, and the equilibrium adsorption of ethyl benzoate and diethyl phthalate on phenolic resin adsorbent in hexane solutions within the temperature range of 293-313 K. The experimental results show that the Freundlich adsorption law is applicable to the adsorption of ethyl benzoate and diethyl phthalate on the adsorbent, since all the correlative factors R' are larger than 0.99. The negative values of all the isosteric adsorption enthalpies for ethyl benzoate and diethyl phthalate indicate that they undergo exothermic processes, while their magnitudes (19-28 kJ/mol) manifest a hydrogen bonding sorption process. Other thermodynamic properties: the free energy changes and the entropy change associated with the adsorption have been calculated from the Gibbs adsorption equation and the Gibbs-Helmholtz equation展开更多
The solubility and hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water are studied as a function of composition. The use of an aqueous solution of diethylene glycol diethyl et...The solubility and hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water are studied as a function of composition. The use of an aqueous solution of diethylene glycol diethyl ether enhances the solubility and hydrolysis rate of carbonyl sulfide compared with that in pure water. The composition of the mixture with maximum hydrolysis rate varies with temperature. The thermophysical properties including density, viscosity, and surface tension as a function of composition at 20℃ under atmospheric pressure as well as liquid-liquid equilibrium (LLE) data over the temperature range from 28℃ to 90℃ are also measured for the binary mixture.展开更多
This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster u...This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster under 365 nm light irradiation than in the dark in the presence of iron(hydr)oxides. The apparent kinetic rates of DEP degradation followed the order HFO > goethite ≈ hematite in the dark and HFO > hematite > goethite under 365 nm light irradiation. Two pathways governed H2 O2 decomposition efficiency on iron(hydr)oxide surfaces:(1) forming UOH on inherent surface hydroxyl groups(Fe-OH) and(2) producing O2 and H2 O on the surface oxygen vacancies. X-ray photoelectron spectroscopy(XPS) analyses indicated that HFO not only has high Fe-OH content but also has high Vo content, resulting in its low H2 O2 utilization efficiency(η). DEP was degraded through hydrogen abstraction and deesterification, and the major products were(OH)2-DEP, mono-ethyl phthalate(MEP), OH-MEP,and phthalate acid(PA). The study is important in understanding the transformation of phthalate esters in top surface soils and surface waters under ultraviolet light.展开更多
ZrO2-MnO2-ZnO supports were prepared by the co-precipitation method,and then Ni-Na/ZrO2-MnO2-ZnO catalysts were prepared by the impregnation method.In this paper,the reactions to synthesize methyl isopropyl ketone and...ZrO2-MnO2-ZnO supports were prepared by the co-precipitation method,and then Ni-Na/ZrO2-MnO2-ZnO catalysts were prepared by the impregnation method.In this paper,the reactions to synthesize methyl isopropyl ketone and diethyl ketone by the one-step synthesis method over this catalyst were studied,and meanwhile,the impact of the catalyst preparation conditions and the reaction conditions on catalyst performance was also investigated.It was observed that under the conditions when Ni loading was 25%,calcination temperature was 400℃ and reduction temperature was 410℃,this catalyst had good catalytic performance on the reaction.The suitable reaction conditions were achieved:reaction temperature was 400℃;reaction at atmospheric pressure;liquid hourly space velocity of raw material of 0.5 h 1 ;and the molar ratio of(methanol)/(methyl ethyl ketone)/(water) was equal to 1/1/1.Under such conditions,the conversion of methyl ethyl ketone could achieve 41.7%,and the overall selectivity of methyl isopropyl ketone and diethyl ketone could achieve 83.3%,which was comparable to the conversion of 38.1% and the selectivity of 82.2% achieved by using palladium as the active material.The good stability made this catalyst have good prospects for industrial application.展开更多
This article describes a process for the synthesis of diethyl oxalate by a coupling reaction of carbon monoxide, catalyzed by palladium in the presence of ethyl nitrite. The kinetics and mechanism of the coupling and ...This article describes a process for the synthesis of diethyl oxalate by a coupling reaction of carbon monoxide, catalyzed by palladium in the presence of ethyl nitrite. The kinetics and mechanism of the coupling and regeneration reaction are also discussed. This paper presents the results of a scale-up test of the catalyst and the process based on an a priori computer simulation.展开更多
The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in ...The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in boron trifluoride diethyl etherate （BFEE） and its mixed electrolytes with acetonitrile （ACN）. The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy （SEM）, respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT：MeT = 1：2, was about 1.08：1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.展开更多
Ionic liquids （ILs） based on 1,3-dialkylimidazolium and tetraalkylammonium cations were employed as a series of efficient, environmentally benign phase-transfer catalysts （PTCs） for the base-promoted monoalkylatio...Ionic liquids （ILs） based on 1,3-dialkylimidazolium and tetraalkylammonium cations were employed as a series of efficient, environmentally benign phase-transfer catalysts （PTCs） for the base-promoted monoalkylation of diethyl malonate. The influence of various heterogeneous bases on yields was studied. Good yields and high selectivity were obtained. Solvent-free, mild reaction condition, short reaction time, and easy purification were the merits of this method. The catalytic system （IL-hase） could also be recycled after the extraction of products with ether.展开更多
The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of ap...The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of applied polymerization potential and the monomer concentration ratios on the copolymerization were investigated by linear sweep voltammetry and cyclic voltammetry(CV).The structure of copolymer films were investigated by UV-Vis,infrared spectroscopy,thermal analysis.As-formed novel copolymers own...展开更多
A novel Pd-Fe/α-Al_(2)O_(3) catalyst was synthesized by incipient-wetness impregnation method with bayberry tannin as chelating promoter and commercial hollow column Raschig ring a-Al_(2)O_(3) as support for the synt...A novel Pd-Fe/α-Al_(2)O_(3) catalyst was synthesized by incipient-wetness impregnation method with bayberry tannin as chelating promoter and commercial hollow column Raschig ring a-Al_(2)O_(3) as support for the synthesis of diethyl oxalate from CO and ethyl nitrite.A variety of characterization techniques including N2 physical adsorption,optical microscopy,scanning electron microscopy and energy dispersive system(SEM-EDS),inductively coupled plasma optical emission spectroscopy(ICP-OES),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM),were employed to explore the relationship between the physicochemical properties and activity of catalysts.It indicated that a large number of phenolic hydroxyl groups in bayberry tannin can efficiently anchor the active component Pd,reduce the particle size and make the active Pd as a multi-ring distribution on the commercial a-Al2O3 suppo rt,which we re beneficial to improve the catalytic activity for the production of diethyl oxalate from CO and ethyl nitrite.0.3 wts Pd-Fe/α-Al_(2)O_(3) showed excelle nt catalytic activity and selectivity in a continuous flow,fixed-bed reactor with the loading amount of 10 mL catalysts,Under the mild reaction conditions,the space-time yield of diethyl oxalate was 978 g L^(-1) h^(-1) and CO conversion was 44% with the selectivity to diethyl oxalate of 95.5%.展开更多
The title complexes Ln(DEP),(Ln=La,Sm,Eu,Ho and Yb)were synthesized by reaction of triethyl phosphate with trivalent rare earth chlorides.The mechanism of thermo-decomposition of the complexes has been studied.Accordi...The title complexes Ln(DEP),(Ln=La,Sm,Eu,Ho and Yb)were synthesized by reaction of triethyl phosphate with trivalent rare earth chlorides.The mechanism of thermo-decomposition of the complexes has been studied.According to their IR spectra,the residues of the thermo-decomposition of the complexes were identified as Ln(PO_3)_3.Their IR spectra were measured and principal IR bands were assigned.The experimental results of the IR spectra of the complexes show that the title complexes have the same coordination form and mo- lecular configuration as rare earth,e.g.Sm,complex with dimethyl phosphate(Sm(DMP)_3).Each of the rare earth ion links three rare earth ions nearby through double“O-P-O”bridges to form a special network of rings-linking-rings,each of which consists of twenty-four atoms.The Ln-O bond is principally ionic.展开更多
A green synthesis route of diethyl malonate by palladium catalyzed carbonylation of ethyl chloroacetate in the presence of phase transfer agent is carried out under mild conditions in good yield. The effects of reacti...A green synthesis route of diethyl malonate by palladium catalyzed carbonylation of ethyl chloroacetate in the presence of phase transfer agent is carried out under mild conditions in good yield. The effects of reaction temperature and different bases on the yield of diethyl malonate are also discussed.展开更多
Destructive tests of the catalyst was carried out to study the effect oftemperature on the catalytic activity of CO coupling to diethyl oxalate (DEO) over a Pd-Fe/Al_2O_3catalyst. It was found that a temperature jump ...Destructive tests of the catalyst was carried out to study the effect oftemperature on the catalytic activity of CO coupling to diethyl oxalate (DEO) over a Pd-Fe/Al_2O_3catalyst. It was found that a temperature jump could cause the deactivation of the Pd-Fe/α-Al_2O_3catalyst. The catalyst deactivated at different temperatures has different characteristics. Afterdeactivation the crystal structure of α-Al_2O_3 did not change, but the Pd particle size wasenlarged. Most of the Pd^0 were oxidized to Pd^(2+), and Fe^(2+) was oxidized to Fe^(3+) on thesurface of the deactivated catalyst. The catalyst could be regenerated, but its original activitycould not be recovered completely.展开更多
Lithium metal batteries have obtained increasing interest due to their high specific capacity.Nonetheless,the growth of lithium dendrites brings safety risks to batteries and further deteriorates the performance.Herei...Lithium metal batteries have obtained increasing interest due to their high specific capacity.Nonetheless,the growth of lithium dendrites brings safety risks to batteries and further deteriorates the performance.Herein,we explore diethyl phenylphosphonite(DEPP) as the electrolyte additive to alleviate this problem.DEPP can be preferentially decomposed than carbonate solvents to form the stable interface between electrolyte and lithium anode for inhibiting the dendrite growth.As expected,the symmetrical LiIILi cells could achieve a stable cycling performance with 200 h at 1 mA cm^(-2).Moreover,DEPP can be preferentially oxidized on the surface of lithium cobalt oxides(LiCoO_(2)) to form a dense cathode electrolyte interphase(CEI) film for suppressing the continuous oxidative decomposition of the electrolyte and eliminating the adverse effects of HF on the battery.This endows LiCoO_(2) IILi full battery with the enhanced cycling and rate performance.展开更多
Diethyl carbonate has been synthesized via the alcoholysis of ethyl carbamate in supercritical ethanol under catalyst-free conditions.The influences of various parameters such as reaction temperature,reaction time,rea...Diethyl carbonate has been synthesized via the alcoholysis of ethyl carbamate in supercritical ethanol under catalyst-free conditions.The influences of various parameters such as reaction temperature,reaction time,reaction pressure,ethanol/ethyl molar ratios and reaction loading volume on the yield of DEC were studied systematically.The experimental results indicated that the alcoholysis of ethyl carbamate was greatly improved in supercritical ethanol.The optimal reaction conditions were as follows：a reaction temperature of 573 K,a reaction time of 30 min,a reaction pressure of 13.2 MPa,an ethanol/ethyl carbamate molar ratio of 10 and a reactor loading volume of 285 μL respectively.The optimal yield of DEC was 22.9%.展开更多
Cupric oxide （CuO） and copper-cuprous oxide （Cu-Cu2O） nanoparticles were prepared by a simple hydrothermal method for the synthesis of diethyi carbonate （DEC） from ethanol. During these syntheses, varying NaOH a...Cupric oxide （CuO） and copper-cuprous oxide （Cu-Cu2O） nanoparticles were prepared by a simple hydrothermal method for the synthesis of diethyi carbonate （DEC） from ethanol. During these syntheses, varying NaOH and glucose concentrations were applied to explore and pinpoint the active species. It was found that PdCl2/CuO and PdCI2/Cu-Cu2O both catalysts exhibited good thermal stability and morphology. The results of catalytic tests showed that the catalysts prepared with 5 mol/L NaOH show superior catalytic performances because of their lower extent of agglomeration. It is noteworthy that the PdC12/Cu-Cu2O catalysts were the most active, especially the PdCl2/Cu-Cu2O catalyst prepared with 10 mmol glucose and having a higher Cu2O concentration. In Pd（ll）-Cu（II） （PdCl2/CuO） catalysts, there is an induction period, during which Pd（II） is reduced to Pd（0）, that must occur prior to electron transfer between Pd and Cu, and this can slow the catalytic reaction. To further pinpoint the active species, PdCl2/Cu-Cu2O catalysts with different Cu2O contents were prepared by controlling the dosages of glucose. The maximum DEC yield obtained with these catalysts was 151.9 mg.g-1.h-1, corresponding to an ethanol conversion of 7.2% and 97.9% DEC selectivity on an ethanol basis. Therefore, it was concluded that Cu＋ was the active species in this catalytic system, possibly because a higher proportion of Cu＋ reduces the Pd2＋ concentration and limits the CO oxidation side reaction, thus increasing DEC selectivity. In addition, Cu＋ promotes electron transfer between Pd and Cu without an induction period, which could also promote the catalytic activity.展开更多
基金the financial support of the National Natural Science Foundation of China(No.22168009)。
文摘Highly toxic phosgene,diethyl chlorophosphate(DCP)and volatile acyl chlorides endanger our life and public security.To achieve facile sensing and discrimination of multiple target analytes,herein,we presented a single fluorescent probe(BDP-CHD)for high-throughput screening of phosgene,DCP and volatile acyl chlorides.The probe underwent a covalent cascade reaction with phosgene to form boron dipyrromethene(BODIPY)with bright green fluorescence.By contrast,DCP,diphosgene and acyl chlorides can covalently assembled with the probe,giving rise to strong blue fluorescence.The probe has demonstrated high-throughput detection capability,high sensitivity,fast response(within 3 s)and parts per trillion(ppt)level detection limit.Furthermore,a portable platform based on BDP-CHD was constructed,which has achieved high-throughput discrimination of 16 analytes through linear discriminant analysis(LDA).Moreover,a smartphone adaptable RGB recognition pattern was established for the quantitative detection of multi-analytes.Therefore,this portable fluorescence sensing platform can serve as a versatile tool for rapid and high-throughput detection of toxic phosgene,DCP and volatile acyl chlorides.The proposed“one for more”strategy simplifies multi-target discrimination procedures and holds great promise for various sensing applications.
基金funded by the Key Projects of Xinjiang Production and Construction Corps(2022AB007)the Key Projects of innovation team of Xinjiang eighth division Construction Corps 2023TD04)Liaoning Innovation Capability Fund(2021-NLTS-12-02).
文摘The catalytic performance of different acidic catalysts for diethyl oxalate synthesis from the one-step transesterification of dimethyl oxalate and ethanol was evaluated.The effects of different factors(e.g.,acidity,electron accepting capacity,cations type and crystalline water)on the catalytic activity of acidic catalysts were investigated respectively.It was proposed and confirmed that the transesterification reaction catalyzed by a Lewis acid(FeCl3)and a Bronsted acid(H2SO4)follows a first-order kinetic reaction process.In addition,the Lewis acid-catalyzed transesterification processes with different ester structures were used to further explore and understand the speculated reaction mechanism.This work enriches the theoretical understanding of acid-catalyzed transesterification reactions and is of great significance for the development of highly active catalysts for diethyl oxalate synthesis,diminishing the industrial production cost of diethyl oxalate,and developing downstream bulk or high-value-added industrial products.
文摘Cu/SiO2 catalysts prepared by the ammonia evaporation method were applied to hydrogenation of diethyl malonate to 1,3‐propanediol. The calcination temperature played an important role in the structural evolution and catalytic performance of the Cu/SiO2 catalysts, which were systematically characterized by N2 adsorption‐desorption, inductively coupled plasma‐atomic emission spectros‐copy, N2O chemisorption, X‐ray diffraction, Fourier transform infrared spectroscopy, H2 tempera‐ture‐programmed reduction, transmission electron microscopy, and X‐ray photoelectron spectros‐copy. When the Cu/SiO2 catalyst was calcined at 723 K, 90.7%conversion of diethyl malonate and 32.3%selectivity of 1,3‐propanediol were achieved. Compared with Cu/SiO2 catalysts calcined at other temperatures, the enhanced catalytic performance of the Cu/SiO2 catalyst calcined at 723 K can be attributed to better dispersion of copper species, larger cupreous surface area and greater amount of copper phyllosilicate, which results in a higher ratio of Cu＋/Cu0. The synergetic effect of Cu0 and Cu＋is suggested to be responsible for the optimum activity.
基金Supported by the Innovation Fund for Technology Based Firms(10C26224212340)
文摘Diethyl malonate being an initial raw material, processed with chlorination-replacement-desalination-vacuum rectification, is used to produce carbonyl diethyl malonate. An experiment for optimization determines that the best reaction condition was： （1 reaction for 7 h at 10 ℃ with mole-ratio being 2.4 ＂ 1 between chloride and raw material （diethyl malonate）; （2 reaction for 4.5 h at 118 ℃ with mole-ratio being 1.2 ： 1 between the anhydrous sodium acetate and intermediate I. The final product carbonyl diethyl rnalonate recovery ratio reaches up to as high as 79.12% with a purity of 96.4%, which meets the market requirement. This synthesis technique has the advantages of simple process, moderate reaction conditions, high yield and low cost, being suitable for industrial scale production.
基金Project(30770388) supported by the National Natural Science Foundation of China
文摘A gram negative bacterium,named JDC-16,which can grow well on the substrate of phthalic acid esters(PAEs) as the sole source of carbon and energy,was isolated from river sludge.Based on the morphology,physiological and biochemical properties and analysis of 16S rRNA gene sequence,it was preliminarily identified belonging to the genus Acinetobacter.The result of substrates utilization range indicates that strain JDC-16 can utilize a variety of phthalates except for diisononyl phthalate(DINP) .The degradation tests using diethyl phthalate(DEP) as the model compound show that the optimal pH and temperature for DEP degradation by Acinetobacter sp.JDC-16 is 8.0 and 35℃,respectively.Meanwhile,degradation kinetics under various initial concentrations of DEP reveals that substrate depletion curves fit well with the modified Gompertz model with high correlation coefficient(R 2 >0.99) .Furthermore,the substrate induction test indicates that DEP-induction can apparently shorten the lag phase and enhance the degradation rate.This work highlights the potential of this isolate for bioremediation of phthalates-contaminated environments.
基金This project was supported by the National Natural Science Foundation of China (No. 29974015).
文摘This paper presents experimental observations on the adsorption of individual solutes by a simple thermodynamic framework, and the equilibrium adsorption of ethyl benzoate and diethyl phthalate on phenolic resin adsorbent in hexane solutions within the temperature range of 293-313 K. The experimental results show that the Freundlich adsorption law is applicable to the adsorption of ethyl benzoate and diethyl phthalate on the adsorbent, since all the correlative factors R' are larger than 0.99. The negative values of all the isosteric adsorption enthalpies for ethyl benzoate and diethyl phthalate indicate that they undergo exothermic processes, while their magnitudes (19-28 kJ/mol) manifest a hydrogen bonding sorption process. Other thermodynamic properties: the free energy changes and the entropy change associated with the adsorption have been calculated from the Gibbs adsorption equation and the Gibbs-Helmholtz equation
文摘The solubility and hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water are studied as a function of composition. The use of an aqueous solution of diethylene glycol diethyl ether enhances the solubility and hydrolysis rate of carbonyl sulfide compared with that in pure water. The composition of the mixture with maximum hydrolysis rate varies with temperature. The thermophysical properties including density, viscosity, and surface tension as a function of composition at 20℃ under atmospheric pressure as well as liquid-liquid equilibrium (LLE) data over the temperature range from 28℃ to 90℃ are also measured for the binary mixture.
基金funded by the National Natural Science Foundation of China (No. 41773125)the Research Instrument Development Program of Chinese Academy of Sciences (No. YZ201638)the 135 Research Program of the Chinese Academy of Sciences (No. ISSASIP1620)
文摘This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster under 365 nm light irradiation than in the dark in the presence of iron(hydr)oxides. The apparent kinetic rates of DEP degradation followed the order HFO > goethite ≈ hematite in the dark and HFO > hematite > goethite under 365 nm light irradiation. Two pathways governed H2 O2 decomposition efficiency on iron(hydr)oxide surfaces:(1) forming UOH on inherent surface hydroxyl groups(Fe-OH) and(2) producing O2 and H2 O on the surface oxygen vacancies. X-ray photoelectron spectroscopy(XPS) analyses indicated that HFO not only has high Fe-OH content but also has high Vo content, resulting in its low H2 O2 utilization efficiency(η). DEP was degraded through hydrogen abstraction and deesterification, and the major products were(OH)2-DEP, mono-ethyl phthalate(MEP), OH-MEP,and phthalate acid(PA). The study is important in understanding the transformation of phthalate esters in top surface soils and surface waters under ultraviolet light.
基金Supported by the National Science and Technology Support Program Project (2006BAE03B06)
文摘ZrO2-MnO2-ZnO supports were prepared by the co-precipitation method,and then Ni-Na/ZrO2-MnO2-ZnO catalysts were prepared by the impregnation method.In this paper,the reactions to synthesize methyl isopropyl ketone and diethyl ketone by the one-step synthesis method over this catalyst were studied,and meanwhile,the impact of the catalyst preparation conditions and the reaction conditions on catalyst performance was also investigated.It was observed that under the conditions when Ni loading was 25%,calcination temperature was 400℃ and reduction temperature was 410℃,this catalyst had good catalytic performance on the reaction.The suitable reaction conditions were achieved:reaction temperature was 400℃;reaction at atmospheric pressure;liquid hourly space velocity of raw material of 0.5 h 1 ;and the molar ratio of(methanol)/(methyl ethyl ketone)/(water) was equal to 1/1/1.Under such conditions,the conversion of methyl ethyl ketone could achieve 41.7%,and the overall selectivity of methyl isopropyl ketone and diethyl ketone could achieve 83.3%,which was comparable to the conversion of 38.1% and the selectivity of 82.2% achieved by using palladium as the active material.The good stability made this catalyst have good prospects for industrial application.
文摘This article describes a process for the synthesis of diethyl oxalate by a coupling reaction of carbon monoxide, catalyzed by palladium in the presence of ethyl nitrite. The kinetics and mechanism of the coupling and regeneration reaction are also discussed. This paper presents the results of a scale-up test of the catalyst and the process based on an a priori computer simulation.
基金This work was financially supported by the National Natural Science Foundation of China (No. 20564001)the Natural Science Foundation of Jiangxi Province (No. 050017)
文摘The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in boron trifluoride diethyl etherate （BFEE） and its mixed electrolytes with acetonitrile （ACN）. The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy （SEM）, respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT：MeT = 1：2, was about 1.08：1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.
文摘Ionic liquids （ILs） based on 1,3-dialkylimidazolium and tetraalkylammonium cations were employed as a series of efficient, environmentally benign phase-transfer catalysts （PTCs） for the base-promoted monoalkylation of diethyl malonate. The influence of various heterogeneous bases on yields was studied. Good yields and high selectivity were obtained. Solvent-free, mild reaction condition, short reaction time, and easy purification were the merits of this method. The catalytic system （IL-hase） could also be recycled after the extraction of products with ether.
基金This work was financially supported by the Natural Science Foundation of China(Nos.50663001,20564001)Ministry of Education(No.2007-207058).
文摘The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of applied polymerization potential and the monomer concentration ratios on the copolymerization were investigated by linear sweep voltammetry and cyclic voltammetry(CV).The structure of copolymer films were investigated by UV-Vis,infrared spectroscopy,thermal analysis.As-formed novel copolymers own...
基金Financial support by the National Key R&D Program of China (No.2017YFB0307300) is gratefully acknowledged。
文摘A novel Pd-Fe/α-Al_(2)O_(3) catalyst was synthesized by incipient-wetness impregnation method with bayberry tannin as chelating promoter and commercial hollow column Raschig ring a-Al_(2)O_(3) as support for the synthesis of diethyl oxalate from CO and ethyl nitrite.A variety of characterization techniques including N2 physical adsorption,optical microscopy,scanning electron microscopy and energy dispersive system(SEM-EDS),inductively coupled plasma optical emission spectroscopy(ICP-OES),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM),were employed to explore the relationship between the physicochemical properties and activity of catalysts.It indicated that a large number of phenolic hydroxyl groups in bayberry tannin can efficiently anchor the active component Pd,reduce the particle size and make the active Pd as a multi-ring distribution on the commercial a-Al2O3 suppo rt,which we re beneficial to improve the catalytic activity for the production of diethyl oxalate from CO and ethyl nitrite.0.3 wts Pd-Fe/α-Al_(2)O_(3) showed excelle nt catalytic activity and selectivity in a continuous flow,fixed-bed reactor with the loading amount of 10 mL catalysts,Under the mild reaction conditions,the space-time yield of diethyl oxalate was 978 g L^(-1) h^(-1) and CO conversion was 44% with the selectivity to diethyl oxalate of 95.5%.
文摘The title complexes Ln(DEP),(Ln=La,Sm,Eu,Ho and Yb)were synthesized by reaction of triethyl phosphate with trivalent rare earth chlorides.The mechanism of thermo-decomposition of the complexes has been studied.According to their IR spectra,the residues of the thermo-decomposition of the complexes were identified as Ln(PO_3)_3.Their IR spectra were measured and principal IR bands were assigned.The experimental results of the IR spectra of the complexes show that the title complexes have the same coordination form and mo- lecular configuration as rare earth,e.g.Sm,complex with dimethyl phosphate(Sm(DMP)_3).Each of the rare earth ion links three rare earth ions nearby through double“O-P-O”bridges to form a special network of rings-linking-rings,each of which consists of twenty-four atoms.The Ln-O bond is principally ionic.
文摘A green synthesis route of diethyl malonate by palladium catalyzed carbonylation of ethyl chloroacetate in the presence of phase transfer agent is carried out under mild conditions in good yield. The effects of reaction temperature and different bases on the yield of diethyl malonate are also discussed.
基金Supported by National"Ninth-Five" Scientific Research Project(Grant number:96-539-01)
文摘Destructive tests of the catalyst was carried out to study the effect oftemperature on the catalytic activity of CO coupling to diethyl oxalate (DEO) over a Pd-Fe/Al_2O_3catalyst. It was found that a temperature jump could cause the deactivation of the Pd-Fe/α-Al_2O_3catalyst. The catalyst deactivated at different temperatures has different characteristics. Afterdeactivation the crystal structure of α-Al_2O_3 did not change, but the Pd particle size wasenlarged. Most of the Pd^0 were oxidized to Pd^(2+), and Fe^(2+) was oxidized to Fe^(3+) on thesurface of the deactivated catalyst. The catalyst could be regenerated, but its original activitycould not be recovered completely.
基金supported by the National Natural Science Foundation of China (91961126,22078029)the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions+2 种基金Qinglan Project of Education Department of Jiangsu ProvinceJiangsu Development &Reform CommissionChangzhou Development and Reform Commission for their support。
文摘Lithium metal batteries have obtained increasing interest due to their high specific capacity.Nonetheless,the growth of lithium dendrites brings safety risks to batteries and further deteriorates the performance.Herein,we explore diethyl phenylphosphonite(DEPP) as the electrolyte additive to alleviate this problem.DEPP can be preferentially decomposed than carbonate solvents to form the stable interface between electrolyte and lithium anode for inhibiting the dendrite growth.As expected,the symmetrical LiIILi cells could achieve a stable cycling performance with 200 h at 1 mA cm^(-2).Moreover,DEPP can be preferentially oxidized on the surface of lithium cobalt oxides(LiCoO_(2)) to form a dense cathode electrolyte interphase(CEI) film for suppressing the continuous oxidative decomposition of the electrolyte and eliminating the adverse effects of HF on the battery.This endows LiCoO_(2) IILi full battery with the enhanced cycling and rate performance.
基金supported by the National Natural Science Foundation of China(No.21073064)
文摘Diethyl carbonate has been synthesized via the alcoholysis of ethyl carbamate in supercritical ethanol under catalyst-free conditions.The influences of various parameters such as reaction temperature,reaction time,reaction pressure,ethanol/ethyl molar ratios and reaction loading volume on the yield of DEC were studied systematically.The experimental results indicated that the alcoholysis of ethyl carbamate was greatly improved in supercritical ethanol.The optimal reaction conditions were as follows：a reaction temperature of 573 K,a reaction time of 30 min,a reaction pressure of 13.2 MPa,an ethanol/ethyl carbamate molar ratio of 10 and a reactor loading volume of 285 μL respectively.The optimal yield of DEC was 22.9%.
基金supported by the National Natural Science Foundation of China(21106054)~~
文摘Cupric oxide （CuO） and copper-cuprous oxide （Cu-Cu2O） nanoparticles were prepared by a simple hydrothermal method for the synthesis of diethyi carbonate （DEC） from ethanol. During these syntheses, varying NaOH and glucose concentrations were applied to explore and pinpoint the active species. It was found that PdCl2/CuO and PdCI2/Cu-Cu2O both catalysts exhibited good thermal stability and morphology. The results of catalytic tests showed that the catalysts prepared with 5 mol/L NaOH show superior catalytic performances because of their lower extent of agglomeration. It is noteworthy that the PdC12/Cu-Cu2O catalysts were the most active, especially the PdCl2/Cu-Cu2O catalyst prepared with 10 mmol glucose and having a higher Cu2O concentration. In Pd（ll）-Cu（II） （PdCl2/CuO） catalysts, there is an induction period, during which Pd（II） is reduced to Pd（0）, that must occur prior to electron transfer between Pd and Cu, and this can slow the catalytic reaction. To further pinpoint the active species, PdCl2/Cu-Cu2O catalysts with different Cu2O contents were prepared by controlling the dosages of glucose. The maximum DEC yield obtained with these catalysts was 151.9 mg.g-1.h-1, corresponding to an ethanol conversion of 7.2% and 97.9% DEC selectivity on an ethanol basis. Therefore, it was concluded that Cu＋ was the active species in this catalytic system, possibly because a higher proportion of Cu＋ reduces the Pd2＋ concentration and limits the CO oxidation side reaction, thus increasing DEC selectivity. In addition, Cu＋ promotes electron transfer between Pd and Cu without an induction period, which could also promote the catalytic activity.
