Five Br?nsted acidic ionic liquids(ILs) were prepared and characterized by FT-IR,~1H NMR and ^(13)C NMR. Their catalytic activities for the synthesis of 2-propanol(IPOH) via transesterification of isopropyl acetate(IP...Five Br?nsted acidic ionic liquids(ILs) were prepared and characterized by FT-IR,~1H NMR and ^(13)C NMR. Their catalytic activities for the synthesis of 2-propanol(IPOH) via transesterification of isopropyl acetate(IPAc) with methanol(Me OH) were investigated. Among all the tested ILs, [Ps-mim]HSO_4 performed best and was used as catalyst for further studies. The reaction kinetics were carried out to correlate the parameters in a homogeneous second order kinetic model. It has been found that there is close agreement between the calculated and experimental values. The high-pressure batch reactive distillation experimental apparatus was set up in order to enhance the conversion of IPAc. A high conversion of IPAc of 99.4% was obtained under the optimal reaction conditions. The catalyst [Ps-mim]HSO_4 can be recycled easily by a rotary evaporator and reused without any further treatment. The catalyst had been repeatedly used for four times and no obvious changes in the structure of catalyst could be observed.展开更多
The catalysis of ionic liquids (ILs) in the traditional stirred reactor suffers from insufficient mass and heat transfer, which always needs a long reaction time and results in a low reaction rate. In this work, highl...The catalysis of ionic liquids (ILs) in the traditional stirred reactor suffers from insufficient mass and heat transfer, which always needs a long reaction time and results in a low reaction rate. In this work, highly efficient synthesis of 1-methoxy-2-propanol via the alcoholysis reaction of propylene oxide (PO) with methanol was proposed and achieved by the combination of micro-tubular circulating reactor with the IL [N4444] [Buty] catalyst. Compared with the stirred reactor, the rate of alcoholysis reaction in a micro-tubular circulating reactor was found to be significantly improved. The reaction time was remarkably shortened to 20 min from 180 min as well as the yield of 1-methoxy-2-propanol reached 92%. Moreover, the kinetic study further demonstrated that the main reaction rate to 1-methoxy-2-propanol (K1) was about 20 times larger than the side reaction rate to byproduct 2-methoxy-1-propanol (K2) in the temperature range of 363–383 K. Such combination of micro-tubular circulating reactor with IL catalysts is believed to be a class of effective process intensification technique for highly efficient synthesis of 1-methoxy-2-propanol.展开更多
Binary vapor liquid equilibrium （VLE） data were measured for the systems of 2-propanol/ ethanediol and ethanediol/potassium acetate （KAc）. VLE data for the system of propanol/ethanediol was tested using thermodyna...Binary vapor liquid equilibrium （VLE） data were measured for the systems of 2-propanol/ ethanediol and ethanediol/potassium acetate （KAc）. VLE data for the system of propanol/ethanediol was tested using thermodynamic consistency test. The average values of Ayj and A P were 0.0776 and 0.1542 kPa, respectively. The above two sets of VLE data were correlated with the NRTL model. Ternary VLE data for the system of 2-propanol/water/KAc was used to obtain the more suitable parameters of NRTL model for binary systems of 2-propanol/KAc and water/KAc （called TDCM）. For multicomponent systems, ternary and quaternary, the VLE values predicted by the NRTL model agreed well with the literature data. Influence of KAc, ethanediol, and the mixture of KAc and ethanediol on volatility between 2- propanol and water was investigated respectively. The results showed that the above-mentioned materials and mixture had different influence on volatility between 2-propanol and water. The method for correlation and prediction of salt-containing VLE is simple and effective for the said system.展开更多
Density, ρ, ultrasonic speed, u, and viscosity, η, of binary mixtures of 2-methyl-2-propanol (2M2P) with acetonitrile (AN), propionitrile (PN) and butyronitrile (BN) including those of pure liquids are measured over...Density, ρ, ultrasonic speed, u, and viscosity, η, of binary mixtures of 2-methyl-2-propanol (2M2P) with acetonitrile (AN), propionitrile (PN) and butyronitrile (BN) including those of pure liquids are measured over the entire composition range at temperatures 298.15, 303.15 and 308.15 K. From these experimental data, the excess available volume, E a V , excess free volume, E f V , excess isothermal compressibility, E T β , excess thermal expansion coefficient, E α , and excess internal pressure, E i π , are calculated. The variation of these properties with composition and temperature are discussed in terms of molecular interactions between unlike molecules of the mixtures. It is found that the values of E a V , E f V , E T β and E α are positive and those of E i π are negative for all the mixtures at each temperature studied, indicating the presence of weak interactions between 2M2P and AN/PN/BN molecules. The variations of E a V , E f V , E T β , E α and E i π values with composition indicate that the interactions in these mixtures follow the order: AN<PN<BN, i.e., the 2M2P-nitrile interaction decreases with the increase of alkyl chain length in these nitrile molecules. In addition, the theoretical ultrasonic velocity is calculated using the scaled particle theory and compared with the experimental values.展开更多
The crystal form of TiO_2 is a crucial focus of research on the photocatalytic degradation of gaseous pollutants by TiO_2-based composite photocatalysts. To explore the synergistic effect of mixed crystalline TiO_2 on...The crystal form of TiO_2 is a crucial focus of research on the photocatalytic degradation of gaseous pollutants by TiO_2-based composite photocatalysts. To explore the synergistic effect of mixed crystalline TiO_2 on gaseous organic-pollutant photocatalytic degradation, we synthesized a series of TiO_2 nanoparticles with controllable phase ratios. We explored the role of the TiO_2 phase ratio on the photocatalytic activity and degradation pathway in the photodegradation of 2-propanol(IPA). We estimated the crystallite size and crystal proportions of anatase and rutile by X-ray diffraction. We used the Brunauer-Emmett-Teller method to calculate the specific surface area and Fourier transform infrared spectroscopy to characterize the surface chemistry of the samples. Our results show the photocatalytic activities of pure anatase and the sample with 8.6% rutile to be much better than those of the samples with a phase junction and pure rutile. As such, anatase is the better option for the study of photodegradation design and preparation of gas-phase organic pollutants.展开更多
Phenol oxidase in Drosophila melanogaster occurs as folded phase precursors designated as prophenol oxidase A1 and A3, and prophenol oxidase is activated with alcohol, especially 2-propanol, within a few minutes as un...Phenol oxidase in Drosophila melanogaster occurs as folded phase precursors designated as prophenol oxidase A1 and A3, and prophenol oxidase is activated with alcohol, especially 2-propanol, within a few minutes as unfolded-phase in vitro. To clarify a common effect of alcohols on proteins and peptides, the extract containing prophenol oxidase protein was prepared. Phenol oxidase activity activated with 2-propanol has been maintained stable at least 24 hours remains as it is. Protein of prophenol oxidase was not denatured opposite hypnoses known as the instability of protein with alcohol. Activated prophenol oxidase with 2-propanol remain enzyme activity with no aggregation, stable, renaturation, and the refolding phenomena occurred around the active phase within the catalytic active center of prophenol oxidase protein in Drosophila melanogaster. This study is important to induce the wide range applications of the effect in many fields for rational drag design.展开更多
In an alkaline 2-propanol solution with 5,10,15,20-tetra(4-methoxyl phenyl) porphyrin iron chloride(TOMPPFeCl) as a catalyst and oxygen as a cheap green oxidant, 2-naphthol was conversed to 2-hydroxy-\{1,4-naphthoquin...In an alkaline 2-propanol solution with 5,10,15,20-tetra(4-methoxyl phenyl) porphyrin iron chloride(TOMPPFeCl) as a catalyst and oxygen as a cheap green oxidant, 2-naphthol was conversed to 2-hydroxy-\{1,4-naphthoquinone(HNQ)\} with a yield of 62.17% and a selectivity of 100%, and the conversion number of TMOPPFeCl catalyst was 8.32/min. The catalytic oxidation products were characterized by means of UV-Vis, IR, GC-MS, ~ 1H NMR and melting point determination. In this catalytic oxidation, the catalytic activity of TMOPPFeCl was researched in detail and the reacting conditions were optimized. A possible reaction mechanism is summarized based on in situ EPR determination.展开更多
Vapor-liquid equilibrium(VLE)data for water+2-propanol+1-butyl-3-methylimidazolium chloride([bmim]Cl)were measured.Six sets of complete T,x,y data are reported,in which the 2-propanol mole fraction on IL-free basis is...Vapor-liquid equilibrium(VLE)data for water+2-propanol+1-butyl-3-methylimidazolium chloride([bmim]Cl)were measured.Six sets of complete T,x,y data are reported,in which the 2-propanol mole fraction on IL-free basis is fixed separately at 0.1,0.2,0.4,0.6,0.8,and approximate 0.98,while the IL mass fraction is varied from 0.1 to 0.8,in an interval of 0.1.The non-random-two-liquid(NRTL)and electrolyte non-random-two-liquid(eNRTL)equations are used to correlate the experimental data with satisfactory results.The ternary VLE behavior is also modeled with the parameters obtained by correlating two data sets,in which the mole fraction of 2-propanol on IL-free basis is approximately 0.1 and 0.98.In this way,the six sets of data are reproduced satisfactorily.With the eNRTL model,the root-mean-square deviation for temperature is 0.82 K and that for vapor-phase mole fraction is 0.0078.The influences of IL on activity coefficients and relative volatility of the volatile components are also graphically illustrated.展开更多
The microcosmic reaction mechanism of K2CO3-catalyzed 1-chlo-2-propanol and carbon dioxide has been investigated by density functional theory（DFT） at the GGA/PW91/DNP level.We optimize the geometric configurations o...The microcosmic reaction mechanism of K2CO3-catalyzed 1-chlo-2-propanol and carbon dioxide has been investigated by density functional theory（DFT） at the GGA/PW91/DNP level.We optimize the geometric configurations of reactants,intermediates,transition states,and products.The energy analysis calculation approves the authenticity of intermediates and transition states.According to our calculations,four feasible reaction pathways are found.The main pathway of the reaction is ReA → IMA1 → TSA1 → IMA2 → IMA5 → TSA5 → P.Besides,we also in-vestigate the reaction mechanism of 1-chlo-2-propanol and carbon dioxide without K2CO3-catalyzation by the same theory and level.The computational results indicate that the activation barrier with K2CO3-catalyzed is smaller than the activation barrier without K2CO3-catalyzed.That is to say,K2CO3 can promote the reaction to give the product in a high yield,which is in agreement with the experimental results.展开更多
Photocatalysis of 2-propanol on A-TiO2（101） has been investigated using a temperature programed desorption method with 266 nm laser light. A clear mechanism is proposed for photodissociation of 2-propanol on A-TiO2...Photocatalysis of 2-propanol on A-TiO2（101） has been investigated using a temperature programed desorption method with 266 nm laser light. A clear mechanism is proposed for photodissociation of 2-propanol on A-TiO2（101）. Acetone product on five coordinate Ti4＋ sites is formed in a stepwise manner in which the O-H dissociation proceeds first and then followed by secondary C-H dissociation of 2-propanol while H atoms are transferred to the adjacent bridge bond oxygen （BBO） sites. Low temperature water is formed in a thermally driven process via H-atom on BBO in exchange with isopropyl groups of molecule 2-propanol, while isopropyl radical desorbs at high temperature during the TPD process. The observation demonstrates the prospect of TiO2 as a photocatalyst for degradation of organics.展开更多
The salt-containing extractive distillation column and the salt-containing agent recovery column for the 2-propanol/water/ethanediol/KAc system were simulated by the NRTL model and the modified Rose Relaxation method....The salt-containing extractive distillation column and the salt-containing agent recovery column for the 2-propanol/water/ethanediol/KAc system were simulated by the NRTL model and the modified Rose Relaxation method. The simulation results showed that prediction of the salt effect in vapor-liquid equilibrium and the correlation method （TDCM） of NRTL parameters were suitable for the said system. Four different distillation technology processes were investigated; the results showed that the salt-containing extractive distillation process was the best one. The simulating design of the extractive distillation column was performed under the conditions of different total stage number, feeding location, reflux ratio, amount of mixed agent and concentration of KAc. The results showed that such factors as 17 stages, a feeding location at the 9th stage, a reflux ratio of 1.2, and a mixed agent feeding rate of 1.141 kmol/h, might be the best suited operating conditions. The simulating design was also done for the column for recovering the salt-containing agent. The simulation method of the salt-containing extractive distillation is simple and effective in this work.展开更多
In order to obtain the solubility data of propylene in 2-propanol-water solutions, gas-liquid equilibrium (GLE) experiments were carried out at 303.15-333.15 K, 0.27-0.98 MPa in a static equilibrium still. The origina...In order to obtain the solubility data of propylene in 2-propanol-water solutions, gas-liquid equilibrium (GLE) experiments were carried out at 303.15-333.15 K, 0.27-0.98 MPa in a static equilibrium still. The original mass ratio of 2-propanol to water was 9∶1,8∶2,7∶3,1∶0, respectively. The equilibrium data were correlated with an empirical model and the regression of model parameters was completed by Gauss-Newton nonlinear least square (NLS). The average relative deviation (ARD) between the experimental and calculated value is 1.570 0, and the maximum relative deviation (MRD) is 4.820 0. In addition, a simple approach that correlated the model parameters with the system composition was also provided.展开更多
We report the construction of a graphene/tourmaline/TiO2(G/T/TiO2)composite system with enhanced charge‐carrier separation,and therefore enhanced photocatalytic properties,based on tailoring the surface‐charged stat...We report the construction of a graphene/tourmaline/TiO2(G/T/TiO2)composite system with enhanced charge‐carrier separation,and therefore enhanced photocatalytic properties,based on tailoring the surface‐charged state of graphene and/or by introducing an external electric field arising from tourmaline.A simple two‐step hydrothermal method was used to synthesize G/T/TiO2composites and poly(diallyldimethylammonium chloride)‐G/T/TiO2composites.In the photocatalytic degradation of2‐propanol(IPA),the catalytic activity of the composite containing negatively charged graphene was higher than of the composite containing positively charged graphene.The highest acetone evolution rate(223?mol/h)was achieved using the ternary composite with the optimum composition,i.e.,G0.5/T5/TiO2(0.5wt%graphene and5wt%tourmaline).The involvement of tourmaline and graphene in the composite is believed to facilitate the separation and transportation of electrons and holes photogenerated in TiO2.This synergetic effect could account for the enhanced photocatalytic activity of the G/T/TiO2composite.A mechanistic study indicated that O2??radicals and holes were the main reactive oxygen species in photocatalytic degradation of IPA.展开更多
Eleven 1-(1H-1,2,4-triazole)-2-(2,4-diflurophenyl)-3-(N-methyl-N-substituted benzylamino)-2-propanols were designed and synthesized, on the basis of the crystal structure of P450 cytochrome 14α-sterol demethylase(CYP...Eleven 1-(1H-1,2,4-triazole)-2-(2,4-diflurophenyl)-3-(N-methyl-N-substituted benzylamino)-2-propanols were designed and synthesized, on the basis of the crystal structure of P450 cytochrome 14α-sterol demethylase(CYP51) and the docking results of inhibitors to the active site of the enzyme. All title compounds were first by reported. Results of preliminary biological tests showed that most of title compounds exhibited activity against the seven common pathogenic fungi. Compound 11 showed best antifungal activity with broad antifungal spectrum and proved to be more active against Cryptococcus neoformans, Candida albicans, Microsporum lanosum and Trichophyton rubrum than ketoconazole. Compounds 3, 10 and 4 also had high activities.展开更多
We compared two different strategies to increase the catches oflps typographus （L.）, particularly males, in pheromone-baited traps. The first of these strategies, the barrier approach, used alternating pheromone ble...We compared two different strategies to increase the catches oflps typographus （L.）, particularly males, in pheromone-baited traps. The first of these strategies, the barrier approach, used alternating pheromone blends, targeting males and females respectively, in closely-spaced traps forming a barrier around forest stands. The second strategy, the single trap approach, used widely-spaced traps that were all baited with the same lure and intended to trap the highest possible numbers of males without compromising trapping of females. In the blend used for the barrier traps targeting primarily males, with a lower percentage of （4S）-cis-verbenol （cV）, the （-）-α-pinene was replaced step wise with （＋）-limonene at rates of 0%, 1%, 10%, 35%, 60% and 90%. This replacement had no significant effect on the numbers of responding 1. typographus males, but there was a slight effect on the percentage of males caught. In the attractant blend for the barrier traps targeting females, with a higher percentage of cV, the 2-methyl-3-buten-2-ol （MB） was replaced with 1-methoxy-2-propanol （MP） in a similar fashion as for the male-specific blends. The replacement did not significantly affect the catch of females. Thus, it is pos- sible to use the MP in the blend with cV and ipsdienol without significant change in catch efficacy. In the blends for single traps, the （-）-α- pinene was replaced with （＋）-limonene and MB with MP. The replacement of （-）-α-pinene had only a slight effect on the percentage of males, but the results suggest that replacing MB with MP in the blend will not significantly reduce trapping efficacy.展开更多
Ultrasonic speeds have been measured at 298.15 K and 308.15 K for mixtures of formamide ＋ 1 -propanol or 2-propanol. For an equimolar mixture, excess molar compressibility follows the sequence of l-propanol 〉 2-prop...Ultrasonic speeds have been measured at 298.15 K and 308.15 K for mixtures of formamide ＋ 1 -propanol or 2-propanol. For an equimolar mixture, excess molar compressibility follows the sequence of l-propanol 〉 2-propanol. The ultrasonic speed data are correlated by various correlations such as Nomoto＇s relation, van Dael＇s mixing relation and impedance dependence relation, and analyzed in terms of Jacobson＇s free length theory and Schaaffs collision factor theory. Excess isentropic compressibility is calculated from ex- perimental ultrasonic speed data and previously reported excess volume data. The excess molar ultrasonic speed and isentropic compressibility values are fitted to Redlich-Kister polynomial equation. Other proper- ties such as molecular association, available volume, free volume, and intermolecular free length are also calculated. The excess isentropic compressibility data are also interpreted in terms of graph theoretical ap- proach. The calculated isentropic compressibility values are well consistent with the experimental data. It is found that the interaction between formamide and propanol increases when hydroxyl group attached to a carbon atom has more -CH3 groups.展开更多
基金Supported by the National Natural Science Foundation of China(21576053,91534106,21306025)the International S&T Cooperation Program of China(2013DFR90540)+3 种基金the Science Foundation of Distinguished Young Scholars of Fujian(2014J06004)the New Century Excellent Talents in Fujian Province University(JA12014)the Natural Science Foundation of Fujian Province(2016J01689)the Key Project of Fujian Provincial Department of Science and Technology(2014Y0066)
文摘Five Br?nsted acidic ionic liquids(ILs) were prepared and characterized by FT-IR,~1H NMR and ^(13)C NMR. Their catalytic activities for the synthesis of 2-propanol(IPOH) via transesterification of isopropyl acetate(IPAc) with methanol(Me OH) were investigated. Among all the tested ILs, [Ps-mim]HSO_4 performed best and was used as catalyst for further studies. The reaction kinetics were carried out to correlate the parameters in a homogeneous second order kinetic model. It has been found that there is close agreement between the calculated and experimental values. The high-pressure batch reactive distillation experimental apparatus was set up in order to enhance the conversion of IPAc. A high conversion of IPAc of 99.4% was obtained under the optimal reaction conditions. The catalyst [Ps-mim]HSO_4 can be recycled easily by a rotary evaporator and reused without any further treatment. The catalyst had been repeatedly used for four times and no obvious changes in the structure of catalyst could be observed.
基金We thank the National Natural Science Foundations of China(Nos.21566011,31570560)the Jiangxi Province Sponsored Programs for Distinguished Young Scholars(No.20162BCB23026)and the Science&Technology Programs of Jiangxi Province Department of Education(No.GJJ160272)for financial support.
文摘The catalysis of ionic liquids (ILs) in the traditional stirred reactor suffers from insufficient mass and heat transfer, which always needs a long reaction time and results in a low reaction rate. In this work, highly efficient synthesis of 1-methoxy-2-propanol via the alcoholysis reaction of propylene oxide (PO) with methanol was proposed and achieved by the combination of micro-tubular circulating reactor with the IL [N4444] [Buty] catalyst. Compared with the stirred reactor, the rate of alcoholysis reaction in a micro-tubular circulating reactor was found to be significantly improved. The reaction time was remarkably shortened to 20 min from 180 min as well as the yield of 1-methoxy-2-propanol reached 92%. Moreover, the kinetic study further demonstrated that the main reaction rate to 1-methoxy-2-propanol (K1) was about 20 times larger than the side reaction rate to byproduct 2-methoxy-1-propanol (K2) in the temperature range of 363–383 K. Such combination of micro-tubular circulating reactor with IL catalysts is believed to be a class of effective process intensification technique for highly efficient synthesis of 1-methoxy-2-propanol.
文摘Binary vapor liquid equilibrium （VLE） data were measured for the systems of 2-propanol/ ethanediol and ethanediol/potassium acetate （KAc）. VLE data for the system of propanol/ethanediol was tested using thermodynamic consistency test. The average values of Ayj and A P were 0.0776 and 0.1542 kPa, respectively. The above two sets of VLE data were correlated with the NRTL model. Ternary VLE data for the system of 2-propanol/water/KAc was used to obtain the more suitable parameters of NRTL model for binary systems of 2-propanol/KAc and water/KAc （called TDCM）. For multicomponent systems, ternary and quaternary, the VLE values predicted by the NRTL model agreed well with the literature data. Influence of KAc, ethanediol, and the mixture of KAc and ethanediol on volatility between 2- propanol and water was investigated respectively. The results showed that the above-mentioned materials and mixture had different influence on volatility between 2-propanol and water. The method for correlation and prediction of salt-containing VLE is simple and effective for the said system.
文摘Density, ρ, ultrasonic speed, u, and viscosity, η, of binary mixtures of 2-methyl-2-propanol (2M2P) with acetonitrile (AN), propionitrile (PN) and butyronitrile (BN) including those of pure liquids are measured over the entire composition range at temperatures 298.15, 303.15 and 308.15 K. From these experimental data, the excess available volume, E a V , excess free volume, E f V , excess isothermal compressibility, E T β , excess thermal expansion coefficient, E α , and excess internal pressure, E i π , are calculated. The variation of these properties with composition and temperature are discussed in terms of molecular interactions between unlike molecules of the mixtures. It is found that the values of E a V , E f V , E T β and E α are positive and those of E i π are negative for all the mixtures at each temperature studied, indicating the presence of weak interactions between 2M2P and AN/PN/BN molecules. The variations of E a V , E f V , E T β , E α and E i π values with composition indicate that the interactions in these mixtures follow the order: AN<PN<BN, i.e., the 2M2P-nitrile interaction decreases with the increase of alkyl chain length in these nitrile molecules. In addition, the theoretical ultrasonic velocity is calculated using the scaled particle theory and compared with the experimental values.
基金supported by the National Natural Science Foundation of China (Nos.21406164,21466035,51203111)the National Basic Research Program of China("973" program,Nos.2012CB720100,2014CB239300)
文摘The crystal form of TiO_2 is a crucial focus of research on the photocatalytic degradation of gaseous pollutants by TiO_2-based composite photocatalysts. To explore the synergistic effect of mixed crystalline TiO_2 on gaseous organic-pollutant photocatalytic degradation, we synthesized a series of TiO_2 nanoparticles with controllable phase ratios. We explored the role of the TiO_2 phase ratio on the photocatalytic activity and degradation pathway in the photodegradation of 2-propanol(IPA). We estimated the crystallite size and crystal proportions of anatase and rutile by X-ray diffraction. We used the Brunauer-Emmett-Teller method to calculate the specific surface area and Fourier transform infrared spectroscopy to characterize the surface chemistry of the samples. Our results show the photocatalytic activities of pure anatase and the sample with 8.6% rutile to be much better than those of the samples with a phase junction and pure rutile. As such, anatase is the better option for the study of photodegradation design and preparation of gas-phase organic pollutants.
文摘Phenol oxidase in Drosophila melanogaster occurs as folded phase precursors designated as prophenol oxidase A1 and A3, and prophenol oxidase is activated with alcohol, especially 2-propanol, within a few minutes as unfolded-phase in vitro. To clarify a common effect of alcohols on proteins and peptides, the extract containing prophenol oxidase protein was prepared. Phenol oxidase activity activated with 2-propanol has been maintained stable at least 24 hours remains as it is. Protein of prophenol oxidase was not denatured opposite hypnoses known as the instability of protein with alcohol. Activated prophenol oxidase with 2-propanol remain enzyme activity with no aggregation, stable, renaturation, and the refolding phenomena occurred around the active phase within the catalytic active center of prophenol oxidase protein in Drosophila melanogaster. This study is important to induce the wide range applications of the effect in many fields for rational drag design.
文摘In an alkaline 2-propanol solution with 5,10,15,20-tetra(4-methoxyl phenyl) porphyrin iron chloride(TOMPPFeCl) as a catalyst and oxygen as a cheap green oxidant, 2-naphthol was conversed to 2-hydroxy-\{1,4-naphthoquinone(HNQ)\} with a yield of 62.17% and a selectivity of 100%, and the conversion number of TMOPPFeCl catalyst was 8.32/min. The catalytic oxidation products were characterized by means of UV-Vis, IR, GC-MS, ~ 1H NMR and melting point determination. In this catalytic oxidation, the catalytic activity of TMOPPFeCl was researched in detail and the reacting conditions were optimized. A possible reaction mechanism is summarized based on in situ EPR determination.
基金Supported by the National Natural Science Foundation of China(20776132)the Natural Science Foundation of Zhejiang Province(Y4100699)
文摘Vapor-liquid equilibrium(VLE)data for water+2-propanol+1-butyl-3-methylimidazolium chloride([bmim]Cl)were measured.Six sets of complete T,x,y data are reported,in which the 2-propanol mole fraction on IL-free basis is fixed separately at 0.1,0.2,0.4,0.6,0.8,and approximate 0.98,while the IL mass fraction is varied from 0.1 to 0.8,in an interval of 0.1.The non-random-two-liquid(NRTL)and electrolyte non-random-two-liquid(eNRTL)equations are used to correlate the experimental data with satisfactory results.The ternary VLE behavior is also modeled with the parameters obtained by correlating two data sets,in which the mole fraction of 2-propanol on IL-free basis is approximately 0.1 and 0.98.In this way,the six sets of data are reproduced satisfactorily.With the eNRTL model,the root-mean-square deviation for temperature is 0.82 K and that for vapor-phase mole fraction is 0.0078.The influences of IL on activity coefficients and relative volatility of the volatile components are also graphically illustrated.
基金Project supported by the Natural Science Foundation of Education Committee of Chongqing (No. KJ091311)
文摘The microcosmic reaction mechanism of K2CO3-catalyzed 1-chlo-2-propanol and carbon dioxide has been investigated by density functional theory（DFT） at the GGA/PW91/DNP level.We optimize the geometric configurations of reactants,intermediates,transition states,and products.The energy analysis calculation approves the authenticity of intermediates and transition states.According to our calculations,four feasible reaction pathways are found.The main pathway of the reaction is ReA → IMA1 → TSA1 → IMA2 → IMA5 → TSA5 → P.Besides,we also in-vestigate the reaction mechanism of 1-chlo-2-propanol and carbon dioxide without K2CO3-catalyzation by the same theory and level.The computational results indicate that the activation barrier with K2CO3-catalyzed is smaller than the activation barrier without K2CO3-catalyzed.That is to say,K2CO3 can promote the reaction to give the product in a high yield,which is in agreement with the experimental results.
基金This work was supported by the Chinese Academy of Sciences, the National Natural Science Foundation of China （No.21403224）, the Chinese Ministry of Science and Technology （No.2013CB834605）, the Youth Innovation Promotion Association CAS, and the Key Research Program of the Chinese Academy of Sciences.
文摘Photocatalysis of 2-propanol on A-TiO2（101） has been investigated using a temperature programed desorption method with 266 nm laser light. A clear mechanism is proposed for photodissociation of 2-propanol on A-TiO2（101）. Acetone product on five coordinate Ti4＋ sites is formed in a stepwise manner in which the O-H dissociation proceeds first and then followed by secondary C-H dissociation of 2-propanol while H atoms are transferred to the adjacent bridge bond oxygen （BBO） sites. Low temperature water is formed in a thermally driven process via H-atom on BBO in exchange with isopropyl groups of molecule 2-propanol, while isopropyl radical desorbs at high temperature during the TPD process. The observation demonstrates the prospect of TiO2 as a photocatalyst for degradation of organics.
文摘The salt-containing extractive distillation column and the salt-containing agent recovery column for the 2-propanol/water/ethanediol/KAc system were simulated by the NRTL model and the modified Rose Relaxation method. The simulation results showed that prediction of the salt effect in vapor-liquid equilibrium and the correlation method （TDCM） of NRTL parameters were suitable for the said system. Four different distillation technology processes were investigated; the results showed that the salt-containing extractive distillation process was the best one. The simulating design of the extractive distillation column was performed under the conditions of different total stage number, feeding location, reflux ratio, amount of mixed agent and concentration of KAc. The results showed that such factors as 17 stages, a feeding location at the 9th stage, a reflux ratio of 1.2, and a mixed agent feeding rate of 1.141 kmol/h, might be the best suited operating conditions. The simulating design was also done for the column for recovering the salt-containing agent. The simulation method of the salt-containing extractive distillation is simple and effective in this work.
文摘In order to obtain the solubility data of propylene in 2-propanol-water solutions, gas-liquid equilibrium (GLE) experiments were carried out at 303.15-333.15 K, 0.27-0.98 MPa in a static equilibrium still. The original mass ratio of 2-propanol to water was 9∶1,8∶2,7∶3,1∶0, respectively. The equilibrium data were correlated with an empirical model and the regression of model parameters was completed by Gauss-Newton nonlinear least square (NLS). The average relative deviation (ARD) between the experimental and calculated value is 1.570 0, and the maximum relative deviation (MRD) is 4.820 0. In addition, a simple approach that correlated the model parameters with the system composition was also provided.
基金supported by the National Basic Research Program of China (973 Program,2014CB239300)the National Natural Science Foundation of China (51572191)the Natural Science Foundation of Tianjin (13JCYBJC16600)~~
文摘We report the construction of a graphene/tourmaline/TiO2(G/T/TiO2)composite system with enhanced charge‐carrier separation,and therefore enhanced photocatalytic properties,based on tailoring the surface‐charged state of graphene and/or by introducing an external electric field arising from tourmaline.A simple two‐step hydrothermal method was used to synthesize G/T/TiO2composites and poly(diallyldimethylammonium chloride)‐G/T/TiO2composites.In the photocatalytic degradation of2‐propanol(IPA),the catalytic activity of the composite containing negatively charged graphene was higher than of the composite containing positively charged graphene.The highest acetone evolution rate(223?mol/h)was achieved using the ternary composite with the optimum composition,i.e.,G0.5/T5/TiO2(0.5wt%graphene and5wt%tourmaline).The involvement of tourmaline and graphene in the composite is believed to facilitate the separation and transportation of electrons and holes photogenerated in TiO2.This synergetic effect could account for the enhanced photocatalytic activity of the G/T/TiO2composite.A mechanistic study indicated that O2??radicals and holes were the main reactive oxygen species in photocatalytic degradation of IPA.
文摘Eleven 1-(1H-1,2,4-triazole)-2-(2,4-diflurophenyl)-3-(N-methyl-N-substituted benzylamino)-2-propanols were designed and synthesized, on the basis of the crystal structure of P450 cytochrome 14α-sterol demethylase(CYP51) and the docking results of inhibitors to the active site of the enzyme. All title compounds were first by reported. Results of preliminary biological tests showed that most of title compounds exhibited activity against the seven common pathogenic fungi. Compound 11 showed best antifungal activity with broad antifungal spectrum and proved to be more active against Cryptococcus neoformans, Candida albicans, Microsporum lanosum and Trichophyton rubrum than ketoconazole. Compounds 3, 10 and 4 also had high activities.
基金supported by Slovak Research and Development Agency (APVV-51-P06005 and APVV-27-P05205)the Scientific Grant Agency of the Ministry of Education of the Slovak Republic and the Slovak Academy of Sciences (2/6153/26)
文摘We compared two different strategies to increase the catches oflps typographus （L.）, particularly males, in pheromone-baited traps. The first of these strategies, the barrier approach, used alternating pheromone blends, targeting males and females respectively, in closely-spaced traps forming a barrier around forest stands. The second strategy, the single trap approach, used widely-spaced traps that were all baited with the same lure and intended to trap the highest possible numbers of males without compromising trapping of females. In the blend used for the barrier traps targeting primarily males, with a lower percentage of （4S）-cis-verbenol （cV）, the （-）-α-pinene was replaced step wise with （＋）-limonene at rates of 0%, 1%, 10%, 35%, 60% and 90%. This replacement had no significant effect on the numbers of responding 1. typographus males, but there was a slight effect on the percentage of males caught. In the attractant blend for the barrier traps targeting females, with a higher percentage of cV, the 2-methyl-3-buten-2-ol （MB） was replaced with 1-methoxy-2-propanol （MP） in a similar fashion as for the male-specific blends. The replacement did not significantly affect the catch of females. Thus, it is pos- sible to use the MP in the blend with cV and ipsdienol without significant change in catch efficacy. In the blends for single traps, the （-）-α- pinene was replaced with （＋）-limonene and MB with MP. The replacement of （-）-α-pinene had only a slight effect on the percentage of males, but the results suggest that replacing MB with MP in the blend will not significantly reduce trapping efficacy.
文摘Ultrasonic speeds have been measured at 298.15 K and 308.15 K for mixtures of formamide ＋ 1 -propanol or 2-propanol. For an equimolar mixture, excess molar compressibility follows the sequence of l-propanol 〉 2-propanol. The ultrasonic speed data are correlated by various correlations such as Nomoto＇s relation, van Dael＇s mixing relation and impedance dependence relation, and analyzed in terms of Jacobson＇s free length theory and Schaaffs collision factor theory. Excess isentropic compressibility is calculated from ex- perimental ultrasonic speed data and previously reported excess volume data. The excess molar ultrasonic speed and isentropic compressibility values are fitted to Redlich-Kister polynomial equation. Other proper- ties such as molecular association, available volume, free volume, and intermolecular free length are also calculated. The excess isentropic compressibility data are also interpreted in terms of graph theoretical ap- proach. The calculated isentropic compressibility values are well consistent with the experimental data. It is found that the interaction between formamide and propanol increases when hydroxyl group attached to a carbon atom has more -CH3 groups.
