The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in ele...The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.展开更多
To investigate the degradation of FB1 in aqueous acetonitrile and corn af-ter γ-ray irradiation, the radiolytic products of FB1 was detected preliminarily. The results showed that γ-ray irradiation could degrade FB1...To investigate the degradation of FB1 in aqueous acetonitrile and corn af-ter γ-ray irradiation, the radiolytic products of FB1 was detected preliminarily. The results showed that γ-ray irradiation could degrade FB1 in aqueous acetonitrile;When the radiation dose was below 9 kGy, the degradation of FB1 in corn was not significant. The degradation rates of FB1 with concentrations of 0.8 mg/ml, 10.0 μg/ml, 1.0 μg/ml and 50 ng/ml after irradiation at 9 kGy were 22.5%, 51.0%, 59.0% and 64.8% respectively; when irradiation dose was increased to 100 kGy, the degrada-tion rate of FB1 with concentration of 0.8 mg/ml was up to 90%, and it was nearly 100% when irradiation dose was increased to 200 kGy. No representative products of FB1 were detected by LC/MS/MS analysis.展开更多
The benzene and acetonitrile azeotropic mixture was proposed to be separated by extractive distillation using an ionic liquid(IL)as the entrainer.The suitable IL was selected by the COSMO-RS model,and 1-ethyl-3-methyl...The benzene and acetonitrile azeotropic mixture was proposed to be separated by extractive distillation using an ionic liquid(IL)as the entrainer.The suitable IL was selected by the COSMO-RS model,and 1-ethyl-3-methylimidazolium tetrafluoroborate([EMIM][BF_(4)])was considered as the suitable entrainer mainly due to its high selectivity,low viscosity,and low price.The experimental vapor pressure data of the IL-containing systems(benzene+[EMIM][BF_(4)]and acetonitrile+[EMIM][BF_(4)])were measured in the full concentration range.The results show that acetonitrile has a stronger interaction with IL than benzene,and the low deviations between the experimental and UNIFAC predicted values show the reliability of the UNFIAC model.The UNIFAC predicted vapor-liquid equilibrium data of the benzene+acetonitrile+dimethyl sulfoxide(DMSO)/[EMIM][BF_(4)]system show that the relative volatility of benzene to acetonitrile is higher when the entrainer is[EMIM][BF_(4)].The process simulation results show that[EMIM][BF_(4)]can reduce the material and energy consumptions compared with DMSO.展开更多
The corrosion behaviors of hafnium in Et4NBr isopropanol and acetonitrile(ACN)solutions were investigated usingelectrochemical measurements,ICP-AES and SEM techniques.Results revealed that the open circuit potential g...The corrosion behaviors of hafnium in Et4NBr isopropanol and acetonitrile(ACN)solutions were investigated usingelectrochemical measurements,ICP-AES and SEM techniques.Results revealed that the open circuit potential gets more positive dueto the increased passivity of the surface oxide film with increasing immersion time until it reaches a steady state value.Thepotentiodynamic anodic polarization curves did not exhibit an active dissolution region near corrosion potential due to the presenceof an oxide film on the electrode surface,which was followed by pitting corrosion.SEM images confirmed the existence of pits onthe electrode surface.Cyclic voltammetry and galvanostatic measurements allowed the pitting potential(φpit)and the repassivationpotential(φp)to be determined.φpit increased with increasing potential scanning rate but decreased with increasing temperature,Br-concentration and ACN concentration.The impedance spectra showed that the resistances of the solution and charge transferdecreased with the increase of ACN concentration.展开更多
Temperature and pressure were shown to vary significantly with solvent mixing, showing maxima at differ-ent solvent ratios. Acetonitrile/water mixing resulted in temperature reduction of solutions whereas metha-nol/wa...Temperature and pressure were shown to vary significantly with solvent mixing, showing maxima at differ-ent solvent ratios. Acetonitrile/water mixing resulted in temperature reduction of solutions whereas metha-nol/water mixing caused temperature increases. On the other hand, maximum recorded chromatographic pressure of acetonitrile:water mixtures occurred at a solvent ratio of 1:6 compared with methanol:water, which showed a maximum pressure at a solvent ratio of 1:1. These findings can be of use in stabilizing re-tention time shifts during HPLC-based studies associated with compound identification based on retention time such as analysis of complex mixtures.展开更多
Vapor pressures were measured for acetonitrile+1-butyl-3-methylimidazolium chloride([C4mim][Cl]),+1-butyl-3-methylimidazolium tetrafluoroborate([C4mim][BF4])and+1-hexyl-3-methylimidazolium chloride([C6mim][Cl])at temp...Vapor pressures were measured for acetonitrile+1-butyl-3-methylimidazolium chloride([C4mim][Cl]),+1-butyl-3-methylimidazolium tetrafluoroborate([C4mim][BF4])and+1-hexyl-3-methylimidazolium chloride([C6mim][Cl])at temperatures of 313 to 353 K by a quasi-static method.The experimental data for the binary systems were correlated by the non-random two liquid(NRTL)equation with an average absolute relative deviation(AARD)of within 1.84%.The results indicate that the three ionic liquids(ILs)can result in a negative deviation from the Raoult's law for the binary solutions containing acetonitrile,and the affinity between ILs and acetonitrile molecules follows the order[C4mim][BF4]+acetonitrile N[C4mim][Cl]+acetonitrile N[C6mim][Cl]+acetonitrile.展开更多
Ultrafast cyclic voltammetry was used to study the redox behavior of a gold electrode in acetonitrile. The direct electrochemical evidence of the dissociation and adsorption behavior of acetonitrile at gold electrodes...Ultrafast cyclic voltammetry was used to study the redox behavior of a gold electrode in acetonitrile. The direct electrochemical evidence of the dissociation and adsorption behavior of acetonitrile at gold electrodes was found. It could be stated that two consecutive redox paths are involved, each with a special adsorption state acting as the reaction intermediate. The mean value, obtained of the electron-transfer rate constant of the second path, was 1.3 × 10^5 s^-1 with a standard deviation of 0.24 × 10^5 s^-1.展开更多
This paper reports the development and validation of an assay for the determination of acetonitrile in the recycled mobile phase using high performance liquid chromatography（HPLC）. The method is based on that the re...This paper reports the development and validation of an assay for the determination of acetonitrile in the recycled mobile phase using high performance liquid chromatography（HPLC）. The method is based on that the retention in reversed-phase liquid chromatography increases with decreasing concentration of organic phase in the mobile phase. The natural logarithm of the capacity ratio for a given solute is linearly related to the volume fraction of the organic modifier in the mobile phase. For dimethylphthalate and diethylphthalate, the linearity range is 30%--60%, and for biphenyl and terphenyl, the range is 60%--95%. Precision values（RSD） were both 〈1% and the accuracy（RE） was in the range of ±1%. The assay was successfully applied to the determination of acetonitrile concentration of recycled mobile phase after the distillation of the column eluent in our laboratory.展开更多
In the present work,a comparative study of the extractive distillation and pressure swing distillation for methanol-acetonitrile separation is performed for the first time.Different separation alternatives,including t...In the present work,a comparative study of the extractive distillation and pressure swing distillation for methanol-acetonitrile separation is performed for the first time.Different separation alternatives,including the conventional extractive distillation,the extractive distillation with vapor or liquid side-stream,the pressure-swing distillation with or without full heat integration,and the heat-pump assisted pressure-swing distillation are rigorously simulated and optimized based on the minimum total annual cost(TAC)via the sequential iterative strategy.The results show that TAC and CO2 emission of the new extractive distillation with vapor side-stream(Vapor-SED)are similar to those of the extractive distillation with liquid side-stream(Liquid-SED).Furthermore,the Vapor-SED and Liquid-SED can achieve 30.01%and 30.56%reduction in TAC and 23.32%and 23.49%reduction in CO2 emission,respectively,over the most competitive fully heat-integrated PSD configuration.Hence,the extractive distillation with vapor or liquid side-stream appears to be a better option economically and environmentally for the separation of methanol and acetonitrile.展开更多
The objective of this research was to study the treatment of acetonitrile by catalytic supercritical water oxi-dation in a compact-sized tubular reactor, with an internal volume of 4.71 mL. Manganese dioxide was used ...The objective of this research was to study the treatment of acetonitrile by catalytic supercritical water oxi-dation in a compact-sized tubular reactor, with an internal volume of 4.71 mL. Manganese dioxide was used as the catalyst and H2O2 was used as the oxidant. The oxidation of acetonitrile in supercritical water was studied at 400-500 oC, 25-35 MPa, the flow rate of 2-4 mL/min, the initial concentration of acetonitrile 0.077-0.121 M and the %excess O2 of 50-200%. As a result, the products were mainly N2, CO2 and CO and acetonitrile can be decomposed > 93 % within a very short contact time (1.45-6.19 s). The oxidation process was carried out with respect to the conversion of acetonitrile by 25 factorial design. Regression models were obtained for correlating the conversion of acetonitrile with temperature and flow rate. The complete oxida-tion can be achieved at a condition as moderate as 400 oC, 25 MPa with the flow rate of 2 mL/min.展开更多
The title compound (PhNHNH)2C=OCH3CN has been prepared and characterized by elemental analysis and IR spectrum studies. The single-crystal X-ray structure determination of the title compound was carried out. It crysta...The title compound (PhNHNH)2C=OCH3CN has been prepared and characterized by elemental analysis and IR spectrum studies. The single-crystal X-ray structure determination of the title compound was carried out. It crystallizes in the monoclinic system, space group P21/n with a = 5.7818(2), b = 15.320(1), c = 17.469(1) ? b = 97.476(1)? V = 1534.2(1) 3, Mr = 283.34 (C15H17N5O), Z = 4, Dc = 1.227 g/cm3 , F(000) = 600, ?= 0.082 mm-1, R = 0.0561 and wR = 0.1538. The total reflections were 8214 and the independent ones were 2624 (Rint = 0.0559), of which 1756 were observed with I > 2s(I). The torsion angles of the important groups (C(6)N(1) N(2)C(7) and C(7)N(3)N(4)C(8)) are 68.3(3) and 93.3(3), respectively. In the crystal lattice, the molecules form a network structure through hydrogen bonds. The crystal structure is stabilized by NH…N and NH…O hydrogen bonds. FT-IR spectra clearly show there exist acetonitrile molecules in the crystal lattice.展开更多
The adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibit...The adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibited strong interaction with the fresh Mo2C/γ-Al2O3 catalyst and was adsorbed mainly on Moδ+ sites of fresh Mo2C/γ-Al2O3 catalyst. Moreover, CH3CN could affect the shifting of IR spectra for CO adsorption towards a lower wave number. The IR spectroscopic study on acetonitrile hydrogenation showed that CH3CN could be easily hydrogenated in the presence of H2 on the Mo2C/γ-Al2O3 catalyst. Furthermore, it was observed that CH3 CN could be selectively hydrogenated to imines on fresh Mo2C/γ-Al2O3 catalyst. Additionally, the active sites of fresh Mo2C/γ-Al2O3 catalyst might be covered with coke during the hydrogenation reaction of acetonitrile. The treatment of catalyst with hydrogen at 673 K could not completely remove coke deposits on the surface of the Mo2C/γ-Al2O3 catalyst.展开更多
The adsorption of CH3CN and CH3NC on the Pt（lll） surface at the 1/4 monolayer （ML） coverage has been car-ried out at the level of density functional theory for understanding hydrogenation processes of nitriles. Th...The adsorption of CH3CN and CH3NC on the Pt（lll） surface at the 1/4 monolayer （ML） coverage has been car-ried out at the level of density functional theory for understanding hydrogenation processes of nitriles. The most favored ad-sorption structure for CH3 CN is the C--N bond almost parallel to the surface with the C-N bond interaction with adjacent surface Pt atoms. For CH3NC, the most stable configuration is the CH3 NC locates at the face center cubic （fcc） site with the C-atom bonded to three Pt atoms. In addition, the HCN and HNC adsorption has been computed, and the adsorption pattern is nearly similar to the CH3CN and CH3NC, respectively. The adsorbed molecules rehybridize on the surface, be-coming non-linear with a bent C-C-N or C-N-C angle. Furthermore, the binding mechanism of these molecules on the Pt（111） surface is also analyzed.展开更多
The behaviour of cyanothioacetamide 1 and the acetonitrile derivatives 6 and 10, respectively, towards the nitrones 2a-i induced by free solar thermal energy is reported. Structures and reaction mechanisms are also di...The behaviour of cyanothioacetamide 1 and the acetonitrile derivatives 6 and 10, respectively, towards the nitrones 2a-i induced by free solar thermal energy is reported. Structures and reaction mechanisms are also discussed.展开更多
This paper presents the vapor–liquid equilibrium(VLE) data of acetonitrile–water system containing ionic liquids(ILs) at atmospheric pressure(101.3 k Pa). Since ionic liquids dissociate into anions and cations, the ...This paper presents the vapor–liquid equilibrium(VLE) data of acetonitrile–water system containing ionic liquids(ILs) at atmospheric pressure(101.3 k Pa). Since ionic liquids dissociate into anions and cations, the VLE data for the acetonitrile + water + ILs systems are correlated by salt effect models, Furter model and improved Furter model. The overall average relative deviation of Furter model and improved Furter model is 5.43% and 4.68%, respectively. Thus the salt effect models are applicable for the correlation of IL containing systems. The salting-out effect theory can be used to explain the change of relative volatility of acetonitrile–water system.展开更多
Formation and decay processes of pyrene excimer in acetonitrile have been measured by laser flash spectroscopy at 475nm,and the dependence of λ_1+λ_2 on the pyrene concentration has also been measured at 290°K....Formation and decay processes of pyrene excimer in acetonitrile have been measured by laser flash spectroscopy at 475nm,and the dependence of λ_1+λ_2 on the pyrene concentration has also been measured at 290°K.On the basis of these measurements,six rate parameters which describe the behaviour of pyrene excimer system in acetonitrile solution have been evaluated.At 355 nm laser light irradiation,the ΔG of the pyrene excimer formation in acetonitrile is evaluated to be -30.18kJ/mol. This value is quite different from the corresponding ΔG in cyclohexane (-16.72kJ/mol).展开更多
The X-ray crystal structure of the inclusion complex of p-tert-butylcalix [4] crown-6 with actonitrile is reported. C54H70O10·3CH3CN, Mr=1002. 3 ,monoclinic, space group C2/c with cell dimensions of a=23.587(7),b...The X-ray crystal structure of the inclusion complex of p-tert-butylcalix [4] crown-6 with actonitrile is reported. C54H70O10·3CH3CN, Mr=1002. 3 ,monoclinic, space group C2/c with cell dimensions of a=23.587(7),b=21.153(6),c=15.608(8) A,β=116.99(3)°,V=6939.2 A3,Z=4, F(000)=2160,Dc=0.959 g/cm3,μ=1.114 cm-1; R=0.088 for 2066 reflections with I>3σ(I).The calixarene subunit exists in a distorted cone conformation. One of the three acetonitrile molecules is located in the intracavity of the calixarene subunit and the other two in the intermolecular channels.展开更多
Electrochemical reduction of acetonitrile to ethylamine with a high selectivity is a novel approach to manufacture valuable primary amines which are important raw material in organic chemical industry. However, the po...Electrochemical reduction of acetonitrile to ethylamine with a high selectivity is a novel approach to manufacture valuable primary amines which are important raw material in organic chemical industry. However, the poor ethylamine Faradic efficiency(FE_(ethylamine)) and catalyst stability at the high current density prohibit this method from being practically used. Herein, CuNi alloy ultrafine-nano-particles based on the d-orbital coupling modulation were synthesized through the electrodeposition and their catalytic performance towards acetonitrile reduction reaction(ACNRR) has been systematically studied. The highest FE_(ethylamine)(97%) is achieved with the current density of-114 mA cm^(-2). For practical application, the current density can reach-602.8 mA cm^(-2) with 82.8% FE_(ethylamine)maintained. With the appearance of other organics which co-exist with acetonitrile in the SOHIO process, CuNi can also hydrogenate acetonitrile in it with more than 80% FE_(ethylamine). Our in-situ spectroscopy analysis and DFT calculations towards the acetonitrile hydrogenation behavior reveal that the evenly dispersed Ni in Cu modulates the dband so as to endow CuNi with the better acetonitrile adsorption, milder binding energy with the reaction intermediates, smaller barrier for *CH_3CH_2NH_2 desorption and higher ability for H_2O dissociation to provide *H.展开更多
Large scale applications of metal-iodine batteries working at sub-zero degree have been challenged by the limited capacity and performance degradation.Herein,we firstly propose a Zn-I_(2)battery working at low tempera...Large scale applications of metal-iodine batteries working at sub-zero degree have been challenged by the limited capacity and performance degradation.Herein,we firstly propose a Zn-I_(2)battery working at low temperature with a carbon composite material/iodine(CCM-I_(2))cathode,a Zn anode and an environmentally tolerable Zn(ClO4)2-ACN electrolyte.The CCM framework with hierarchical porous structure endows a powerful iodine-anchoring to overcome undesirable dissolution of iodine in organic electrolyte,and the Zn(ClO4)2-ACN electrolyte with low freezing point and high ionic conductivity enhances the low temperature performance.The synergies enable an efficiently reversible conversion of Zn-I_(2)battery even at-40℃.Therefore,the resultant Zn-I_(2)battery delivers a high specific capacity of 200 mAh·g^(-1),which is fairly approximate to the theoretical capacity of I_(2)(211 mAh·g^(-1))and a superior cycling stability with minimal capacity fading of 0.00043%per cycle over 7,000 times under 2C at-20℃.Furthermore,even at-40℃,this Zn-I_(2)battery still exhibits a good capacity retention of 68.7%compared to the capacity at 25℃ and a rapid capacity-recover ability with elevating temperature change.Our results distinctly indicate this Zn-I_(2)battery can be 1competent for the practical application under low temperature operation.展开更多
Acetonitrile inorganic salt aqueous two-phase extraction method was established for the determination of triazine herbicides(simeton,cyanazine,desmetryn,terbumeton,terbuthylazine and dimethametryn)in environmental wat...Acetonitrile inorganic salt aqueous two-phase extraction method was established for the determination of triazine herbicides(simeton,cyanazine,desmetryn,terbumeton,terbuthylazine and dimethametryn)in environmental water samples by high-performance liquid chromatography(HPLC).The extraction solvents types and volume of acetonitrile,the inorganic salt types and amount of(NH_(4))_(2)SO_(4),extraction time and pH of sample solution were optimized by single-factor experiment and central composite design.Under the optimum extraction conditions,all linear ranges were obtained with coefficients of determination(r)≥0.9993.The limits of detection for this proposed method were in the range of 0.16-0.28μg/L for six triazine herbicides.The developed method has been successfully applied to the analysis of target triazine herbicides from lake,canal and moat in real-world water samples.The recoveries of target analytes were in the range from 87.0 to 110.9%and the relative standard deviation was lower than 7.3%.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant Nos.52161135302,22105087)the Postdoctoral Research Foundation of China(Grant No.2022M721360)the Natural Science Foundation of Jiangsu Province(Grant No.BK20210446)。
文摘The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.
基金Supported by Agricultural Science and Technology Innovation Fund of Jiangsu Province(CX(12)5014)~~
文摘To investigate the degradation of FB1 in aqueous acetonitrile and corn af-ter γ-ray irradiation, the radiolytic products of FB1 was detected preliminarily. The results showed that γ-ray irradiation could degrade FB1 in aqueous acetonitrile;When the radiation dose was below 9 kGy, the degradation of FB1 in corn was not significant. The degradation rates of FB1 with concentrations of 0.8 mg/ml, 10.0 μg/ml, 1.0 μg/ml and 50 ng/ml after irradiation at 9 kGy were 22.5%, 51.0%, 59.0% and 64.8% respectively; when irradiation dose was increased to 100 kGy, the degrada-tion rate of FB1 with concentration of 0.8 mg/ml was up to 90%, and it was nearly 100% when irradiation dose was increased to 200 kGy. No representative products of FB1 were detected by LC/MS/MS analysis.
基金financially supported by the National Key R&D Program of China(no.2018YFB0604902)
文摘The benzene and acetonitrile azeotropic mixture was proposed to be separated by extractive distillation using an ionic liquid(IL)as the entrainer.The suitable IL was selected by the COSMO-RS model,and 1-ethyl-3-methylimidazolium tetrafluoroborate([EMIM][BF_(4)])was considered as the suitable entrainer mainly due to its high selectivity,low viscosity,and low price.The experimental vapor pressure data of the IL-containing systems(benzene+[EMIM][BF_(4)]and acetonitrile+[EMIM][BF_(4)])were measured in the full concentration range.The results show that acetonitrile has a stronger interaction with IL than benzene,and the low deviations between the experimental and UNIFAC predicted values show the reliability of the UNFIAC model.The UNIFAC predicted vapor-liquid equilibrium data of the benzene+acetonitrile+dimethyl sulfoxide(DMSO)/[EMIM][BF_(4)]system show that the relative volatility of benzene to acetonitrile is higher when the entrainer is[EMIM][BF_(4)].The process simulation results show that[EMIM][BF_(4)]can reduce the material and energy consumptions compared with DMSO.
基金Project(51374254) supported by the National Natural Science Foundation of China
文摘The corrosion behaviors of hafnium in Et4NBr isopropanol and acetonitrile(ACN)solutions were investigated usingelectrochemical measurements,ICP-AES and SEM techniques.Results revealed that the open circuit potential gets more positive dueto the increased passivity of the surface oxide film with increasing immersion time until it reaches a steady state value.Thepotentiodynamic anodic polarization curves did not exhibit an active dissolution region near corrosion potential due to the presenceof an oxide film on the electrode surface,which was followed by pitting corrosion.SEM images confirmed the existence of pits onthe electrode surface.Cyclic voltammetry and galvanostatic measurements allowed the pitting potential(φpit)and the repassivationpotential(φp)to be determined.φpit increased with increasing potential scanning rate but decreased with increasing temperature,Br-concentration and ACN concentration.The impedance spectra showed that the resistances of the solution and charge transferdecreased with the increase of ACN concentration.
文摘Temperature and pressure were shown to vary significantly with solvent mixing, showing maxima at differ-ent solvent ratios. Acetonitrile/water mixing resulted in temperature reduction of solutions whereas metha-nol/water mixing caused temperature increases. On the other hand, maximum recorded chromatographic pressure of acetonitrile:water mixtures occurred at a solvent ratio of 1:6 compared with methanol:water, which showed a maximum pressure at a solvent ratio of 1:1. These findings can be of use in stabilizing re-tention time shifts during HPLC-based studies associated with compound identification based on retention time such as analysis of complex mixtures.
基金Supported by the National Natural Science Foundation of China(21276073,21136004)the National Basic Research Program of China(2009CB219902)the Fundamental Research Funds for the Central Universities of China(222201313001)
文摘Vapor pressures were measured for acetonitrile+1-butyl-3-methylimidazolium chloride([C4mim][Cl]),+1-butyl-3-methylimidazolium tetrafluoroborate([C4mim][BF4])and+1-hexyl-3-methylimidazolium chloride([C6mim][Cl])at temperatures of 313 to 353 K by a quasi-static method.The experimental data for the binary systems were correlated by the non-random two liquid(NRTL)equation with an average absolute relative deviation(AARD)of within 1.84%.The results indicate that the three ionic liquids(ILs)can result in a negative deviation from the Raoult's law for the binary solutions containing acetonitrile,and the affinity between ILs and acetonitrile molecules follows the order[C4mim][BF4]+acetonitrile N[C4mim][Cl]+acetonitrile N[C6mim][Cl]+acetonitrile.
基金This work was financed by the National Natural Science Foundation of China （No. 20173054）.
文摘Ultrafast cyclic voltammetry was used to study the redox behavior of a gold electrode in acetonitrile. The direct electrochemical evidence of the dissociation and adsorption behavior of acetonitrile at gold electrodes was found. It could be stated that two consecutive redox paths are involved, each with a special adsorption state acting as the reaction intermediate. The mean value, obtained of the electron-transfer rate constant of the second path, was 1.3 × 10^5 s^-1 with a standard deviation of 0.24 × 10^5 s^-1.
文摘This paper reports the development and validation of an assay for the determination of acetonitrile in the recycled mobile phase using high performance liquid chromatography（HPLC）. The method is based on that the retention in reversed-phase liquid chromatography increases with decreasing concentration of organic phase in the mobile phase. The natural logarithm of the capacity ratio for a given solute is linearly related to the volume fraction of the organic modifier in the mobile phase. For dimethylphthalate and diethylphthalate, the linearity range is 30%--60%, and for biphenyl and terphenyl, the range is 60%--95%. Precision values（RSD） were both 〈1% and the accuracy（RE） was in the range of ±1%. The assay was successfully applied to the determination of acetonitrile concentration of recycled mobile phase after the distillation of the column eluent in our laboratory.
文摘In the present work,a comparative study of the extractive distillation and pressure swing distillation for methanol-acetonitrile separation is performed for the first time.Different separation alternatives,including the conventional extractive distillation,the extractive distillation with vapor or liquid side-stream,the pressure-swing distillation with or without full heat integration,and the heat-pump assisted pressure-swing distillation are rigorously simulated and optimized based on the minimum total annual cost(TAC)via the sequential iterative strategy.The results show that TAC and CO2 emission of the new extractive distillation with vapor side-stream(Vapor-SED)are similar to those of the extractive distillation with liquid side-stream(Liquid-SED).Furthermore,the Vapor-SED and Liquid-SED can achieve 30.01%and 30.56%reduction in TAC and 23.32%and 23.49%reduction in CO2 emission,respectively,over the most competitive fully heat-integrated PSD configuration.Hence,the extractive distillation with vapor or liquid side-stream appears to be a better option economically and environmentally for the separation of methanol and acetonitrile.
文摘The objective of this research was to study the treatment of acetonitrile by catalytic supercritical water oxi-dation in a compact-sized tubular reactor, with an internal volume of 4.71 mL. Manganese dioxide was used as the catalyst and H2O2 was used as the oxidant. The oxidation of acetonitrile in supercritical water was studied at 400-500 oC, 25-35 MPa, the flow rate of 2-4 mL/min, the initial concentration of acetonitrile 0.077-0.121 M and the %excess O2 of 50-200%. As a result, the products were mainly N2, CO2 and CO and acetonitrile can be decomposed > 93 % within a very short contact time (1.45-6.19 s). The oxidation process was carried out with respect to the conversion of acetonitrile by 25 factorial design. Regression models were obtained for correlating the conversion of acetonitrile with temperature and flow rate. The complete oxida-tion can be achieved at a condition as moderate as 400 oC, 25 MPa with the flow rate of 2 mL/min.
基金the Educational Administration Key Project of Shandong province (No. J01C05) and the Outstanding Adult-Young Scientific Research Encouraging Foundation of Shandong province (No. O1BS18)
文摘The title compound (PhNHNH)2C=OCH3CN has been prepared and characterized by elemental analysis and IR spectrum studies. The single-crystal X-ray structure determination of the title compound was carried out. It crystallizes in the monoclinic system, space group P21/n with a = 5.7818(2), b = 15.320(1), c = 17.469(1) ? b = 97.476(1)? V = 1534.2(1) 3, Mr = 283.34 (C15H17N5O), Z = 4, Dc = 1.227 g/cm3 , F(000) = 600, ?= 0.082 mm-1, R = 0.0561 and wR = 0.1538. The total reflections were 8214 and the independent ones were 2624 (Rint = 0.0559), of which 1756 were observed with I > 2s(I). The torsion angles of the important groups (C(6)N(1) N(2)C(7) and C(7)N(3)N(4)C(8)) are 68.3(3) and 93.3(3), respectively. In the crystal lattice, the molecules form a network structure through hydrogen bonds. The crystal structure is stabilized by NH…N and NH…O hydrogen bonds. FT-IR spectra clearly show there exist acetonitrile molecules in the crystal lattice.
基金financially supported by the National Natural Science Foundation of China (No. 21573101)the Liaoning Provincial Natural Science Foundation (No. 2014020107)+1 种基金the Program for Liaoning Excellent Talents in Universities (No. LJQ2014041)sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (SRF for ROCS, SEM)
文摘The adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibited strong interaction with the fresh Mo2C/γ-Al2O3 catalyst and was adsorbed mainly on Moδ+ sites of fresh Mo2C/γ-Al2O3 catalyst. Moreover, CH3CN could affect the shifting of IR spectra for CO adsorption towards a lower wave number. The IR spectroscopic study on acetonitrile hydrogenation showed that CH3CN could be easily hydrogenated in the presence of H2 on the Mo2C/γ-Al2O3 catalyst. Furthermore, it was observed that CH3 CN could be selectively hydrogenated to imines on fresh Mo2C/γ-Al2O3 catalyst. Additionally, the active sites of fresh Mo2C/γ-Al2O3 catalyst might be covered with coke during the hydrogenation reaction of acetonitrile. The treatment of catalyst with hydrogen at 673 K could not completely remove coke deposits on the surface of the Mo2C/γ-Al2O3 catalyst.
基金Natural Science Foundation of Shanxi Province(No. 2009011014)
文摘The adsorption of CH3CN and CH3NC on the Pt（lll） surface at the 1/4 monolayer （ML） coverage has been car-ried out at the level of density functional theory for understanding hydrogenation processes of nitriles. The most favored ad-sorption structure for CH3 CN is the C--N bond almost parallel to the surface with the C-N bond interaction with adjacent surface Pt atoms. For CH3NC, the most stable configuration is the CH3 NC locates at the face center cubic （fcc） site with the C-atom bonded to three Pt atoms. In addition, the HCN and HNC adsorption has been computed, and the adsorption pattern is nearly similar to the CH3CN and CH3NC, respectively. The adsorbed molecules rehybridize on the surface, be-coming non-linear with a bent C-C-N or C-N-C angle. Furthermore, the binding mechanism of these molecules on the Pt（111） surface is also analyzed.
文摘The behaviour of cyanothioacetamide 1 and the acetonitrile derivatives 6 and 10, respectively, towards the nitrones 2a-i induced by free solar thermal energy is reported. Structures and reaction mechanisms are also discussed.
基金Supported by the National Natural Science Foundation of China(21306036)the Youth Scholars of Educational Commission of Hebei Province of China(Y2012040)the Joint Specialized Research Fund for the Doctoral Program of Higher Education(20131317120014)
文摘This paper presents the vapor–liquid equilibrium(VLE) data of acetonitrile–water system containing ionic liquids(ILs) at atmospheric pressure(101.3 k Pa). Since ionic liquids dissociate into anions and cations, the VLE data for the acetonitrile + water + ILs systems are correlated by salt effect models, Furter model and improved Furter model. The overall average relative deviation of Furter model and improved Furter model is 5.43% and 4.68%, respectively. Thus the salt effect models are applicable for the correlation of IL containing systems. The salting-out effect theory can be used to explain the change of relative volatility of acetonitrile–water system.
文摘Formation and decay processes of pyrene excimer in acetonitrile have been measured by laser flash spectroscopy at 475nm,and the dependence of λ_1+λ_2 on the pyrene concentration has also been measured at 290°K.On the basis of these measurements,six rate parameters which describe the behaviour of pyrene excimer system in acetonitrile solution have been evaluated.At 355 nm laser light irradiation,the ΔG of the pyrene excimer formation in acetonitrile is evaluated to be -30.18kJ/mol. This value is quite different from the corresponding ΔG in cyclohexane (-16.72kJ/mol).
文摘The X-ray crystal structure of the inclusion complex of p-tert-butylcalix [4] crown-6 with actonitrile is reported. C54H70O10·3CH3CN, Mr=1002. 3 ,monoclinic, space group C2/c with cell dimensions of a=23.587(7),b=21.153(6),c=15.608(8) A,β=116.99(3)°,V=6939.2 A3,Z=4, F(000)=2160,Dc=0.959 g/cm3,μ=1.114 cm-1; R=0.088 for 2066 reflections with I>3σ(I).The calixarene subunit exists in a distorted cone conformation. One of the three acetonitrile molecules is located in the intracavity of the calixarene subunit and the other two in the intermolecular channels.
基金the National Natural Science Foundation of China (12025503, 12105208)the Fundamental Research Funds for the Central Universities of China (2042022kf1181)China Postdoctoral Science Foundation (2020M682469)。
文摘Electrochemical reduction of acetonitrile to ethylamine with a high selectivity is a novel approach to manufacture valuable primary amines which are important raw material in organic chemical industry. However, the poor ethylamine Faradic efficiency(FE_(ethylamine)) and catalyst stability at the high current density prohibit this method from being practically used. Herein, CuNi alloy ultrafine-nano-particles based on the d-orbital coupling modulation were synthesized through the electrodeposition and their catalytic performance towards acetonitrile reduction reaction(ACNRR) has been systematically studied. The highest FE_(ethylamine)(97%) is achieved with the current density of-114 mA cm^(-2). For practical application, the current density can reach-602.8 mA cm^(-2) with 82.8% FE_(ethylamine)maintained. With the appearance of other organics which co-exist with acetonitrile in the SOHIO process, CuNi can also hydrogenate acetonitrile in it with more than 80% FE_(ethylamine). Our in-situ spectroscopy analysis and DFT calculations towards the acetonitrile hydrogenation behavior reveal that the evenly dispersed Ni in Cu modulates the dband so as to endow CuNi with the better acetonitrile adsorption, milder binding energy with the reaction intermediates, smaller barrier for *CH_3CH_2NH_2 desorption and higher ability for H_2O dissociation to provide *H.
基金This work was financially supported by the National Key R&D Program of China(No.2017YFA0700104)the Tianjin Natural Science Foundation of China(No.20JCZDJC00280)the National Natural Science Foundation of China(No.U1804255).
文摘Large scale applications of metal-iodine batteries working at sub-zero degree have been challenged by the limited capacity and performance degradation.Herein,we firstly propose a Zn-I_(2)battery working at low temperature with a carbon composite material/iodine(CCM-I_(2))cathode,a Zn anode and an environmentally tolerable Zn(ClO4)2-ACN electrolyte.The CCM framework with hierarchical porous structure endows a powerful iodine-anchoring to overcome undesirable dissolution of iodine in organic electrolyte,and the Zn(ClO4)2-ACN electrolyte with low freezing point and high ionic conductivity enhances the low temperature performance.The synergies enable an efficiently reversible conversion of Zn-I_(2)battery even at-40℃.Therefore,the resultant Zn-I_(2)battery delivers a high specific capacity of 200 mAh·g^(-1),which is fairly approximate to the theoretical capacity of I_(2)(211 mAh·g^(-1))and a superior cycling stability with minimal capacity fading of 0.00043%per cycle over 7,000 times under 2C at-20℃.Furthermore,even at-40℃,this Zn-I_(2)battery still exhibits a good capacity retention of 68.7%compared to the capacity at 25℃ and a rapid capacity-recover ability with elevating temperature change.Our results distinctly indicate this Zn-I_(2)battery can be 1competent for the practical application under low temperature operation.
基金the major project of Natural Science Foundation of Jiangsu Higher Education Institutions of China(no:15KJA610003)Natural Science Foundation of Jiangsu Province(no.BK20160359)Natural Science and Technology Program on Water Pollution Control and Treatment(2017ZX07205-2).
文摘Acetonitrile inorganic salt aqueous two-phase extraction method was established for the determination of triazine herbicides(simeton,cyanazine,desmetryn,terbumeton,terbuthylazine and dimethametryn)in environmental water samples by high-performance liquid chromatography(HPLC).The extraction solvents types and volume of acetonitrile,the inorganic salt types and amount of(NH_(4))_(2)SO_(4),extraction time and pH of sample solution were optimized by single-factor experiment and central composite design.Under the optimum extraction conditions,all linear ranges were obtained with coefficients of determination(r)≥0.9993.The limits of detection for this proposed method were in the range of 0.16-0.28μg/L for six triazine herbicides.The developed method has been successfully applied to the analysis of target triazine herbicides from lake,canal and moat in real-world water samples.The recoveries of target analytes were in the range from 87.0 to 110.9%and the relative standard deviation was lower than 7.3%.
