The liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) using fuming sulfuric acid as a catalyst is a traditional method for preparing ε-caprolactam (CPL). This process has drawbacks, such as environment...The liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) using fuming sulfuric acid as a catalyst is a traditional method for preparing ε-caprolactam (CPL). This process has drawbacks, such as environmental pollution, corrosion of equipment, and low added value of by-product ammonium sulfate. This article designed and prepared a green silica gel-supported trifluoromethanesulfonic acid catalyst for the liquid-phase Beckmann rearrangement of CHO to prepare (CPL). The influencing factors of catalyst preparation and the optimal reaction conditions for Beckmann rearrangement were investigated. It was found that the optimal conditions for catalyst preparation were as follows: raw material silica gel:trifluoromethanesulfonic acid = 1:0.2 (mass ratio), room temperature, stirring time of 2.5 hours, and solvent of acetonitrile, silica gel mesh size is 100 - 200. The optimal reaction conditions for Beckmann rearrangement are CHO: catalyst = 1:2 (mass ratio), temperature of 130˚C, solvent of benzonitrile, volume of 30 mL/g CHO, and reaction time of 4 hours. Under the above conditions, the conversion of CHO is 90%, and the selectivity of CPL is 90%.展开更多
The efficiency of TFMSA as a cleaving reagent for peptidyl resin(I-VIII)was evaluated by quantitative ninhydrin test of peptide substitution degree(SD)on resin.Under different conditions,such as variation of C-termina...The efficiency of TFMSA as a cleaving reagent for peptidyl resin(I-VIII)was evaluated by quantitative ninhydrin test of peptide substitution degree(SD)on resin.Under different conditions,such as variation of C-terminal residue,resin linkage,the temperature and reaction time etc.,TFMSA can be used very conveniently instead of HF in many cases.展开更多
A polyetheramine(PEA)-based Br?nsted-acidic ionic liquid(IL)was firstly prepared and used to promote the alkylation of isobutane with isobutene catalyzed by trifluoromethanesulfonic acid(TfOH).PEA-IL not only can reso...A polyetheramine(PEA)-based Br?nsted-acidic ionic liquid(IL)was firstly prepared and used to promote the alkylation of isobutane with isobutene catalyzed by trifluoromethanesulfonic acid(TfOH).PEA-IL not only can resolve the persistent problem of poor solubility of the volatile and refractory reactants,but also can satisfactorily exhibit the separation of the catalyst from product oil for reuse.The PEA-IL/TfOH catalytic system with an adjustable acidity ensures a high alkylate selectivity.Under the conditions covering a VIL/VTfOH ratio of 10:3,a temperature of 25°C,and a reaction time of 25 min,the C8-product selectivity reaches 86.63%.The PEA-IL/TfOH catalyst can be reused 13 times without a decrease in the catalytic performance.After many operating cycles,the hydrophobic PEA-IL can be easily regenerated by simply adding water.This study provides a green,economic,and highly efficient method for producing high-octane alkylate gasoline.展开更多
Nonfullerene organic solar cells(OSCs)have achieved breakthrough with pushing the efficiency exceeding 17%.While this shed light on OSC commercialization,high-performance flexible OSCs should be pursued through soluti...Nonfullerene organic solar cells(OSCs)have achieved breakthrough with pushing the efficiency exceeding 17%.While this shed light on OSC commercialization,high-performance flexible OSCs should be pursued through solution manufacturing.Herein,we report a solution-processed flexible OSC based on a transparent conducting PEDOT:PSS anode doped with trifluoromethanesulfonic acid(CF3SO3H).Through a low-concentration and low-temperature CF3SO3H doping,the conducting polymer anodes exhibited a main sheet resistance of 35Ωsq−1(minimum value:32Ωsq−1),a raised work function(≈5.0 eV),a superior wettability,and a high electrical stability.The high work function minimized the energy level mismatch among the anodes,hole-transporting layers and electron-donors of the active layers,thereby leading to an enhanced carrier extraction.The solution-processed flexible OSCs yielded a record-high efficiency of 16.41%(maximum value:16.61%).Besides,the flexible OSCs afforded the 1000 cyclic bending tests at the radius of 1.5 mm and the long-time thermal treatments at 85°C,demonstrating a high flexibility and a good thermal stability.展开更多
文摘The liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) using fuming sulfuric acid as a catalyst is a traditional method for preparing ε-caprolactam (CPL). This process has drawbacks, such as environmental pollution, corrosion of equipment, and low added value of by-product ammonium sulfate. This article designed and prepared a green silica gel-supported trifluoromethanesulfonic acid catalyst for the liquid-phase Beckmann rearrangement of CHO to prepare (CPL). The influencing factors of catalyst preparation and the optimal reaction conditions for Beckmann rearrangement were investigated. It was found that the optimal conditions for catalyst preparation were as follows: raw material silica gel:trifluoromethanesulfonic acid = 1:0.2 (mass ratio), room temperature, stirring time of 2.5 hours, and solvent of acetonitrile, silica gel mesh size is 100 - 200. The optimal reaction conditions for Beckmann rearrangement are CHO: catalyst = 1:2 (mass ratio), temperature of 130˚C, solvent of benzonitrile, volume of 30 mL/g CHO, and reaction time of 4 hours. Under the above conditions, the conversion of CHO is 90%, and the selectivity of CPL is 90%.
文摘The efficiency of TFMSA as a cleaving reagent for peptidyl resin(I-VIII)was evaluated by quantitative ninhydrin test of peptide substitution degree(SD)on resin.Under different conditions,such as variation of C-terminal residue,resin linkage,the temperature and reaction time etc.,TFMSA can be used very conveniently instead of HF in many cases.
基金financially supported by the National Natural Science Foundation of China(Nos.21476120,21805158)the Shandong Province Priority Development Plan of China(Nos.2017GGX40107,2019GGX102021)。
文摘A polyetheramine(PEA)-based Br?nsted-acidic ionic liquid(IL)was firstly prepared and used to promote the alkylation of isobutane with isobutene catalyzed by trifluoromethanesulfonic acid(TfOH).PEA-IL not only can resolve the persistent problem of poor solubility of the volatile and refractory reactants,but also can satisfactorily exhibit the separation of the catalyst from product oil for reuse.The PEA-IL/TfOH catalytic system with an adjustable acidity ensures a high alkylate selectivity.Under the conditions covering a VIL/VTfOH ratio of 10:3,a temperature of 25°C,and a reaction time of 25 min,the C8-product selectivity reaches 86.63%.The PEA-IL/TfOH catalyst can be reused 13 times without a decrease in the catalytic performance.After many operating cycles,the hydrophobic PEA-IL can be easily regenerated by simply adding water.This study provides a green,economic,and highly efficient method for producing high-octane alkylate gasoline.
基金The authors acknowledge funding from the National Natural Science Foundation of China(61974150 and 51773213)Key Research Program of Frontier Sciences,CAS(QYZDB-SSW-JSC047)+1 种基金the Fundamental Research Funds for the Central Universities,the CAS-EU S&T cooperation partner program(174433KYSB20150013)the Natural Science Foundation of Ningbo(2018A610135).
文摘Nonfullerene organic solar cells(OSCs)have achieved breakthrough with pushing the efficiency exceeding 17%.While this shed light on OSC commercialization,high-performance flexible OSCs should be pursued through solution manufacturing.Herein,we report a solution-processed flexible OSC based on a transparent conducting PEDOT:PSS anode doped with trifluoromethanesulfonic acid(CF3SO3H).Through a low-concentration and low-temperature CF3SO3H doping,the conducting polymer anodes exhibited a main sheet resistance of 35Ωsq−1(minimum value:32Ωsq−1),a raised work function(≈5.0 eV),a superior wettability,and a high electrical stability.The high work function minimized the energy level mismatch among the anodes,hole-transporting layers and electron-donors of the active layers,thereby leading to an enhanced carrier extraction.The solution-processed flexible OSCs yielded a record-high efficiency of 16.41%(maximum value:16.61%).Besides,the flexible OSCs afforded the 1000 cyclic bending tests at the radius of 1.5 mm and the long-time thermal treatments at 85°C,demonstrating a high flexibility and a good thermal stability.