CuCl-based catalysts are the most commonly used catalysts for the“direct synthesis”of trimethoxysilane(M3).CuCl species are sensitive to air and water,and are prone to oxidation deactivation.When CuCl is directly us...CuCl-based catalysts are the most commonly used catalysts for the“direct synthesis”of trimethoxysilane(M3).CuCl species are sensitive to air and water,and are prone to oxidation deactivation.When CuCl is directly used as a catalyst,it needs to be purified before the utilization,and the operating conditions for the catalyst preparation are relatively harsh,requiring the inert gas environment.Considering a high-temperature activation step required for CuCl-based catalysts used for catalyzing synthesis of M3 to form active phase Cu–Si alloys(Cu_(x)Si)with Si powder,in this work,a series of catalysts for the“direct synthesis”of M3 were obtained by a one-step high-temperature activation of the mixture of stable CuCl_(2) precursors,activated carbon-reducing agent,and Si powder,simultaneously achieving the reduction of CuCl_(2) to CuCl and the formation of active phase Cu_(x)Si alloys of CuCl with Si powder.The prepared samples were characterized through various characterization techniques,and investigated for the catalytic performance for the“direct synthesis”of M3.Moreover,the operation conditions were optimized,including the activation temperature,catalyst dosage,Si powder particle size,and reaction temperature.The characterization results indicate that during the one-step activation process,the CuCl_(2) precursor is reduced to CuCl,and the resulting CuCl simultaneously reacts with Si powder to form active phases Cu3Si and Cu15Si4 alloys.The optimal catalyst Sacm(250,0.8:10)exhibits a good catalytic activity with selectivity of 95%and yield of 77%for M3,and shows a good universality for various alcohol substrates.Furthermore,the catalytic mechanism of the prepared catalyst for the“direct synthesis”of M3 was discussed.展开更多
In this paper, for the first time, we report the synthesis of nanoscale cuprous chloride(Cu Cl) cubic structure by a facile hydrothermal route. A possible mechanism for the growth of those nanostructures is proposed b...In this paper, for the first time, we report the synthesis of nanoscale cuprous chloride(Cu Cl) cubic structure by a facile hydrothermal route. A possible mechanism for the growth of those nanostructures is proposed based on the experimental results. It is discovered that the existence of HCl could affect the surface of Cu Cl nanocubes. This unique cube-like nanostructure with rough surface significantly enhances the electroactive surface areas of Cu Cl, leading to a high special capacitance of 376 m F cm-2at the current density of 1.0 m A cm-2. There is still a good reversibility with cycling efficiency of 88.8 % after 2,000 cycles, demonstrating its excellent long-term cycling stability and might be the promising candidates as the excellent electrode material.展开更多
The waste water system generated in the process of production of cuprous chloride was studied.The existing forms of copper in the system and the influence of temperature and pH on the existing forms of copper ion were...The waste water system generated in the process of production of cuprous chloride was studied.The existing forms of copper in the system and the influence of temperature and pH on the existing forms of copper ion were analyzed and determined through calculating the coefficients of copper complex distribution.In the waste water system,the main forms of copper are CuSO4, Cu2 +,CuCl + ,CuCl, 2-and2- 3 CuCl.Temperature has little influence on the distribution coefficient of Cu(Ⅱ),but has significant influence on distribution coefficient of Cu(Ⅰ).With the increase of temperature,the distribution coefficient ofCuCl, 2-increases significantly while the distribution coefficient of2- 3 CuCl decreases.The pH has nearly no influence on the distribution coefficients of various Cu(Ⅰ)-compounds,but has sizable influence on the distribution coefficients of Cu(Ⅱ)-compounds.With the increase of pH,the distribution coefficient of CuSO4(aq)increases while the distribution coefficients of Cu 2+ and CuCl + decrease.According to these results,the anion resin of 201×7 OH-and the cation resin of 732 Na were chosen to dispose the waste water solution of cuprous chloride.Finally,97.9%copper in the waste water is recovered.展开更多
CuCl-catalyzed oxidative N-demethylation of arylamines proceeded in the presence of tert-butyl hydroperoxide. The one-electron transfer route of oxidative N-demethylation competed favorably with the H-atom abstraction...CuCl-catalyzed oxidative N-demethylation of arylamines proceeded in the presence of tert-butyl hydroperoxide. The one-electron transfer route of oxidative N-demethylation competed favorably with the H-atom abstraction route.展开更多
The effects of SO2,SO3 on de novo synthesis of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were studied using model fly ashes incorporating copper oxide and activated carbon. It was found that ...The effects of SO2,SO3 on de novo synthesis of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were studied using model fly ashes incorporating copper oxide and activated carbon. It was found that the inhibitive effect of SO2 on PCDD/Fs formation is similar to that of SO3. To investigate the inhibition mechanism,CuSO4 formations from both CuO and CuCl2 were examined. The ability of SO3 to convert CuCl2 and CuO on a silica support into sulfate is much stronger than that of SO2. However,replacing silica by activated carbon leads to a much high conversion of CuCl2 to CuSO4 in the presence of SO2. The promotion by activated carbon is explained by the reduction of CuCl2 to Cu2Cl2 and the eventual conversion of Cu2Cl2 into CuSO4 is the main inhibition mechanism of SO2 on de novo synthesis of PCDD/Fs.展开更多
基金supported by the Key Research & Development Plan of Shandong Province (the Major Scientific and Technological Innovation Projects, 2021ZDSYS13)the Natural Science Foundation of Shandong Province (ZR2021MB135)
文摘CuCl-based catalysts are the most commonly used catalysts for the“direct synthesis”of trimethoxysilane(M3).CuCl species are sensitive to air and water,and are prone to oxidation deactivation.When CuCl is directly used as a catalyst,it needs to be purified before the utilization,and the operating conditions for the catalyst preparation are relatively harsh,requiring the inert gas environment.Considering a high-temperature activation step required for CuCl-based catalysts used for catalyzing synthesis of M3 to form active phase Cu–Si alloys(Cu_(x)Si)with Si powder,in this work,a series of catalysts for the“direct synthesis”of M3 were obtained by a one-step high-temperature activation of the mixture of stable CuCl_(2) precursors,activated carbon-reducing agent,and Si powder,simultaneously achieving the reduction of CuCl_(2) to CuCl and the formation of active phase Cu_(x)Si alloys of CuCl with Si powder.The prepared samples were characterized through various characterization techniques,and investigated for the catalytic performance for the“direct synthesis”of M3.Moreover,the operation conditions were optimized,including the activation temperature,catalyst dosage,Si powder particle size,and reaction temperature.The characterization results indicate that during the one-step activation process,the CuCl_(2) precursor is reduced to CuCl,and the resulting CuCl simultaneously reacts with Si powder to form active phases Cu3Si and Cu15Si4 alloys.The optimal catalyst Sacm(250,0.8:10)exhibits a good catalytic activity with selectivity of 95%and yield of 77%for M3,and shows a good universality for various alcohol substrates.Furthermore,the catalytic mechanism of the prepared catalyst for the“direct synthesis”of M3 was discussed.
基金supported by the Program for New Century Excellent Talents in Heilongjiang Provincial University (1252-NCET-018)the Scientific Research Fund of Heilongjiang Provincial Education Department (12531179)
文摘In this paper, for the first time, we report the synthesis of nanoscale cuprous chloride(Cu Cl) cubic structure by a facile hydrothermal route. A possible mechanism for the growth of those nanostructures is proposed based on the experimental results. It is discovered that the existence of HCl could affect the surface of Cu Cl nanocubes. This unique cube-like nanostructure with rough surface significantly enhances the electroactive surface areas of Cu Cl, leading to a high special capacitance of 376 m F cm-2at the current density of 1.0 m A cm-2. There is still a good reversibility with cycling efficiency of 88.8 % after 2,000 cycles, demonstrating its excellent long-term cycling stability and might be the promising candidates as the excellent electrode material.
基金Projects(5087408750978212)supported by the National Natural Science Foundation of China+1 种基金Project(2006E106)supported by Natural Science Foundation of Shaanxi Province,ChinaProject(07JK302)supported by Special Natural Science Foundation of Shaanxi Province Education Office,China
文摘The waste water system generated in the process of production of cuprous chloride was studied.The existing forms of copper in the system and the influence of temperature and pH on the existing forms of copper ion were analyzed and determined through calculating the coefficients of copper complex distribution.In the waste water system,the main forms of copper are CuSO4, Cu2 +,CuCl + ,CuCl, 2-and2- 3 CuCl.Temperature has little influence on the distribution coefficient of Cu(Ⅱ),but has significant influence on distribution coefficient of Cu(Ⅰ).With the increase of temperature,the distribution coefficient ofCuCl, 2-increases significantly while the distribution coefficient of2- 3 CuCl decreases.The pH has nearly no influence on the distribution coefficients of various Cu(Ⅰ)-compounds,but has sizable influence on the distribution coefficients of Cu(Ⅱ)-compounds.With the increase of pH,the distribution coefficient of CuSO4(aq)increases while the distribution coefficients of Cu 2+ and CuCl + decrease.According to these results,the anion resin of 201×7 OH-and the cation resin of 732 Na were chosen to dispose the waste water solution of cuprous chloride.Finally,97.9%copper in the waste water is recovered.
基金Supported by the National Natural Science Foundation of China(No.20572058)
文摘CuCl-catalyzed oxidative N-demethylation of arylamines proceeded in the presence of tert-butyl hydroperoxide. The one-electron transfer route of oxidative N-demethylation competed favorably with the H-atom abstraction route.
基金Project supported by the National High-Tech Research and Devel-opment Program (863) of China (Nos. 2007AA061302 and 2007AA06Z336)the National Nature Science Foundation of China (No. 50576082)+2 种基金the Important Project on Science and Technology of Zhejiang Province of China (No. 2007C13084)the Zhejiang Provincial Natural Science Foundation of China (No. R107532)the Project on Science and Technology of Zhejiang Province of China (No. 2008C23090)
文摘The effects of SO2,SO3 on de novo synthesis of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were studied using model fly ashes incorporating copper oxide and activated carbon. It was found that the inhibitive effect of SO2 on PCDD/Fs formation is similar to that of SO3. To investigate the inhibition mechanism,CuSO4 formations from both CuO and CuCl2 were examined. The ability of SO3 to convert CuCl2 and CuO on a silica support into sulfate is much stronger than that of SO2. However,replacing silica by activated carbon leads to a much high conversion of CuCl2 to CuSO4 in the presence of SO2. The promotion by activated carbon is explained by the reduction of CuCl2 to Cu2Cl2 and the eventual conversion of Cu2Cl2 into CuSO4 is the main inhibition mechanism of SO2 on de novo synthesis of PCDD/Fs.