在有 stoichiometric 等价比率(=1 ) 的 2.667 kPa 的 premixed 乙烯 / 氧 / 氩火焰的全面试验性的研究与悦耳的同步加速器光电游离和分子横梁的采样团 spectrometry 技术被执行。在火焰的最观察的种类的异构体被光电游离效率系列的大...在有 stoichiometric 等价比率(=1 ) 的 2.667 kPa 的 premixed 乙烯 / 氧 / 氩火焰的全面试验性的研究与悦耳的同步加速器光电游离和分子横梁的采样团 spectrometry 技术被执行。在火焰的最观察的种类的异构体被光电游离效率系列的大小明白地识别,例如 C <SUB>3</SUB > H <SUB>4</SUB>, C <SUB>2</SUB > H <SUB>4</SUB > O 和 C <SUB>4</SUB > H <SUB>4</SUB> 。直到 C <SUB>7</SUB 的种类的鼹鼠部分侧面 > H <SUB>8</SUB> 被在电离阀值,和火焰温度侧面附近在选择光子精力扫描炉子位置测量被使用 Pt/Pt-13%Rh 热电偶获得。与以前的研究相比,很多新火焰种类: C <SUB>3</SUB > H <SUB>2</SUB>, C <SUB>3</SUB > H <SUB>3</SUB>, C <SUB>3</SUB > H <SUB>5</SUB>, C <SUB>2</SUB > H <SUB>6</SUB > O , C <SUB>4</SUB > H <SUB>2</SUB>, C <SUB>4</SUB > H <SUB>4</SUB>, C <SUB>4</SUB > H <SUB>6</SUB>, C <SUB>3</SUB > H <SUB>4</SUB > O , C <SUB>3</SUB > H <SUB>6</SUB > O , C <SUB>3</SUB > H <SUB>8</SUB > O , C <SUB>5</SUB > H <SUB>6</SUB>, C <SUB>4</SUB > H <SUB>8</SUB > O 和 C <SUB>7</SUB > H <SUB>8</SUB>,被观察。在火焰的一系列自由激进分子被检测是 CH <SUB>3</SUB>, C <SUB>2</SUB > H <SUB>3</SUB>, C <SUB>2</SUB > H <SUB>5</SUB>, HCO, C <SUB>3</SUB > H <SUB>3</SUB> 和 C <SUB>3</SUB > H <SUB>5</SUB> 。基于试验性的工作,减少的反应机制包括 40 种类和 223 反应被开发。建模并且大小为主要种类和大多数中介同意很好。一个详细运动模型为这火焰被需要。展开更多
The effective valuation of catalyst supports in the catalytic oxidation makes the contribution to understand the support effect of great interest.Here,the role of active substrate in the performance and stability of C...The effective valuation of catalyst supports in the catalytic oxidation makes the contribution to understand the support effect of great interest.Here,the role of active substrate in the performance and stability of CuFe-Co ternary oxides was studied towards the complete catalytic oxidation of CO.The Cu-Fe-Co oxide thin films were deposited on copper grid mesh(CUGM)using one-step pulsed-spray evaporation chemical vapor deposition method.Crystalline structure and morphology analyses revealed nano-crystallite sizes and do me-top-like morphology.Synergistic effects between Cu,Fe and Co,which affect the surface Cu^2+,Fe^3+,Co^3+and chemisorbed oxygen species(O2 and OH)of thin films over the active support and thus result in better reducibility.The thin film catalysts supported on CUGM exhibited attractive catalytic activity compared to the te rnary oxides supported on ine rt grid mesh at a high gas hourly space velocity.Moreove r,the stability in time-on-stream of the ternary oxides on CUGM was evaluated in the CO oxidation for 30 h.The ad opted deposition strategy ofternary oxides on CUGM presents an excessive amount of adsorbed active oxygen species that play an impo rtant role in the complete CO oxidation.The catalysts supported on CUGM showed better catalytic conve rsion than that on inert grid mesh and some literature-reported noble metal oxides as well as transition metal oxides counterparts,revealing the beneficial effect of the CUGM suppo rt in the improvement of the catalytic performance.展开更多
Efficient mixing and thermal control are important in the flow reactor for obtaining a high product yield and selectivity.Here,we report a heterogeneous chemical kinetic study of propene oxidation within a newly desig...Efficient mixing and thermal control are important in the flow reactor for obtaining a high product yield and selectivity.Here,we report a heterogeneous chemical kinetic study of propene oxidation within a newly designed catalytic jet-stirred reactor(CJSR).To better understand the interplay between the catalytic performances and properties,the CuO thin films have been characterized and the adsorbed energies of propene on the adsorbed and lattice oxygen were calculated using density functional theory(DFT)method.Structure and morphology analyses revealed a monoclinic structure with nano-crystallite size and porous microstructure,which is responsible for holding an important quantity of adsorbed oxygen.The residence time inside the flow CJSR(1.12–7.84 s)makes it suitable for kinetic study and gives guidance for scale-up.The kinetic study revealed that using CJSR the reaction rate increases with O_2concentration that is commonly not achievable for catalytic flow tube reactor,whereas the reaction rate tends to increase slightly above 30%of O_2due to the catalyst surface saturation.Moreover,DFT calculations demonstrated that adsorbed oxygen is the most involved oxygen,and it has found that the pathway of producing propene oxide makes the reaction of C_3H_6over CuO surface more likely to proceed.Accordingly,these findings revealed that CJSR combined with theoretical calculation is suitable for kinetic study,which can pave the way to investigate the kinetic study of other exhaust gases.展开更多
基金Ⅵ. ACKN0WLEDGMENTS This work was supported by the National Natural Science Foundation of China (No.20473081 and No.20533040), and Chinese Academy of Sciences. The authors are also thankful for the valuable help in the experimental work from Aigou Zhu. Fei Qi thanks the Combustion Research Facility of Sandia National Labs to provide a Chemkin program package for kinetic modeling study.
文摘在有 stoichiometric 等价比率(=1 ) 的 2.667 kPa 的 premixed 乙烯 / 氧 / 氩火焰的全面试验性的研究与悦耳的同步加速器光电游离和分子横梁的采样团 spectrometry 技术被执行。在火焰的最观察的种类的异构体被光电游离效率系列的大小明白地识别,例如 C <SUB>3</SUB > H <SUB>4</SUB>, C <SUB>2</SUB > H <SUB>4</SUB > O 和 C <SUB>4</SUB > H <SUB>4</SUB> 。直到 C <SUB>7</SUB 的种类的鼹鼠部分侧面 > H <SUB>8</SUB> 被在电离阀值,和火焰温度侧面附近在选择光子精力扫描炉子位置测量被使用 Pt/Pt-13%Rh 热电偶获得。与以前的研究相比,很多新火焰种类: C <SUB>3</SUB > H <SUB>2</SUB>, C <SUB>3</SUB > H <SUB>3</SUB>, C <SUB>3</SUB > H <SUB>5</SUB>, C <SUB>2</SUB > H <SUB>6</SUB > O , C <SUB>4</SUB > H <SUB>2</SUB>, C <SUB>4</SUB > H <SUB>4</SUB>, C <SUB>4</SUB > H <SUB>6</SUB>, C <SUB>3</SUB > H <SUB>4</SUB > O , C <SUB>3</SUB > H <SUB>6</SUB > O , C <SUB>3</SUB > H <SUB>8</SUB > O , C <SUB>5</SUB > H <SUB>6</SUB>, C <SUB>4</SUB > H <SUB>8</SUB > O 和 C <SUB>7</SUB > H <SUB>8</SUB>,被观察。在火焰的一系列自由激进分子被检测是 CH <SUB>3</SUB>, C <SUB>2</SUB > H <SUB>3</SUB>, C <SUB>2</SUB > H <SUB>5</SUB>, HCO, C <SUB>3</SUB > H <SUB>3</SUB> 和 C <SUB>3</SUB > H <SUB>5</SUB> 。基于试验性的工作,减少的反应机制包括 40 种类和 223 反应被开发。建模并且大小为主要种类和大多数中介同意很好。一个详细运动模型为这火焰被需要。
基金financial support from the MOST(No.2017YFA0402800)the Basic Science Center Program for Ordered Energy Conversion of the National Natural Science Foundation of China(No.51888103)。
文摘The effective valuation of catalyst supports in the catalytic oxidation makes the contribution to understand the support effect of great interest.Here,the role of active substrate in the performance and stability of CuFe-Co ternary oxides was studied towards the complete catalytic oxidation of CO.The Cu-Fe-Co oxide thin films were deposited on copper grid mesh(CUGM)using one-step pulsed-spray evaporation chemical vapor deposition method.Crystalline structure and morphology analyses revealed nano-crystallite sizes and do me-top-like morphology.Synergistic effects between Cu,Fe and Co,which affect the surface Cu^2+,Fe^3+,Co^3+and chemisorbed oxygen species(O2 and OH)of thin films over the active support and thus result in better reducibility.The thin film catalysts supported on CUGM exhibited attractive catalytic activity compared to the te rnary oxides supported on ine rt grid mesh at a high gas hourly space velocity.Moreove r,the stability in time-on-stream of the ternary oxides on CUGM was evaluated in the CO oxidation for 30 h.The ad opted deposition strategy ofternary oxides on CUGM presents an excessive amount of adsorbed active oxygen species that play an impo rtant role in the complete CO oxidation.The catalysts supported on CUGM showed better catalytic conve rsion than that on inert grid mesh and some literature-reported noble metal oxides as well as transition metal oxides counterparts,revealing the beneficial effect of the CUGM suppo rt in the improvement of the catalytic performance.
基金financial support from the Ministry of Science and Technology of China (2017YFA0402800)the National Natural Science Foundation of China (51476168 and 91541102)+1 种基金Recruitment Program of Global Youth Expertsthe support of Chinese Academy of Sciences for senior international scientists within the framework of PIFI program (2017PE0009)
文摘Efficient mixing and thermal control are important in the flow reactor for obtaining a high product yield and selectivity.Here,we report a heterogeneous chemical kinetic study of propene oxidation within a newly designed catalytic jet-stirred reactor(CJSR).To better understand the interplay between the catalytic performances and properties,the CuO thin films have been characterized and the adsorbed energies of propene on the adsorbed and lattice oxygen were calculated using density functional theory(DFT)method.Structure and morphology analyses revealed a monoclinic structure with nano-crystallite size and porous microstructure,which is responsible for holding an important quantity of adsorbed oxygen.The residence time inside the flow CJSR(1.12–7.84 s)makes it suitable for kinetic study and gives guidance for scale-up.The kinetic study revealed that using CJSR the reaction rate increases with O_2concentration that is commonly not achievable for catalytic flow tube reactor,whereas the reaction rate tends to increase slightly above 30%of O_2due to the catalyst surface saturation.Moreover,DFT calculations demonstrated that adsorbed oxygen is the most involved oxygen,and it has found that the pathway of producing propene oxide makes the reaction of C_3H_6over CuO surface more likely to proceed.Accordingly,these findings revealed that CJSR combined with theoretical calculation is suitable for kinetic study,which can pave the way to investigate the kinetic study of other exhaust gases.