用浸渍法制得0.2%铁元素改性的SiO2为载体负载5%Pd催化剂,用于3-硝基三氟甲苯常压催化加氢合成3-三氟甲基苯胺,用沸点、元素分析、IR和1 H NMR对它的结构表征为目标产物;确定优化工艺条件为:0.1mol硝基物,0.26g催化剂,80mL无水乙醇作溶...用浸渍法制得0.2%铁元素改性的SiO2为载体负载5%Pd催化剂,用于3-硝基三氟甲苯常压催化加氢合成3-三氟甲基苯胺,用沸点、元素分析、IR和1 H NMR对它的结构表征为目标产物;确定优化工艺条件为:0.1mol硝基物,0.26g催化剂,80mL无水乙醇作溶剂,反应温度为50℃,0.1MPa下加氢反应3h,收率为97.8%,产物的纯度达98.2%。展开更多
The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffrac...The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), temperature-programmed desorption of hydrogen (H2-TPD) and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.展开更多
To investigate how the physicochemical properties and NH3‐selective catalytic reduction(NH3‐SCR)performance of supported ceria‐based catalysts are influenced as a function of support type,a series of CeO2/SiO2,CeO2...To investigate how the physicochemical properties and NH3‐selective catalytic reduction(NH3‐SCR)performance of supported ceria‐based catalysts are influenced as a function of support type,a series of CeO2/SiO2,CeO2/γ‐Al2O3,CeO2/ZrO2,and CeO2/TiO2catalysts were prepared.The physicochemical properties were probed by means of X‐ray diffraction,Raman spectroscopy,Brunauer‐Emmett‐Teller surface area measurements,X‐ray photoelectron spectroscopy,H2‐temperature programmed reduction,and NH3‐temperature programmed desorption.Furthermore,the supported ceria‐based catalysts'catalytic performance and H2O+SO2tolerance were evaluated by the NH3‐SCR model reaction.The results indicate that out of the supported ceria‐based catalysts studied,the CeO2/γ‐Al2O3catalyst exhibits the highest catalytic activity as a result of having a high relative Ce3+/Ce4+ratio,optimum reduction behavior,and the largest total acid site concentration.Finally,the CeO2/γ‐Al2O3catalyst also presents excellent H2O+SO2tolerance during the NH3‐SCR process.展开更多
Carbon black is utilized as a conventional electrocatalyst support material for proton exchange membrane fuel cells. However, this support is prone to corrosion under oxidative and harsh environments, thus limiting th...Carbon black is utilized as a conventional electrocatalyst support material for proton exchange membrane fuel cells. However, this support is prone to corrosion under oxidative and harsh environments, thus limiting the durability of the fuel cells. Meanwhile, carbon corrosion would also weaken the linkage between Pt and the support material, which causes Pt agglomeration, and consequently, deterioration of the cell performance. To overcome the drawbacks of a Pt/C electrocatalyst, a hybrid support material comprising molybdenum disulfide and reduced graphene oxide is proposed and synthesized in this study to exploit the graphitic nature of graphene and the availability of the exposed edges of MoS2. TEM results show the uniform dispersion of Pt nanoparticles over the MoS2-rGO surface. Electrochemical measurements indicate higher ECSA retention and better ORR activity after 10000 potential cycles for Pt/MoS2-rGO as compared to Pt/C, demonstrating the improved durability for this hybrid support material.展开更多
Ordered mesoporous Mn2O3 (meso‐Mn2O3) and meso‐Mn2O3‐supported Pd, Pt, and Pd‐Pt alloy x(PdyPt)/meso‐Mn2O3; x = (0.10?1.50) wt%; Pd/Pt molar ratio (y) = 4.9?5.1 nanocatalysts were prepared using KIT‐6‐templated...Ordered mesoporous Mn2O3 (meso‐Mn2O3) and meso‐Mn2O3‐supported Pd, Pt, and Pd‐Pt alloy x(PdyPt)/meso‐Mn2O3; x = (0.10?1.50) wt%; Pd/Pt molar ratio (y) = 4.9?5.1 nanocatalysts were prepared using KIT‐6‐templated and poly(vinyl alcohol)‐protected reduction methods, respectively.The meso‐Mn2O3 had a high surface area, i.e., 106 m2/g, and a cubic crystal structure. Noble‐metalnanoparticles (NPs) of size 2.1?2.8 nm were uniformly dispersed on the meso‐Mn2O3 surfaces. AlloyingPd with Pt enhanced the catalytic activity in methane combustion; 1.41(Pd5.1Pt)/meso‐Mn2O3gave the best performance; T10%, T50%, and T90% (the temperatures required for achieving methaneconversions of 10%, 50%, and 90%) were 265, 345, and 425 °C, respectively, at a space velocity of20000 mL/(g?h). The effects of SO2, CO2, H2O, and NO on methane combustion over1.41(Pd5.1Pt)/meso‐Mn2O3 were also examined. We conclude that the good catalytic performance of1.41(Pd5.1Pt)/meso‐Mn2O3 is associated with its high‐quality porous structure, high adsorbed oxygen species concentration, good low‐temperature reducibility, and strong interactions between Pd‐Pt alloy NPs and the meso‐Mn2O3 support.展开更多
The effect of a wide variety of metal oxide (MOx) supports has been discussed for CO oxidation on nanoparticulate gold catalysts. By using typical co‐precipitation and deposition–precipitation methods and under id...The effect of a wide variety of metal oxide (MOx) supports has been discussed for CO oxidation on nanoparticulate gold catalysts. By using typical co‐precipitation and deposition–precipitation methods and under identical calcination conditions, supported gold catalysts were prepared on a wide variety of MOx supports, and the temperature for 50%conversion was measured to qualita‐tively evaluate the catalytic activities of these simple MOx and supported Au catalysts. Furthermore, the difference in these temperatures for the simple MOx compared to the supported Au catalysts is plotted against the metal–oxygen binding energies of the support MOx. A clear volcano‐like correla‐tion between the temperature difference and the metal–oxygen binding energies is observed. This correlation suggests that the use of MOx with appropriate metal–oxygen binding energies (300–500 kJ/atom O) greatly improves the catalytic activity of MOx by the deposition of Au NPs.展开更多
文摘用浸渍法制得0.2%铁元素改性的SiO2为载体负载5%Pd催化剂,用于3-硝基三氟甲苯常压催化加氢合成3-三氟甲基苯胺,用沸点、元素分析、IR和1 H NMR对它的结构表征为目标产物;确定优化工艺条件为:0.1mol硝基物,0.26g催化剂,80mL无水乙醇作溶剂,反应温度为50℃,0.1MPa下加氢反应3h,收率为97.8%,产物的纯度达98.2%。
文摘The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), temperature-programmed desorption of hydrogen (H2-TPD) and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.
基金supported by the National Natural Science Foundation of China (21507130)the Chongqing Science and Technology Commission (cstc2016jcyjA 0070,cstc2014pt-gc20002,cstc2014yykfC 20003,cstckjcxljrc13)the Open Project Program of Chongqing Key Laboratory of Ca-talysis and Functional Organic Molecules from Chongqing Technology and Business University (1456029)~~
文摘To investigate how the physicochemical properties and NH3‐selective catalytic reduction(NH3‐SCR)performance of supported ceria‐based catalysts are influenced as a function of support type,a series of CeO2/SiO2,CeO2/γ‐Al2O3,CeO2/ZrO2,and CeO2/TiO2catalysts were prepared.The physicochemical properties were probed by means of X‐ray diffraction,Raman spectroscopy,Brunauer‐Emmett‐Teller surface area measurements,X‐ray photoelectron spectroscopy,H2‐temperature programmed reduction,and NH3‐temperature programmed desorption.Furthermore,the supported ceria‐based catalysts'catalytic performance and H2O+SO2tolerance were evaluated by the NH3‐SCR model reaction.The results indicate that out of the supported ceria‐based catalysts studied,the CeO2/γ‐Al2O3catalyst exhibits the highest catalytic activity as a result of having a high relative Ce3+/Ce4+ratio,optimum reduction behavior,and the largest total acid site concentration.Finally,the CeO2/γ‐Al2O3catalyst also presents excellent H2O+SO2tolerance during the NH3‐SCR process.
基金financially aided by the National Key R&D Program of China(2016YFB0101201)the National Natural Science Foundation of China(21706158,21533005)~~
文摘Carbon black is utilized as a conventional electrocatalyst support material for proton exchange membrane fuel cells. However, this support is prone to corrosion under oxidative and harsh environments, thus limiting the durability of the fuel cells. Meanwhile, carbon corrosion would also weaken the linkage between Pt and the support material, which causes Pt agglomeration, and consequently, deterioration of the cell performance. To overcome the drawbacks of a Pt/C electrocatalyst, a hybrid support material comprising molybdenum disulfide and reduced graphene oxide is proposed and synthesized in this study to exploit the graphitic nature of graphene and the availability of the exposed edges of MoS2. TEM results show the uniform dispersion of Pt nanoparticles over the MoS2-rGO surface. Electrochemical measurements indicate higher ECSA retention and better ORR activity after 10000 potential cycles for Pt/MoS2-rGO as compared to Pt/C, demonstrating the improved durability for this hybrid support material.
基金supported by the Ph.D.Program Foundation of Ministry of Education of China(20131103110002)the NNSF of China(21377008)+2 种基金National High Technology Research and Development Program(863 Program,2015AA034603)Foundation on the Creative Research Team Con-struction Promotion Project of Beijing Municipal InstitutionsScientific Research Base Construction-Science and Technology Creation Plat-form-National Materials Research Base Construction~~
文摘Ordered mesoporous Mn2O3 (meso‐Mn2O3) and meso‐Mn2O3‐supported Pd, Pt, and Pd‐Pt alloy x(PdyPt)/meso‐Mn2O3; x = (0.10?1.50) wt%; Pd/Pt molar ratio (y) = 4.9?5.1 nanocatalysts were prepared using KIT‐6‐templated and poly(vinyl alcohol)‐protected reduction methods, respectively.The meso‐Mn2O3 had a high surface area, i.e., 106 m2/g, and a cubic crystal structure. Noble‐metalnanoparticles (NPs) of size 2.1?2.8 nm were uniformly dispersed on the meso‐Mn2O3 surfaces. AlloyingPd with Pt enhanced the catalytic activity in methane combustion; 1.41(Pd5.1Pt)/meso‐Mn2O3gave the best performance; T10%, T50%, and T90% (the temperatures required for achieving methaneconversions of 10%, 50%, and 90%) were 265, 345, and 425 °C, respectively, at a space velocity of20000 mL/(g?h). The effects of SO2, CO2, H2O, and NO on methane combustion over1.41(Pd5.1Pt)/meso‐Mn2O3 were also examined. We conclude that the good catalytic performance of1.41(Pd5.1Pt)/meso‐Mn2O3 is associated with its high‐quality porous structure, high adsorbed oxygen species concentration, good low‐temperature reducibility, and strong interactions between Pd‐Pt alloy NPs and the meso‐Mn2O3 support.
文摘The effect of a wide variety of metal oxide (MOx) supports has been discussed for CO oxidation on nanoparticulate gold catalysts. By using typical co‐precipitation and deposition–precipitation methods and under identical calcination conditions, supported gold catalysts were prepared on a wide variety of MOx supports, and the temperature for 50%conversion was measured to qualita‐tively evaluate the catalytic activities of these simple MOx and supported Au catalysts. Furthermore, the difference in these temperatures for the simple MOx compared to the supported Au catalysts is plotted against the metal–oxygen binding energies of the support MOx. A clear volcano‐like correla‐tion between the temperature difference and the metal–oxygen binding energies is observed. This correlation suggests that the use of MOx with appropriate metal–oxygen binding energies (300–500 kJ/atom O) greatly improves the catalytic activity of MOx by the deposition of Au NPs.