The reduction behavior of CuO supported on ZrO2 and Al2O3 has been investigated by temperature-programmed reduction (TPR) and TG techniques. The oaldation activity of CO on the catalysts has also been studied. It has ...The reduction behavior of CuO supported on ZrO2 and Al2O3 has been investigated by temperature-programmed reduction (TPR) and TG techniques. The oaldation activity of CO on the catalysts has also been studied. It has been found that there is obvious difference between TPR profiles of ZrO2 supported CuO and Al2O3 supported catalysts, the monolayer CuO on ZrO2 is easily reduced, and which leads to a dramatic increase in oxidation activity.展开更多
Seven transition metal molybdovanadoarsenic heteropoly compounds have been synthesized and characterize d using IR,UV,TG-DTA,pH potential ti tration techniques￡(r)The molecular f ormulae of these compounds are pro-po...Seven transition metal molybdovanadoarsenic heteropoly compounds have been synthesized and characterize d using IR,UV,TG-DTA,pH potential ti tration techniques￡(r)The molecular f ormulae of these compounds are pro-posed to be HxMyAsMO10V2O40·zH2 O￡¨x￡1/21?￡3￡?y￡1/2￡±￡?￡2￡?M￡1/2Cr￡?Mn￡?Fe￡?Co￡?Ni￡?Cu￡?Zn￡(c)￡(r)They are all keggin structure￡(r)Surface nature of these compounds have been investigated by temperature programmed desorption and temperature programmed reducti on techniques￡(r)NH 3 -TPD results show that in TPD profile s of the compounds there are two desorption peaks corre sponding to weak acid sites of desorp tion,respectively￡(r)Desorbing activativon energy and preexponential factor of weak acid site of desorption for comp ounds have been calculated￡(r)H2 -TPR re-sults show that introducting transtion metal to molybdovanarsenic acid,the reduction peak temperatures of H2 -TPR shift regularly with increasing d electron numbers of transition metals￡(r)In addition,Zn and Cu heteropoly com-pounds have yet apparent effect of hydrogen spill over￡(r)展开更多
A series of sulfided tertiary NiMoP/ γ Al 2O 3 catalysts with different contents of MoO 3 were prepared by using molybdophosphoric acid of Keggin structure(H 3PMo 12 O 40 ) and nickel nitrate as origins of active pha...A series of sulfided tertiary NiMoP/ γ Al 2O 3 catalysts with different contents of MoO 3 were prepared by using molybdophosphoric acid of Keggin structure(H 3PMo 12 O 40 ) and nickel nitrate as origins of active phase components of molybdenum, phosphorus and nickel, and characterized by TPR technique, with their HDS activity being investigated with thiophene as a model substrate. For the sulfided Mo 0 catalyst containing no nickel as promoter, the only hydrogen sulfide evolution peak Ⅰ is observed at 462 K and attributed to the hydrogenation of the so called edge sulfur atoms chemisorbed on coordinatively unsaturated(cus) Mo x+ sites on the MoS 2 phase(MoS 2 slab). With the introduction of nickel into the active phase of the sulfided Mo 0 catalyst and with the increase of the molybdenum loading, a new hydrogen sulfide evolution peak Ⅱ gradually develops at the low temperature side of the peak Ⅰ, at the same time accompanied by both the increase of the area ratio of the peak Ⅱ to the peak Ⅰ and the shift of the hydrogen sulfide evolution maximum rate to lower temperatures, which may imply the existence of two kinds of active centers related to molybdenum and nickel respectively and the synergic action between the two centers above. It should be noted that for the sulfided NiMoP/ γ Al 2O 3 catalysts, the thiophene HDS rate and the quantity of hydrogen sulfide evolved during TPR process increase monotonously with the atomic ratio of molybdenum to nickel in the form of [ n (Ni)+ n (Mo)]/ n (Ni). On the basis of the results here, the conclusion may be reached that the two kinds of vacancies can be formed on the edge of Ni Mo S slab due to the loss of S during TPR process and vacancies or sites related to the H 2S evolution peak II should be regarded as the mainly active reaction centers of thiophene HDS.展开更多
文摘The reduction behavior of CuO supported on ZrO2 and Al2O3 has been investigated by temperature-programmed reduction (TPR) and TG techniques. The oaldation activity of CO on the catalysts has also been studied. It has been found that there is obvious difference between TPR profiles of ZrO2 supported CuO and Al2O3 supported catalysts, the monolayer CuO on ZrO2 is easily reduced, and which leads to a dramatic increase in oxidation activity.
文摘Seven transition metal molybdovanadoarsenic heteropoly compounds have been synthesized and characterize d using IR,UV,TG-DTA,pH potential ti tration techniques￡(r)The molecular f ormulae of these compounds are pro-posed to be HxMyAsMO10V2O40·zH2 O￡¨x￡1/21?￡3￡?y￡1/2￡±￡?￡2￡?M￡1/2Cr￡?Mn￡?Fe￡?Co￡?Ni￡?Cu￡?Zn￡(c)￡(r)They are all keggin structure￡(r)Surface nature of these compounds have been investigated by temperature programmed desorption and temperature programmed reducti on techniques￡(r)NH 3 -TPD results show that in TPD profile s of the compounds there are two desorption peaks corre sponding to weak acid sites of desorp tion,respectively￡(r)Desorbing activativon energy and preexponential factor of weak acid site of desorption for comp ounds have been calculated￡(r)H2 -TPR re-sults show that introducting transtion metal to molybdovanarsenic acid,the reduction peak temperatures of H2 -TPR shift regularly with increasing d electron numbers of transition metals￡(r)In addition,Zn and Cu heteropoly com-pounds have yet apparent effect of hydrogen spill over￡(r)
文摘A series of sulfided tertiary NiMoP/ γ Al 2O 3 catalysts with different contents of MoO 3 were prepared by using molybdophosphoric acid of Keggin structure(H 3PMo 12 O 40 ) and nickel nitrate as origins of active phase components of molybdenum, phosphorus and nickel, and characterized by TPR technique, with their HDS activity being investigated with thiophene as a model substrate. For the sulfided Mo 0 catalyst containing no nickel as promoter, the only hydrogen sulfide evolution peak Ⅰ is observed at 462 K and attributed to the hydrogenation of the so called edge sulfur atoms chemisorbed on coordinatively unsaturated(cus) Mo x+ sites on the MoS 2 phase(MoS 2 slab). With the introduction of nickel into the active phase of the sulfided Mo 0 catalyst and with the increase of the molybdenum loading, a new hydrogen sulfide evolution peak Ⅱ gradually develops at the low temperature side of the peak Ⅰ, at the same time accompanied by both the increase of the area ratio of the peak Ⅱ to the peak Ⅰ and the shift of the hydrogen sulfide evolution maximum rate to lower temperatures, which may imply the existence of two kinds of active centers related to molybdenum and nickel respectively and the synergic action between the two centers above. It should be noted that for the sulfided NiMoP/ γ Al 2O 3 catalysts, the thiophene HDS rate and the quantity of hydrogen sulfide evolved during TPR process increase monotonously with the atomic ratio of molybdenum to nickel in the form of [ n (Ni)+ n (Mo)]/ n (Ni). On the basis of the results here, the conclusion may be reached that the two kinds of vacancies can be formed on the edge of Ni Mo S slab due to the loss of S during TPR process and vacancies or sites related to the H 2S evolution peak II should be regarded as the mainly active reaction centers of thiophene HDS.
