The rate determining step and the energy barrier involved in hydrogen adsorption on Pt/WO3- ZrO2 were studied based on the assumption that the hydrogen adsorption occurs only through Pt sites. The rate of hydrogen ads...The rate determining step and the energy barrier involved in hydrogen adsorption on Pt/WO3- ZrO2 were studied based on the assumption that the hydrogen adsorption occurs only through Pt sites. The rate of hydrogen adsorption on Pt/WOa-ZrO2 was measured in the adsorption temperature range of 323-573 K and an initial hydrogen pressure of 50 Torr. The rates of hydrogen uptake were very high for the initial few minutes and the adsorption continued for more than 5 h below 523 K. The hydrogen uptake far exceeded the H/Pt ratio of unity for all adsorption temperatures, indicating that the adsorption of hydrogen involved the dissociative adsorption of hydrogen on Pt sites to form hydrogen atoms, the spillover of hydrogen atoms onto the surface of the WO3-ZrO2 catalyst, the diffusion of spiltover hydrogen atom over the surface of the WO3-ZrO2 catalyst, and the formation of protonic acid site originated from hydrogen atom by releasing an electron in which the electron may react with a second hydrogen atom to form a hydride near the Lewis acid site. The rate determining step was the spillover with the activation energy of 12.3 kJ/mol. The rate of hydrogen adsorption cannot be expressed by the rate equation based on the assumption that the rate determining step is the surface diffusion. The activity of Pt/WO3-ZrO2 was examined on n-heptane isomerization in which the increase of hydrogen partial pressure provided positive-effect on the conversion of n-heptane and negative-effect on the selectivity towards iso-heptane.展开更多
The electrical conductivity of NaF-AlF3-CaF2-Al2O3-ZrO2 system was studied by a tube-type cell with fixed cell constant. The results show that the electrical conductivity of NaF-AlF3-3%Al2O3-3%CaF2-ZrO2 molten salt sy...The electrical conductivity of NaF-AlF3-CaF2-Al2O3-ZrO2 system was studied by a tube-type cell with fixed cell constant. The results show that the electrical conductivity of NaF-AlF3-3%Al2O3-3%CaF2-ZrO2 molten salt system decreases with increase of ZrO2 content in an interval of 0-5%. The increase of 1%ZrO2 results in a corresponding electrical conductivity decrease of 0.02 S/cm, and the equivalent conductivity increases with the increase of molar ratio of NaF to AlF3. When the temperature increases by 1 °C, the electrical conductivity increases by 0.004 S/cm. At last, the regression equations of electrical conductivity relative to temperature and ZrO2 are obtained by quadratic regression analysis.展开更多
摘要The rate determining step and the energy barrier involved in hydrogen adsorption on Pt/WO3- ZrO2 were studied based on the assumption that the hydrogen adsorption occurs only through Pt sites. The rate of hydrogen adsorption on Pt/WOa-ZrO2 was measured in the adsorption temperature range of 323-573 K and an initial hydrogen pressure of 50 Torr. The rates of hydrogen uptake were very high for the initial few minutes and the adsorption continued for more than 5 h below 523 K. The hydrogen uptake far exceeded the H/Pt ratio of unity for all adsorption temperatures, indicating that the adsorption of hydrogen involved the dissociative adsorption of hydrogen on Pt sites to form hydrogen atoms, the spillover of hydrogen atoms onto the surface of the WO3-ZrO2 catalyst, the diffusion of spiltover hydrogen atom over the surface of the WO3-ZrO2 catalyst, and the formation of protonic acid site originated from hydrogen atom by releasing an electron in which the electron may react with a second hydrogen atom to form a hydride near the Lewis acid site. The rate determining step was the spillover with the activation energy of 12.3 kJ/mol. The rate of hydrogen adsorption cannot be expressed by the rate equation based on the assumption that the rate determining step is the surface diffusion. The activity of Pt/WO3-ZrO2 was examined on n-heptane isomerization in which the increase of hydrogen partial pressure provided positive-effect on the conversion of n-heptane and negative-effect on the selectivity towards iso-heptane.
基金Project (2007CB210305) supported by the National Basic Research Program of ChinaProject (51074045) supported by the National Natural Science Foundation of China
摘要The electrical conductivity of NaF-AlF3-CaF2-Al2O3-ZrO2 system was studied by a tube-type cell with fixed cell constant. The results show that the electrical conductivity of NaF-AlF3-3%Al2O3-3%CaF2-ZrO2 molten salt system decreases with increase of ZrO2 content in an interval of 0-5%. The increase of 1%ZrO2 results in a corresponding electrical conductivity decrease of 0.02 S/cm, and the equivalent conductivity increases with the increase of molar ratio of NaF to AlF3. When the temperature increases by 1 °C, the electrical conductivity increases by 0.004 S/cm. At last, the regression equations of electrical conductivity relative to temperature and ZrO2 are obtained by quadratic regression analysis.