Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-...Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.展开更多
A new scheme for the preparation of highly dispersed precious metal catalysts is proposed in this work. Samples of LaCol-xPtxO3/SiO2 (x = 0.03, 0.05, 0.07, 0.09, and 0.10) were prepared through a simple method of ci...A new scheme for the preparation of highly dispersed precious metal catalysts is proposed in this work. Samples of LaCol-xPtxO3/SiO2 (x = 0.03, 0.05, 0.07, 0.09, and 0.10) were prepared through a simple method of citrate acid complexa-tion combined with impregnation. In a nanocrystallite of LaCOl-xPtxO3, ions of lanthanum, cobalt, and platinum are evenly mixed at the atomic level and confined within the nanocrystallite. In the reduction process, platinum ions were reduced and migrated onto the surface of the nanocrystallite, and the platinum should be highly dispersed owing to the even mixing of the platinum ions in the precursor. When x = 0.05 or lower, the highest dispersion of Pt could be achieved. The highly dispersed Pt is stable, because of the strong interaction between Pt atoms and the support. The catalysts were characterized by BET surface area, temperature-programmed reduction, X-ray diffraction, transmission electron microscopy, CO temperature-programmed desorption, and turnover frequency. Compared with general precious metal Pt catalysts, the LaCo0.95Pt0.05O3/ SiO2 catalyst exhibited better activity for CO oxidation, and it maintained stability at a high temperature of 400 ℃ for 250 h with complete CO conversion.展开更多
In this work, the nature, location and evolution of Cu+ ions in Cu-SAPO-34 are investigated by diffuse reflectance infrared Fourier transform spectrum(DRIFTS) of CO adsorption and density functional theory(DFT) calcul...In this work, the nature, location and evolution of Cu+ ions in Cu-SAPO-34 are investigated by diffuse reflectance infrared Fourier transform spectrum(DRIFTS) of CO adsorption and density functional theory(DFT) calculation. By combination with DFT results, characteristic Cu+–CO bands located at 2154 and 2136 cm.1 are attributed to CO adsorbed on Cu+ ions located at sites I(in the plane of six-membered ring connected to the large cages) and site II(in the eight-membered ring cages near the tilted four membered ring) in the framework of H-SAPO-34 zeolite. Subsequently, both the influences of Cu loading and preparation method are considered and discussed. By varying the Cu loading, the site-occupation preference of Cu+ ions on site I is confirmed,especially at low Cu loadings. Through elevating the desorption temperature, migration of Cu+ ions is revealed because of the adsorption-induced effect. Furthermore, a facile and more efficient approach to introduce Cu+ ions into CHA zeolite, compared with solid-state ion exchange with CuCl and conventional ion exchange in aqueous solution, and the different preparation methods also result in different occupations of Cu+ ions.展开更多
基金supported by the National Natural Science Foundation of China(21403070 and 21373088)Innovation Program of Shanghai Municipal Education Commission(13zz038)+2 种基金Key Project of the Shanghai Committee of Science and Technology(12JC1403600)National Key Technology R&D Program(2012BAE05B02)Shanghai Leading Academic Discipline Project(B409)~~
文摘Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.
基金supported by the National Natural Science Foundation of China(Nos.21576192,21776214)
文摘A new scheme for the preparation of highly dispersed precious metal catalysts is proposed in this work. Samples of LaCol-xPtxO3/SiO2 (x = 0.03, 0.05, 0.07, 0.09, and 0.10) were prepared through a simple method of citrate acid complexa-tion combined with impregnation. In a nanocrystallite of LaCOl-xPtxO3, ions of lanthanum, cobalt, and platinum are evenly mixed at the atomic level and confined within the nanocrystallite. In the reduction process, platinum ions were reduced and migrated onto the surface of the nanocrystallite, and the platinum should be highly dispersed owing to the even mixing of the platinum ions in the precursor. When x = 0.05 or lower, the highest dispersion of Pt could be achieved. The highly dispersed Pt is stable, because of the strong interaction between Pt atoms and the support. The catalysts were characterized by BET surface area, temperature-programmed reduction, X-ray diffraction, transmission electron microscopy, CO temperature-programmed desorption, and turnover frequency. Compared with general precious metal Pt catalysts, the LaCo0.95Pt0.05O3/ SiO2 catalyst exhibited better activity for CO oxidation, and it maintained stability at a high temperature of 400 ℃ for 250 h with complete CO conversion.
基金supported by the National Natural Science Foundation of China(21325626,21406120)
文摘In this work, the nature, location and evolution of Cu+ ions in Cu-SAPO-34 are investigated by diffuse reflectance infrared Fourier transform spectrum(DRIFTS) of CO adsorption and density functional theory(DFT) calculation. By combination with DFT results, characteristic Cu+–CO bands located at 2154 and 2136 cm.1 are attributed to CO adsorbed on Cu+ ions located at sites I(in the plane of six-membered ring connected to the large cages) and site II(in the eight-membered ring cages near the tilted four membered ring) in the framework of H-SAPO-34 zeolite. Subsequently, both the influences of Cu loading and preparation method are considered and discussed. By varying the Cu loading, the site-occupation preference of Cu+ ions on site I is confirmed,especially at low Cu loadings. Through elevating the desorption temperature, migration of Cu+ ions is revealed because of the adsorption-induced effect. Furthermore, a facile and more efficient approach to introduce Cu+ ions into CHA zeolite, compared with solid-state ion exchange with CuCl and conventional ion exchange in aqueous solution, and the different preparation methods also result in different occupations of Cu+ ions.