High-temperature treatment is key to the preparation of zeolite catalysts.Herein,the effects of hightemperature treatment on the property and performance of HZSM-5 zeolites were studied in this work.X-Ray diffraction,...High-temperature treatment is key to the preparation of zeolite catalysts.Herein,the effects of hightemperature treatment on the property and performance of HZSM-5 zeolites were studied in this work.X-Ray diffraction,N2physisorption,27Al magic angle spinning nuclear magnetic resonance(MAS NMR),and temperature-programmed desorption of ammonia results indicated that the hightemperature treatment at 650℃ hardly affected the inherent crystal and texture of HZSM-5zeolites but facilitated the conversion of framework Al to extra-framework Al,reducing the acid site and enhancing the acid strength.Moreover,the high-temperature treatment improved the performance of HZSM-5 zeolites in n-heptane catalytic cracking,promoting the conversion and light olefins yield while inhibiting coke formation.Based on the kinetic and mechanism analysis,the improvement of HZSM-5 performance caused by high-temperature treatment has been attributed to the formation of extra-framework Al,which enhanced the acid strength,facilitated the bimolecular reaction,and promoted the entropy change to overcome a higher energy barrier in n-heptane catalytic cracking.展开更多
The conversion of CO_(2) into specific aromatics by modulating the morphology of zeolites is a promising strategy.HZSM-5 zeolite with hollow tubular morphology is reported.The morphology of zeolite was precisely contr...The conversion of CO_(2) into specific aromatics by modulating the morphology of zeolites is a promising strategy.HZSM-5 zeolite with hollow tubular morphology is reported.The morphology of zeolite was precisely controlled,and the acid sites on its outer surface were passivated by steam-assisted crystallization method,so that the zeolite exhibits higher aromatic selectivity than sheet HZSM-5 zeolite and greater p-xylene selectivity than chain HZSM-5 zeolite.The tandem catalyst was formed by combining hollow tubular HZSM-5 zeolites with ZnZrO_(x)metal oxides.The para-selectivity of p-xylene reached 76.2%at reaction temperature of 320℃,pressure of 3.0 MPa,and a flow rate of 2400 mL g^(-1)h^(-1)with an H_(2)/CO_(2) molar ratio of 3/1.Further research indicates that the high selectivity of p-xylene is due to the pore structure of hollow tubular HZSM-5 zeolite,which is conducive to the formation of p-xylene.Moreover,the passivation of the acid site located on the outer surface of zeolite effectively prevents the isomerization of p-xylene.The reaction mechanism of CO_(2) hydrogenation over the tandem catalyst was investigated using in-situ diffuse reflectance Fourier transform infrared spectroscopy and density functional theory.The results showed that the CO_(2) to p-xylene followed a methanol-mediated route over ZnZrO_(x)/hollow tubular HZSM-5 tandem catalysts.In addition,the catalyst showed no significant deactivation in the 100 h stability test.This present study provides an effective strategy for the design of catalysts aimed at selectively preparing aromatics through CO_(2)hydrogenation.展开更多
Nanocrystalline Gd3Ga5O12:Eu3+ with cubic phase was prepared by a urea homogeneous precipitation method. X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), Fourier transform infrared spectrosc...Nanocrystalline Gd3Ga5O12:Eu3+ with cubic phase was prepared by a urea homogeneous precipitation method. X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric and differential thermal analysis (TG-DTA) and photoluminescence spectra were used to characterize the samples. The effects of the initial solution pH value and urea content on the structure of the sample were studied. The XRD results show that pure phase Gd3Ga5O12 can be obtained at pH =6 and pH =8 of the initial solution. The average crystallite size can be calculated as in the range of 24~33 nm. The average crystallite size decreases with increasing molar ratio of urea to metal ion. The results of excitation spectra and emission spectra show that the emission peaks are ascribed to 5D0→7FJ transitions of Eu3+, and the magnetic dipole transition originated from 5D0 →7F1 of Eu3+ is the strongest; the broad excitation bands belong to change transfer band of Eu?O and the host absorption of Gd3Ga5O12. An efficient energy transfer occurs from Gd3+ to Eu3+.展开更多
The catalytic conversion of polystyrene (PS) was studied in the presence of the materials type HZSM-5, CeO<sub>2</sub>, 10% CeO<sub>2</sub>/HZSM-5 and 20% CeO<sub>2</sub>/HZSM-5, wh...The catalytic conversion of polystyrene (PS) was studied in the presence of the materials type HZSM-5, CeO<sub>2</sub>, 10% CeO<sub>2</sub>/HZSM-5 and 20% CeO<sub>2</sub>/HZSM-5, which were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and nitrogen adsorption at 77K. The catalytic tests were performed via thermogravimetric analysis (TG) at heating rates of 5, 10 and 20˚C min<sup>−1</sup> in a temperature range from 30˚C to 900˚C. For the tests, a ratio of 30% by mass of each catalytic material mixed with PS was used and the activation energy of the degradation process was determined by the Vyazovkin method. The obtained results showed that the addition of the catalyst to the PS in general reduced its degradation temperature. The 10% CeO<sub>2</sub>/HZSM-5 catalyst showed greater efficiency, as it resulted in lower activation energy for PS degradation. Thus, the combination of CeO<sub>2</sub> with HZSM-5 resulted in materials with potential for application in the catalytic degradation of polystyrene and the results indicate that the production of a composite material can be a good strategy to generate an increase in catalytic activity and a decrease in energy process activation.展开更多
There are two types of Pr3+ ion in the Pr3+ doped oxyfluoride glass containing LaF3 nanocrystal: the lowest 4f5d state of Pr3+ in LaF3 nanocrystal is located energetically higher than the 1S0 state, while in glass the...There are two types of Pr3+ ion in the Pr3+ doped oxyfluoride glass containing LaF3 nanocrystal: the lowest 4f5d state of Pr3+ in LaF3 nanocrystal is located energetically higher than the 1S0 state, while in glass the lowest 4f5d state is lower than the 1S0 state. We deduce the positions of the lowest 4f5d band of these two types of Pr3+ ion by vacuum ultraviolet (VUV) and ultraviolet (UV) excitation spectra. When the sample is excited by 181 nm, the narrow band emission of 4f2→4f2 of Pr3+ ion in the nanocrystal and the broad band emission of 4f5d→4f2 in the glass appear at the same time. However, the second step of the photon cascade emission(PCE) of Pr3+ in the LaF3 nanocrystal, corresponding to the emission of 3P0→3H4, can be observed at 20 K, but not at room temperature. The reason accounting for this phenomenon was discussed in detail.展开更多
A series of Er3＋, Tm3＋ and Yb3＋ doped Gd3Ga5O12 nanocrystals were prepared by a combustion method. The X-ray diffraction （XRD）, field emission scanning electron microscope （FESEM） and upconversion （UC） emissi...A series of Er3＋, Tm3＋ and Yb3＋ doped Gd3Ga5O12 nanocrystals were prepared by a combustion method. The X-ray diffraction （XRD）, field emission scanning electron microscope （FESEM） and upconversion （UC） emission spectra were used to characterize the samples. The results of XRD indicate that Gd3Ga5O12：Er3＋, Tm3＋, Yb3＋ nanocrystals with cubic phase can be obtained. Under the excitation of a 980 nm laser, the different rare earth ions doped Gd3Ga5O12 nanoerystals show upconversion luminescence involving the green emission attributed to the ^2H11/2→^4I15/2, 4^S3/2→^4I15/2 transitions of Er3＋ ions, respectively, the red emissions assigned to the ^4F9/2→^4I15/2 transitions of Er3＋ ions and the ^1G4→^3F4 as well as 3F2,3→^3H6 transitions of Tm3＋ ions, respectively, the blue emission attributed to ^1G4→^3H6 transitions of Tm3＋ ions, and the near-infrared assigned to the ^3H4→^3H6 transitions of Tm3＋ ions. The CIE coordinates for the samples are calculated. The dependence of their upconversion luminescence properties on Yb3＋ ion concentration is investieated.展开更多
基金the financial support from the National Natural Science Foundation of China(21908010)Jilin Provincial Department of Science and Technology(20220101089JC)the Education Department of Jilin Province(JJKH20220694KJ)。
文摘High-temperature treatment is key to the preparation of zeolite catalysts.Herein,the effects of hightemperature treatment on the property and performance of HZSM-5 zeolites were studied in this work.X-Ray diffraction,N2physisorption,27Al magic angle spinning nuclear magnetic resonance(MAS NMR),and temperature-programmed desorption of ammonia results indicated that the hightemperature treatment at 650℃ hardly affected the inherent crystal and texture of HZSM-5zeolites but facilitated the conversion of framework Al to extra-framework Al,reducing the acid site and enhancing the acid strength.Moreover,the high-temperature treatment improved the performance of HZSM-5 zeolites in n-heptane catalytic cracking,promoting the conversion and light olefins yield while inhibiting coke formation.Based on the kinetic and mechanism analysis,the improvement of HZSM-5 performance caused by high-temperature treatment has been attributed to the formation of extra-framework Al,which enhanced the acid strength,facilitated the bimolecular reaction,and promoted the entropy change to overcome a higher energy barrier in n-heptane catalytic cracking.
基金financially supported by the National Natural Science Foundation of China(22268039)the Natural Science Foundation for Distinguished Young Scholars of Gansu Province(23JRRA682)。
文摘The conversion of CO_(2) into specific aromatics by modulating the morphology of zeolites is a promising strategy.HZSM-5 zeolite with hollow tubular morphology is reported.The morphology of zeolite was precisely controlled,and the acid sites on its outer surface were passivated by steam-assisted crystallization method,so that the zeolite exhibits higher aromatic selectivity than sheet HZSM-5 zeolite and greater p-xylene selectivity than chain HZSM-5 zeolite.The tandem catalyst was formed by combining hollow tubular HZSM-5 zeolites with ZnZrO_(x)metal oxides.The para-selectivity of p-xylene reached 76.2%at reaction temperature of 320℃,pressure of 3.0 MPa,and a flow rate of 2400 mL g^(-1)h^(-1)with an H_(2)/CO_(2) molar ratio of 3/1.Further research indicates that the high selectivity of p-xylene is due to the pore structure of hollow tubular HZSM-5 zeolite,which is conducive to the formation of p-xylene.Moreover,the passivation of the acid site located on the outer surface of zeolite effectively prevents the isomerization of p-xylene.The reaction mechanism of CO_(2) hydrogenation over the tandem catalyst was investigated using in-situ diffuse reflectance Fourier transform infrared spectroscopy and density functional theory.The results showed that the CO_(2) to p-xylene followed a methanol-mediated route over ZnZrO_(x)/hollow tubular HZSM-5 tandem catalysts.In addition,the catalyst showed no significant deactivation in the 100 h stability test.This present study provides an effective strategy for the design of catalysts aimed at selectively preparing aromatics through CO_(2)hydrogenation.
基金financially supported by the Science and Technology Research Project of Department of Education of Liaoning Province,China(No.L2011063)
文摘Nanocrystalline Gd3Ga5O12:Eu3+ with cubic phase was prepared by a urea homogeneous precipitation method. X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric and differential thermal analysis (TG-DTA) and photoluminescence spectra were used to characterize the samples. The effects of the initial solution pH value and urea content on the structure of the sample were studied. The XRD results show that pure phase Gd3Ga5O12 can be obtained at pH =6 and pH =8 of the initial solution. The average crystallite size can be calculated as in the range of 24~33 nm. The average crystallite size decreases with increasing molar ratio of urea to metal ion. The results of excitation spectra and emission spectra show that the emission peaks are ascribed to 5D0→7FJ transitions of Eu3+, and the magnetic dipole transition originated from 5D0 →7F1 of Eu3+ is the strongest; the broad excitation bands belong to change transfer band of Eu?O and the host absorption of Gd3Ga5O12. An efficient energy transfer occurs from Gd3+ to Eu3+.
文摘The catalytic conversion of polystyrene (PS) was studied in the presence of the materials type HZSM-5, CeO<sub>2</sub>, 10% CeO<sub>2</sub>/HZSM-5 and 20% CeO<sub>2</sub>/HZSM-5, which were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and nitrogen adsorption at 77K. The catalytic tests were performed via thermogravimetric analysis (TG) at heating rates of 5, 10 and 20˚C min<sup>−1</sup> in a temperature range from 30˚C to 900˚C. For the tests, a ratio of 30% by mass of each catalytic material mixed with PS was used and the activation energy of the degradation process was determined by the Vyazovkin method. The obtained results showed that the addition of the catalyst to the PS in general reduced its degradation temperature. The 10% CeO<sub>2</sub>/HZSM-5 catalyst showed greater efficiency, as it resulted in lower activation energy for PS degradation. Thus, the combination of CeO<sub>2</sub> with HZSM-5 resulted in materials with potential for application in the catalytic degradation of polystyrene and the results indicate that the production of a composite material can be a good strategy to generate an increase in catalytic activity and a decrease in energy process activation.
文摘There are two types of Pr3+ ion in the Pr3+ doped oxyfluoride glass containing LaF3 nanocrystal: the lowest 4f5d state of Pr3+ in LaF3 nanocrystal is located energetically higher than the 1S0 state, while in glass the lowest 4f5d state is lower than the 1S0 state. We deduce the positions of the lowest 4f5d band of these two types of Pr3+ ion by vacuum ultraviolet (VUV) and ultraviolet (UV) excitation spectra. When the sample is excited by 181 nm, the narrow band emission of 4f2→4f2 of Pr3+ ion in the nanocrystal and the broad band emission of 4f5d→4f2 in the glass appear at the same time. However, the second step of the photon cascade emission(PCE) of Pr3+ in the LaF3 nanocrystal, corresponding to the emission of 3P0→3H4, can be observed at 20 K, but not at room temperature. The reason accounting for this phenomenon was discussed in detail.
基金Funded by the Science and Technology Research Project of Department of Education of Liaoning Province,China(No.L2011063)
文摘A series of Er3＋, Tm3＋ and Yb3＋ doped Gd3Ga5O12 nanocrystals were prepared by a combustion method. The X-ray diffraction （XRD）, field emission scanning electron microscope （FESEM） and upconversion （UC） emission spectra were used to characterize the samples. The results of XRD indicate that Gd3Ga5O12：Er3＋, Tm3＋, Yb3＋ nanocrystals with cubic phase can be obtained. Under the excitation of a 980 nm laser, the different rare earth ions doped Gd3Ga5O12 nanoerystals show upconversion luminescence involving the green emission attributed to the ^2H11/2→^4I15/2, 4^S3/2→^4I15/2 transitions of Er3＋ ions, respectively, the red emissions assigned to the ^4F9/2→^4I15/2 transitions of Er3＋ ions and the ^1G4→^3F4 as well as 3F2,3→^3H6 transitions of Tm3＋ ions, respectively, the blue emission attributed to ^1G4→^3H6 transitions of Tm3＋ ions, and the near-infrared assigned to the ^3H4→^3H6 transitions of Tm3＋ ions. The CIE coordinates for the samples are calculated. The dependence of their upconversion luminescence properties on Yb3＋ ion concentration is investieated.
