The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glyco...The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers（CNF）,Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles（~12 nm） supported on α-Al2O3 were found to outgrow Ni particles with initially larger size（~20 nm）. It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.展开更多
Effects of nano-particle size on hydrocarbon production rates and distributions for precipitated Fe/Cu/La catalysts in Fischer-Tropsch synthesis were investigated.Nano-structured iron catalyst was prepared by micro-em...Effects of nano-particle size on hydrocarbon production rates and distributions for precipitated Fe/Cu/La catalysts in Fischer-Tropsch synthesis were investigated.Nano-structured iron catalyst was prepared by micro-emulsion method.The concept of two superimposed AndersonSchulz-Flory （ASF） distributions has been applied for the representation of the effects of reaction conditions and nano-particles size on kinetics parameters and product distributions.These results reveal that by reducing the particle size of catalyst,the break in ASF distributions was decreased.Also useful different kinetics equations for synthesis of C3 to C9 and C10 to C22 were determined by using α1 and α2 chain growth probabilities.展开更多
Mesoporous silica supported Cs2.5H0.5PW12O40 catalysts were prepared by impregnation method, and several silica supports with different pore size were utilized. N2 adsorption, XRD and ICP-AES techniques were utilized ...Mesoporous silica supported Cs2.5H0.5PW12O40 catalysts were prepared by impregnation method, and several silica supports with different pore size were utilized. N2 adsorption, XRD and ICP-AES techniques were utilized to characterize the silica supports and catalysts. XRD results showed that the dispersion of Cs2.5H0.5PW12 was better for the silica support with larger pore size. The catalytic activity results showed that the pore size played important role on the catalyst activity and the molecular weight of PTHF. When Cs2.5H0.5PW12O40 was dispersed on larger pore size silica support, the catalysts showed good performances for the synthesis of PTHE The molecular weight of PTHF product on the sample in which Cs2.5H0.5PW12O40 was dispersed on larger pore support was higher than that on the catalyst with smaller pore support. The leaching amounts of the active components for the supported Cs2.5H0.5PW12O40 catalysts were much lower. After five reaction cycles, there were still good activities and stabilities for the supported Cs2.5H0.5PW12O40 catalysts with larger pore silica supports. These results were much better than those of the supported heteropolyacid H3PW12O40 catalyst.展开更多
A series of nano-size gold catalysts were prepared by deposition-precipitation method using silica material promoted with different amounts of MgO as the carrier. The influences of MgO addition on the structure and pr...A series of nano-size gold catalysts were prepared by deposition-precipitation method using silica material promoted with different amounts of MgO as the carrier. The influences of MgO addition on the structure and property of the nano-size gold catalysts were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, O2 temperature-programmed desorption （O2-TPD）, and inductively coupled with plasma atomic emission spectroscopy （ICP-AES） techniques. The total oxidation of CO was chosen as the probe reaction. The results suggest that for the gold catalysts supported on the silica material after MgO modification, the size of the gold particles is pronouncedly reduced, the oxygen mobility is enhanced, and the catalytic activity for low-temperature CO oxidation is greatly improved. The gold catalyst modified by 6 wt% MgO （Mg/SiO2 weight ratio） shows higher CO oxidation activity, over which the temperature of CO total oxidation is lower about 150 K than that over the silica directly supported gold catalyst.展开更多
Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH_4/CO_2 reforming.To explore the reason of this phenomenon,Ni4,Ni8,and Ni12 which re flect the different cluster thicknesses su...Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH_4/CO_2 reforming.To explore the reason of this phenomenon,Ni4,Ni8,and Ni12 which re flect the different cluster thicknesses supported on the MgO(100) slabs,have been employed to simulate Ni/MgO catalysts,and the reaction pathways of CH_4/CO_2 reforming on Nix/MgO(100) models are investigated by density functional theory.The reforming mechanisms of CH_4/CO_2 on different Nix/MgO(100) indicate the energy barriers of CH_4 dissociated adsorption,CH dissociation,and C oxidation three factors are all declining with the decrease of the Ni cluster sizes.The Hirshfeld charges analyses of three steps as described above show only Ni atoms in bottom two layers can obtain electrons from the MgO supporters,and the main electron transfer occurs between adsorbed species and their directly contacted Ni atoms.Due to more electron-rich Ni atoms in contact with the MgO supporters,the Ni/MgO catalysts with small Ni particles have a strong metal particle size effect and lead to its better catalytic activity.展开更多
The crystal size distribution（CSD）was determined with small angle X-ray scattering technique.Theanticoking property of Ni-catalysts was investigated with the steam reforming of n-heptane in a TG-monitoredflow reacto...The crystal size distribution（CSD）was determined with small angle X-ray scattering technique.Theanticoking property of Ni-catalysts was investigated with the steam reforming of n-heptane in a TG-monitoredflow reactor.The results of this study show that the rate of coking on the supported Ni-catalysts depends main-ly on the percentage content of the large size fraction（25-70nm）of Ni-crystallites,and that the dispersion ofNi-crystallites and the anticoking property of the Ni/α-Al<sub>2</sub>O<sub>3</sub> catalysts were promoted obviously by theLa<sub>2</sub>O<sub>3</sub>-modification method.The variation of the Ni-CSD and the anticoking property of the catalysts were fur-ther tested through different periods of hydrothermal treatment.It is found that the content of the largeNi-crystal size fraction and the coking rate pass correspondingly through a maximum.展开更多
Catalytic conversion of synthesis gas （CO＋H2） into hydrocarbons, also known as Fischer-Tropsch （FT） synthesis, is a crucial reaction for the translbrmation of non-petroleum carbon resources such as coal, natural ...Catalytic conversion of synthesis gas （CO＋H2） into hydrocarbons, also known as Fischer-Tropsch （FT） synthesis, is a crucial reaction for the translbrmation of non-petroleum carbon resources such as coal, natural gas, shale gas, coal-bed gas and biogas, as well as biomass into liquid fuels and chemicals. Many factors can influence the catalytic behavior of a FT catalyst. This review highlights recent advances in understanding some key catalyst factors, including the chemical state of active phases, the promoters, the size and the microenvironment of active phase, which determine the CO conversion activity and the product selectivity, particularly the selectivity to C5 ＋ hydrocarbons.展开更多
基金the support of the Smart Mix Program of The Netherlands Ministry of Economic Affairs, Agriculture and Innovation and The Netherlands Ministry of Education, Culture and Science (Grant no. 053.70.011)
文摘The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers（CNF）,Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles（~12 nm） supported on α-Al2O3 were found to outgrow Ni particles with initially larger size（~20 nm）. It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.
文摘Effects of nano-particle size on hydrocarbon production rates and distributions for precipitated Fe/Cu/La catalysts in Fischer-Tropsch synthesis were investigated.Nano-structured iron catalyst was prepared by micro-emulsion method.The concept of two superimposed AndersonSchulz-Flory （ASF） distributions has been applied for the representation of the effects of reaction conditions and nano-particles size on kinetics parameters and product distributions.These results reveal that by reducing the particle size of catalyst,the break in ASF distributions was decreased.Also useful different kinetics equations for synthesis of C3 to C9 and C10 to C22 were determined by using α1 and α2 chain growth probabilities.
基金supported by the National Natural Science Foundation of China(No.20776089)
文摘Mesoporous silica supported Cs2.5H0.5PW12O40 catalysts were prepared by impregnation method, and several silica supports with different pore size were utilized. N2 adsorption, XRD and ICP-AES techniques were utilized to characterize the silica supports and catalysts. XRD results showed that the dispersion of Cs2.5H0.5PW12 was better for the silica support with larger pore size. The catalytic activity results showed that the pore size played important role on the catalyst activity and the molecular weight of PTHF. When Cs2.5H0.5PW12O40 was dispersed on larger pore size silica support, the catalysts showed good performances for the synthesis of PTHE The molecular weight of PTHF product on the sample in which Cs2.5H0.5PW12O40 was dispersed on larger pore support was higher than that on the catalyst with smaller pore support. The leaching amounts of the active components for the supported Cs2.5H0.5PW12O40 catalysts were much lower. After five reaction cycles, there were still good activities and stabilities for the supported Cs2.5H0.5PW12O40 catalysts with larger pore silica supports. These results were much better than those of the supported heteropolyacid H3PW12O40 catalyst.
基金supported by the Youth Fund Project(2002B25)of Sichuan Department of Educationthe Scientific Research Foundation for Doctor from Yibin College of China(2010B12)
文摘A series of nano-size gold catalysts were prepared by deposition-precipitation method using silica material promoted with different amounts of MgO as the carrier. The influences of MgO addition on the structure and property of the nano-size gold catalysts were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, O2 temperature-programmed desorption （O2-TPD）, and inductively coupled with plasma atomic emission spectroscopy （ICP-AES） techniques. The total oxidation of CO was chosen as the probe reaction. The results suggest that for the gold catalysts supported on the silica material after MgO modification, the size of the gold particles is pronouncedly reduced, the oxygen mobility is enhanced, and the catalytic activity for low-temperature CO oxidation is greatly improved. The gold catalyst modified by 6 wt% MgO （Mg/SiO2 weight ratio） shows higher CO oxidation activity, over which the temperature of CO total oxidation is lower about 150 K than that over the silica directly supported gold catalyst.
基金Supported by the National Natural Science Foundation of China(U1361202,51276120)
文摘Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH_4/CO_2 reforming.To explore the reason of this phenomenon,Ni4,Ni8,and Ni12 which re flect the different cluster thicknesses supported on the MgO(100) slabs,have been employed to simulate Ni/MgO catalysts,and the reaction pathways of CH_4/CO_2 reforming on Nix/MgO(100) models are investigated by density functional theory.The reforming mechanisms of CH_4/CO_2 on different Nix/MgO(100) indicate the energy barriers of CH_4 dissociated adsorption,CH dissociation,and C oxidation three factors are all declining with the decrease of the Ni cluster sizes.The Hirshfeld charges analyses of three steps as described above show only Ni atoms in bottom two layers can obtain electrons from the MgO supporters,and the main electron transfer occurs between adsorbed species and their directly contacted Ni atoms.Due to more electron-rich Ni atoms in contact with the MgO supporters,the Ni/MgO catalysts with small Ni particles have a strong metal particle size effect and lead to its better catalytic activity.
文摘The crystal size distribution（CSD）was determined with small angle X-ray scattering technique.Theanticoking property of Ni-catalysts was investigated with the steam reforming of n-heptane in a TG-monitoredflow reactor.The results of this study show that the rate of coking on the supported Ni-catalysts depends main-ly on the percentage content of the large size fraction（25-70nm）of Ni-crystallites,and that the dispersion ofNi-crystallites and the anticoking property of the Ni/α-Al<sub>2</sub>O<sub>3</sub> catalysts were promoted obviously by theLa<sub>2</sub>O<sub>3</sub>-modification method.The variation of the Ni-CSD and the anticoking property of the catalysts were fur-ther tested through different periods of hydrothermal treatment.It is found that the content of the largeNi-crystal size fraction and the coking rate pass correspondingly through a maximum.
基金the National Basic Research Program of China(No.2013CB933100)the National Natural Science Foundation of China(No.21173174,No.21161130522,No.21033006and No.20923004)the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT1036)
文摘Catalytic conversion of synthesis gas （CO＋H2） into hydrocarbons, also known as Fischer-Tropsch （FT） synthesis, is a crucial reaction for the translbrmation of non-petroleum carbon resources such as coal, natural gas, shale gas, coal-bed gas and biogas, as well as biomass into liquid fuels and chemicals. Many factors can influence the catalytic behavior of a FT catalyst. This review highlights recent advances in understanding some key catalyst factors, including the chemical state of active phases, the promoters, the size and the microenvironment of active phase, which determine the CO conversion activity and the product selectivity, particularly the selectivity to C5 ＋ hydrocarbons.
