A series of Ni/La2Zr2O7 pyrochlore catalysts prepared by impregnation method and treated by dielectric barrier discharge（DBD） plasma in different atmospheres and varied sequences were prepared and applied for dry re...A series of Ni/La2Zr2O7 pyrochlore catalysts prepared by impregnation method and treated by dielectric barrier discharge（DBD） plasma in different atmospheres and varied sequences were prepared and applied for dry reforming of methane（DRM）. It is found that all of the plasma treated catalysts show evidently improved activity and coke resistance in comparison with the non-plasma treated one. The best performance is achieved on Ni/La2Zr2O7–H2P–C,a catalyst treated in H2 plasma before calcination. TGA-DSC and SEM demonstrate that carbon deposition is significantly suppressed on all of the plasma treated samples. Moreover,XRD and TEM results testify that both Ni O and Ni sizes on the calcined and reduced samples treated by plasma are also decreased,which results in higher Ni metal dispersion on the reduced and used catalysts and enhances the interactions between Ni sites and the support. It is believed that these are the inherent reasons accounting for the promotional effects of plasma treatment on the reaction performance of the Ni/La2Zr2O7 pyrochlore catalysts.展开更多
To understand the dispersion behavior of metal oxides on composite oxide supports and with the expectation of developing more feasible catalysts for soot oxidation,CuO/La_(2)Sn_(2)O_(7)samples containing varied CuO lo...To understand the dispersion behavior of metal oxides on composite oxide supports and with the expectation of developing more feasible catalysts for soot oxidation,CuO/La_(2)Sn_(2)O_(7)samples containing varied CuO loadings were fabricated and characterized by different techniques and density functional theory calculations.In these catalysts,a spontaneous dispersion of CuO on the La_(2)Sn_(2)O_(7)pyrochlore support formed,having a monolayer dispersion capacity of 1.90 mmol CuO/100 m^(2) La_(2)Sn_(2)O_(7)surface.When loaded below this capacity,CuO exists in a sub-monolayer or monolayer state.X-ray photoelectron spectroscopy(XPS),Raman spectroscopy,and Bader charge and density of states analyses indicate that there are strong interactions between the sub-monolayer/monolayer CuO and the La_(2)Sn_(2)O_(7)support,mainly through the donation of electrons from Cu to Sn at the B-sites of the structure.In contrast,Cu has negligible interactions with La at the A-sites.This suggests that,in composite oxide supports containing multiple metals,the supported metal oxide interacts preferentially with one kind of metal cation in the support.The Raman,in situ diffuse reflectance infrared Fourier transform spectroscopy,and XPS results confirmed the formation of both O2^(-)and O2^(2-)as the active sites on the surfaces of the CuO/La_(2)Sn_(2)O_(7)catalysts,and the concentration of these active species determines the soot combustion activity.The number of active oxygen anions increased with increase in CuO loading until the monolayer dispersion capacity was reached.Above the monolayer dispersion capacity,microsized CuO crystallites formed,and these had a negative effect on the generation of active surface oxygen sites.In summary,a highly active catalyst can be prepared by covering the surface of the La_(2)Sn_(2)O_(7)support with a CuO monolayer.展开更多
In this study, Ni/YZrOcatalysts prepared with impregnation method and treated by dielectric barrier discharge plasma(DBD) in different atmospheres have been investigated for methane dry reforming. It is revealed by H-...In this study, Ni/YZrOcatalysts prepared with impregnation method and treated by dielectric barrier discharge plasma(DBD) in different atmospheres have been investigated for methane dry reforming. It is revealed by H-TPR that plasma treatment can enhance the interaction between Ni O/Ni particles and the YZrOpyrochlore support. Therefore, catalysts with smaller Ni O and Ni grains sizes, higher metallic Ni active surface areas can be achieved, as evidenced by XRD, TEM and Hadsorption-desorption measurements. As a consequence, the plasma-treated catalysts show significantly improved activity, stability and coke resistance, as testified by the TEM and TGA-DSC results. Plasma treatment in H/Ar gas mixture is found to be the best condition to prepare Ni/YZrO, which can be used to obtain a catalyst with the highest activity, stability and most potent coke resistance. It is believed that the smaller Ni grain size and higher metallic Ni active surface area induced by plasma treatment are the inherent reasons accounting for the promoted reaction performance of the Ni/YZrOpyrochlore catalysts.展开更多
基金supported by the Chinese Natural Science Foundation (21263015 and 21203088)the Education Department of Jiangxi Province (KJLD14005 and GJJ14205)the Natural Science Foundation of Jiangxi Province (20142BAB213013)
文摘A series of Ni/La2Zr2O7 pyrochlore catalysts prepared by impregnation method and treated by dielectric barrier discharge（DBD） plasma in different atmospheres and varied sequences were prepared and applied for dry reforming of methane（DRM）. It is found that all of the plasma treated catalysts show evidently improved activity and coke resistance in comparison with the non-plasma treated one. The best performance is achieved on Ni/La2Zr2O7–H2P–C,a catalyst treated in H2 plasma before calcination. TGA-DSC and SEM demonstrate that carbon deposition is significantly suppressed on all of the plasma treated samples. Moreover,XRD and TEM results testify that both Ni O and Ni sizes on the calcined and reduced samples treated by plasma are also decreased,which results in higher Ni metal dispersion on the reduced and used catalysts and enhances the interactions between Ni sites and the support. It is believed that these are the inherent reasons accounting for the promotional effects of plasma treatment on the reaction performance of the Ni/La2Zr2O7 pyrochlore catalysts.
文摘To understand the dispersion behavior of metal oxides on composite oxide supports and with the expectation of developing more feasible catalysts for soot oxidation,CuO/La_(2)Sn_(2)O_(7)samples containing varied CuO loadings were fabricated and characterized by different techniques and density functional theory calculations.In these catalysts,a spontaneous dispersion of CuO on the La_(2)Sn_(2)O_(7)pyrochlore support formed,having a monolayer dispersion capacity of 1.90 mmol CuO/100 m^(2) La_(2)Sn_(2)O_(7)surface.When loaded below this capacity,CuO exists in a sub-monolayer or monolayer state.X-ray photoelectron spectroscopy(XPS),Raman spectroscopy,and Bader charge and density of states analyses indicate that there are strong interactions between the sub-monolayer/monolayer CuO and the La_(2)Sn_(2)O_(7)support,mainly through the donation of electrons from Cu to Sn at the B-sites of the structure.In contrast,Cu has negligible interactions with La at the A-sites.This suggests that,in composite oxide supports containing multiple metals,the supported metal oxide interacts preferentially with one kind of metal cation in the support.The Raman,in situ diffuse reflectance infrared Fourier transform spectroscopy,and XPS results confirmed the formation of both O2^(-)and O2^(2-)as the active sites on the surfaces of the CuO/La_(2)Sn_(2)O_(7)catalysts,and the concentration of these active species determines the soot combustion activity.The number of active oxygen anions increased with increase in CuO loading until the monolayer dispersion capacity was reached.Above the monolayer dispersion capacity,microsized CuO crystallites formed,and these had a negative effect on the generation of active surface oxygen sites.In summary,a highly active catalyst can be prepared by covering the surface of the La_(2)Sn_(2)O_(7)support with a CuO monolayer.
基金supported by the National Natural Science Foundation of China (21567016, 21566022, 21263015)the Natural Science Foundation of Jiangxi Province (20151BBE50006, 20151BAB203024)the Education Department of Jiangxi Province (KJLD14005, GJJ150016)
文摘In this study, Ni/YZrOcatalysts prepared with impregnation method and treated by dielectric barrier discharge plasma(DBD) in different atmospheres have been investigated for methane dry reforming. It is revealed by H-TPR that plasma treatment can enhance the interaction between Ni O/Ni particles and the YZrOpyrochlore support. Therefore, catalysts with smaller Ni O and Ni grains sizes, higher metallic Ni active surface areas can be achieved, as evidenced by XRD, TEM and Hadsorption-desorption measurements. As a consequence, the plasma-treated catalysts show significantly improved activity, stability and coke resistance, as testified by the TEM and TGA-DSC results. Plasma treatment in H/Ar gas mixture is found to be the best condition to prepare Ni/YZrO, which can be used to obtain a catalyst with the highest activity, stability and most potent coke resistance. It is believed that the smaller Ni grain size and higher metallic Ni active surface area induced by plasma treatment are the inherent reasons accounting for the promoted reaction performance of the Ni/YZrOpyrochlore catalysts.
