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.
A series of CO3O4 spinel catalysts modified by Sm were prepared by co-precipitation method and tested for CH4 and CO oxidation. The addition of a small amount of Sm into Co3O4 led to an improvement in the catalytic activity for both reactions. Co0.98Sm0. 02 and Co0.95Sm0.05, the two samples with Co/Sm molar ratio of 0.98/0.02 and 0.95/0.05 in sequence, showed the similar and the highest activity for CH4 oxidation, with CH4 complete conversion at 450 ℃. In contrast, Coo.90Smo l0 was the most active sample for CO oxidation, with CO complete conversion at 120 ℃. The catalysts were characterized by techniques of N2 adsor- tion-desorption with Brunauer-Emmett-Teller technique （N2-BET）, X-ray powder diffraction （XRD）, thermal gravity analy- sis-differential scanning calorimetry （TGA-DSC）, Hz temperature programmed reduction （H2-TPR） and X-ray photoelectron spec- troscopy analysis （XPS）. Compared with pure Co3O4, for CO1-xSmx catalysts with 0.02≤x≤0.10, the addition of a small amount of Sm resulted in the formation of spinel Co3O4 and amorphous SmCoO3, hence increasing the number of Co3＋ and the active surface oxygen species, which was responsible for the improvement of the activity. C00.95Sm0.05 catalyst showed not only high thermal stability and activity but also good reaction durability in the presence of 5% water vapor for CH4 oxidation.
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.
