Influence of surface Ce/Zr ratio on formation of κ-Ce_(2)Zr_(2)O_(8) superstructure and its application in three-way catalysis

Ceria-zirconia based(CZ) materials are still a crucial component of three-way catalysts(TWCs) now.Compared with traditional cubic or tetragonal phase,CZ material with pyrochlore-type κ-Ce_(2)Zr_(2)O_(8) phase shows an excellent oxygen storage capacity,and thus is examined as a promising material for developing TWCs.Considering the remarkable surface Ce/Zr ratio change during the κ-Ce_(2)Zr_(2)O_(8) formation,we investigated the effects of surface Ce/Zr ratio on the formation of κ-Ce_(2)Zr_(2)O_(8) and on the supported Pdonly three-way catalysts.Raman and transmission electron microscopy(TEM) results demonstrate that partial κ-Ce_(2)Zr_(2)O_(8) structure is formed in the three oxides,and the content of κ-Ce_(2)Zr_(2)O_(8) structure increases with increasing surface Ce/Zr ratio,but its stability declines.After thermal aging,the proportions of Ce^(3+) and oxidized palladium(Pd^(δ+)+Pd^(2+)) in the catalysts,which are shown to be positively correlated with catalytic activity,follow the same sequence as the stability of κ-Ce_(2)Zr_(2)O_(8),namely Pd/M0.33 ROa> Pd/M0.4 ROa> Pd/CeM0.33 ROa.In particular,Pd/M0.33 RO,which possesses 100%((Pd^(δ+)+Pd^(2+))/Pd) even after thermal aging at 900℃ for 4 h,owing to the strengthened metal-support interaction by the presence of stable κ-Ce_(2)Zr_(2)O_(8),shows the best catalytic performance.This work is instructive to the application of κ-Ce_(2)Zr_(2)O_(8) in three-way catalysis.