采用溶液燃烧法制备出PdO/Ce(1-x)PdxO(2-δ)和PdO/Ce(1-x)PdxO(2-δ)(Pd O/CPZ)催化剂,通过硝酸处理去除催化剂表面的Pd O物种得到对应的Ce(1-x)PdxO(2-δ)(CP)和Ce(1-x)PdxO(2-δ)(CPZ)催化剂。考究四种催化剂(Pd O/CP、Pd O/CPZ、CP、CPZ)对CO和CH4的氧化活性,并计算得出表面Pd O和Pdn+物种的转化频率(TOF)。结果表明Zr的添加对Pd O催化剂上CO和CH4的催化氧化活性具有不同的影响。Zr的添加对Pd O/CPZ和CPZ催化剂的CO催化活性具有明显的促进作用,前者归因于PdO/CPZ催化剂表面生成了更小颗粒的Pd O粒子,后者归因于CPZ催化剂中含有更多的氧空位。对于CH4的催化氧化,Pd^(n+)物种起到关键的作用。由于Zr的掺杂导致Ce O2的晶格中Pd物种的含量减少,致使PdO/CPZ催化剂和CPZ催化剂对CH4氧化活性的降低。
PdO/Ce(1-x)PdxO(2-δ)(Pd O/CP) and PdO/Ce(1-x)PdxO(2-δ)(Pd O/CPZ) catalysts were prepared via a solution combustion method. The corresponding Ce1-xPdxO2-δ(CP) and Ce(1-x-y)PdxZryO(2-δ)(CPZ) catalysts were obtained by nitric acid treatment of the Pd O/CP and Pd O/CPZ catalysts to remove the surface Pd O species.These catalysts were tested for CO and CH4 catalytic oxidation. The turnover frequencies(TOFs) of surface Pd O and Pdn+cations in the CP and CPZ solid solutions were calculated. The results showed that Zr addition in the Pd O/CP catalyst had very different effects on CO and CH4 oxidation. A significant improvement in CO oxidation activity was observed over the Zr-containing catalysts; this could be related to the formation of smaller Pd O particles on the surface of the Pd O/CPZ catalyst and a higher oxygen vacancy concentration in the CPZ solid solution. For CH4 oxidation, Pdn +cations in the solid solution play a key role in the catalytic oxidation process. The penetration of Zr~(4+)cations into the Ce O2 lattice decreased the amount of Pd~(2+)cations in the CPZ solid solution and thus inhibited the activities of the Zr-containing catalysts(Pd O/CPZ and CPZ) for CH4 oxidation.