Preparation of Ce0.67Zr0.33O2 mixed oxides as supports of improved Pd-only three-way catalysts

Four types of Ce0.67Zr0.33O2 (CZCP, CZH, CZHP and CZM) mixed oxides as supports were prepared by coprecipitation, hydrothermal, homogeneous precipitation and microemulsion methods, respectively. The results show that both the preparation methods and the aging procedures have significant influences on the physicochemical properties of Ce0.67Zr0.33O2 mixed oxides. All these fresh Ce0.67Zr0.33O2 samples develop mesopore structure, especially that, CZCP obtains the largest diameter (20.87 nm) and volume (0.455 cm3/g). The XRD results indicate that fresh CZHP and CZCP samples contain cubic and tetragonal phases, while only cubic solid solution is found in fresh CZH and CZM samples, which show better low-temperature reducibility. Moreover, higher oxygen storage capacity complete (OSCC) values and faster O2 uptake are observed in CZH and CZM samples compared with those of fresh CZCP and CZHP. After calcination at 1100 °C, it is found that the OSCC values and the kinetics of the O2 uptake for CZM and CZHP samples are deteriorated due to the coexistence of cubic and tetragonal phases as well as strong sintering of samples. On the contrary, the aged CZCP and CZH samples keep satisfactory low-temperature reducibility and oxygen storage capacity. For fresh catalysts, the pore-size distribution of mixed oxides seems to be important for catalytic activities. In contrast, for aged catalysts, their activities are related to both the redox properties and the textural properties of aged mixed oxides. Therefore, the Pd-only three-way catalyst supported on the CZCP exhibits the most promising amplified amplitude of stoichiometric window.