Effects of ammonia concentration in hydrothermal treatment on structure and redox properties of cerium zirconium solid solution

Cerium zirconium solid solution is a key washcoat material for automotive three-way catalysts(TWCs).However,improving the redox ability and high temperature thermal stability of cerium zirconium solid solution is still a challenge.In this paper,the cerium zirconium solid solution was prepared by a coprecipitation-hydrothermal method,and the effects of the ammonia concentration on their structures and redox properties were investigated.The results show that when the ammonia concentration is 0.8 mol/L,the aged sample(1100℃/10 h)of cerium zirconium solid solution has the highest specific surface area of 23.01 m^(2)/g.Additionally,the increase of ammonia concentration improves the uniformity of phase compositions and increases the oxygen vacancies.When the ammonia concentration reaches 0.4 mol/L,the cerium zirconium solid solution exhibits the best redox activity,with the lowest reduction temperature of 565℃.Therefore,increasing ammonia concentration in the hydrothermal treatment is beneficial to the thermal stability and redox performance of cerium zirconium solid solution.

CO_(2)hydrogenation to methanol promoted by Cu and metastable tetragonal Ce_(x)Zr_(y)O_(z) interface

Designing effective catalyst to improve the activity of CO_(2) hydrogenation to methanol is a potential avenue to realize the utilization of CO_(2) resources. Herein we construct three kinds of Cu/Ce_(x)Zr_(y)O_(z)(CCZ) catalysts with different crystal phases of Ce_(x)Zr_(y)O_(z)solid solutions, which demonstrate distinct activity and methanol selectivity in the order of metastable tetragonal-CCZ(CCZ-t’’, parts of oxygen in Ce_(x)Zr_(y)O_(z) were replaced by tetragonal phase from cubic fluorite phase) > tetragonal-CCZ(CCZ-t) > cubic-CCZ(CCZ-c) for CO_(2) hydrogenation to methanol. Structural analysis reveals that oxygen vacancies, surface hydroxyls and unsaturated Cu species of CCZ all follow the same sequence as that of activity and methanol selectivity,indicating that the above features are beneficial to improve the catalytic reaction performance.Temperature programmed experiments and mechanism studies show that the interface between Cu and tetragonal(t and t’’) Ce_(x)Zr_(y)O_(z) can promote CO_(2) adsorption, and the adsorbed CO_(2) is more reactive and can generate active bidentate carbonate species, which can be hydrogenated to form active monodentate and bidentate formate species under CO_(2) and H_(2) atmosphere. These intermediates should be crucial to the formation of methanol product. CCZ-t’’has stronger H_(2) activation ability than CCZ-t, which makes the former catalyst have more intermediates and higher methanol selectivity. In contrast, CO_(2) mainly adsorbs on cubic Ce_(x)Zr_(y)O_(z) support of CCZ-c, but its H_(2) spillover ability is low, which hinders the reaction process. In addition, the strong adsorption of surface intermediates on CCZ-c is also not conducive to methanol formation. Results here demonstrate that constructing active Cu-support interfaces may be an important approach to design effective catalyst for CO_(2)hydrogenation.

Fabrication and characterization of Ce_(0.7)Zr_( 0.3)O_2 nanorods having high specific surface area and large oxygen storage capacity

Nanorod-like Ce0.7Zr0.3O2 solid solutions were synthesized by a sodium dodecyl sulfate-assisted precipitation method. The samples were characterized by means of scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and specific surface area measurement. Typical Ce0.7Zr0.3O2 nanorods were 40 nm in average diameter and 450 nm in length, with specific surface area and oxygen storage capacity of 194 m2/g and 374 μmol/g, respectively.