Formation mechanism of zirconia nano-particles containing pores prepared via sol–gel-hydrothermal method

Zirconia single crystal nano-particles containing pores were prepared by a sol–gel-hydrothermal method. The unique character of the particles is that some irregular pores are embedded within the single crystals. The results of XRD, TEM and FT-IR show that the gaseous hydrolysates of the superstoichiometric urotropine are the origin of the pores. The gel structure and the hydrothermal treatment are the required conditions resulting in the pores in crystals. The formation mechanism was proposed: zirconia gel was formed after the reaction of ZrOCl2 with urotropine. The superstoichiometric urotropine was dissolved and distributed uniformly in the gel. The small pores were generated because gaseous hydrolysates of urotropine were constrained in the gel during the hydrothermal treatment. During the process of the amorphous gel transferred into the crystals, some of the pores coarsened with the crystals growth. Big pores disappeared due to the break of the crystals. And only the small pores were remained in the interior of crystals, which could hardly be eliminated by the subsequent crystal growth if the calcination temperature is below 550 °C. Thus, the zirconia nano-particles containing pores were generated.