From Layered Double Hydroxides to ZnO-based Mixed Metal Oxides by Thermal Decomposition: Transformation Mechanism and UV-Blocking Properties of the Product

详细信息    查看全文

• 作者：Xiaofei Zhao ; Fazhi Zhang ; Sailong Xu ; David G. Evans ; Xue Duan
• 刊名：Chemistry of Materials
• 出版年：2010
• 出版时间：July 13, 2010
• 年：2010
• 卷：22
• 期：13
• 页码：3933-3942
• 全文大小：1017K
• 年卷期：v.22,no.13(July 13, 2010)
• ISSN：1520-5002

文摘

Thermal decomposition of layered double hydroxides (LDHs) is a way of fabricating mixed metal oxide (MMO) nanocomposite materials composed of metal oxide and spinel phases. A detailed understanding of the mechanism of the transformation of the LDH precursor to the MMO should allow the properties of the resulting MMO nanocomposites to be tailored to specific applications. Here we report a systematic investigation of the structure, composition, and morphology evolution from ZnAl-LDHs to ZnO-based MMO nanocomposites composed of ZnO and ZnAl₂O₄ on calcination at different temperatures. The nucleation and oriented growth of ZnO crystallites and the formation of ZnAl₂O₄ were monitored by high resolution transmission electron microscopy (HRTEM) combined with selected-area electron diffraction (SAED), in situ X-ray diffraction (XRD), solid-state ²⁷Al magic-angle spinning nuclear magnetic resonance (²⁷Al MAS NMR), and thermogravimetric and differential thermal analyses (TG−DTA). The layered structure of the LDH precursor was maintained as the temperature was increased from room temperature to 180 °C. Upon further heating from 200 to 400 °C, ZnO nuclei doped with Al³⁺ were first formed as an amorphous phase and then underwent oriented growth along the 100 direction. The high aspect ratio of the LDH platelets is responsible for the oriented growth of the resulting ZnO crystallites. On further increasing the calcination temperature, Zn²⁺ ions were continuously released from the amorphous phase resulting in the formation of crystalline ZnO nanoparticles doped with Al³⁺, which are homogeneously dispersed throughout the amorphous phase. When the calcination temperature reached 500 °C, Al³⁺ ions were released from the ZnO-like structure resulting in the formation of ZnAl₂O₄ spinel and the crystallinity of the spinel increased gradually with increasing temperature. Sintering of ZnO and ZnAl₂O₄, with concomitant loss of the platelet-like morphology, occurred below 800 °C. UV−visible spectroscopy showed that the ZnO/ZnAl₂O₄ nanocomposite prepared by calcination of the ZnAl-LDH precursor at 800 °C has superior UV-blocking properties to both commercial ZnO and a physical mixture of ZnO and ZnAl₂O₄.