Tetragonal Zirconia Nanoparticles Research Articles

Facile Synthesis of Pure Monoclinic and Tetragonal Zirconia Nanoparticles and Their Phase Effects on the Behavior of Supported Molybdena Catalysts for Methanol-Selective Oxidation

Pure monoclinic (m) and tetragonal (t) zirconia nanoparticles were readily synthesized from the reaction of inorganic zirconium salts (e.g., hydrated zirconyl nitrate) and urea in water and methanol, respectively, via a facile solvothermal method. The role of the solvents was crucial in the formation of the pure ZrO(2) phases, whereas their purity was essentially insensitive to other variables, including reaction temperature, reactant concentration, pH, and zirconium salts. Water as the solvent led to the transformation of hydrous ZrO(2) precipitates initially formed with tetragonal structures to thermodynamically more stable m-ZrO(2) via the dissolution-precipitation process, whereas methanol favored the removal of water molecules from the precursors via their reaction with urea, consequently maintaining the tetragonal structures. The obtained tetragonal samples were found to possess superior hydrothermal stability compared to those reported previously, which provides the possibility for systematically studying the effects of ZrO(2) phases on many catalytic reactions involving water as a reactant or product. Using these pure m- and t-ZrO(2) phases as supports, dispersed MoO(x) catalysts were synthesized at MoO(x) surface densities of approximately 5.0 Mo/nm(2), which is close to one monolayer of coverage. Characterization by X-ray diffraction and Raman spectroscopy confirmed that the pure ZrO(2) phases remained unchanged in the presence of the MoO(x) domains and the MoO(x) domains existed preferentially as 2D polymolybdate structures. The catalysts were subsequently examined for selective methanol oxidation as a test reaction. m-ZrO(2) support led to 2-fold greater oxidation rates than for t-ZrO(2) support, reflecting the higher intrinsic reactivity of the MoO(x) domains on m-ZrO(2). This is consistent with their higher reducibility probed by temperature-programmed reduction with H(2) (H(2) TPR). These observed effects of the ZrO(2) phases provide the basis for designing catalysts with tunable redox properties and reactivity.

Stabilization of Isolated Hydrous Amorphous and Tetragonal Zirconia Nanoparticles Through the Formation of a Passivating Alumina Shell

AbstractIn this work, we explore the high‐temperature phase stability of isolated, alumina‐coated zirconia nanocrystals with a goal of understanding how interfacial energy affects phase stability. Isolated tetragonal and hydrous amorphous zirconia colloids were synthesized and coated with alumina through the hydrolysis of aluminum isopropoxide. Alumina‐coated samples exhibited phase behavior that was markedly different from that of the uncoated analogs. Uncoated tetragonal particles transformed to the monoclinic phase at 1100 °C while alumina‐coated tetragonal particles did not transform until 1400 °C. Uncoated hydrous amorphous particles crystallized to the tetragonal phase after heating at 600 °C and transformed to the monoclinic phase after heating at 800 °C. Alumina‐coated hydrous amorphous particles crystallized only after heating at 1050 °C, and transformed to the monoclinic phase after heating at 1400 °C. Differences in phase behavior are postulated to depend on the zirconia–alumina interface, which must be disrupted before zirconia particles can fuse and facilitate the tetragonal‐to‐monoclinic phase transition. By coating the nanocrystals with a thin alumina shell and studying the resultant phase stability, we explore the effect of reproducibly modified interfacial chemistry on phase behavior in nanoscale ceramic composites.