Gonghua Wang

Defect Engineering in Cubic Cerium Oxide Nanostructures for Catalytic Oxidation

Traditional nanostructured design of cerium oxide catalysts typically focuses on their shape, size, and elemental composition. We report a different approach to enhance the catalytic activity of cerium oxide nanostructures through engineering high density of oxygen vacancy defects in these catalysts without dopants. The defect engineering was accomplished by a low pressure thermal activation process that exploits the nanosize effect of decreased oxygen storage capacity in nanostructured cerium oxides.

Lotus Effect in Engineered Zirconia

Patterned micro- and nanostructured surfaces have received increasing attention because of their ability to tune the hydrophobicity and hydrophilicity of their surfaces. However, the mechanical properties of these studied surfaces are not sufficiently robust for load-bearing applications. Here we report transparent nanocrystalline ZrO 2 films possessing combined properties of hardness and complete wetting behavior, which are expected to benefit tribology, wear reduction, and biomedical applications where ultrahydrophilic surfaces are required. This ultrahydrophilic behavior may be explained by the Wenzel model.

Thermal stability of nanostructurally stabilized zirconium oxide

Nanostructurally stabilized zirconium oxide (NSZ) hard transparent films were produced without chemical stabilizers by the ion beam assisted deposition technique (IBAD). A transmission electron microscopy study of the samples produced below 150 °C revealed that these films are composed of zirconium oxide (ZrO2) nanocrystallites of diameters 7.5 ± 2.3 nm. X-ray and selected-area electron diffraction studies suggested that the as-deposited films are consistent with cubic phase ZrO2. Rutherford backscattering spectroscopy (RBS) indicated the formation of stoichiometric ZrO2. The phase identity of these optically transparent NSZ films was in agreement with cubic ZrO2, as indicated by the matching elastic modulus values from the calculated results for pure cubic zirconium oxide and results of nanoindentation measurements. Upon annealing in air for 1 h, these NSZ films were found to retain most of their room temperature deposited cubic phase x-ray diffraction signature up to 850 °C. Size effect and vacancy stabilization mechanisms and the IBAD technique are discussed to explain the present results.

Local structures surrounding Zr in nanostructurally stabilized cubic zirconia: Structural origin of phase stability

Local environment surrounding Zr atoms in the thin films of nanocrystalline zirconia (ZrO2) has been investigated by using the extended x-ray absorption fine structure (EXAFS) technique. These films prepared by the ion beam assisted deposition exhibit long-range structural order of cubic phase and high hardness at room temperature without chemical stabilizers. The local structure around Zr probed by EXAFS indicates a cubic Zr sublattice with O atoms located on the nearest tetragonal sites with respect to the Zr central atoms, as well as highly disordered locations. Similar Zr local structure was also found in a ZrO2 nanocrystal sample prepared by a sol-gel method. Variations in local structures due to thermal annealing were observed and analyzed. Most importantly, our x-ray results provide direct experimental evidence for the existence of oxygen vacancies arising from local disorder and distortion of the oxygen sublattice in nanocrystalline ZrO2. These oxygen vacancies are regarded as the essential stabil...

Phase stabilization in nitrogen-implanted nanocrystalline cubic zirconia

The phase stability of nanocrystallites with metastable crystal structures under ambient conditions is usually attributed to their small grain size. It remains a challenging problem to maintain such phase integrity of these nanomaterials when their crystallite sizes become larger. Here we report an experimental-modelling approach to study the roles of nitrogen dopants in the formation and stabilization of cubic ZrO(2) nanocrystalline films. Mixed nitrogen and argon ion beam assisted deposition (IBAD) was applied to produce nitrogen-implanted cubic ZrO(2) nanocrystallites with grain sizes of 8-13 nm. Upon thermal annealing, the atomic structure of these ZrO(2) films was observed to evolve from a cubic phase, to a tetragonal phase and then a monoclinic phase. Our X-ray absorption near edge structure study on the annealed samples together with first-principle modelling revealed the significance of the interstitial nitrogen in the phase stabilization of nitrogen implanted cubic ZrO(2) crystallites via the soft mode hardening mechanism.

Probing the bifunctional catalytic activity of ceria nanorods towards the cyanosilylation reaction

Ceria nanorods were demonstrated to be an active, bifunctional catalyst for the cyanosilylation of aldehydes. The catalytic activity of ceria was shown to be positively correlated with a decrease in the coordination numbers of neighbouring oxygen atoms around cerium atoms in the catalyst. Chemisorption and density functional theory studies suggested that the coordinatively unsaturated cerium sites exposed by the surface oxygen vacancy defects functioned as Lewis acid sites and the neighbouring oxygen atoms behaved as Lewis base sites in the catalytic cycle.

Metal–Organic Frameworks Capable of Healing at Low Temperatures

Filling crystalline gaps with small molecules can drive interfacial healing between anisotropic solids. Sufficient mobility from these fillers allows the process to happen at a low temperature of -56 °C. Mended bulk crystals show modulus leap from 4 to 12 GPa and hardness from 400 to 1000 MPa.