Chin Li Cheung

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.

High aspect ratio composite structures with 48.5% thermal neutron detection efficiency

The pillar structured thermal neutron detector is based on the combination of high aspect ratio silicon p-i-n pillars surrounded by the neutron converter material 10B. By etching high aspect ratio pillar structures into silicon, the result is a device that efficiently absorbs the thermal neutron flux by accommodating a large volume fraction of 10B within the silicon pillar array. Here, we report a thermal neutron detection efficiency of 48.5% using a 50 μm pillar array with an aspect ratio of 25:1.

Techniques for Consecutive TEM and Atom Probe Tomography Analysis of Nanowires

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Influence of nanostructured ceria support on platinum nanoparticles for methanol electrooxidation in alkaline media

The catalytic activity of platinum (Pt) nanoparticles (NPs) towards methanol electrooxidation in alkaline media was demonstrated to be dependent on their interactions with their nanostructured ceria support. Ceria nanorods (NRs) with diameters of 5 to 10 nm and lengths of 15 to 50 nm as well as ceria NPs with diameters of 2 to 6 nm were applied as supports for similarly sized Pt NPs with diameters of 2 to 5 nm. Cyclic voltammetry data showed that Pt NPs supported on ceria NPs exhibited a 2-to-5-fold higher catalytic current density versus ceria NRs. X-ray photoelectron spectroscopic data indicated that Pt NPs deposited onto ceria NRs were disproportionally composed of oxidized species (Pt2+, Pt4+ and Pt–O–M) rather than Pt0 while Pt NPs on ceria NPs mainly consisted of Pt0. Stronger metal-support interactions between Pt NPs and ceria NRs are postulated to induce preferential oxidation of Pt NPs and consequently decrease the catalytic sites and overall activity.

Steric and Electrostatic Complementarity in the Assembly of Two-Dimensional Virus Arrays

A highly ordered assembly of biological molecules provides a powerful means to study the organizational principles of objects at the nanoscale. Two-dimensional cowpea mosaic virus arrays were assembled in an ordered manner on mica using osmotic depletion effects and a drop-and-dry method. The packing of the virus array was controlled systematically from rhombic packing to hexagonal packing by modulating the concentrations of poly(ethylene glycol) surfactant in the virus solutions. The orientation and packing symmetry of the virus arrays were found to be tuned by the concentrations of surfactants in the sample solutions. A phenomenological model for the present system is proposed to explain the assembly array morphology under the influence of the surfactant. Steric and electrostatic complementarity of neighboring virus capsids is found to be the key factors in controlling the symmetry of packing.

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.

Resonant Photoemission Observations and DFT Study of s–d Hybridization in Catalytically Active Gold Clusters on Ceria Nanorods

Gold clusters have garnered intense interest because of their unusual catalytic activities towards chemical reactions of industrial importance. Electronic structures of oxide supported gold clusters can provide critical clues to the mechanisms for their catalytic activity. Gold atoms possess an electronic configuration of [Xe] 4f145d106s1. However, both relativistic effects and 5d band upshift of gold clusters result in a theoretically expected hybridization of the 5d and 6s orbitals. These s-d hybridized orbitals are expected to, essentially, increase the number of free d states (or d holes) available for bonding with incoming reactant molecules, thus lowering the transition state energy and promoting the reactions.

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.

Preparation and characterization of Pt/Pt:CeO2-x nanorod catalysts for short chain alcohol electrooxidation in alkaline media

Multi-functional anode catalysts composed of platinum (Pt) nanoparticles electrodeposited on 2 wt% Pt decorated ceria (Pt:CeO2−x) nanorod supports were shown to enhance the alkaline electrocatalytic oxidation of methanol, ethanol and n-butanol over electrodeposited Pt nanoparticles alone or ones supported with pure ceria nanorods. The Pt:CeO2−x nanorod support was demonstrated to increase the current density of the investigated alkaline electrooxidation of methanol, ethanol and n-butanol by more than 30% over the other two catalysts.

Planarization of high aspect ratio p-i-n diode pillar arrays for blanket electrical contacts

Two planarization techniques for high aspect ratio three dimensional pillar structured p-i-n diodes have been developed in order to enable a continuous coating of metal on the top of the structures. The first technique allows for coating of structures with topography through the use of a planarizing photoresist followed by reactive ion etch-back to expose the tops of the pillar structure. The second technique also utilizes photoresist but instead allows for planarization of a structure in which the pillars are filled and coated with a conformal coating by matching the etch rate of the photoresist to the underlying layers. These techniques enable deposition using either sputtering or electron beam evaporation of metal films to allow for electrical contact to the tops of the underlying pillar structure. These processes have potential applications for many devices comprised of three dimensional high aspect ratio structures.