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Harold H Kung

Publications and source records attributed to Harold H Kung.

6 recordsLinked to original sources

In situ transient FTIR and XANES studies of the evolution of surface species in CO oxidation on Au/TiO2.

The adsorption of CO and its reaction with oxygen were investigated using a combination of in situ Fourier transform infrared spectroscopy, step response measurements in a microreactor, (18)O isotopic labeling, and X-ray absorption near edge structure spectroscopy. An as-prepared sample in which Au is present as a surface oxyhydroxy complex does not adsorb CO. On an activated sample in which only metallic Au is detected, 0.18 +/- 0.03 mol CO/(mol Au) are adsorbed on Au at -60 degrees C, which shows an IR band at 2090 cm(-1). When oxygen is present in the gas phase, this species reacts with a turnover rate of 1.4 +/- 0.2 mol CO(mol Au min)(-1), which is close to the steady-state turnover rate. In contrast, there is a very small quantity of adsorbed oxygen on Au. A small IR peak at 1242 cm(-1) appears when an activated sample is exposed to CO. It reacts rapidly with oxygen and is shifted to 1236 cm(-1) if (18)O is used. It is assigned to the possible intermediate hydroxycarbonyl.

Adsorption↗

Size-selective shell cross-linked interior functionalized siloxane nanocages.

A new structure, consisting of a shell cross-linked, 2 nm size siloxane nanocage containing propylamine groups tethered to the interior face of the shell was synthesized, starting with micelles of the surfactant molecule, (triethoxysilyl)propylcetylcarbamate. After hydrolysis of the ethoxysilyl groups and condensation and capping of the silanols to form a cross-linked, one-atom-layer-thick siloxane shell, the carbamate was converted to amine, releasing the cetyl group from the structure and resulting in the desired spherical nanocage. The intermediates in the synthesis process and the final structure were characterized by 1H and 29Si NMR, DLS, TEM, and mass spectroscopy. The amine groups tethered to the interior surface of the shell react readily with ninhydrin but do not interact with the larger ZnTPP, indicating molecular size selectivity by the cross-linked shell. The structure also exhibits confinement effect in the amine-catalyzed decarboxylation of acetoacetic acid, exhibiting higher activity and higher selectivity for acetal than (aminopropyl)triethoxysilane.

Journal Article↗

Activation of Au/TiO2 catalyst for CO oxidation.

Changes in a Au/TiO(2) catalyst during the activation process from an as-prepared state, consisting of supported AuO(x)(OH)(4-2x)(-) species, were monitored with X-ray absorption spectroscopy and FTIR spectroscopy, complemented with XPS, microcalorimetry, and TEM characterization. When the catalyst was activated with H(2) pulses at 298 K, there was an induction period when little changes were detected. This was followed by a period of increasing rate of reduction of Au(3+) to Au(0), before the reduction rate decreased until the sample was fully reduced. A similar trend in the activation process was observed if CO pulses at 273 K or a steady flow of CO at about 240 K was used to activate the sample. With both activation procedures, the CO oxidation activity of the catalyst at 195 K increased with the degree of reduction up to 70% reduction, and decreased slightly beyond 80% reduction. The results were consistent with metallic Au being necessary for catalytic activity.

Journal Article↗

Rational synthesis of asymmetric bicyclic siloxane.

A rational and versatile method to synthesize bicyclosiloxane of design structures is presented. The method is used to synthesize a new, asymmetric bicyclo[7.5.3]octasiloxane and other bicyclosiloxanes.

Bridged Bicyclo Compounds, Heterocyclic↗

Stepwise synthesis of siloxane chains.

Siloxane chains of designated lengths can be synthesized with high yields by reacting tris(tert-butoxy)silanol alternately with dichlorosilane and silanediol.

Journal Article↗