Chia-Kuang Tsung

Thermally stable Pt/mesoporous silica core-shell nanocatalysts for high-temperature reactions

Recent advances in colloidal synthesis enabled the precise control of the size, shape and composition of catalytic metal nanoparticles, enabling their use as model catalysts for systematic investigations of the atomic-scale properties affecting catalytic activity and selectivity. The organic capping agents stabilizing colloidal nanoparticles, however, often limit their application in high-temperature catalytic reactions. Here, we report the design of a high-temperature-stable model catalytic system that consists of a Pt metal core coated with a mesoporous silica shell (Pt@mSiO(2)). Inorganic silica shells encaged the Pt cores up to 750 degrees C in air and the mesopores providing direct access to the Pt core made the Pt@mSiO(2) nanoparticles as catalytically active as bare Pt metal for ethylene hydrogenation and CO oxidation. The high thermal stability of Pt@mSiO(2) nanoparticles enabled high-temperature CO oxidation studies, including ignition behaviour, which was not possible for bare Pt nanoparticles because of their deformation or aggregation. The results suggest that the Pt@mSiO(2) nanoparticles are excellent nanocatalytic systems for high-temperature catalytic reactions or surface chemical processes, and the design concept used in the Pt@mSiO(2) core-shell catalyst can be extended to other metal/metal oxide compositions.

Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation

Platinum nanocubes and nanopolyhedra with tunable size from 5 to 9 nm were synthesized by controlling the reducing rate of metal precursor ions in a one-pot polyol synthesis. A two-stage process is proposed for the simultaneous control of size and shape. In the first stage, the oxidation state of the metal ion precursors determined the nucleation rate and consequently the number of nuclei. The reaction temperature controlled the shape in the second stage by regulation of the growth kinetics. These well-defined nanocrystals were loaded into MCF-17 mesoporous silica for examination of catalytic properties. Pt loadings and dispersions of the supported catalysts were determined by elemental analysis (ICP-MS) and H(2) chemisorption isotherms, respectively. Ethylene hydrogenation rates over the Pt nanocrystals were independent of both size and shape and comparable to Pt single crystals. For pyrrole hydrogenation, the nanocubes enhanced ring-opening ability and thus showed a higher selectivity to n-butylamine as compared to nanopolyhedra.

Sub-Two Nanometer Single Crystal Au Nanowires

Ultrathin single crystal Au nanowires with diameter of approximately 1.6 nm and length of few micrometers were synthesized with high yield by simply mixing HAuCl 4 and oleylamine at room temperature. High resolution transmission electron microscopy studies revealed that all of these nanowires are single crystalline and grew along the [111] direction. The valency evolution of the gold species during the synthesis was studied by X-ray photoelectron spectroscopy, which showed a clear Au (3+) --> Au (+) --> Au stepwise reduction at different reaction stages. Small angle X-ray scattering and small-angle X-ray diffraction suggest mesostructure formation upon HAuCl 4 and oleylamine mixing. The slow in situ reduction of this mesostructure leads to the formation of ultrathin nanowires in solution. This novel nanowire growth mechanism relies on cooperative interaction, organization, and reaction between inorganic precursor salts and oleylamine.

Yolk–Shell Nanocrystal@ZIF-8 Nanostructures for Gas-Phase Heterogeneous Catalysis with Selectivity Control

A general synthetic strategy for yolk-shell nanocrystal@ZIF-8 nanostructures has been developed. The yolk-shell nanostructures possess the functions of nanoparticle cores, microporous shells, and a cavity in between, which offer great potential in heterogeneous catalysis. The synthetic strategy involved first coating the nanocrystal cores with a layer of Cu(2)O as the sacrificial template and then a layer of polycrystalline ZIF-8. The clean Cu(2)O surface assists in the formation of the ZIF-8 coating layer and is etched off spontaneously and simultaneously during this process. The yolk-shell nanostructures were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, and nitrogen adsorption. To study the catalytic behavior, hydrogenations of ethylene, cyclohexene, and cyclooctene as model reactions were carried out over the Pd@ZIF-8 catalysts. The microporous ZIF-8 shell provides excellent molecular-size selectivity. The results show high activity for the ethylene and cyclohexene hydrogenations but not in the cyclooctene hydrogenation. Different activation energies for cyclohexene hydrogenation were obtained for nanostructures with and without the cavity in between the core and the shell. This demonstrates the importance of controlling the cavity because of its influence on the catalysis.

Nanocrystal bilayer for tandem catalysis

Supported catalysts are widely used in industry and can be optimized by tuning the composition and interface of the metal nanoparticles and oxide supports. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical to achieve better reaction activities and selectivities. We introduce here a new class of nanocrystal tandem catalysts that have multiple metal-metal oxide interfaces for the catalysis of sequential reactions. We utilized a nanocrystal bilayer structure formed by assembling platinum and cerium oxide nanocube monolayers of less than 10 nm on a silica substrate. The two distinct metal-metal oxide interfaces, CeO(2)-Pt and Pt-SiO(2), can be used to catalyse two distinct sequential reactions. The CeO(2)-Pt interface catalysed methanol decomposition to produce CO and H(2), which were subsequently used for ethylene hydroformylation catalysed by the nearby Pt-SiO(2) interface. Consequently, propanal was produced selectively from methanol and ethylene on the nanocrystal bilayer tandem catalyst. This new concept of nanocrystal tandem catalysis represents a powerful approach towards designing high-performance, multifunctional nanostructured catalysts.

Optimized Metal–Organic-Framework Nanospheres for Drug Delivery: Evaluation of Small-Molecule Encapsulation

We have developed a general synthetic route to encapsulate small molecules in monodisperse zeolitic imid-azolate framework-8 (ZIF-8) nanospheres for drug delivery. Electron microscopy, powder X-ray diffraction, and elemental analysis show that the small-molecule-encapsulated ZIF-8 nanospheres are uniform 70 nm particles with single-crystalline structure. Several small molecules, including fluorescein and the anticancer drug camptothecin, were encapsulated inside of the ZIF-8 framework. Evaluation of fluorescein-encapsulated ZIF-8 nanospheres in the MCF-7 breast cancer cell line demonstrated cell internalization and minimal cytotoxicity. The 70 nm particle size facilitates cellular uptake, and the pH-responsive dissociation of the ZIF-8 framework likely results in endosomal release of the small-molecule cargo, thereby rendering the ZIF-8 scaffold an ideal drug delivery vehicle. To confirm this, we demonstrate that camptothecin encapsulated ZIF-8 particles show enhanced cell death, indicative of internalization and intracellular release of the drug. To demonstrate the versatility of this ZIF-8 system, iron oxide nanoparticles were also encapsulated into the ZIF-8 nanospheres, thereby endowing magnetic features to these nanospheres.

Room‐Temperature Formation of Hollow Cu2O Nanoparticles

Monodisperse Cu and Cu2O nanoparticles (NPs) are synthesized using tetradecylphosphonic acid as a capping agent. Dispersing the NPs in chloroform and hexane at room temperature results in the formation of hollow Cu2O NPs and Cu@Cu2O core/shell NPs, respectively. The monodisperse Cu2O NPs are used to fabricate hybrid solar cells with efficiency of 0.14percent under AM 1.5 and 1 Sun illumination.

Converting homogeneous to heterogeneous in electrophilic catalysis using monodisperse metal nanoparticles

A continuing goal in catalysis is to unite the advantages of homogeneous and heterogeneous catalytic processes. To this end, nanoparticles represent a new frontier in heterogeneous catalysis, where this unification can also be supplemented by the ability to obtain new or divergent reactivity and selectivity. We report a novel method for applying heterogeneous catalysts to known homogeneous catalytic reactions through the design and synthesis of electrophilic platinum nanoparticles. These nanoparticles are selectively oxidized by the hypervalent iodine species PhICl(2), and catalyse a range of π-bond activation reactions previously only catalysed through homogeneous processes. Multiple experimental methods are used to unambiguously verify the heterogeneity of the catalytic process. The discovery of treatments for nanoparticles that induce the desired homogeneous catalytic activity should lead to the further development of reactions previously inaccessible in heterogeneous catalysis. Furthermore, a size and capping agent study revealed that Pt PAMAM dendrimer-capped nanoparticles demonstrate superior activity and recyclability compared with larger, polymer-capped analogues.

Dendrimer Templated Synthesis of One Nanometer Rh and Pt Particles Supported on Mesoporous Silica: Catalytic Activity for Ethylene and Pyrrole Hydrogenation.

Monodisperse rhodium (Rh) and platinum (Pt) nanoparticles as small as approximately 1 nm were synthesized within a fourth generation polyaminoamide (PAMAM) dendrimer, a hyperbranched polymer, in aqueous solution and immobilized by depositing onto a high-surface-area SBA-15 mesoporous support. X-ray photoelectron spectroscopy indicated that the as-synthesized Rh and Pt nanoparticles were mostly oxidized. Catalytic activity of the SBA-15 supported Rh and Pt nanoparticles was studied with ethylene hydrogenation at 273 and 293 K in 10 torr of ethylene and 100 torr of H 2 after reduction (76 torr of H 2 mixed with 690 torr of He) at different temperatures. Catalysts were active without removing the dendrimer capping but reached their highest activity after hydrogen reduction at a moderate temperature (423 K). When treated at a higher temperature (473, 573, and 673 K) in hydrogen, catalytic activity decreased. By using the same treatment that led to maximum ethylene hydrogenation activity, catalytic activity was also evaluated for pyrrole hydrogenation.

Evolution of Structure and Chemistry of Bimetallic Nanoparticle Catalysts under Reaction Conditions

Three series of bimetallic nanoparticle catalysts (Rh(x)Pd(1-x), Rh(x)Pt(1-x), and Pd(x)Pt(1-x), x = 0.2, 0.5, 0.8) were synthesized using one-step colloidal chemistry. X-ray photoelectron spectroscopy (XPS) depth profiles using different X-ray energies and scanning transmission electron microscopy showed that the as-synthesized Rh(x)Pd(1-x) and Pd(x)Pt(1-x) nanoparticles have a core-shell structure whereas the Rh(x)Pt(1-x) alloys are more homogeneous in structure. The evolution of their structures and chemistry under oxidizing and reducing conditions was studied with ambient-pressure XPS (AP-XPS) in the Torr pressure range. The Rh(x)Pd(1-x) and Rh(x)Pt(1-x) nanoparticles undergo reversible changes of surface composition and chemical state when the reactant gases change from oxidizing (NO or O(2) at 300 degrees C) to reducing (H(2) or CO at 300 degrees C) or catalytic (mixture of NO and CO at 300 degrees C). In contrast, no significant change in the distribution of the Pd and Pt atoms in the Pd(x)Pt(1-x) nanoparticles was observed. The difference in restructuring behavior under these reaction conditions in the three series of bimetallic nanoparticle catalysts is correlated with the surface free energy of the metals and the heat of formation of the metallic oxides. The observation of structural evolution of bimetallic nanoparticles under different reaction conditions suggests the importance of in situ studies of surface structures of nanoparticle catalysts.