Jung-Nam Park

Highly active and sinter-resistant Pd-nanoparticle catalysts encapsulated in silica

) that aresufficiently porous to allow unhindered mass transfer? 2) Howdoes the activity of the encapsulated catalysts compare totraditional supported Pd catalysts for CO oxidation andacetylene hydrogenation? 3) Do the shell structures providestability with respect to sintering at high temperatures?Nanoscale core/shell Pd@SiO

Silica‐Encapsulated Pd Nanoparticles as a Regenerable and Sintering‐Resistant Catalyst

Irreversible, thermally induced sintering of heterogeneous catalysts is one of the most deleterious causes of activity loss during catalytic reaction and/or regeneration. Silica‐coated Pd catalysts (Pd@SiO2) were prepared by a simple one‐pot, water‐in‐oil microemulsion method and investigated as models for a general synthesis to encapsulate active nanoparticle catalysts to provide stability during extended periods of cycling and regeneration under harsh experimental conditions. An idealized stability test would involve both a catalyst whose activity changes significantly as particles sinter and test conditions that could readily induce sintering. Acetylene hydrogenation was chosen as the test reaction because its catalytic and regenerative (oxidative coke removal) cycling induce the destructive sintering conditions desired for such a test. When compared with Pd particles deposited on the outside of an identical silica support (Pd/SiO2 catalyst), the silica‐encapsulated catalyst Pd@SiO2 deactivates at a much slower rate and is readily regenerated without sintering over multiple reaction and regeneration cycles. It is also found that silica encapsulation suppresses coking and in situ formation of PdC. TEM, XRD, BET, XPS, and TGA, before and after reaction and regeneration, were used to characterize the encapsulated Pd@SiO2 catalysts and compare them to conventionally supported Pd/SiO2.

Room-temperature heterogeneous hydroxylation of phenol with hydrogen peroxide over Fe2+, Co2+ ion-exchanged Naβ zeolite

Ion-exchanged Na beta zeolite with Fe2+ and Co2+ cations shows high catalytic activity at room temperature in phenol hydroxylation with H2O2, where the conversion of phenol is ca. 21% and the selectivity of benzoquinone is below 3% at a molar ratio of phenol to H2O2 of 3 in the starting aqueous reaction medium.

Synthesis and characterization of sintering-resistant silica-encapsulated Fe3O4 magnetic nanoparticles active for oxidation and chemical looping combustion

A nanocomposite catalyst composed of ferromagnetic magnetite cores (15.5 +/- 2.0 nm) and silica shells with a thickness of 4.5 +/- 1.0 nm (Fe(3)O(4)@SiO(2)) was prepared by a two-step microemulsion-based synthesis. X-ray photoelectron spectroscopy and Raman spectroscopy after oxidation support the presence of a stable Fe(3)O(4) core and a surface phase of gamma-Fe(2)O(3). The nanocomposite structure exhibited 100% conversion of CO in oxygen at a residence time of 0.1 s at 310 degrees C. When pre-oxidized, the Fe(3)O(4)@SiO(2) catalyst is shown to be a suitable solid oxygen carrier for chemical looping combustion of methane at 700 degrees C. The nanocomposites retain their magnetism following the reaction which provides the potential for use of magnetic separation and capture in moving bed reactor applications. The core magnetite within the silica shell is resistant to sintering and a bulk phase transition to temperatures as high as 700 degrees C. These catalysts can be of use in applications of high temperature applications where catalyst recovery by magnetic separation may be required.

Isopropylation of naphthalene by isopropyl alcohol over USY catalyst: an investigation in the high-pressure fixed-bed flow reactor

Catalytic performances of USY, H-mordenite, dealuminated H-mordenite, and H-MCM-22 zeolite catalysts in the isopropylation of naphthalene by isopropyl alcohol with decalin or cyclohexane as a solvent were compared in a high-pressure fixed-bed flow reactor. For the USY catalyst, reaction conditions, such as reaction temperature and pressure, reactant ratio and space velocity, and solvent concentration and type, were controlled to investigate in detail the effect of reaction conditions on the catalytic activity. Over H-mordenite, it was found that 2,6-diisopropylnaphthalene (2,6-DIPN) could be selectively synthesized with a 2,6-/2,7-DIPN ratio of 2.46, and dealumination could enhance not only the selectivity of 2,6-DIPN, with a 2,6-/2,7-DIPN ratio of 2.67, but also the conversion of naphthalene, which was 27.4%, three times as high as that over the unmodified one at 6 h of reaction time on stream. However, neither the H-mordenite or the dealuminated one were catalytically stable and the selectivity of DIPN was at a very low level of less than 12%. In contrast, over the USY catalyst, a high and stable conversion of about 90%, a high selectivity of DIPN of more than 40%, and a considerable 2,6-/2,7-DIPN ratio of 1.46 could be achieved by adjusting the reaction conditions, although no shape selectivity was observed on USY. On the other hand, only a low 2,6-/2,7-DIPN ratio of 0.47 with a low conversion of about 30% was revealed over H-MCM-22, which indicates that the reaction takes place on the external surface of this zeolite. An attempt has been made to explain the catalytic activity, selectivity, and stability in relation to the zeolite structures, product properties, and reaction conditions.

Mesoporous delafossite CuCrO2 and spinel CuCr2O4: synthesis and catalysis

Delafossite CuCrO2 and spinel CuCr2O4 with mesoporous structures have been successfully synthesized using nanocasting methods based on a KIT-6 template. The functional activity of the mesoporous materials was evaluated in applications as heterogeneous catalysts. The activity for photocatalytic hydrogen production of the delafossite structures with different morphologies was characterized and the oxidation state changes associated with photocorrosion of Cu(+) investigated using electron energy loss spectroscopy (EELS). Mg(2+) doping was found to facilitate the casting of ordered structures for CuCrO2 and improves the photocorrosion resistance of delafossite structures. The mesoporous spinel CuCr2O4 nanostructures were found to be active for low temperature CO oxidation.