• Journal of the Korean Society of Industry Convergence
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• v.7 no.1
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• pp.107-113
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• 2004

Several transition metal complexes, [$M(L)X_2$](M=Pd(II), Ni(II); X=CI, Br) are prepared with aminophosphine ligands such as 1,2-bis{(diphenylphosphino)amino}ethane{$Ph_2PNHCH_2CH_2NHPPh_2$}($L_1$), 1,2-bis{(diphenylphosphino)amino}propane{$Ph_2PNHCH(CH_3)CH_2NHPPh_2$}($L_2$), trans-1,2-bis{(diphenylphosphino)amino}cyclohexane{$Ph_2PNHC_6H_{10}NHPPh_2$}($L_3$) and 1,2-bis{(diphenylphosphino)amino}benzene{$Ph_2PNHC_6H_4NHPPh_2$}($L_4$). The properties of these complexes are characterized by optical spectroscopic methods including UV/vis spectroscopy, CD, IR, $^1H$- and $^{31}P-NMR$ together with conductometer and elemental analysis. All complexes are stable under atmospheric environment. Catalytic reactivity for C-C coupling between [$M(L)X_2$] and Grignard reagents(RMgX; R=phenyl, propyl, buthyl) by thermolysis were investigated utilizing GC/mass, $^1H$- and $^{13}C-NMR$. When mol scale is 1:20 at [$Pd(L)Cl_2$] and Grignard reagents, the high catalytic activity for C-C coupling is apparent. The [$M(L)X_2$](X=Cl, Br) complexes which have strong bond at M-P exhibit high yields for C-C coupling reactions. When the central metal ion is Pd(II), the high catalytic activity for C-C coupling is apparent. The complex coordinated with Br shows higher catalytic activity for C-C coupling reactions compared to Cl.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2009.11a
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• pp.278-278
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• 2009

A photovoltaic device consisting of arrays of radial p-n junction wires enables a decoupling of the requirements for light absorption and carrier extraction into orthogonal spatial directions. Each individual p-n junction wire in the cell is long in the direction of incident light, allowing for effective light absorption, but thin in orthogonal direction, allowing for effective carrier collection. To fabricate radial p-n junction solar cells, p or n-type vertical Si wire cores need to be produced. The majority of Si wires are produced by the vapor-liquid-solid (VLS) method. But contamination of the Si wires by metallic impurities such as Au, which is used for metal catalyst in the VLS technique, results in reduction of conversion efficiency of solar cells. To overcome impurity issue, top-down methods like noble metal catalytic etching is an excellent candidate. We used noble metal catalytic etching methods to make Si wire arrays. The used noble metal is two; Au and Pt. The method is noble metal deposition on photolithographycally defined Si surface by sputtering and then etching in various BOE and $H_2O_2$ solutions. The Si substrates were p-type ($10{\sim}20ohm{\cdot}cm$). The areas that noble metal was not deposited due to photo resist covering were not etched in noble metal catalytic etching. The Si wires of several tens of ${\mu}m$ in height were formed in uncovered areas by photo resist. The side surface of Si wires was very rough. When the distance of Si wires is longer than diameter of that Si nanowires are formed between Si wires. Theses Si nanowires can be removed by immersing the specimen in KOH solution. The optimum noble metal thickness exists for Si wires fabrication. The thicker or the thinner noble metal than the optimum thickness could not show well defined Si wire arrays. The solution composition observed in the highest etching rate was BOE(16.3ml)/$H_2O_2$(0.44M) in Au assisted chemical etching method. The morphology difference was compared between Au and Pt metal assisted chemical etching. The efficiencies of radial p-n junction solar Cells made of the Si wire arrays were also measured.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.246-246
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• 2012

Smart catalyst design though novel catalyst preparation methods can improve catalytic activity of transition metals on reducible oxide supports such as titania by enhancement of metal oxide interface effects. In this work, we investigated Pt nanoparticles/titania catalysts under CO oxidation reaction by using novel preparation methods in order to enhance its catalytic activity by optimizing metal oxide interface. Arc plasma deposition (APD) and metal impregnation techniques are employed to achieve Pt metal deposition on titania supports which are prepared by multi-target sputtering and Sol-gel techniques. In order to tailor metal-support interface for catalytic CO oxidation reaction, Pt nanoparticles and thin films are deposited in varying surface coverages on sputtered titania films using APD. To assess the role of oxide support at the interface, APD-Pt is deposited on sputtered and Sol-gel prepared titania films. Lastly, characteristics of APD-Pt process are compared with Pt impregnation technique. Our results show that activity of Pt nanoparticles is improved when supported over Sol-Gel prepared titania than sputtered titania film. It is suggested that this enhanced activity can be partly ascribed to a very rough titania surface with the higher free metal surface area and higher number of sites at the interface between the metal and the support. Also, APD-Pt shows superior catalytic activity under CO oxidation as compared to Pt impregnation on sputtered titania support. XPS results show that bulk oxide is formed on Pt when deposited through impregnation and has higher proportion of oxidized Pt in the form of $Pt^{2+/4+}$ oxidation states than Pt metal. APD-Pt shows, however, mild oxidation with large proportion of active Pt metal. APD-Pt also shows trend of increasing CO oxidation activity with number of shots. The activity continues to increase with surface coverage beyond 100%, thus suggesting a very rough and porous Pt films with higher active surface metal sites due to an increased surface area available for the reactant CO and $O_2$ molecules. The results suggest a novel approach for systematic investigation into metal oxide interface by rational catalysts design which can be extended to other metal-support systems in the future.

• Carbon letters
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• v.3 no.3
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• pp.146-151
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• 2002

Activated carbon fibers were prepared from the petroleum isotropic pitch and organometallic compounds. The metalsvwere dispersed uniformly in the ACFs. The specific surface area and pore size distributions of metal containing ACFsvwere measured. The mesopores of ACFs were developed by Co, Ni, and Mn metals addition and the catalytic reactivityvof ACFs'SOx removal was increased by adding Ni and Pd metals. It was found that the mesopores did not work forvthe improvement of catalytic reactivity of ACFs' SOx removal with the blank experiment using the metal removedvACFs.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.245-245
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• 2012

Syntheses of oxide supported metal catalysts by wet-chemical routes have been well known for their use in heterogeneous catalysis. However, uniform deposition of metal nanoparticles with controlled size and shape on the support with high reproducibility is still a challenge for catalyst preparation. Among various synthesis methods, arc plasma deposition (APD) of metal nanoparticles or thin films on oxide supports has received great interest recently, due to its high reproducibility and large-scale production, and used for their application in catalysis. In this work, Au and Pt nanoparticles with size of 1-2 nm have been deposited on titania powder by APD. The size of metal nanoparticles was controlled by number of shots of metal deposition and APD conditions. These catalytic materials were characterized by x-ray diffraction (XRD), inductively coupled plasma (ICP-AES), CO-chemisorption and transmission electron microscopy (TEM). Catalytic activity of the materials was measured by CO oxidation using oxygen, as a model reaction, in a micro-flow reactor at atmospheric pressure. We found that Au/$TiO_2$ is reactive, showing 100% conversion at $110^{\circ}C$, while Pt/$TiO_2$ shows 100% conversion at $200^{\circ}C$. High activity of metal nanoparticles suggests that APD can be used for large scale synthesis of active nanocatalysts. We will discuss the effect of the structure and metal-oxide interactions of the catalysts on catalytic activity.

• Journal of the Korean Society of Combustion
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• v.8 no.2
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• pp.27-33
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• 2003

Synthesis of carbon nanomaterials on a metal substrate by an ethylene fueled inverse diffusion flame was illustrated. Stainless steel plates were used for the catalytic metal substrate. The effects of catalyst metal particles were investigated through $Fe(NO_3){_3}$ (ferric nitrate, nonahydrate) and $Ni(NO_3){_2}$ (nickel nitrate, hexahydrate). Carbon nanotubes and nanofibers with diameters of $30{\sim}70nm$ were found on the substrate for the case of using SUS304 substrates only and using them with metal nitrates. In case of using metal nitrates, due to the easy activation of the metal particles, the formation and growth of carbon nanomaterials were occurred in the lower temperature region than that of using SUS304 substrates only.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.304-304
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• 2010

The study on the catalytic oxidation of carbon monoxide (CO) to carbon dioxide ($CO_2$) using the noble metals has long been the interest subject and the recent progress in nanoscience provides the opportunity to develop new model systems of catalysts in this field. Of the noble metal catalysts, we selected ruthenium (Ru) as metal catalyst due to its unusual catalytic behavior. The size of colloid Ru NPs was controlled by the concentration of Ru precursor and the final reduction temperatures. For catalytic activity of CO oxidation, it was found that the trend is dependent on the size of Ru NPs. In order to explain this trend, the surface oxide layer surrounding the metal core has been suggested as the catalytically active species through several studies. In this poster, we show the influence of surface oxide on Ru NPs on the catalytic activity of CO oxidation using chemical treatments including oxidation, reduction and UV-Ozone surface treatment. The changes occurring to UV-Ozone surface treatment will be characterized with XPS and SEM. The catalytic activity before and after the chemical modification were measured. We discuss the trend of catalytic activity in light of the formation of core-shell type oxide on nanoparticles surfaces.

• Journal of Korean Society of Environmental Engineers
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• v.22 no.10
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• pp.1809-1816
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• 2000

The catalytic combustion of methanol as a model volatile organic compound(VOC) was been investigated over metal-phthalocyanine(PC) in a fixed bed flow reactor system. The catalytic activity of Co-PC pretreated with air and methanol mixture at $450^{\circ}C$ and 60 cc/min for 1 hr was very excellent. The order of catalytic activity on methanol combustion was summarized as follows: metal free-PC < Zn-PC < Fe-PC < Cu($\alpha$)-PC < Co-PC. By TG/DTA analysis, the tendency of thermal decomposition was increased as follows: metal free-PC < Zn-PC < Cu($\alpha$)-PC < Co-PC < Fe-PC. Under this pretreatment condition, the basic structures of Co-PC, Cu($\alpha$)-PC and Fe-PC were destroyed, and the new metal oxide such as $Co_3O_4$ from Co-PC was confirmed by EA and XRD analysis. But Zn-PC and metal free-PC were retained its basic structure under this pretreatment condition. On the combustion of methanol over Co-PC, HCHO and $HCOOCH_3$ were observed as an intermediate products in the high concentration of reactant or the short contact time(W/F).

• Proceedings of the KSME Conference
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• 2004.04a
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• pp.1304-1309
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• 2004

Synthesis of carbon nanotubes and nanofibers on a catalytic metal substrate, using an ethylene fueled inverse diffusion flame, was investigated. Multi-walled carbon nanotubes, with diameters of 20 - 60nm, were formed on the substrate coated with nickel-nitrate in the region of 5 - 6mm from the flame center along the radial direction. The gas temperature for this region was ranging from about 1400 to 900K. Nickel particles originated from the coated nickel-nitrate on the substrate were the major catalyst for the formation of the nanomaterials. HR-TEM and Raman spectrum revealed that synthesized carbon nanotubes had multi-walled structures with some defective graphite layers at walls.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2153-2161
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• 2007

The transition metal-induced in situ generation of carbene complexes from alkynes having a carbonyl or imino group as a nucleophilic functionality has been investigated. These reactive carbenoid species are generated with high atom efficiency through a 6-endo-dig cyclization mode based on the electrocyclization of vinylidene complexes or a 5-exo-dig cyclization mode in π-alkyne complexes, and have been found to serve as versatile intermediates in catalytic carbene transfer reactions. Highlighted and reviewed in this account are the generation and preparation of pyranylidene, furylcarbene, pyrrolylcarbene, and vinylcarbene complexes and their application to [3,3]sigmatropic rearrangement of acylcyclopropylvinylidenes, catalytic cyclopropanation reactions, [2,3]sigmatropic rearrangement or condensation reactions via ylides, ring-opening and substitution reactions with heteroaromatic compounds, and catalytic isomerization of oligoynes.