• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.317.2-317.2
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• 2013

Ultrathin oxide encapsulated metal-oxide hybrid nanocatalysts have been fabricated by a soft chemical and facile route. First, SiO2 nanoparticles of 25~30 nm size have been synthesized by modified Stobber's method followed by amine functionalization. Metal nanoparticles (Ru, Rh, Pt) capped with polymer/citrate have been deposited on functionalized SiO2 and finally an ultrathin layer of TiO2 coated on surface which prevents sintering and provides high thermal stability while maximizing the metal-oxide interface for higher catalytic activity. TEM studies confirmed that 2.5 nm sized metal nanoparticles are well dispersed and distributed throughout the surface of 25 nm SiO2 nanoparticles with a 3-4 nm TiO2 ultrathin layer. The metal nanoparticles are still well exposed to outer surface, being enabled for surface characterization and catalytic activity. Even after calcination at $600^{\circ}C$, the structure and morphology of hybrid nanocatalysts remain intact confirm the high thermal stability. XPS spectra of hybrid nanocatalyst suggest the metallic states as well as their corresponding oxide states. The catalytic activity has been evaluated for high temperature CO oxidation reaction as well as photocatalytic H2 generation under solar simulation. The design of hybrid structure, high thermal stability, and better exposure of metal active sites are the key parameters for the high catalytic activity. The maximization of metal-TiO2 interface interaction has the great role in photocatalytic H2 production.

• Korean Chemical Engineering Research
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• v.50 no.5
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• pp.795-801
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• 2012

Nanoparticles have received significant attention because of their unusual characteristics including high surface area to volume ratios. Thiol ligand have been used as stabilizers of metal nanoparticles since Brust et al. They reported the preparation method of ligand capped metal nanoparticles by protecting the nanoparticles with a self-assembled monolayer of dodecanethiolate. In this method, volatile organic compounds (VOCs) were used as sovents. This study was carried out to replace these VOCs with room temperature ionic liquids (RTILs). We used two type of ILs to prepare metal nanoparticles. One is a hydrophobic IL, [BMIM][[$PF_6$] (1-Butyl-3-methylimidazolium hexafluorophosphate) purchased from IL maker, C-Tri from Korea and the other one is a hydrophilic one, [BMIM][Cl] (1-Buthy-3-methylimdazolium chloride) sinthesized by us. In the case of preparing Ag and Au nanoparticles using [BMIM][Cl], we didn't use phase transition reagents and ethanol because it has hydrophilic property and preparing Au, Ag nanoparticles using [BMIM][[$PF_6$] the method is as same as Brust et al.'s except using [BMIM][[$PF_6$] instead of organic solvent because it has hydrophobic property. FT-IR and UV-vis, TEM, TGA analysis have been used in an attempt to determine the particle size and verify functional groups. The particle size obtained from TEM was very similar to those obtained by Brust et al. This is a clear example of ligand capped metal nanoparticles prepared using ionic liquids. And the experimental result demonstrated ionic liquids can act as a highly effective medium for the preparation and stabilization of gold and silver metal nanoparticles.

• Proceedings of the Korean Vacuum Society Conference
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• 2015.08a
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• pp.230.2-230.2
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• 2015

Nanoparticles of magnesium ferrite are used as a heterogeneous catalyst, humidity sensor, oxygen sensor and cure of local hyperthermia. These applications usually utilize the magnetic behavior of these nanoparticles. Moreover, magnetic properties of nanoferrites exhibit rather complex behavior compared to bulk ferrite. The magnetic properties of ferrites are complicated by spins at vortices, surface spins. Reports till date indicate strong dependency on the structural parameters, oxidation state of metal ions and their presence in octahedral and tetrahedral environment. Thus we have carried out investigation on magnesium ferrite nanoparticles in order to study coordination, oxidation state and structural distortion. For present work, magnesium ferrite nanoparticles were synthesized using nitrates of metal ions and citric acid. Fe L-edge spectra measured for these nanoparticles shows attributes of $Fe^{3+}$ in high spin state. Moreover O K-edge spectra for these nanoparticles exhibit spectral features that arises due to unoccupied states of O 2p character hybridized with metal ions. Mg K-edge spectra shows spectral features at 1304, 1307, 1311 and 1324 eV for nanoparticles obtained after annealing at 400, 500, 600, 800, 1000, and $1200^{\circ}C$. Apart from this, spectra for precursor and nanoparticles obtained at $300^{\circ}C$ exhibit a broad peak centered around 1305 eV. A shoulde rlike structure is present at 1301 eV in spectra for precursor. This feature does not appear after annealing. After annealing a small kink appear at ~1297 eV in Mg K-edge spectra for all nanoparticles. This indicates changes in local electronic structure during annealing of precursor. Observed behavior of change in local electronic structure will be discussed on the basis of existing theories.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.11a
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• pp.368-368
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• 2007

Zinc oxide (ZnO) has drawn much interest as a potential transparent conducting oxide (TCO) for applying to solar cell and front electrode of electro-luminescent devices. For the enhancement of electrical property of TCOs, dopant introduction and hybridization with conductive nanoparticles have been investigated. In this work, ZnO films were formed on glass substrate by using photochemical solution deposition of Ag nanoparticles dispersed or various metal (Ag, Cd, In, or Sn) contained photosensitive ZnO solutions. The usage of photosensitive solution permits us to obtain a micron-sized direct patterning of ZnO film without using conventional dry etching procedure. The structural, optical, and electrical characteristics of ZnO films with the introduction of metal dopants with/without Ag nanoparticles have been investigated to check whether there is a combined effect between metal dopants and Ag nanoparticles on the characteristics of ZnO film. The phase formation and crystallinity of ZnO film were monitored with X-ray diffractometer. The optical transmittance measurement was carried out using UV-VIS-NIR spectrometer and the electrical properties such as sheet resistance and conductivity were observed by using four-point probe.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.217-217
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• 2011

Recently, demand for thermally stable metal nanoparticles suitable for chemical reactions at high temperatures has increased to the point to require a solution to nanoparticle coalescence. Thermal stability of metal nanoparticles can be achieved by adopting core-shell models and encapsulating supported metal nanoparticles with mesoporous oxides [1,2]. However, to understand the role of metal-support interactions on catalytic activity and for surface analysis of complex structures, we developed a novel catalyst design by coating an ultra-thin layer of titania on Pt supported silica ($SiO_2/Pt@TiO_2$). This structure provides higher metal dispersion (~52% Pt/silica), high thermal stability (~600$^{\circ}C$) and maximization of the interaction between Pt and titania. The high thermal stability of $SiO_2/Pt@TiO_2$ enabled the investigation of CO oxidation studies at high temperatures, including ignition behavior, which is otherwise not possible on bare Pt nanoparticles due to sintering [3]. It was found that this hybrid catalyst exhibited a lower activation energy for CO oxidation because of the metal-support interaction. The concept of an ultra-thin active metal oxide coating on supported nanoparticles opens-up new avenues for synthesis of various hybrid nanocatalysts with combinations of different metals and oxides to investigate important model reactions at high-temperatures and in industrial reactions.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.11a
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• pp.19-19
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• 2008

We investigated the programmable memory characteristics of nanoparticle-based memory devices based on the elementary metal nanoparticles (Co and Au) and their binary mixture synthesized by a micellar route to ordered arrays of metal nanoparticles as charge trapping layers. According to the metal nanoparticle species quite different programming/erasing efficiencies were observed, resulting in the tunable memory characteristics at the same programming/erasing bias conditions. This finding will be a good implication for further device scaling and novel device applications since most processes are based on the conventional semiconductor processes.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.133-133
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• 2013

For both oxygen reduction (ORR) and hydrogen oxidation reactions (HOR) of proton electrolyte membrane fuel cells (PEMFCs), alloying Pt with another transition metal usually results in a higher activity relative to pure Pt, mainly due to electronic modification of Pt and bifunctional behaviour of alloy surface for ORR and HOR, respectively. However, activity and stability are closely related to the preparation of alloy nanoparticles. Preparation conditions of alloy nanoparticles have strong influence on surface composition, oxidation state, nanoparticle size, shape, and contamination, which result from a large difference in redox priority of metal precursors, intrinsic properties of metals, increasedreactivity of nanocrystallites, and interactions with constituents for the synthesis such as solvent, stabilizer, and reducing agent, etc. Carbon-supported Pt-Ni alloy nanoparticles were prepared by the borohydride reduction method in anhydrous solvent. Pt-Ru alloy nanoparticles supported on carbon black were also prepared by the similar synthetic method to that of Pt-Ni. Since electrocatalytic reactions are strongly dependent on the surface structure of metal catalysts, the atom-leveled design of the surface structure plays a significant role in a high catalytic activity and the utilization of electrocatalysts. Therefore, surface-modified electrocatalysts have attracted much attention due to their unique structure and new electronic and electrocatalytic properties. The carbon-supported Au and Pd nanoparticles were adapted as the substrate and the successive reduction process was used for depositing Pt and PtM (M=Ru, Pd, and Rh) bimetallic elements on the surface of Au and Pd nanoparticles. Distinct features of the overlayers for electrocatalytic activities including methanol oxidation, formic acid oxidation, and oxygen reduction were investigated.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.261-261
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• 2013

The smart design of nanocatalysts can improve the catalytic activity of transition metals on reducible oxide supports, such as titania, via strong metal-support interactions. In this work, we investigatedtwo-dimensional Pt nanoparticle/titania catalytic systems under the CO oxidation reaction. Arc plasma deposition (APD) and metal impregnation techniques were employed to achieve Pt nanoparticle deposition on titania supports, which were prepared by multitarget sputtering and sol-gel techniques. APD Pt nanoparticles with an average size of 2.7 nm were deposited on sputtered and sol-gel-prepared titania films to assess the role of the titania support on the catalytic activity of Pt under CO oxidation. In order to study the nature of the dispersed metallic phase and its effect on the activity of the catalytic CO oxidation reaction, Pt nanoparticles were deposited in varying surface coverages on sputtered titania films using arc plasma deposition. Our results show an enhanced activity of Pt nanoparticles when the nanoparticle/titania interfaces are exposed. APD Pt shows superior catalytic activity under CO oxidation, as compared to impregnated Pt nanoparticles, due to the catalytically active nature of the mild surface oxidation and the active Pt metal, suggesting that APD can be used for large-scale synthesis of active metal nanocatalysts.

• Advances in nano research
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• v.2 no.2
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• pp.77-88
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• 2014

Solvothermal treatment of late transition metal acetylacetonates in a novel medium composed either of pure acetophenone or acetophenone mixtures with amino alcohols offers a general approach to uniform hydrophilic metal nanoparticles with high crystallinity and low degree of aggregation. Both pure metal and mixed-metal particles can be accesses by this approach. The produced materials have been characterized by SEM-EDS, TEM, FTIR in the solid state and by Nanoparticle Tracking Analysis in solutions. The chemical mechanisms of the reactions producing nanoparticles has been followed by NMR. Carrying out the process in pure acetophenone produces palladium metal, copper metal with minor impurity of $Cu_2O$, and NiO. The synthesis starting from the mixtures of Pd and Ni acetylacetonates with up to 20 mol% of Pd, renders in minor yield the palladium-based metal alloy along with nickel oxide as the major phase. Even the synthesis starting from a mixed solution of $Cu(acac)_2$ and $Ni(acac)_2$ produces oxides as major products. The situation is improved when aminoalcohols such as 2-aminoethanol or 2-dimethylamino propanol are added to the synthesis medium. The particles in this case contain metallic elements and pairs of individual metals (not metal alloys) when produced from mixed precursor solutions in this case.