• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.130-131
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• 2013

Nanostructured oxides are widely used in heterogeneous catalysis where their catalytic properties are closely associated with the size and morphology at nanometer level. The effect of particle size has been well decumented in the past two decades, but the shape of the nanoparticles has rarely been concerned. Here we illustrate that the redox and acidic-basic properties of oxides are largely dependent on their shapes by taking $Co_3O_4$, $Fe_2O_3$, $CeO_2$ and $La_2O_3$ nanorods as typical examples. The catalytic activities of these rod-shaped oxides are mainly governed by the nature of the exposed crystal planes. For instance, the predominant presence of {110} planes which are rich in active $Co^{3+}$ on $Co_3O_4$ nanorods led to a much higher activity for CO oxidation than the nanoparticles that mainly exposed the {111} planes. The simultaneous exposure of iron and oxygen ions on the surface of $Fe_2O_3$ nanorods have significantly enhanced the adsorption and activation of NO and thereby promoted the efficiency of DeNOx process. Moreover, the exposed surface planes of these rod-shaped oxides mediated the reaction performance of the integrated metal-oxide catalysts. Au/$CeO_2$ catalysts exhibited outstanding stability under water-gas shift conditions owing to the strong bonding of gold particle on the $CeO_2$ nanorods where the formed gold-ceria interface was resistant towards sintering. Cu nanoparticles dispersed on $La_2O_3$ nanorods efficiently catalyzed transfer dehydrogenation of primary aliphatic alcohols based on the uniue role of the exposed {110} planes on the support. Morphology control at nanometer level allows preferential exposure of the catalytically active sites, providing a new stragegy for the design of highly efficient nanostructured catalysts.

• Journal of Electrochemical Science and Technology
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• v.1 no.1
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• pp.10-18
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• 2010

Controlled electrodeposition of dendritic nano-structured gold-platinum (AuPt) alloy onto an electrochemically pretreated carbon paper substrate was conducted in an attempt to improve catalyst utilization and to secure an electronic percolation network toward formic acid (FA) fuel cell application. The AuPt catalysts were obtained by potentiostatic deposition. AuPt catalysts synthesized as bimetallic alloys with 60% Au content exhibited the highest catalytic activity towards formic acid electro-oxidation. The origin of this high activity and the role of Au were evaluated, in particular, by XPS analysis. Polarization and stability measurements with 1 mg $cm^{-2}$ AuPt catalyst (only 0.4 mg $cm^{-2}$ Pt) showed 52 mW $cm^{-2}$ and sustainable performance using 3M formic acid and dry air at $40^{\circ}C$.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.906-910
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• 2012

Hollow gold-silver bimetallic nanoparticles (AuAg-HNPs) have been synthesized and their optical and structural properties were characterized. Initially Ag nanoparticles (Ag-NPs) were prepared using poly(ethylenimine) (PEI) as a reducing and a stabilizing agent simultaneously. AuAg-HNPs could then be synthesized via galvanic replacement reaction in a PEI aqueous solution by reacting sacrificial Ag template with a precursor compound of Au, i.e., $HAuCl_4$. Due to the presence of abundant amine functional groups in PEI, which could act as the dissolving ligand for AgCl, the precipitation problem of $Ag^+$ in the presence of Cl from $HAuCl_4$ salt was avoided. On this basis, the relatively high concentrations of $HAuCl_4$ and PEI-stabilized Ag nanoparticles could be used for the fabrication of AuAg-HNPs. Because of their increased surface areas and reduced densities, the AuAg-HNPs were expected and confirmed to outperform their solid counterparts in applications such as catalysis for the reduction of 4-nitrophenol in the presence of $NaBH_4$.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.588-588
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• 2013

Nanoscale noble-metals have attracted enormous attention from researchers in various fields of study because of their unusual optical properties as well as novel chemical properties. They have possible uses in diverse applications such as devices, transistors, optoelectronics, information storages, and energy converters. It is well-known that nanoparticles of noble-metals such as silver and gold show strong absorption bands in the visible region due to their surface-plasmon oscillation modes of conductive electrons. Silver nanocubes stand out from various types of Silver nanostructures (e.g., spheres, rods, bars, belts, and wires) due to their superior performance in a range of applications involvinglocalized surface plasmon resonance, surface-enhanced Raman scattering, and biosensing. In addition, extensive efforts have been devoted to the investigation of Gold-based nanocomposites to achieve high catalytic performances and utilization efficiencies. Furthermore, as the catalytic reactivity of Silver nanostructures depends highly on their morphology, hollow Gold nanoparticles having void interiors may offer additional catalytic advantages due to their increased surface areas. Especially, hollow nanospheres possess structurally tunable features such as shell thickness, interior cavity size, and chemical composition, leading to relatively high surface areas, low densities, and reduced costs compared with their solid counterparts. Thus, hollow-structured noblemetal nanoparticles can be applied to nanometer-sized chemical reactors, efficient catalysts, energy-storage media, and small containers to encapsulate multi-functional active materials. Silver nanocubes dispersed in water have been transformed into Ag@Au nanoboxes, which show highly enhanced catalytic properties, by adding $HAuCl_4$. By using this concept, $SiO_2$-coated Ag@Au nanoboxes have been synthesized via galvanic replacement of $SiO_2$-coated Ag nanocubes. They have lower catalytic ability but more stability than Ag@Au nanoboxes do. Thus, they could be recycled. $SiO_2$-coated Ag@Au nanoboxes have been found to catalyze the degradation of 4-nitrophenol efficiently in the presence of $NaBH_4$. By changing the amount of the added noble metal salt to control the molar ratio Au to Ag, we could tune the catalytic properties of the nanostructures in the reduction of the dyes. The catalytic ability of $SiO_2$-coated Ag@Au nanoboxes has been found to be much more efficient than $SiO_2$-coated Ag nanocubes. Catalytic performances were affected noteworthily by the metals, sizes, and shapes of noble-metal nanostructures.

• Korean Chemical Engineering Research
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• v.59 no.3
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• pp.373-378
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• 2021

The study aimed to develop a high-power enzymatic electrode for a wearable fuel cell that generates electricity utilizing lactate present in a sweat as fuel. Anode was fabricated by immobilizing lactate oxidase (LOx) on flexible carbon paper. As the lactate concentration in the electrolyte solution increased, the amount of current generated by catalysis of lactate oxidase increased. The immobilized LOx generated 1.5-times greater oxidation current density in the presence of gold nanoparticles than carbon paper only. Bilirubin oxidase (BOD)-immobilized cathode generated a larger amount of reduction current in the electrolyte saturated with oxygen than purged with nitrogen. A fuel cell composed of two electrodes was fabricated and cell voltage was measured under different discharge current. At the discharge current density of 66.7 ㎂/cm², the cell voltage was 0.5±0.0 V leading to maximum cell power density of 33.8±2.5 ㎼/cm².

• Korean Journal of Materials Research
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• v.27 no.4
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• pp.229-235
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• 2017

Through density functional theory calculations, to provide insight into the origins of the catalytic activity of Au nanoparticles (NPs) toward oxidation reactions, we have scrutinized the oxygen adsorption chemistry of 9 types of small unsupported Au NPs of around 1 nm in size (Au13, Au19, Au20, Au25, Au38, and Au55) looking at several factors (size, shape, and coordination number). We found that these NPs, except for the icosahedral Au13, do not strongly bind to $O_2$ molecules. Energetically most feasible $O_2$ adsorption that potentially provides high CO oxidation activity is observed in the icosahedral Au13, our smallest Au NP. In spite of the chemical inertness of bulk Au, the structural fluxionality of such very small Au NP enables strong $O_2$ adsorption. Our results can support recent experimental findings that the exceptional catalytic activity of Au NPs comes from very small Au species consisting of around 10 atoms each.

• Korean Journal of Materials Research
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• v.33 no.11
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• pp.447-457
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• 2023

Single-atom Pd clusters anchored on t-BaTiO₃ material was synthesized using hydrothermal and ultrasonic methods for the effective piezoelectric catalytic degradation of pollutants using vibration energy. XRD patterns of BaTiO₃ loaded with monoatomic Pd were obtained before and after calcining, and showed typical cubic-phase BTO. TEM and HAADF-STEM images indicated single-atom Pd clusters were successfully introduced into the BaTiO₃. The piezoelectric current density of the prepared Pd-BaTiO₃ binary composite was significantly higher than that of the pristine BaTiO₃. Under mechanical vibration, the nanomaterial exhibited a tetracycline decomposition rate of ~95 % within 7 h, which is much higher than the degradation rate of 56.7 % observed with pure BaTiO₃. Many of the piezo-induced electrons escaped to the Pd-doped BaTiO₃ interface because of Pd's excellent conductivity. Single-atom Pd clusters help promote the separation of the piezo-induced electrons, thereby achieving synergistic catalysis. This work demonstrates the feasibility of combining ultrasonic technology with the piezoelectric effect and provides a promising strategy for the development of ultrasonic and piezoelectric materials.

• Journal of the Korean Electrochemical Society
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• v.2 no.1
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• pp.31-37
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• 1999

Copper-containig enzyme, laccase (Rhus vernicifera) was immobilized onto gold electrode using self-assembly technique and its surface properties and catalytic activities were examined. Laccase is an oxidoreductase capable to oxidize diphenols or diamines by 4-electron reduction of molecular oxygen without superoxide or peroxide intermediates. The electrode surface were modified by $\beta-mercaptopropionate$ to have a net negative charge in neutral solution and positively charged laccase (pI=9) was immobilized by electrostatic interaction. The successful immobilization was confirmed by cyclic voltammograms which showed typical surface-confined shapes and behaviors. The amount of charge to reduce the surface was similar to the charge calculated assuming the surface being covered by monolayer. The activity of the immobilized enzyme was tested by the capbility of oxidizing a substrate, ABTS (2,2-azine-bis-(3-ethylbenzthioline-6-sulfonic acid) and it was maintained for $2\~3$ days at $4^{\circ}C$. The immobilzed laccase showed about $10\~15\%$ activity compared to that in solution. The laccase-modified electrode showed the activity of elefoocatalytic reduction of oxygen in the presence of mediator, $Fe(CN)_6^{3-}$ The addtion of azide which is an inhibitor of laccase compeletly eliminated the catalytic current.