• Bulletin of the Korean Chemical Society
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• v.19 no.9
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• pp.934-942
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• 1998

$^13CO$ chemisorbed on platinum particles in L-zeolite has been investigated by static and magic angle spinning NMR spectroscopy. The representative spectra are composed of a broad asymmetric peak with a center of gravity at 230±30 ppm and a sharp symmetric peak at 124±2 ppm which is tentatively assigned to physisorbed $CO_2$, on inner walls of L-zeolite. Overall, the broad resonance component is similar to our previous results of highly dispersed (80-96%) CO/Pt/silica or CO/Pt/alumina samples, still showing metallic characters. The principal difference is in the first moment value. The broad peak in the spectra is assigned to CO linearly bound to Pt particles in the L-zeolites, and indicates a distribution of isotropic shifts from bonding site to bonding site. The NMR results reported here manifest that the Pt particles inside of the L-zeolites channels are not collectively the same with the ones supported on silica or alumina with similar dispersion in terms of Pt particle shape and/or ordering of Pt atoms in a particle. As a result, Pt particles of CO/Pt/L-zeolite were agglomerated accompanying CO desorption upon annealing. There were no definite changes in the NMR spectra due to differences of exchanged cations. Comparison of our observation on CO/Pt/L-zeolite with Sharma et al.'s reveals that even when the first moment, the linewidtb, and the relaxation times of the static spectra and the dispersion measured by chemisorption are similar, the properties of Pt particles can be dramatically different. Therefore, it is essential to take advantage of the strengths of several techniques together in order to interpret data reliably, especially for the highly dispersed samples.

• Korean Journal of Materials Research
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• v.21 no.3
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• pp.180-185
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• 2011

This study is aimed to increase the activity of cathodic catalysts for PEMFCs(Polymer Electrolyte Membrane Fuel Cells). we investigated the temperature effect of 20wt% Pt/C catalysts at five different temperatures. The catalysts were synthesized by using chemical reduction method. Before adding the formaldehyde as reducing agent, process was undergone for 2 hours at the room temperature (RT), $40^{\circ}C$, $60^{\circ}C$, $80^{\circ}C$ and $100^{\circ}C$, respectively. The performances of synthesize catalysts are compared. The electrochemical oxygen reduction reaction (ORR) was studied on 20wt% Pt/C catalysts by using a glassy carbon electrode through cyclic voltammetric curves (CV) in a 1M H2SO4 solution. The ORR specific activities of 20wt% Pt/C catalysts increased to give a relative ORR catalytic activity ordering of $80^{\circ}C$ > $100^{\circ}C$ > $60^{\circ}C$ > $40^{\circ}C$ > RT. Electrochemical active surface area (EAS) was calculated with cyclic voltammetry analysis. Prepared Pt/C (at $80^{\circ}C$, $100^{\circ}C$) catalysts has higher ESA than other catalysts. Physical characterization was made by using X-ray diffraction (XRD) and transmission electron microscope (TEM). The TEM images of the carbon supported platinum electrocatalysts ($80^{\circ}C$, $100^{\circ}C$) showed homogenous particle distribution with particle size of about 2~3.5 nm. We found that a higher reaction temperature resulted in more uniform particle distribution than lower reaction temperature and then the XRD results showed that the crystalline structure of the synthesized catalysts are seen FCC structure.

• Korean Chemical Engineering Research
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• v.49 no.1
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• pp.1-9
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• 2011

Platinum catalysts were prepared by impregnating platinum precursor on titania-, vanadia-, zirconia- and ceria-incorporated silicas followed by hydrogen peroxide treatment. The effects of the oxide incorporation and the hydrogen peroxide treatment in the preparation of the platinum catalysts on their platinum dispersion and catalytic activity in carbon monoxide oxidation were investigated. XRD, TEM, EXAFS, XPS and carbon monoxide chemisorption studies confirmed the high dispersion of platinum even on silica by the oxide incorporation and hydrogen peroxide treatment. However, the type of oxides incorporated on silica caused considerable variances in the adsorption and the catalytic activity in the oxidation of carbon monoxide on them. The incorporation of titania, zirconia and ceria on silica and further hydrogen peroxide treatment enhanced the platinum dispersion, resulting in the improved catalytic activities. Among the catalysts supported on the oxide-incorporated silicas, the platinum catalyst supported on zirconia-incorporated silica exhibited the highest activity because of the highest platinum dispersion due to the formation of Pt-O-Zr bonds.

• Applied Chemistry for Engineering
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• v.17 no.2
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• pp.223-228
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• 2006

Pore-size controlled porous carbons for the catalyst supports of the direct methanol fuel cell were prepared from the mesophase pitch by using the silica spheres with different sizes. Pitch solution in THF and spheres were mixed, carbonized and etched by 5 M NaOH to make porous carbon. Specific surface area of the porous carbons was $14.7{\sim}87.7m^2/g$ and average pore diameter was 50~550 nm which were dependent on the size of silica spheres. Aqueous reduction method was used to load 60 wt% PtRu on the prepared porous carbon supports. The electro-oxidation activity of the supported 60 wt% Pt-Ru catalysts was measured by cyclic voltammetry and unit cell test. For the 60 wt% Pt-Ru/porous carbon synthesized by 50 nm silica, current density value in the cyclic voltammetry test was $123mA/cm^2$ at 0.4 V and peak power density in the unit cell test were 105 and $162mW/cm^2$ under oxygen at 60 and $80^{\circ}C$, respectively.

• Korean Chemical Engineering Research
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• v.46 no.1
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• pp.118-123
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• 2008

In the present study, the effect of oxyfluorination treatment on multi-walled nanotubes (MWNTs) supports was investigated by analyzing surface functional groups. The surface characteristics were determined by Fourier transformed-infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS). After the deposition of platinum nanoparticles on the above treated carbon supports, a crystalline size and a loading level had been investigated. Electrochemical properties of the treated MWNTs-supported Pt (Pt/MWNTs) catalysts were analyzed by current-voltage curve measurements. From the results of surface analysis, an oxygen and fluorine-containing functional group had been introduced to the surface of carbon supports. The oxygen and fluorine contents were the highest value at the treatment of 100 temperature. The Pt/100-MWNTs showed the smallest particle crystalline size of 3.5 nm and the highest loading level of 9.4% at the treatment of 100 temperature. However, the sample treated at the higher temperature showed the larger crystalline size and the lower loading level. This indicated that the crystalline size and the loading level could be controlled by changing the temperature of oxyfluorination treatment. Accordingly, an electrochemical activity was enhanced by increasing the temperature of treatment upto 100, and then decreased in the case of 200 and 300. The highest specific current density of 120 mA/mg had been obtained in the case of Pt/100-MWNTs.

• Journal of Energy Engineering
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• v.23 no.3
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• pp.157-162
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• 2014

In this research, we investigate electrical performance and electrochemical properties of carbon supported Pt (Pt/C) that is synthesized by polyol method. With the Polyol_Pt/C that is adopted for oxygen reduction reaction (ORR) as cathode of proton exchange membrane fuel cells (PEMFCs), their catalytic activity and ORR performance and electrical performance are estimated and compared with commercial Pt/C(Johnson Mattey) catalyst. Their electrochemically active surface (EAS) area are measured by cyclic voltammetry (CV), respectively. On the other hand, regarding ORR activity and electrical performance of the catalysts, (i) linear sweeping voltammetry by rotating disk electrode and (ii) PEMFC single cell tests are used. The CV measurement demonstrate EAS of Polyol_Pt/C is compared with commercial JM_Pt/C. In case of Polyol_Pt/C, its half-wave potential, kinetic current density are excellent. Based on data obtained by half-cell test, when PEMFC single cell tests are carried out, current density measured at 0.6V and maximum power density of the PEMFC single cell employing Polyol_Pt/C are better than those employing commercial Pt/C. Conclusively, Polyol_Pt/C synthesized by modified polyol process shows better ORR catalytic activity and PEMFC performance than other catalysts.

• Korean Chemical Engineering Research
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• v.49 no.6
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• pp.769-774
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• 2011

Porous carbon nanofibers(CNF) were synthesized via NaOH activation at 700~$900^{\circ}C$, and the porous CNF-supported PtRu catalysts were evaluated for the anode in direct methanol fuel cells. The change of surface characteristics by NaOH activation was examined by analyses of the specific surface area and pore size distribution. The morphological and structural modification was investigated under scanning electron microscopy. The activity of catalysts supported on porous CNFs was examined by cyclic voltammograms and single cell tests. The pore formation on CNF by the NaOH activation was discussed, concerning the catalyst activity, when they were applied as catalyst supports.

• Korean Chemical Engineering Research
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• v.43 no.6
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• pp.756-760
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• 2005

In this study, the effect of $N_2$-plasma treatment on carbon blacks (CBs) was investigated by analyzing acid-base surface values and surface functional groups of CBs. The surface characteristics of the CBs were determined by fourier transformed-infrared (FT-IR) spectrometer, X-ray photoelectron spectroscopy (XPS), and Boehm's titration method. Electrochemical properties of the plasma-treated CBs-supported Pt (Pt/CBs) catalysts were analyzed by cyclic voltammetry (CV) experiments. From the results of FT-IR and acid-base values, $N_2$-plasma treatment at 300 W intensity on the CBs led to the formation of the free radical. The peak intensity was increased with increasing the treatment time due to the formation of new basic functional groups(such as C-N, C=N, $-NH_3{^+}$, -NH, and =NH) by the free radical. Accordingly, the basic values were increased by the basic functional groups. However, after a specific reaction time, $N_2$-plasma treatment could hardly influence change of surface functional groups of CBs, due to the disappearance of free radical. Consequently, it was found that optimal treatment time was 30 second for electro activity of Pt/CBs catalysts.

• Applied Chemistry for Engineering
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• v.25 no.1
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• pp.78-83
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• 2014

In this research, we evaluated the performance and characteristics of carbon supported PtM (M = Ni and Y) alloy catalysts (PtM/Cs) synthesized by a modified polyol method. With the PtM/Cs employed as a catalyst for the oxygen reduction reaction (ORR) of cathodes in proton exchange membrane fuel cells (PEMFCs), their catalytic and ORR activities and electrical performance were investigated and compared with those of commercial Pt/C. Their particle sizes, particle distributions and electrochemically active surface areas (EAS) were measured by TEM and cyclic voltammetry (CV), while their ORR activity and electrical performance were explored using linear sweeping voltammetries with rotating disk electrodes and rotating ring-disk electrodes as well as PEMFC single cell tests. TEM and CV measurements show that PtM/Cs have the compatible particle size and EAS with Pt/C. When it comes to ORR activity, PtM/C showed the equivalent or better half-wave potential, kinetic current density, transferred electron number per oxygen molecule and $H_2O_2$ production(%) to or than commerical Pt/C. Based on results gained by the three electrode tests, when the PEMFC single cell tests were carried out, the current density measured at 0.6 V and maximum power density of PEMFC single cell adopting PtM/C catalysts were better than those adopting Pt/C catalyst. It is therefore concluded that PtM/C catalysts synthesized by modified polyol can result in the equivalent or better ORR catalytic capability and PEMFC performance to or than commercial Pt/C catalyst.

• Applied Chemistry for Engineering
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• v.9 no.4
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• pp.497-503
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• 1998

The catalytic oxidation of 1.2-dichloroethane was investigated over precious metal supported on alumina using a fixed bed microreactor. Among the catalysts tested, the conversion of 1.2-dichloroethane decreased in the following order : Ru > Pt > Pd $${\sim_=}$$ Rh and Pt was found to be the most active catalyst for the complete oxidation of 1.2-dichloroethane to $CO_2$. Major products containing carbon were vinyl chloride and $Co_2$ at temperature ranging from 200 to $400^{\circ}C$. The presence of vinyl chloride in products suggests that the first step in the oxidation of 1.2-dichloroethane is dehydrochlorination and the second is oxidation of vinyl chloride to $CO_2$. To investigate the effect of HCl on the activity of the complete oxidation, some experiments were conducted by adding HCl to the feed. The presence of HCl increased the conversion of 1.2-dichloroethane below $300^{\circ}C$ owing to the increase of surface acidity, but it didn't affect the conversion above $300^{\circ}C$. The reversible adsorption of HCl onto catalyst surface inhibited the complete oxidation to $CO_2$.