• Korean Chemical Engineering Research
• /
• v.61 no.3
• /
• pp.341-347
• /
• 2023

In PEMFC, PtCo/C alloy catalysts are widely used because of good performance and durability. However, few studies have been reported on the durability of carbon supports of PtCo/C evaluated at high voltages (1.0~1.5 V). In this study, the durability of PtCo/C catalysts and Pt/C catalysts were compared after applying the accelerated degradation protocol of catalyst support. After repeating the 1.0↔1.5V voltage change cycles, the mass activity, electrochemical surface area (ECSA), electric double layer capacitance (DLC), Pt dissolution and the particle growth were analyzed. After 2,000 cycles of voltage change, the current density per catalyst mass at 0.9V decreased by more than 1.5 times compared to the Pt/C catalyst. This result was because the degradation rate of the carbon support of the PtCo/C catalyst was higher than that of the Pt/C catalyst. The Pt/C catalyst showed more than 1.5 times higher ECSA reduction than the PtCo/C catalyst, but the corrosion of the carbon support of the Pt/C catalyst was small, resulting in a small decrease in I-V performance. In order to improve the high voltage durability of the PtCo/C catalyst, it was shown that improving the durability of the carbon support is essential.

• Korean Chemical Engineering Research
• /
• v.61 no.2
• /
• pp.189-195
• /
• 2023

As a PEMFC (Polymer Exchange Membrane Fuel Cell) cathode catalyst, Pt-Co/C has recently been widely used because of its improved durability. In a fuel cell, electrodes and electrolytes have a close influence on each other in terms of performance and durability. The effect on the electrochemical durability of the electrolyte membrane when Pt-Co/C was replaced in the Pt/C electrode catalyst was studied. The durability of Pt-Co/C MEA (Membrane Electrode Assembly) was higher than that of Pt/C MEA in the electrochemical accelerated degradation process of PEMFC membrane. As a result of analyzing the FER (Fluorine Emission Rate) and hydrogen permeability, it was shown that the degradation rate of the membrane of Pt-Co/C MEA was lower than that of Pt/C MEA. In the OCV (Open Circuit Voltage) holding process, the rate of decrease of the active area of the Pt-Co/C electrode was lower than that of the Pt/C electrode, and the amount of Pt deposited on the membrane was smaller in Pt-Co/C MEA than in Pt/C MEA. Pt inside the polymer membrane deteriorates the membrane by generating radicals, so the degradation rate of the membrane of Pt/C MEA with a high Pt deposition rate was higher than Pt-Co/C MEA. When the Pt-Co/C catalyst was used, the electrode durability was improved, and the amount of Pt deposited on the membrane was also reduced, thereby improving the electrochemical durability of the membrane.

• Journal of Environmental Science International
• /
• v.18 no.10
• /
• pp.1071-1077
• /
• 2009

A novel pretreatment technique was applied to the conventional Pt/alumina catalyst to prepare for the highly efficient catalyst for the preferential oxidation of carbon monoxide in hydrogen-rich condition. Their performance was investigated by selective CO oxidation reaction. CO conversion with the oxygen-treated Pt/Alumina catalyst increased remarkably especially at the low temperature below $100^{\circ}C$. This result is promising for the normal operation of the proton exchange membrane fuel cell (PEMFC) without CO poisoning of the anode catalyst. XRD analysis results showed that metallic Pt peaks were not observed for the oxygen-treated catalyst. This implies that well dispersed small Pt particles exist on the catalyst. This result was continued by high resolution transmission electron microscopy (HRTEM) analysis. Consequently, it can be concluded that highly dispersed Pt nanoparticles could be prepared by the novel pretreatment technique and thus, CO conversion could be increased considerably especially at the low temperatures below $100^{\circ}C$.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.10
• /
• pp.3660-3665
• /
• 2011

CO-tolerant PtMo/C alloy electrocatalyst was prepared by a colloidal method, and its electrocatalytic activity toward CO oxidation was investigated. Electrochemical study revealed that the alloy catalyst significantly enhanced catalytic activity toward the electro-oxidation of CO compared to Pt/C counterpart. Cyclic voltammetry suggested that Mo plays an important role in promoting CO electro-oxidation by facilitating the formation of active oxygen species. The effect of Mo on the electronic structure of Pt was investigated using X-ray absorption spectroscopy to elucidate the synergetic effect of alloying. Our in-depth spectroscopic analysis revealed that CO is less strongly adsorbed on PtMo/C catalyst than on Pt/C catalyst due to the modulation of the electronic structure of Pt d-band. Our investigation shows that the enhanced CO electrooxidation in PtMo alloy electrocatalyst is originated from two factors; one comes from the facile formation of active oxygen species, and the other from the weak interaction between Pt and CO.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.1
• /
• pp.151-156
• /
• 2010

In this paper, we characterized bimetallic Pt-Ru/C alloy catalysts having four different compositions and compared the catalytic activities of the prepared alloys for CO oxidation. ICP-AES, EDS, XRD, TEM, and XAS were used to investigate the composition, degree of alloying, particle size, and electronic structure of the prepared Pt-Ru/C catalysts. Those results indicated the synthesis of the alloy catalysts with intended composition and uniform size. The electrochemical study of the characterized alloys showed higher catalytic activity for CO oxidation than that of the commercial Pt/C (E-TEK, Inc., 20 wt %) catalyst. Especially, it was shown that the alloy catalyst with Ru composition of 50 atomic % gave the highest catalytic activity for CO oxidation.

• Transactions of the Korean hydrogen and new energy society
• /
• v.23 no.6
• /
• pp.581-587
• /
• 2012

Thermal aging effect on NSR kinetics was studied over Pt/Co/Fe/Ba/$Al_2O_3$ catalyst. The amount of $NO_x$ uptake over Pt/Co/Fe/Ba/$Al_2O_3$ calcined at $400^{\circ}C$ increased with increasing NSR temperature from $200^{\circ}C$ to $400^{\circ}C$, where amount of $NO_x$ uptake is the highest at $400^{\circ}C$ with mol ratio of $NO_x$/Ba = 0.5. Thereafter, the amount of $NO_x$ uptake at $400^{\circ}C$ decreased with the higher calcination temperature, where Pt/Co/Fe/Ba/$Al_2O_3$ catalyst calcined at $700^{\circ}C$ showed an amount of $NO_x$ uptake with the mol ratio of $NO_x$/Ba=0.062. Result of XRD and NSR showed that Fe addition into Pt/Co/Fe/Ba/$Al_2O_3$ suppressed sintering of Pt crystallites and make $NO_x$ uptake larger, compared to no addition of Fe into Pt/Co/Fe/Ba/$Al_2O_3$ catalyst. From BET result, it was found that the change of specific surface area was relatively small by the thermal aging process. Therefore, it was found that the sintering of Pt crystallites caused the decrease of $NO_x$ uptake during NSR reaction and Fe played a role to suppress the sintering process of Pt crystallites caused by thermal aging.

• Journal of the Korean Electrochemical Society
• /
• v.11 no.4
• /
• pp.313-318
• /
• 2008

The influence of the particle size of platinum(Pt) on the stability and activity was studied. The particle size of platinum was controlled in the range of $3.5{\sim}9\;nm$ by heat treatment of commercial Pt/C and confirmed by XRD and TEM. An accelerated degradation test was performed to evaluate the stability of platinum catalysts. Oxygen reduction reaction was monitored for the measurement of activity. As increasing the Pt particle size, the stability of Pt/C electrode was enhanced and the activity was reduced. It was confirmed that the stability of Pt/C electrode was in inverse proportion to the activity. PtCo/C alloy catalyst was used to improve the activity and stability of large-sized platinum particle. The maximum power density of commercial Pt/C was $507.6\;mV/cm^2$ and PtCo/C alloy catalyst was $585.8\;mV/cm^2$. The decrement of electrochemical surface area showed Pt/C(60%) and PtCo/C alloy catalyst(24%). It was possible to enhance both of stability and activity of catalyst by the combination of particle size control and alloying.

• Korean Journal of Materials Research
• /
• v.19 no.5
• /
• pp.233-239
• /
• 2009

The electrocatalytic behavior of the PtCo catalyst supported on the multi-walled carbon nanotubes (MWNTs) has been evaluated and compared with commercial Pt/C catalyst in a polymer electrolyte membrane fuel cell(PEMFC). A PtCo/MWNTs electrocatalyst with a Pt:Co atomic ratio of 79:21 was synthesized and applied to a cathode of PEMFC. The structure and morphology of the synthesized PtCo/MWNTs electrocatalysts were characterized by X-ray diffraction and transmission electron microscopy. As a result of the X-ray studies, the crystal structure of a PtCo particle was determined to be a face-centered cubic(FCC) that was the same as the platinum structure. The particle size of PtCo in PtCo/MWNTs and Pt in Pt/C were 2.0 nm and 2.7 nm, respectively, which were calculated by Scherrer's formula from X-ray diffraction data. As a result we concluded that the specific surface activity of PtCo/MWNTs is superior to Pt/C's activity because of its smaller particle size. From the electrochemical impedance measurement, the membrane electrode assembly(MEA) fabricated with PtCo/MWNTs showed smaller anodic and cathodic activation losses than the MEA with Pt/C, although ohmic loss was the same as Pt/C. Finally, from the evaluation of cyclic voltammetry(CV), the unit cell using PtCo/MWNTs as the cathode electrocatalyst showed slightly higher fuel cell performance than the cell with a commercial Pt/C electrocatalyst.

• Journal of the Semiconductor & Display Technology
• /
• v.7 no.4
• /
• pp.45-49
• /
• 2008

For the commercialization of polymer electrolyte membrane fuel cell (PEMFC), some serious problems such as the decrease of platinum use as catalysts and a larger overpotential of oxygen reduction reaction (ORR) at cathode must be solved. In this study, 20%Pt/C and 20%PtCo/C catalysts for the cathode of PEMFC were synthesized from the chemical reduction method and evaluated using an electrochemical measurement. The ORR activity of synthesized 20%Pt/C and 20%PtCo/C had higher than that of the 20%Pt/C on the market. The synthesized 20%PtCo/C with the cobalt concentration (Pt:Co atomic ratio) from 5 to 20% showed the highest ORR activity.

• Journal of Environmental Science International
• /
• v.20 no.2
• /
• pp.251-260
• /
• 2011

$TiO_2$- and $SiO_2$-supported $Co_3O_4$, Pt and $Co_3O_4$-Pt catalysts have been studied for CO and $C_3H_8$ oxidations at temperatures less than $250^{\circ}C$ which is a lower limit of light-off temperatures to oxidize them during emission test cycles of gasoline-fueled automotives with TWCs (three-way catalytic converters) consisting mainly of Pt, Pd and Rh. All the catalysts after appropriate activation such as calcination at $350^{\circ}C$ and reduction at $400^{\circ}C$ exhibited significant dependence on both their preparation techniques and supports upon CO oxidation at chosen temperatures. A Pt/$TiO_2$ catalyst prepared by using an ion-exchange method (IE) has much better activity for such CO oxidation because of smaller Pt nanoparticles, compared to a supported Pt obtained via an incipient wetness (IW). Supported $Co_3O_4$-only catalysts are very active for CO oxidation even at $100^{\circ}C$, but the use of $TiO_2$ as a support and the IW technique give the best performances. These effects on supports and preparation methods were indicated for $Co_3O_4$-Pt catalysts. Based on activity profiles of CO oxidation at $100^{\circ}C$ over a physical mixture of supported Pt and $Co_3O_4$ after activation under different conditions, and typical light-off temperatures of CO and unburned hydrocarbons in common TWCs as tested for $C_3H_8$ oxidation at $250^{\circ}C$ with a Pt-exchanged $SiO_2$ catalyst, this study may offer an useful approach to substitute $Co_3O_4$ for a part of platinum group metals, particularly Pt, thereby lowering the usage of the precious metals.