• Clean Technology
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• v.14 no.1
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• pp.61-68
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• 2008

There have been great attentions on polymer electrolyte membrane fuel cell (PEMFC) due to their advantageous characteristics such as zero emission of hazardous pollutant and high energy density. In this work, we evaluated degradation phenomena and stability of single cell performance via one dimensional single cell modeling. Here, CO poisoning on anode on anode was considered for cell performance degradation. Modeling results showed that the performance and stability were highly degraded with CO concentration in fuel gas. In addition, cell performance was reduced by slow oxygen reduction on cathode in long term operation. In order to overcome, it is required to increase ratio o#hydrogen in the fuel gas of anode and high Pt loading contained in the cathodic catalyst layer.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2442-2444
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• 2007

CO adsorbates on the surface of Pt supported on carbon catalysts (Pt/C) were investigated by CO stripping voltammetry. Three types of CO adsorbed samples were prepared: by methanol dehydrogenation only (COm), by CO gas bubbling only (COg), and by methanol dehydrogenation followed by CO gas bubbling (COm+g). Our coverage data show that CO gas can be adsorbed on Pt/C catalyst already saturated with CO adsorbates by methanol dehydrogenation. The COm+g sample showed the properties of both COm as well as COg samples in terms of the potential although the CO adsorbed by dehydrogenation was completely exchanged with CO in the electrolyte solution. Therefore, the oxidation pathways of CO on Pt/C were observed to depend on the initial adsorption conditions of CO more strongly than on the CO coverage. Our results imply that an initial CO poisoning condition in fuel cell operation is an important factor to determine the difficulty in removing the adsorbed CO and confirm that the properties of the adsorbed CO do not change even with chemical replacement with CO in different conditions. In addition, our results indicate a low CO surface mobility on the Pt in an electrolyte solution.

• Korean Journal of Crystallography
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• v.16 no.1
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• pp.43-53
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• 2005

The dihydrido P-C-P pincer complex, $IrH_2{C_6H_3-2,6-(CH_2PBu_2^t)_2}$ (1), was successfully prepared from the reaction of the hydrochloride complex, $IrClH (C_6H_3-2,6-(CH_2PBu_2^t)_2}$, and super acid $(LiBEt_3H)$ under 1 atm of hydrogen in pentane solution at room temperature and followed by Heating at $130^{\circ}C$ in vacuo. Jensen recently found that the dihydrido P-C-P pincer complex 1 is a highly active homogeneous catalyst for the transfer dehydrogenation of alkanes with unusual longterm stability at temperatures as high as $200^{\circ}C$. The treatment of dihydrido complex 1 with nitrogen, water, carbon dioxide, and carbon monoxide in presence of tert-butylethylene (the) at room temperature in an appropriate solution gave the dinitrogen complex, $[Ir{C-6H_3-2,6-(CH_2PBu_2^t)_2}]_2({\mu}-N_2)$ (2), the hydrido hydroxyl complex, $IrH(OH){C_6H_3-2,6-(CH_2PBu_2^t)_2}$ (3), the carbon dioxide complex, $Ir({\eta}^2-CO_2) {C_6H_3-2,6-(CH_2PBu_2^t)_2}$ (including the bicarbonate complex, $IrH({\kappa}^2-O_2COH){C_6H_3-2,6-(CH_2PBu_2^t)_2}\;(4))$, and the carbonyl complex, $Ir(CO) {C_6H_3-2,6-(CH_2PBu_2^t)_2}\;(5)$ (including the carboxyl complex, $IrH(C(O)OH) {C_6H_3-2,6-(CH_2PBu_2^t)_2}\;(6))$, in good yield, respectively. These P-C-P iridium complexes were isolated and characterized by $^1H,\;^{13}C,\;^{31}P\; NMR$, and IR spectroscopy. In addition, the complexes (1-6) were characterized by a single crystal X-ray crystallography. These complexes account for these small molecules' inhibition of dehydrogenation of alkanes catalyzed by the dihydrido complex 1.

• Journal of the Korean Electrochemical Society
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• v.11 no.1
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• pp.42-46
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• 2008

Even though fuel cell have high efficiency when pure hydrogen from gas tank is used as a fuel source, it is more beneficial to generate hydrogen from city gas (mainly methane) in residential application such as domestic or office environments. Thus hydrogen is generated by reforming process using hydrocarbon. Unfortunately, the reforming process for hydrogen production is accompanied with unavoidable impurities. Impurities such as CO, $CO_2$, $H_2S$, $NH_3$, $CH_4$, and $CH_4$ in hydrogen could cause negative effects on fuel cell performance. Those effects are kinetic losses due to poisoning of the electrode catalysts, ohmic losses due to proton conductivity reduction including membrane and catalyst ionomer layers, and mass transport losses due to degrading catalyst layer structure and hydrophobic property. Hydrogen produced from reformer eventually contains around 73% of $H_2$, 20% or less of $CO_2$, 5.8% of less of $N_2$, or 2% less of $CH_4$, and 10ppm or less of CO. This study is aimed at investigating the effect of carbon dioxide on fuel cell performance. The performance of PEM fuel cell was investigated using current vs. potential experiment, long run(10 hr) test, and electrochemical impedance measurement when the concentrations of carbon dioxide were 10%, 20% and 30%. Also, the concentration of impurity supplied to the fuel cell was verified by gas chromatography(GC).

• Applied Chemistry for Engineering
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• v.18 no.4
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• pp.337-343
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• 2007

The reforming catalyst and the electrodes in fuel cells can be poisoned by the organic sulfur compound which is added as an odorant for checking out the leakage of natural gas, and that makes a big problem of system degradation. In this study, various adsorbents, such as silica, ${\gamma}$-alumina, activated carbon, HZSM-5, Ultra-stable Y zeolite (USY), and beta zeolite (BEA), were utilized to remove tetra-hydrothiophene (THT) and tert-butylmercaptan (TBM), and to confirm the performance in the adsorption of those odorants by using a continuous adsorptive bed. The effects of Si/Al ratio of zeolites, adsorption temperature and the type of balance gas (methane or He) on the adsorption performance in the packed bed have been investigated. In addition, the competitive adsorption between TBM and THT on the adsorbents was also estimated. The result shows that H-type BEA zeolite exhibited the highest adsorption capacity for TBM and THT odorant, and the higher amount of THT was removed adsorptively on the same adsorbent than TBM. The physical and chemical adsorption of those compounds on acid sites of zeolite were confirmed by temperature programmed desorption (TPD) and infrared spectrum (IR) analyses.

• Korean Chemical Engineering Research
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• v.46 no.5
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• pp.1002-1007
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• 2008

The purpose of this paper studied the optimal hydrogen production condition of plasma reforming system to operate the PEMFC. Plasma reforming reactor used with Ni catalyst reactor at the same time, So $H_2$ concentration increased. Also the WGS and PrOx reactor were designed to remove CO concentration under 10 ppm, because CO has effect on catalyst poisoning of PEMFC. The maximum $H_2$ production condition in plasma reforming system was S/C ratio 3.2, $CH_4$ flow rate 2.0 L/min, catalytic reactor temperature $700{\pm}5^{\circ}C$ and input power 900 W. At this time, the concentration of produced syngas was $H_2$ 70.2%, CO 7.5%, $CO_2$ 16.2%,$CH_4$ 1.8%. The hydrogen yield, hydrogen selectivity and $CH_4$ conversion rate were 56.8%, 38.1% and 92.2% respectively. The energy efficiency and specific energy requirement were 37.0%, 183.6 kJ/mol. In additional, The experiment of $CO_2/CH_4$ ratio proceeded. Also WGS reactor experiment was proceeding on optimum condition of plasma reactor and the exit concentration were $H_2$ 68%, CO 337 ppm, $CO_2$ 24.0%, $CH_4$ 2.2%, $C_2H_4$ 0.4%, $C_2H_6$ 4.1%. At this time, experiment result of PrOx reactor were $H_2$ 51.9%, CO 0%, $CO_2$ 17.3%.

• Korean Journal of Materials Research
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• v.28 no.6
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• pp.365-369
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• 2018

We perform density functional theory calculations to study the CO and $O_2$ adsorption chemistry of Pt@X core@shell bimetallic nanoparticles (X = Pd, Rh, Ru, Au, or Ag). To prevent CO-poisoning of Pt nanoparticles, we introduce a Pt@X core-shell nanoparticle model that is composed of exposed surface sites of Pt and facets of X alloying element. We find that Pt@Pd, Pt@Rh, Pt@Ru, and Pt@Ag nanoparticles spatially bind CO and $O_2$, separately, on Pt and X, respectively. Particularly, Pt@Ag nanoparticles show the most well-balanced CO and $O_2$ binding energy values, which are required for facile CO oxidation. On the other hand, the $O_2$ binding energies of Pt@Pd, Pt@Ru, and Pt@Rh nanoparticles are too strong to catalyze further CO oxidation because of the strong oxygen affinity of Pd, Ru, and Rh. The Au shell of Pt@Au nanoparticles preferentially bond CO rather than $O_2$. From a catalysis design perspective, we believe that Pt@Ag is a better-performing Pt-based CO-tolerant CO oxidation catalyst.

• 한국신재생에너지학회:학술대회논문집
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• 2007.06a
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• pp.141-145
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• 2007

Due to their excellent catalytic activity with respect to methanol oxidation on platinum at low temperature, platinum nanosized catalysts have been a topic of great interest for use in direct methanol fuel cells (DMFCs). Since pure platinum is readily poisoned by CO, a by-product of methanol electrooxidation, and is extremely expensive, a number of efforts to design and characterize Pt-based alloy nanosized catalysts or Pt nanophase-support composites have been attempted in order to reduce or relieve the CO poisoning effect. In this review paper, we summarize these efforts based upon our recent research results. The Pt-based nanocatalysts were designed by chemical synthesis and thin-film technology, and were characterized by a variety of analyses. According to bifunctional mechanism, it was concluded that good alloy formation with $2^{nd}$ metal (e.g., Ru) as well as the metallic state and optimum portion of Ru element in the anode catalyst contribute to an enhanced catalytic activity for methanol electrooxidation. In addition, we found that the modified electronic properties of platinum in Pt alloy electrodes as well as the surface and bulk structure of Pt alloys with a proper composition could be attributed to a higher catalytic activity for methanol electooxdation. Proton conducting contribution of nanosized electrocatalysts should also be considered to be excellent in methanol electrooxidation (Spillover effect). Finally, we confirmed the ensemble effect, which combined all above effects, in Pt-based nanocatalsyts especially, such as PtRuRhNi and $PtRuWO_{3}$, contribute to an enhanced catalytic activity.

• Journal of the Korean Electrochemical Society
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• v.10 no.4
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• pp.279-282
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• 2007

When reformer for fuel cell is used, CO in hydrogen gas leads to a seriously decreased membrane electrode assembly (MEA) performance by catalyst poisoning. The effect of CO on performance of modified MEA by sputtering method is studied in this paper. The experimental results show that sputtered Pt and Ru thin film improve a single cell performance of MEA and sputtered metal thin film has a CO tolerance. The air injection process on anode show improved CO tolerance test result. Moreover, Pt, Ru and PtRu thin film by sputtering had influence on the CO tolerance with air injection process.

• Clean Technology
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• v.20 no.1
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• pp.88-94
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• 2014

During the past decades much attention has been paid to the desulfurization of diesel oil which is important as a source for the fuel cells to prevent the sulfur poisoning of both diesel steam reforming catalyst and electrode of fuel cell. Although alternative desulfurization techniques have been investigated, desulfurization for ultra-low sulfur diesel (ULSD) is still challenged. Therefore, this research focuses on the desulfurization of commercial ULSD for the application to molten carbonate fuel cell (MCFC). Herein, the performances of several kinds of commercial adsorbents based on activated carbons, zeolites, and metal oxides for desulfurization of ULSD were screened. The results showed that metal oxides based materials can feasibly reduce sulfur concentration in ULSD to a level of 0.1 ppmw while activated carbons and zeolites did not reach this level at current conditions.