• 한국신재생에너지학회:학술대회논문집
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• 2006.11a
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• pp.459-462
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• 2006

Formic acid recently attracted attention as an alternative fuel for direct liquid fuel cells(DLFCs) due to its high theoretical open circuit voltage(1.45V). In this paper, a novel chemical strategy is described for the preparation and characterization of carbon-supported and surface-alloys, which were prepared by using a successive reduction process. After preparing Au colloid nanoparticles, the deposition of Au colloid nanoparticles occurred spontaneously in the carbon black-dispersed aqueous solution. Then nano-scaled Pt layer were formed on the surface of carbon-supported Au nanoparticles. The Au-Pt[x] showed the higher electrocatalytic activity than those of the particle-alloys and commercial one (Johnson-Matthey) for the reaction of formic acid oxidation when the mass-specific currents were compared. The increased electrocatalytic activity might be attributed to the effective surface structure of surface-alloys, which have a high utilization of active materials for the surface reaction of electrode.

• Journal of Electrochemical Science and Technology
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• v.12 no.3
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• pp.323-329
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• 2021

This work presents a contrasting behavior of formic acid oxidation (FAO) on the Pt and Bi deposits on different Pt substrates. Using irreversible adsorption method, Bi and Pt were sequentially deposited on Pt electrodes of nanoparticle (Pt NP) and disk (Pt disk). The deposited layers of Bi and Pt on the Pt substrates were characterized with X-ray photoelectron spectroscopy, transmission microscopy and scanning tunneling microscopy. The electrochemical behaviors and FAO enhancements of Pt NP and Pt disk with deposited Bi only (i.e., Bi/Pt NP and Bi/Pt disk), were similar to each other. However, additional deposition of Pt on Bi/Pt NP and Bi/Pt disk (i.e., Pt/Bi/Pt NP and Pt/Bi/Pt disk) changed the electrochemical behavior and FAO activity in different ways depending on the shapes of the Pt substrates. With Pt/Bi/Pt NP, the hydrogen adsorption was suppressed and the surface oxidation of Pt was enhanced; while with Pt/Bi/Pt disk, the opposite behavior was observed. This difference was interpreted as a stronger interaction between the deposited Bi and Pt on Pt NP than that on Pt disk. The FAO performance on Pt/Bi/Pt NP is much better than that on Pt/Bi/Pt disk, most likely due to the difference in the interaction between the deposited Pt and Bi depending on the shapes of Pt substrates. In designing FAO electrochemical catalysts using Pt and Bi, the shape of a Pt substrate was concluded to be critically considered.

• Textile Coloration and Finishing
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• v.13 no.4
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• pp.264-271
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• 2001

Catalytic wet oxidation of ethylene glycol as refractory compound was studied in a batch slurry reactor using lwt% $Pt/A1_2O_3$, lwt% $Pt/TiO_2,\;Mn/CeO_2$(1:1) and 5wt% $Mn/Al_2O_3$. Experiments were conducted to investigate theeffects of temperature, initial ethylene glycol concentration, catalyst dosage and PH on the ethylene glycol decomposition. When compared with the uncatalyzed reaction, the use of catalysts could increase the rate of ethylene glycol decomposition. The lwt% $Pt/A1_2O_3$ catalyst was preferable to the other catalysts for the destructive oxidation of ethylene glycol. The reaction rate was first order with respect to initial concentration of ethylene glycol. In acidic condition the removal efficiency of ethylene glycol was good, but there was a significant leaching of platinum. Small amount of acetic acid, oxalic acid, masonic acid and formic acid as intermediates were detected during catalytic wet air oxidation of ethylene glycol.

• Korean Chemical Engineering Research
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• v.47 no.3
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• pp.362-367
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• 2009

Recently, the use of formic acid as a fuel for direct liquid fuel cells has emerged as a promising alternative to methanol. In the work presented herein, we evaluated direct formic acid fuel cells(DFAFCs) with various components under operating conditions, for example, the thickness of the proton exchange membrane, concentration of formic acid, gas diffusion layer, and commercial catalyst. The thickness of the proton exchange membrane influenced performance related to the fuel cross-over. To optimize the cell performance, we investigated on the proper concentration of formic acid and catalyst for the formic acid oxidation. Consequently, membrance-electrode assembly(MEA) consisted of $Nafion^{(R)}$-115 and the Pt-Ru black as a anode catalyst showed the maximum performance. This performance was superior to the DMFCs' one.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2539-2545
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• 2012

In the present study, we suggest a new way to reactivate performance of direct formic acid fuel cell (DFAFC) and explain its mechanism by employing electrochemical analyses like chronoamperometry (CA) and cyclic voltammogram (CV). For the evaluation of DFAFC performance, palladium (Pd) and platinum (Pt) are used as anode and cathode catalysts, respectively, and are applied to a Nafion membrane by catalyst-coated membrane spraying. After long DFAFC operation performed at 0.2 and 0.4 V and then CV test, DFAFC performance is better than its initial performance. It is attributed to dissolution of anode Pd into $Pd^{2+}$. By characterizations like TEM, Z-potential, CV and electrochemical impedance spectroscopy, it is evaluated that such dissolved $Pd^{2+}$ ions lead to (1) increase in the electrochemically active surface by reduction in Pd particle size and its improved redistribution and (2) increment in the total oxidation charge by fast reaction rate of the Pd dissolution reaction.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.08a
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• pp.206-206
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• 2011

Nanoparticles have been received great attention from many researchers for several decades because of their good and unique properties. In particular, researches in the field of synthesis of bimetallic nanoparticles showed good results for the past ten years. In this research, Pd thinlayer on Au nanoparticles were synthesized by electrochemical deposition method. Well-defined Au(111) nanoparticles were synthesized by solution based reduction method. Electrochemical deposition conditions for Pd thinlayer on Au(111) nanoparticles surface were carefully regulated by controlling parameters of cyclic voltammetry. To calculate exact mass and surface area catalytic activities of deposited Pd thinlayer on Au(111) nanoparticle, electrochemically active surface area (ECSA) and mass of the deposited Pd thinlayer were measured by cyclic voltammetry in 0.1 M HClO4 solution. Afterward, catalytic activities of the deposited Pd thinlayer were measured in 0.1 M HClO4 + 0.2 M formic acid solution. In case of less negative deposition potential, the amounts of deposited Pd mass and surface area were small. However, mass and ECSA activity of the deposited Pd to oxidize formic acid were increased.

• Journal of Electrochemical Science and Technology
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• v.14 no.1
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• pp.21-30
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• 2023

This work presents a correlation between the behavior of formic acid oxidation (FAO) on various Bi-modified Pt(poly) disk electrodes and their morphologies observed on Bi-modified Pt(111) disk electrodes using electrochemical scanning tunneling microscopy (EC-STM) to understand the effects of Bi on Pt. To distinguish the FAO activities of Bi on Pt and plain Pt around Bi, additional Pt was intentionally deposited using two different routes: direct route and iodine route. In direct route, Pt was directly deposited on Bi islands and plain Pt sites around Bi islands, while in iodine route, Pt was exclusively deposited on Bi islands by protecting plain Pt sites with adsorbed iodine. Thus, a comparison of FAO performances on the two Bi-modified Pt electrodes with additional Pt (deposited in the different ways) disclosed a difference in FAO performances on plain Pt sites and Bi islands. When Bi coverage was ~0.04, the Bi deposits were scattered Bi islands enhancing FAO on Pt(poly). The additional Pt deposits using direct route increased FAO efficiency, while the ones using iodine route slightly decreased FAO current. The EC-STM observations indicated that Pt deposits around Bi islands, not on Bi islands, were responsible for the FAO current increase on Bi-modified Pt(poly). The FAO efficiency on Bi-modified Pt(poly) with a Bi coverage of ~0.25 increased by a factor of 2. However, the additional Pt deposits using the two Pt deposition routes notably decreased the FAO current. The dependency of FAO on Bi coverage was discussed in terms of electronic effect and ensemble effect.

• Carbon letters
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• v.6 no.1
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• pp.41-46
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• 2005

Plasma carbon blacks of 20~30 nm diameter were synthesized by direct decomposition of natural gas using a hybrid plasma torch system with 50 kW direct current and 4 MHz of radio frequency. The insulating rector which inside diameter of 400 mm and length of 1500 mm, respectively was kept at 300~$400^{\circ}C$ during the preparation. The ultimate analysis of plasma carbon blacks reveals that the raw plasma carbon blacks contains a large quantity of volatile which is mainly consist of hydrogen. Therefore devolatilization of raw plasma carbon blacks were carried out at $900^{\circ}C$ for one hour under nitrogen atmosphere. The devolatilization leads to the decrease in electrical resistivity and surface oxygen functional groups of plasma carbon black significantly. In order to investigate the plasma carbon as a catalyst support, devolatilized plasma black at $900^{\circ}C$ (DPB) supported PtAu catalyst was synthesized by sodium boronhydride reduction method. Electrochemical measurements and direct formic acid fuel cell test indicated that catalytic activity of DPB supported PtAu catalyst for formic acid oxidation was similar to that of Vulcan XC-72 of commercial carbon black supported one.

• Korean Chemical Engineering Research
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• v.55 no.2
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• pp.270-274
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• 2017

Formic acid has been known as one of key sources of hydrogen. Among various monometallic catalysts, hydrogen can be efficiently produced on Pd catalyst. However, the catalytic activity of Pd is gradually reduced by the blocking of active sites by CO, which is formed from the unwanted indirect oxidation of formic acid. One of promising solutions to overcome such issue is the design of alloy catalyst by adding other metal into Pd since alloying effect (such as ligand and strain effect) can increase the chance to mitigate CO poisoning issue. In this study, we have investigated formic acid deposition on the bimetallic $Pd/Pd_3Fe$ core-shell nanocatalyst using DFT (density functional theory) calculation. In comparison to Pd catalyst, the activation energy of formic acid dehydrogenation is greatly reduced on $Pd/Pd_3Fe$ catalyst. In order to understand the importance of alloying effects in catalysis, we decoupled the strain effect from ligand effect. We found that both strain effect and ligand effect reduced the binding energy of HCOO by 0.03 eV and 0.29 eV, respectively, compared to the pure Pd case. Our DFT analysis of electronic structure suggested that such decrease of HCOO binding energy is related to the dramatic reduction of density of state near the fermi level.

• Journal of Korean Society of Water and Wastewater
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• v.25 no.5
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• pp.643-649
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• 2011

Degradation of benzothiophene(BT) in the aqueous phase by potassium ferrate(VI) was investigated. Potassium ferrate(VI) was prepared by the wet oxidation method. The degradation efficiency of BT was measured at various values of pH, ferrate(VI) dosage and initial concentration of BT. BT was degraded rapidly within 30 seconds by ferrate(VI). While the highest degradation efficiency was achieved at pH 5, the lowest degradation efficiency was achieved at pH 9. Also, the initial rate constant of BT increased with decreasing of the BT initial concentration. In addition, the intermediate analysis for the reaction of BT and ferrate(VI) has been conducted using GC-MS. Benzene, styrene, benzaldehyde, formaldehyde, benzoic acid, formic acid, and acetic acid were identified as reaction intermediates, and ${SO_4}^{2-}$ was identified as an end product.