• Journal of Electrochemical Science and Technology
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• v.15 no.1
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• pp.96-110
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• 2024

Polymer electrolyte membrane fuel cells (PEMFCs) are green energy conversion devices, for which commercial markets have been established, owing to their application in fuel cell vehicles (FCVs). Development of cathode electrocatalysts, replacing commercial Pt/C, plays a crucial role in factors such as cost reduction, high performance, and durability in FCVs. PtNi octahedral catalysts are promising for oxygen reduction reactions owing to their significantly higher mass activity (10-15 times) than that of Pt/C; however, their application in membrane electrode assemblies (MEAs) is challenged by their low stability. To overcome this durability issue, various approaches, such as third-metal doping, composition control, halide treatment, formation of a Pt layer, annealing treatment, and size control, have been explored and have shown promising improvements in stability in rotating disk electrode (RDE) testing. In this review, we aimed to compare the features of each strategy in terms of enhancing stability by introducing a stability improvement factor for a direct and reasonable comparison. The limitations of each strategy for enhancing stability of PtNi octahedral are also described. This review can serve as a valuable guide for the development of strategies to enhance the durability of octahedral PtNi.

• Korean Journal of Materials Research
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• v.30 no.1
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• pp.14-21
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• 2020

Carbon supports for dispersed platinum (Pt) electrocatalysts in direct methanol fuel cells (DMFCs) are being continuously developed to improve electrochemical performance and catalyst stability. However, carbon supports still require solutions to reduce costs and improve catalyst efficiency. In this study, we prepare well-dispersed Pt electrocatalysts by introducing titanium dioxide (TiO₂) into biomass based nitrogen-doped carbon supports. In order to obtain optimized electrochemical performance, different amounts of TiO₂ component are controlled by three types (Pt/TNC-2 wt%, Pt/TNC-4 wt%, and Pt/TNC-6 wt%). Especially, the anodic current density of Pt/TNC-4 wt% is 707.0 mA g^-1_pt, which is about 1.65 times higher than that of commercial Pt/C (429.1 mA g^-1_pt); Pt/TNC-4wt% also exhibits excellent catalytic stability, with a retention rate of 91 %. This novel support provides electrochemical performance improvement including several advantages of improved anodic current density and catalyst stability due to the well-dispersed Pt nanoparticles on the support by the introduction of TiO₂ component and nitrogen doping in carbon. Therefore, Pt/TNC-4 wt% may be electrocatalyst a promising catalyst as an anode for high-performance DMFCs.

• Journal of Electrochemical Science and Technology
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• v.7 no.4
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• pp.269-276
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• 2016

Carbon-supported ordered Pt-Ti alloy nanoparticles were prepared as a durable and efficient oxygen reduction reaction (ORR) electrocatalyst for polymer electrolyte membrane fuel cells (PEMFCs) via wet chemical reduction of Pt and Ti precursors with heat treatment at $800^{\circ}C$. X-ray diffraction analysis confirmed that the prepared electrocatalysts with Ti precursor molar compositions of 40% (PtTi40) and 25% (PtTi25) had ordered $Pt_3Ti$ and $Pt_8Ti$ structures, respectively. Comparison of the ORR polarization before and after 1500 electrochemical cycles between 0.6 and 1.1 V showed little change in the ORR polarization curve of the electrocatalysts, demonstrating the high stability of the PtTi40 and PtTi25 alloys. Under the same conditions, commercial carbon-supported Pt nanoparticle electrocatalysts exhibited a negative potential shift (10 mV) in the ORR polarization curve after electrochemical cycling, indicating degradation of the ORR activity.

• Korean Journal of Materials Research
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• v.25 no.3
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• pp.113-118
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• 2015

To improve the methanol electro-oxidation in direct methanol fuel cells(DMFCs), Pt electrocatalysts embedded on porous carbon nanofibers(CNFs) were synthesized by electrospinning followed by a reduction method. To fabricate the porous CNFs, we prepared three types of porous CNFs using three different amount of a styrene-co-acrylonitrile(SAN) polymer: 0.2 wt%, 0.5 wt%, and 1 wt%, respectively. A SAN polymer, which provides vacant spaces in porous CNFs, was decomposed and burn out during the carbonization. The structure and morphology of the samples were examined using field emission scanning electron microscopy and transmission electron microscopy and their surface area were measured using the Brunauer-Emmett-Teller(BET). The crystallinities and chemical compositions of the samples were examined using X-ray diffraction and X-ray photoelectron spectroscopy. The electrochemical properties on the methanol electro-oxidation were characterized using cyclic voltammetry and chronoamperometry. Pt electrocatalysts embedded on porous CNFs containing 0.5 wt% SAN polymer exhibited the improved methanol oxidation and electrocatalytic stability compared to Pt/conventional CNFs and commercial Pt/C(40 wt% Pt on Vulcan carbon, E-TEK).

• Korean Journal of Materials Research
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• v.28 no.11
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• pp.640-645
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• 2018

The design of non-precious electrocatalysts with low-cost, good stability, and an improved oxygen reduction reaction(ORR) to replace the platinium-based electrocatalyst is significant for application of fuel cells and metal-air batteries with high energy density. In this study, we synthesize iron-carbide($Fe_3C$) embedded nitrogen(N) doped carbon nanofiber(CNF) as electrocatalysts for ORRs using electrospinning, precursor deposition, and carbonization. To optimize electrochemical performance, we study the three stages according to different amounts of iron precursor. Among them, $Fe_3C$-embedded N doped CNF-1 exhibits the most improved electrochemical performance with a high onset potential of -0.18 V, a high $E_{1/2}$ of -0.29 V, and a nearly four-electron pathway (n = 3.77). In addition, $Fe_3C$-embedded N doped CNF-1 displays exellent long-term stabillity with the lowest ${\Delta}E_{1/2}=8mV$ compared to the other electrocatalysts. The improved electrochemical properties are attributed to synergestic effect of N-doping and well-dispersed iron carbide embedded in CNF. Consequently, $Fe_3C$-embedded N doped CNF is a promising candidate for non-precious electrocatalysts for high-performance ORRs.

• Journal of Surface Science and Engineering
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• v.55 no.2
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• pp.38-50
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• 2022

As a low-cost and high-efficiency electrocatalysts with high performance and stability become a key challenge in the development of the practical use of water electrolysis, there is an intense interest in transition-metal oxalate-based materials. Transition-metal oxalate-based catalysts with excellent electrochemical performances have been widely applied in water electrolysis due to its low-cost and ease of synthesis. This review provides a useful summary on the development of transition-metal oxalate as potential catalysts for water electrolysis with a focus on the structural and compositional alteration, role of oxalate anion, and enhanced electrochemical performances.

• Journal of Hydrogen and New Energy
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• v.30 no.6
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• pp.531-539
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• 2019

The development of cost-effective electrocatalysts with high durability is one of the most important challenges for the commercialization of polymer electrolyte fuel cells (PEFCs). The durability of the electrocatalyst has been studied in terms of structural change in the active metal and the support. In particular, in fuel cell vehicles, degradation of the carbon-based support is known to have a significant effect on the electrocatalyst deterioration since the start-up/shut-down cycle is frequently repeated. The requirements for the support of the electrocatalyst include high surface area, electrical conductivity, chemical stability, and so on. In this study, we propose the evaluation methods for choosing better support materials and present the physicochemical properties that promising carbon supports should have. Three kinds of carbon materials with different crystallinity are compared. From in-depth study using X-ray diffraction, Raman spectroscopy, thermogravimetric analysis, and accelerated stress test, it is clearly confirmed that the durability of carbon-supported electrocatalysts is closely related to the physicochemical properties of the carbon supports.

• Journal of Surface Science and Engineering
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• v.49 no.2
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• pp.159-165
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• 2016

The hydrogen has been recognized as a clean, nonpolluting and unlimited energy source that can solve fossil fuel depletion and environmental pollution problems at the same time. Water electrolysis has been the most attractive technology in a way to produce hydrogen because it does not emit any pollutants compared to other method such as natural gas steam reforming and coal gasification etc. In order to improve efficiency and durability of the water electrolysis, comprehensive studies for highly active and stable electrocatalysts have been performed. The platinum group metal (PGM; Pt, Ru, Pd, Rh, etc.) electrocatalysts indicated a higher activity and stability compared with other transition metals in harsh condition such as acid solution. It is necessary to develop inexpensive non-noble metal catalysts such as transition metal oxides because the PGM catalysts is expensive materials with insufficient it's reserves. The optimization of operating parameter and the components is also important factor to develop an efficient water electrolysis cell. In this study, we optimized the operating parameter and components such as the type of AEM and density of gas diffusion layer (GDL) and the temperature/concentration of the electrolyte solution for the anion exchange membrane water electrolysis cell (AEMWEC) with the transition metal oxide alloy anode and cathode electrocatalysts. The maximum current density was $345.8mA/cm^2$ with parameter and component optimization.

• Korean Journal of Materials Research
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• v.33 no.10
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• pp.377-384
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• 2023

Exploring earth-abundant, highly effective and stable electrocatalysts for electrochemical water splitting is urgent and essential to the development of hydrogen (H₂) energy technology. Iron-cobalt layered double hydroxide (FeCo-LDH) has been widely used as an electrocatalystfor OER due to its facile synthesis, tunable components, and low cost. However, LDH synthesized by the traditional hydrothermal method tends to easily agglomerate, resulting in an unstable structure that can change or dissolve in an alkaline solution. Therefore, studying the real active phase is highly significant in the design of electrochemical electrode materials. Here, metal-organic frameworks (MOFs) are used as template precursors to derive FeCo-LDH from different iron sources. Iron salts with different anions have a significant impact on the morphology and charge transfer properties of the resulting materials. FeCo-LDH synthesized from iron sulfate solution (FeCo-LDH-SO₄) exhibits a hybrid structure of nanosheets and nanowires, quite different from other electrocatalysts that were synthesized from iron chloride and iron nitrate solutions. The final FeCo-LDH-SO₄ had an overpotential of 247 mV with a low Tafel-slope of 60.6 mV dec^-1 at a current density of 10 mA cm^-2 and delivered a long-term stability of 40 h for the OER. This work provides an innovative and feasible strategy to construct efficient electrocatalysts.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.133-133
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• 2013

For both oxygen reduction (ORR) and hydrogen oxidation reactions (HOR) of proton electrolyte membrane fuel cells (PEMFCs), alloying Pt with another transition metal usually results in a higher activity relative to pure Pt, mainly due to electronic modification of Pt and bifunctional behaviour of alloy surface for ORR and HOR, respectively. However, activity and stability are closely related to the preparation of alloy nanoparticles. Preparation conditions of alloy nanoparticles have strong influence on surface composition, oxidation state, nanoparticle size, shape, and contamination, which result from a large difference in redox priority of metal precursors, intrinsic properties of metals, increasedreactivity of nanocrystallites, and interactions with constituents for the synthesis such as solvent, stabilizer, and reducing agent, etc. Carbon-supported Pt-Ni alloy nanoparticles were prepared by the borohydride reduction method in anhydrous solvent. Pt-Ru alloy nanoparticles supported on carbon black were also prepared by the similar synthetic method to that of Pt-Ni. Since electrocatalytic reactions are strongly dependent on the surface structure of metal catalysts, the atom-leveled design of the surface structure plays a significant role in a high catalytic activity and the utilization of electrocatalysts. Therefore, surface-modified electrocatalysts have attracted much attention due to their unique structure and new electronic and electrocatalytic properties. The carbon-supported Au and Pd nanoparticles were adapted as the substrate and the successive reduction process was used for depositing Pt and PtM (M=Ru, Pd, and Rh) bimetallic elements on the surface of Au and Pd nanoparticles. Distinct features of the overlayers for electrocatalytic activities including methanol oxidation, formic acid oxidation, and oxygen reduction were investigated.