Tae-Yeol Jeon

Promotional Effect of Palladium on the Hydrogen Oxidation Reaction at a PtPd Alloy Electrode

Although these factors arepivotal for the kinetics of the HOR, direct experimentalinspectionofthecontributionsofthesefactorshasrarelybeeninvestigated in electrochemical oxidation of hydrogen.There are more than enough signs that Pd catalysts havemany of the desired electrocatalytic properties for the HOR/hydrogen evolution reaction (HER), since the electrontransfer from the Pd surface into the antibonding orbital ofthe hydrogen molecule plays an important role in breakingthe hydrogen bonds, and this process lowers the associatedactivation energy.

Multilayered Pt/Ru nanorods with controllable bimetallic sites as methanol oxidation catalysts

A physical synthesis of multilayered Pt/Ru nanorods with controllable bimetallic sites as methanol oxidation catalysts is reported for the first time. The novel nanorods were synthesized via the oblique angle deposition method, deposited prior to the formation of each individual noble metal layer, in a sequential fashion. It has been shown that the oblique angle deposition controls the morphology and electrochemical properties of the resultant nanostructures. Sequentially the multilayered nanorods comprising Pt and Ru segments exhibited superior electrocatalytic activity when compared to equivalent monometallic Pt nanorods with respect to methanol electrooxidation reaction in an acidic medium. Moreover, it has been established that the electrochemical process takes place at the Pt/Ru nanorods followed the bifunctional mechanism. The relative rates of reaction, recorded using chronoamperometry, show a linear relationship between the long-time current density and the number of Pt/Ru interfaces. Interestingly, the best catalyst for methanol oxidation was found to the surface of bimetallic Pt/Ru nanorods produced by the heat treatments via the so-called electronic effect. This reflects the fact that the ensemble effects of combined bifunctional and electronic effects via second elements could be expected in methanol oxidation reactions. Electrocatalytic activities correlate well with bimetallic pair sites and electronic properties analyzed by X-ray photoemission spectroscopy and X-ray absorption near-edge structure.

Surface Structures and Electrochemical Activities of Pt Overlayers on Ir Nanoparticles

Pt overlayers were deposited on carbon-supported Ir nanoparticles with various coverages. Structural and electrochemical characterizations were performed using transmission electron microscopy (TEM), X-ray diffraction, high-resolution powder diffraction (HRPD), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES), cyclic voltammetry (CV), CO stripping voltammetry, and N2O reduction. The surface of Ir nanoparticles was covered with Pt overlayers with thickness varying from the submonolayer scale to more than two monolayers. Surface analyses such as CV and CO stripping voltammetry indicated that the Pt overlayers were uniformly deposited on the Ir nanoparticles, and the resultant Pt overlayers exhibited gradual changes in surface characteristics toward the Pt surface as the surface coverage increased. The distinct CO stripping characteristics and the enhanced Pt utilization affected electrocatalytic activities for methanol oxidation. The electrochemical stability of the Pt overlayer was compared with a commercial carbon-supported Pt catalyst by conducting a potential cycling experiment.

Selective deposition of Pt onto supported metal clusters for fuel cell electrocatalysts

We report a new method for deposition of Pt on a metal core to develop real electrocatalysts with significantly reduced amounts of expensive Pt as well as enhanced activity for oxygen reduction reaction. Ru and Pd have different crystal structures and modify the electronic structure of Pt to a different extent (shifts in d-band center). They were chosen as core materials to examine whether hydroquinone dissolved in ethanol can be used to deposit additional Pt atoms onto preformed core nanoparticles, and whether the modified d-character of Pt on different host metals can result in the enhanced ORR activity. The physicochemical characteristics of Pd-Pt and Ru-Pt core-shell nanoparticles are investigated. The core-shell structure was identified through a combination of experimental methods, employing electron microscopy, electrochemical measurements, and synchrotron X-ray measurements such as powder X-ray diffraction, X-ray absorption fine structure, and X-ray photoelectron spectroscopy. The hydroquinone reduction method proved to be an excellent route for the epitaxial growth of a Pt shell on the metal cores, leading to enhanced ORR activities.

Electrocatalytic effects of carbon dissolution in Pd nanoparticles.

Highly dispersed Pd nanoparticles were prepared by borohydride reduction of Pd(acac)(2) in 1,2-propanediol at an elevated temperature. They were uniformly dispersed on carbon black without significant aggregation. X-ray diffraction showed that carbons from the Pd precursor dissolved in Pd, increasing its lattice parameter. A modified reduction process was tested to remove the carbon impurities. Carbon removal greatly enhanced catalytic activity toward the oxygen reduction reaction. It also generated an inconsistency between the electronic modifications obtained from X-ray photoelectron spectroscopy and the electrochemical method. CO displacement measurements showed that the formation of Pd-C bonds decreased the work function of the surface Pd atoms.

PtRu-Modified Au Nanoparticles as Electrocatalysts for Direct Methanol Fuel Cells

PtRu-modified Au nanoparticles on a carbon support were prepared using a polyol reduction process with various Pt/Ru ratios. The prepared nanoparticles were characterized using transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, cyclic voltammetry, and chronoamperometry. The surfaces of most Au nanoparticles were covered with bimetallic PtRu overlayers with a thickness of 1-2 monolayers. The thin PtRu overlayers represented distinct CO stripping characteristics, which may be attributable to the unique surface structures of the PtRu overlayers on the Au nanoparticles. PtRu utilization was enhanced by as much as two times compared to that of PtRu/C, which can be attributed to the PtRu overlayers that were deposited only on the surface of the Au nanoparticles. The distinct CO stripping characteristics and the enhanced PtRu utilization affected the electrocatalytic activities of methanol oxidation. Pt 2 Ru 1 overlayers exhibited the highest CO tolerance and the highest methanol oxidation activity. The unique electrocatalytic characteristics of the PtRu overlayer structures on the Au nanoparticles are expected to provide methods for reducing the use of active elements.

Realization of Both High-Performance and Enhanced Durability of Fuel Cells: Pt-Exoskeleton Structure Electrocatalysts.

Core-shell structure nanoparticles have been the subject of many studies over the past few years and continue to be studied as electrocatalysts for fuel cells. Therefore, many excellent core-shell catalysts have been fabricated, but few studies have reported the real application of these catalysts in a practical device actual application. In this paper, we demonstrate the use of platinum (Pt)-exoskeleton structure nanoparticles as cathode catalysts with high stability and remarkable Pt mass activity and report the outstanding performance of these materials when used in membrane-electrode assemblies (MEAs) within a polymer electrolyte membrane fuel cell. The stability and degradation characteristics of these materials were also investigated in single cells in an accelerated degradation test using load cycling, which is similar to the drive cycle of a polymer electrolyte membrane fuel cell used in vehicles. The MEAs with Pt-exoskeleton structure catalysts showed enhanced performance throughout the single cell test and exhibited improved degradation ability that differed from that of a commercial Pt/C catalyst.

High Alloying Degree of Carbon Supported Pt-Ru Alloy Nanoparticles Applying Anhydrous Ethanol as a Solvent

Alloying degree is an important structural factor of PtRu catalysts for direct methanol fuel cells (DMFC). In this work, carbon supported PtRu catalysts were synthesized by reduction method using anhydrous ethanol as a solvent and NaBH4 as a reducing agent. Using anhydrous ethanol as a solvent resulted in high alloying degree and good dispersion. The morphological structure and crystallanity of synthesized catalysts were characterized by X-ray diffraction (XRD), high resolution transmission electron microscope (HR-TEM). CO stripping and methanol oxidation reaction were measured. Due to high alloying degree catalyst prepared in anhydrous ethanol, exhibited low onset potential for methanol oxidation and negative peak shift of CO oxidation than commercial sample. Consequently, samples, applying ethanol as a solvent, exhibited not only enhanced CO oxidation, but also increased methanol oxidation reaction (MOR) activity compared with commercial PtRu/C (40 wt%, E-tek) and 40 wt% PtRu/C prepared in water solution.

Theory & Design of Electrocatalyst for Polymer Electrolyte Membrane Fuel Cell

연료전지는 가까운 미래를 위한 핵심 청정 신에너지원 중의 하나로 기대된다. 그러나 고분자 연료전지에서 공기극은 느린 산소환원반응과 많은 백금 사용 때문에 상업화에 어려움을 겪고 있으며, 이것을 해결하는 것이 최근 당면 과제이다. 또한 연료극은 일산화탄소의 피독 현상과 전극의 안정성이 문제시 되고 있다. 본 총설에서는 고분자 연료전지를 위한 연료극, 공기극 전기화학 촉매의 이론적 접근을 통해 촉매를 설계하는 최근 연구 내용을 소개하려 한다. 촉매 설계는 합금 전기 화학 촉매를 통해 접근 했으며, 이는 electronic, geometric, lateral effects를 손쉽게 조절할 수 있게 한다. 이것은 계산되어진 d-band center의 함수에 의존하며, 촉매의 활성과 큰 관계를 가짐을 발견하였다. 본고에서 지향하는 촉매의 최종 방향은 이론적 접근을 통해서 촉매의 사용량을 줄이면서 효율적으로 사용하는 것이다. 【Fuel cells are expected to be one of the major clean new energy sources in the near future. However, the slow kinetics of electrocatalytic hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR), and the high loading of Pt for the anode and cathode material are the urgent issues to be addressed since they determine the efficiency and the cost of this energy source. In this review paper, a new approach was developed for designing electrocatalysts for the HOR and ORR in fuel cells. It was found that the electronic properties of Pt could be fine-tuned by the electronic and geometric effects introduced by the substrate alloy metal and the lateral effects of the neighboring metal atoms. The role of substrate was found reflected in a volcano plot for the HOR and ORR as a function of their calculated d-band centers. This paper demonstrated a viable way to designing the electrocatalysts which could successfully alleviate two issue facing the commercializing of the fuel cell-the cost of electrocatalysts and their efficiency.】

Ethanol Electro-Oxidation and Stability of Pt Supported on Sb-Doped Tin Oxide

Electrocatalytic activities and stabilities of Pt supported on Sb-doped (ATO) were examined for ethanol oxidation reactions. Pt colloidal particles were deposited on ATO nanoparticles (Pt/ATO) and the prepared electrocatalysts were characterized by X-ray diffraction, transmission electron microscopy (TEM), and cyclic voltammetry. Electrochemical activity of the Pt/ATO for ethanol electro-oxidation was compared to those of Pt supported on carbon (Pt/C) and commercial PtRu/C. The activitiy of the Pt/ATO was much higher than those of the Pt/C and commercial PtRu/C. The Pt/ATO exhibited much higher electrochemical stabilities than the Pt/C in 0.5M and in 0.5M /1M . According to TEM, the growth rate of Pt particles was lower in the Pt/ATO than it was in the Pt/C. The ATO nanoparticle appears to be a promising support material that promotes electrochemical reactions and stabilizes catalyst particles in direct ethanol fuel cell.