• Corrosion Science and Technology
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• v.21 no.5
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• pp.412-417
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• 2022

Proton exchange membrane fuel cells (PEMFCs) provide zero emission power sources for electric vehicles and portable electronic devices. Although significant progresses for the widespread application of electrochemical energy technology have been achieved, some drawbacks such as catalytic activity, durability, and high cost of catalysts still remain. Pt-based catalysts are regarded as the most efficient catalysts for sluggish kinetics of oxygen reduction reaction (ORR). However, their prohibitive cost limits the commercialization of PEMFCs. Therefore, we proposed a NiCo@Au core shell structure as Pt-free ORR electrocatalyst in PEMFCs. NiCo alloy was synthesized as core to introduce ionization tendency and autoxidation reaction. Au as a shell was synthesized to prevent oxidation of core NiCo and increase catalytic activity for ORR. Herein, we report the synthesis, characterization, electrochemical properties, and PEMFCs performance of the novel NiCo@Au core-shell as a catalyst for ORR in PEMFCs application. Based on results of this study, possible mechanism for catalytic of autoxidation core@anti-oxidation shell in PEMFCs is suggested.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.232-232
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• 2009

최근 WGS반응용 Pt 촉매의 성능 향상을 위한 다양한 담체 및 조촉매(Promotor) 개발에 대한 연구가 활발하게 진행되고 있다. 선행 연구결과, 입방(Cubic)구조를 가지는 $Ce_{0.8}Zr_{0.2}O_2$ 담체는 정방 입계(Tetragonal)구조를 가지는 $Ce_{0.2}Zr_{0.8}O_2$ 담체 또는 혼합산화물(Mixed oxide)구조를 가지는 $Ce_{0.5}Zr_{0.5}O_2$ 담체 보다 높은 활성과 안전성을 가진다. 이것은 촉매의 성능 향상이 Ce-$ZrO_2$의 결정구조에 의존한다는 것을 나타낸다. 따라서 WGS 반응에서 Ce/Zr 비에 따라 변화된 담체 특성이 Pt 촉매의 활성에 영향이 있을 것으로 예상되며 실험결과 1% Pt/$CeO_2$ 촉매가 가장 높은 활성을 나타내었다. 따라서 Pt/Ce-$ZrO_2$ 촉매의 성능 향상을 위해 Ce-$ZrO_2$ 담체에 조촉매인 Ni을 첨가하여 촉매적 활성을 비교하여 보았다. 촉매는 2%의 Pt과 15%의 Ni로 고정하였고 Ce/Zr 비를 제조변수로 하였다. 제조된 모든 담체는 공침법(Co-precipitation)을 사용하여 제조하였으며 $500^{\circ}C$에서 6시간 소성하였다. Pt 촉매는 함침법 (Incipient wetness impregnation)으로 담지 시켰다. 2% Pt/Ce-$ZrO_2$ 촉매와 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매는 저온영역($200^{\circ}{\sim}320^{\circ}C$)에서 비슷한 CO 전환율을 나타내었으나 고온영역($360^{\circ}C{\sim}400^{\circ}C$)에서는 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매가 더 높은 CO의 전환율을 나타내었다. 이것은 Ni의 영향으로 고온에서 부반응인 메탄화 반응(Methanation reaction)이 생긴 것으로 판단되어 메탄($CH_4$)의 선택도를 살펴본 결과 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매가 고온영역($360^{\circ}{\sim}400^{\circ}C$)에서 급격하게 증가하는 것으로 나타나 메탄화 반응이 일어난 사실을 증명한다.

• Clean Technology
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• v.29 no.4
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• pp.313-320
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• 2023

In order to increase the usability of H₂-SCR, the NOx removal characteristics with catalyst powder of PtNi/CeO₂-W-TiO₂ using Ce as a co-catalyst was synthesized and coated on a porous metal structure (PMS) were evaluated. Catalyst powder of PtNi/CeO₂-W-TiO₂(PtNi nanoparticles onto W-TiO₂, with the incorporation of ceria (CeO₂) as a co-catalysts) was synthesized and coated onto a porous metal structure (PMS) to produce a Selective Catalytic Reduction (SCR) catalyst. H₂-SCR with CeO₂ as a co-catalyst exhibited higher NOx removal efficiency compared to H₂-SCR without CeO₂. Particularly, at a 10wt% CeO₂ loading ratio, the NOx removal efficiency was highest at 90℃. As the amount of catalyst coating on PMS increased, the NOx removal efficiency was improved below 90℃, but it was decreased above 120℃. When the space velocity was changed from 4,000 h^-1 to 20,000 h^-1, the NOx removal efficiency improved at temperatures above 120℃. It was expected that the use of the catalyst could be reduced by applying the PMS with excellent specific surface area as a support.

• Journal of Korean Society for Atmospheric Environment
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• v.15 no.3
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• pp.249-255
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• 1999

We sdudied effect of additives on catalytic activity in thermal catalytic de-NOx process which was composed of thermal reduction, catalytic reduction and catalytic oxidation stage. Pd-Pt/${\gamma}$-$Al_2O_3$ catalysts with the addition of transition metals(Co, Cu, Fe, Ni, W, Zn, Zr) and rare earth metals(Ce, Sr) were prepared by the conventional washcoating method. Those catalysts were characterized by CO pulse chemisorption, ICP, $N_2$ adsorption, SEM and XRD. The effect of catalyst additives on NOx removal for diesel emission was studied in thermal catalytic de-NOx process at reduction temperature(350~50$0^{\circ}C$), space velocity(5,000~20,000 $hr^{-1}$) and the engine load(0~120kW). The concentraton of CO, $CO_2$, NO and $NO_2$ in the exhaust gas increased with the engine load. On the other hand the concentration of $O_2$ decreased. The de-NOx activityof all prepared catalysts increased with respect to high CO and low $O_2$ level in the thermal reduction stage of the process. Insertion of Ce to Pt-Pd/${\gamma}$-$Al_2O_3$ catalyst showed the best activity of all the catalysts under these experimental conditions. De-NOx catalysts are effective to remove CO in addition to NOx in the catalytic reduction stage.

• 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.

• Clean Technology
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• v.21 no.3
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• pp.184-190
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• 2015

Most of LNT catalysts use noble metals such as Pt for low temperature NO_x oxidation but there is an economic weakness. For the purpose of overcoming this, this study is to develop DeNO_x catalyst for LNT excluding PGM (platinum group metal) such as Pt, Pd, Rh, etc. To do so, Al/Co/Ni catalyst selected as a preliminary test is used to study fundamental property and NO_x’s conversion according to calcined temperature. Ultimately, that is, Al/Co/Ni mixed metal oxide which does not use PGM is selected and physicochemical characterization is performed by way of XRD, EDS, SEM, BET and ramp test and NO_x conversion is also analyzed. This study shows that all samples consist of mixed oxides of spinel structure of Co₂AlO₄ and NiAl₂O₄ and have enough pore volume and size for redox. But as a result of NH₃-TPD test, it is desired that calcined temperature needs to be maintained at 700 ℃ or lower. Also only samples which are processed under 500 ℃ satisfied NO and NO_x conversion simultaneously through ramp test. Based on this study’s results, optimum calcined temperature for Al/Co/Ni=1.0/2.5/0.3 mixed metal oxide catalyst is 500 ℃.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.218-221
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• 2009

Solid oxide fuel cells (SOFCs), as high-temperature fuel cells, have various advantages. In some merits of SOFCs, high temperature operation can lead to the capability for internal reforming, providing fuel flexibility. SOFCs can directly use CH4 and CO as fuels with sufficient steam feeds. However, hydrocarbons heavier than CH4, such as ethylene, ethane, and propane, induce carbon deposition on the Ni-based anodes of SOFCs. In the case of the ethylene steam reforming reaction on a Ni-based catalyst, the rate of carbon deposition is faster than among other hydrocarbons, even aromatics. In the reformates of heavy hydrocarbons (diesel, gasoline, kerosene and JP-8), the concentration of ethylene is usually higher than other low hydrocarbons such as methane, propane and butane. It is importatnt that ethylene in the reformate is removed for stlable operation of SOFCs. A new methodology, termed post-reforming was introduced for removing low hydrocarbons from the reformate gas stream. In this work, activity tests of some post-reforming catalysts, such as CGO-Ru, CGO-Ni, and CGO-Pt, are investigated. CGO-Pt catalyst is not good for removing ethylene due to low conversion of ethylene and low selectivity of ethylene dehydrogenation. The other hand, CGO-Ru and CGO-Ni catalysts show good ethylene conversion, and CGO-Ni catalyst shows the best reaction selectivity of ethylene dehydrogenation.

• Clean Technology
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• v.27 no.1
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• pp.69-78
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• 2021

Vegetable oils, such as palm oil and cashew nut shell liquid (CNSL), are used as major raw materials for bio-diesel in transportation and bio-heavy oil in power generation in South Korea. However, due to the high unsaturation degree caused by hydrocarbon double bonds and a high content of oxygen originating from the presence of carboxylic acid, the range of applications as fuel oil is limited. In this study, hydrotreating to saturate unsaturated hydrocarbons and remove oxygen in mixed bio-oil containing 1/1 v/v% palm oil and CNSL on monometallic catalysts (Ni and Cu) and bimetallic catalysts (Ni-Zn, Ni-Fe, Ni-Cu Ni-Co, Ni-Pd, and Ni-Pt) was perform under mild conditions (T = 250 ~ 400 ℃, P = 5 ~ 80 bar and LHSV = 1 h-1). The addition of noble metals and transition metals to Ni showed synergistic effects to improve both hydrogenation (HYD) and hydrodeoxygenation (HDO) activities. The most promising catalyst was Ni-Cu/��-Al2O3, and in the wide range of the Ni/Cu atomic ratio of 9/1~1/4, the conversion for HYD and HDO reactions of the catalysts were 90-93% and 95-99%, respectively. The tendency to exhibit almost constant reaction activity in these catalysts of different Ni/Cu atomic ratios implies a typical structure-insensitive reaction. The refined bio-oil produced by hydrotreating (HDY and HDO) had significantly lower iodine value, acid value, and kinetic viscosity than the raw bio-oil and the higher heating value (HHV) was increased by about 10%.

• Transactions of the Korean hydrogen and new energy society
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• v.34 no.6
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• pp.587-593
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• 2023

This research project focused on the production of hydrogen through ammonia decomposition reactions while investigating how the reactivity of this process varies when employing different catalysts. Several metal oxide supports (Al₂O₃, La₂O₃, CeO₂) were utilized as catalysts, with active metals from both the transition metal group (Co, Ni, Fe, Cr, Cu) and the noble metal group (Ru, Rh, Pd, Pt) impregnated onto these supports. Furthermore, the study examined how the reactivity evolves with changes in reaction temperature when employing the prepared catalysts. Additionally, the research delved into the distinctive activation energies associated with each of the catalysts. In this research, In the noble metal catalyst system, the order of high activity for ammonia decomposition reaction to produce hydrogen is Ru > Rh > Pt ≈ Pd. In the transition metal catalyst system, the order of high activity is Co > Ni > Fe > Cr > Cu.

• Clean Technology
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• v.15 no.1
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• pp.9-15
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• 2009

Catalytic hydrodechlorination of PCBs (polychlorinated biphenyls) included in the transformer oil was carried out to detoxify PCBs and to recycle the treated oil. Catalysts such as 0.98 wt% Pt and 0.79 wt% Pd on ${\gamma}$-alumina (${\gamma}-Al_2O_3$) support, 12.8 wt% Ni on ${\gamma}-Al_2O_3$, and 57.6 wt% Ni on silica-alumina ($SiO_2-Al_2O_3$) support were used for the catalytic hydrodechlorination. Various supercritical fluids such as carbon dioxide, propane and isobutane were used as reaction media. The effects of reaction temperature, reaction time, catalysts, and supercritical fluids on the catalytic hydrodechlorination were examined in detail. The detoxification degree increased in the order of Ni > Pd > Pt. This is possibly due to higher metal loading and larger metal size of the Ni catalyst. Below $175^{\circ}C,\;scCO_2$ was found as the most effective reaction media for the catalytic hydrodechlorination of PCBs included in the transformer oil.