NiO catalysts/Al2O3/FeCrAl alloy foam for hydrogen production was prepared using atomic layer deposition (ALD)and subsequent dip-coating methods. FeCrAl alloy foam and Al2O3 inter-layer were used as catalyst supports. To improve thedispersion and stability of NiO catalysts, an Al2O3 inter-layer was introduced and their thickness was systematically controlledto 0, 20, 50 and 80nm using an ALD technique. The structural, chemical bonding and morphological properties (includingdispersion) of the NiO catalysts/Al2O3/FeCrAl alloy foam were characterized by X-ray diffraction, X-ray photoelectronspectroscopy, field-emission scanning electron microscopy and scanning electron microscopy-energy dispersive spectroscopy. Inparticular, to evaluate the stability of the NiO catalysts grown on Al2O3/FeCrAl alloy foam, chronoamperometry tests wereperformed and then the ingredient amounts of electrolytes were analyzed via inductively coupled plasma spectrometer. We foundthat the introduction of Al2O3 inter-layer improved the dispersion and stability of the NiO catalysts on the supports. Thus, whenan Al2O3 inter-layer with a 80nm thickness was grown between the FeCrAl alloy foam and the NiO catalysts, it indicatedimproved dispersion and stability of the NiO catalysts compared to the other samples. The performance improvement can beexplained by optimum thickness of Al2O3 inter-layer resulting from the role of a passivation layer.
Carbon-supported Pt catalyst systems containing defect adsorption sites on the anode of direct methanol fuel cells were investigated, to elucidate the mechanisms of H2 dissociation and carbon monoxide (CO) poisoning. Density functional theory calculations were carried out to determine the effect of defect sites located neighboring to or distant from the Pt catalyst on H2 and CO adsorption properties, based on electronic properties such as adsorption energy and electronic band gap. Interestingly, the presence of neighboring defect sites led to a reduction of H2 dissociation and CO poisoning due to atomic Pt filling the defect sites. At distant sites, H2 dissociation was active on Pt, but CO filled the defect sites to form carbon π-π bonds, thus enhancing the oxidation of the carbon surface. It should be noted that defect sites can cause CO poisoning, thereby deactivating the anode gradually.
본 연구는 폴리프로필렌(PP) 수지의 Co 및 Mo 촉매에 의한 반응시간과 농도변화에 따른 저온열분해 액화특성을 파악하고자 회분식 반응기를 이용하여 특정 온도(425, 450, 475℃)에서의 전환율을 측정하였다. 열분해 시간은 20~80분으로 설정하였고 생성물은 산업통상자원부에서 고시한 증류성상 온도에 따라 가스, 가솔린, 등유, 경유, 중유로 분류하였다. 그리고 450℃ 반응온도에서 촉매 사용에 따른 전환율은 모든 반응시간에 있어 Mo 촉매 > Co 촉매 > 무촉매 순이었다. Co 및 Mo 촉매 농도별 PP 전환율 및 열분해 생성물 수율은 Co:Mo=50:50 혼합시 가장 우수한 것으로 나타났다.
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).
Methanol was directly produced by the partial oxidation of methane with four-component mixed oxide catalysts. Four-component(Mo-Bi-Cr-Si) mixed oxide catalysts were prepared by the co-precipitation and sol-gel methods. The catalyst prepared by the sol-gel method showed about eleven times higher surface area than that prepared by the co-precipitation method. From the O2-TPD experiment of the prepared catalysts, it was proven that there exists two types of oxygen species, and the oxygen species that participates in the partial oxidation reaction is the lattice oxygen desorbing around 750℃. The optimum reaction condition for methanol production was 420°C, 50 bar, flow rate of 115 mL/min, and CH4/O2 ratio of 10/1.5, providing methane conversion and methanol selectivity of 3.2 and 26.7%, respectively.
NiO catalysts were successfully coated onto FeCrAl metal alloy foam as a catalyst support via a dip-coating method. To demonstrate the optimum amount of NiO catalyst on the FeCrAl metal alloy foam, the molar concentration of the Ni precursor in a coating solution was controlled, with five different amounts of 0.4 M, 0.6 M, 0.8 M, 1.0 M, and 1.2 M for a dip-coating process. The structural, morphological, and chemical bonding properties of the NiO-catalyst-coated FeCrAl metal alloy foam samples were assessed by means of field-emission scanning electron microscopy(FESEM), scanning electron microscopy-energy dispersive spectroscopy(SEM-EDS), X-ray diffraction(XRD), and X-ray photoelectron spectroscopy(XPS). In particular, when the FeCrAl metal alloy foam samples were coated using a coating solution with a 0.8 M Ni precursor, well-dispersed NiO catalysts on the FeCrAl metal alloy foam compared to the other samples were confirmed. Also, the XPS results exhibited the chemical bonding states of the NiO phases and the FeCrAl metal alloy foam. The results showed that a dip-coating method is one of best ways to coat well-dispersed NiO catalysts onto FeCrAl metal alloy foam.
본 연구는 VOC 배출원 중 도장, 인쇄 공정에서 주요 발생물질인 톨루엔을 저온 분해할 수 있는 귀금속 팔라듐촉매 개발에 목적을 두고 있다. 팔라듐은 톨루엔 제거에서 활성이 우수하지만 비용이 높다. 따라서 실용성의 방안으로 Pd 담지량의 최소화 비율(0.1~1.0wt%)로 제조한 촉매의 활성을 측정하였다. 그 결과 1.0wt% Pd(R) 촉매가 모든 조건에서 가장 높은 활성을 나타내었다. 이는 SEM 촬영과 XRD 분석을 통해 촉매 제조과정에서 Pd의 담지량 및 소성 분위기에 따른 분산 형태와 연관이 있는 것으로 사료된다.
The autothermal reforming reaction of methane was investigated to produce hyd rogen with Ni/CeO2-ZrO2, Ni/Al2O3-MgO and Ni-Ru/Al2O3-MgO catalysts. Honeycomb metalli c monolith was applied in order to obtain high catalytic activity and stability in autothermal r eforming. The catalysts were characterized by XRD, BET and SEM. The influence of various catalysts on hydrogen production was studied for the feed ratio(O2/CH4, H2O/CH4). The O2/CH4 and H2O/CH4 ratio governed the methane conversion and temperature profile of reactor. Th e reactor temperature increased as the reaction shifted from endothermic to exothermic reactio n with increasing O2/CH4 ratio. Among the catalysts used in the experiment, the Ni-Ru/Al2O3-MgO catalyst showed the highest activity. The 60% of CH4 conversion was obtained, and th e reactor temperature was maintained 600℃ at the condition of GHSV=10000h-1 and feed ratio S/C/O=0.5/1/0.5.
Pt nanoparticle catalysts incorporated on RuO2 nanowire support were successfully synthesized and their electrochemical properties, such as methanol electro-oxidation and electrochemically active surface (EAS) area, were demonstrated for direct methanol fuel cells (DMFCs). After fabricating RuO2 nanowire support via an electrospinning method, two different types of incorporated Pt nanoparticle electrocatalysts were prepared using a precipitation method via the reaction with NaBH4 as a reducing agent. One electrocatalyst was 20 wt% Pt/RuO2, and the other was 40 wt% Pt/RuO2. The structural and electrochemical properties of the Pt nanoparticle electrocatalysts incorporated on electrospun RuO2 nanowire support were investigated using a bright field transmission electron microscopy (bright field TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry. The bright field TEM, XRD, and XPS results indicate that Pt nanoparticle electrocatalysts with sizes of approximately 2-4 nm were well incorporated on the electrospun RuO2 nanowire support with a diameter of approximately 50 nm. The cyclic voltammetry results showed that the Pt nanoparticle catalysts incorporated on the electrospun RuO2 nanowire support give superior catalytic activity in the methanol electro-oxidation and a higher electrochemically active surface (EAS) area when compared with the electrospun Pt nanowire electrocatalysts without the RuO2 nanowire support. Therefore, the Pt nanoparticle catalysts incorporated on the electrospun RuO2 nanowire support could be a promising electrode for direct methanol fuel cells (DMFCs).
As the performance of microelectronic devices is improved, the use of copper as a heat dissipation member is increasing due to its good thermal conductivity. The high thermal conductivity of copper, however, leads to difficulties in the joining process. Satisfactory bonding with copper is known to be difficult, especially if high shear and peel strengths are desired. The primary reason is that a copper oxide layer develops rapidly and is weakly attached to the base metal under typical conditions. Thus, when a clean copper substrate is bonded, the initial strength of the joint is high, but upon environmental exposure, an oxide layer may develop, which will reduce the durability of the joint. In this study, an epoxy adhesive formulation was investigated to improve the strength and reliability of a copper to copper joint. Epoxy hardeners such as anhydride, dihydrazide, and dicyandiamide and catalysts such as triphenylphosphine and imidazole were added to an epoxy resin mixture of DGEBA and DGEBF. Differential scanning calorimetry (DSC) analyses revealed that the curing temperatures were dependent on the type of hardener rather than on the catalyst, and higher heat of curing resulted in a higher Tg. The reliability of the copper joint against a high temperature and high humidity environment was found to be the lowest in the case of dihydrazide addition. This is attributed to its high water permeability, which led to the formation of a weak boundary layer of copper oxide. It was also found that dicyandiamide provided the highest initial joint strength and reliability while anhydride yielded intermediate performance between dicyandiamide and dihydrazide.
The influence of sulfate on the selective catalytic reduction of on the Ag/ catalyst was studied when was used as a reducing agent. Various preparation methods influenced differently on the activity. Among the methods, cogelation precipitation gave best activity. When sulfates were formed on the surfaces of samples prepared by impregnated and deposition precipitation, activity was enhanced as long as suitable forming condition is satisfied. The major sulfate formed in Ag/ catalyst was the aluminum sulfate and it seems that this sulfate acted as a promoter. When Mg was added to the Ag/ catalyst it promoted activity at high temperature. Intentionally added sulfate also enhanced activity, when their amount was confined less than 3 wt%.
This study is aimed to increase the activity of cathodic catalysts for PEMFCs(Polymer Electrolyte Membrane Fuel Cells). we investigated the temperature effect of 20wt% Pt/C catalysts at five different temperatures. The catalysts were synthesized by using chemical reduction method. Before adding the formaldehyde as reducing agent, process was undergone for 2 hours at the room temperature (RT), 40˚C, 60˚C, 80˚C and 100˚C, respectively. The performances of synthesize catalysts are compared. The electrochemical oxygen reduction reaction (ORR) was studied on 20wt% Pt/C catalysts by using a glassy carbon electrode through cyclic voltammetric curves (CV) in a 1M H2SO4 solution. The ORR specific activities of 20wt% Pt/C catalysts increased to give a relative ORR catalytic activity ordering of 80˚C > 100˚C > 60˚C > 40˚C > RT. Electrochemical active surface area (EAS) was calculated with cyclic voltammetry analysis. Prepared Pt/C (at 80˚C, 100˚C) catalysts has higher ESA than other catalysts. Physical characterization was made by using X-ray diffraction (XRD) and transmission electron microscope (TEM). The TEM images of the carbon supported platinum electrocatalysts (80˚C, 100˚C) showed homogenous particle distribution with particle size of about 2~3.5 nm. We found that a higher reaction temperature resulted in more uniform particle distribution than lower reaction temperature and then the XRD results showed that the crystalline structure of the synthesized catalysts are seen FCC structure.
Nanosized Pt, Pt-Ru and Pt-CeO2 electrocatalysts supported on acid-treated carbon nanotube (CNT) were synthesized by microwave-assisted heating of polyol process using H2Cl6Pt·6H2O, RuCl3, CeCl3 precursors, respectively, and were characterized by XRD and TEM. And then the electrochemical activity of methanol oxidation for catalyst/CNT nanocomposite electrodes was investigated. The microwave assisted polyol process produced the nano-sized crystalline catalysts particles on CNT. The size of Pt supported on CNT was 7~12 nm but it decreased to 3~5 nm in which 10wt% sodium acetate was added as a stabilizer during the polyol process. This fine Pt catalyst particles resulted in a higher current density for Pt/CNT electrode. It was also found that 10 nm size of PtRu alloys were formed by polyol process and the onset potential decreased with Ru addition. Cyclic voltammetry analysis revealed that the Pt75Ru25/CNT electrode had the highest electrochemical activity owing to a higher ratio of the forward to reverse anodic peak current. And the chronoamperemetry test showed that Pt75Ru25 catalyst had a good catalyst stability. The activity of Pt was also found to be improved with the addition of CeO2.
The application of flip chip technology has been growing with the trend of miniaturization of electronic packages, especially in mobile electronics. Currently, several types of adhesive are used for flip chip bonding and these adhesives require some special properties; they must be solvent-free and fast curing and must ensure joint reliability against thermal fatigue and humidity. In this study, imidazole and its derivatives were added as curing catalysts to epoxy resin and their effects on the adhesive properties were investigated. Non-isothermal DSC analyses showed that the curing temperatures and the heat of reaction were dependent primarily on the type of catalyst. Isothermal dielectric analyses showed that the curing time was dependent on the amount of catalysts added as well as their type. The die shear strength increased with the increase of catalyst content while the Tg decreased. From this study, imidazole catalysts with low molecular weight are expected to be beneficial for snap curing and high adhesion strength for flip chip bonding applications.
Different oxidation treatments on CNTs using diluted 4.0 M H2SO4 solution at room temperature and or at 90℃ reflux conditions were investigated to elucidate the physical and chemical changes occurring on the treated CNTs, which might have significant effects on their performance as catalyst supports in PEM fuel cells. Raman spectroscopy, X-ray diffraction and transmission electron microscope analyses were made for the acid treated CNTs to determine the particle size and distribution of the CNT-supported Pt-Ru nanoparticles. These CNT-supported Pt-based nanoparticles were then employed as anode catalysts in PEMFC to investigate their catalytic activity and single-cell performance towards H2 oxidation. Based on PEMFC performance results, refluxed Pt-Ru/CNT catalysts prepared using CNTs treated at 90℃ for 0.5 h as anode have shown better catalytic activity and PEMFC polarization performance than those of the commercially available Pt-Ru/C catalyst from ETEK and other Pt-Ru/CNT catalysts developed using raw CNT, thus demonstrating the importance of acid treatment in improving and optimizing the surface properties of catalyst support.
The continuous transesterification of mixed fat was done on the plug flow reactor packed with the static mixers. The transesterification using 0.5 wt% KOH, 0.8 wt% TMAH and mixed catalyst[40 v/v% KOH(0.5 wt%)+60 v/v% TMAH(0.8 wt%)] was conducted with the changes of molar ratios, weight percentage of beef, flow rates and number of static mixer's elements at 65℃. The overall conversion of mixed fat at 1:8 molar ratio, 50 wt% of beef and 24 of static mixer's elements increased until 0.7mL/min of flow rate. The overall conversion of mixed fat showed 96% at those conditions. So, the optimum operating conditions on tublar reactor were 1:8 molar ratio, 50 wt% of beef, 0.7 mL/min of flow rate and 24 of static mixer' s elements.
Carbon supported electrocatalysts are commonly used as electrode materials for polymer electrolyte membrane fuel cells(PEMFCs). These kinds of electrocatalysts provide large surface area and sufficient electrical conductivity. The support of typical PEM fuel cell catalysts has been a traditional conductive type of carbon black. However, even though the carbon particles conduct electrons, there is still significant portion of Pt that is isolated from the external circuit and the PEM, resulting in a low Pt utilization. Herein, new types of carbon materials to effectively utilize the Pt catalyst are being evaluated. Carbon nanofiber/activated carbon fiber (CNF/ACF) composite with multifunctional surfaces were prepared through catalytic growth of CNFs on ACFs. Nickel nitrate was used as a precursor of the catalyst to synthesize carbon nanofibers(CNFs). CNFs were synthesized by pyrolysising CH4 using catalysts dispersed in acetone and ACF(activated carbon fiber). The as-prepared samples were characterized with transmission electron microscopy(TEM), scanning electron microscopy(SEM). In TEM image, carbon nanofibers were synthesized on the ACF to form a three-dimensional network. Pt/CNF/ACF was employed as a catalyst for PEMFC. As the ratio of prepared catalyst to commercial catalyst was changed from 0 to 50%, the performance of the mixture of 30 wt% of Pt/CNF/ACF and 70wt% of Pt/C commercial catalyst showed better perfromance than that of 100% commercial catalyst. The unique structure of CNF can supply the significant site for the stabilization of Pt particles. CNF/ACF is expected to be promising support to improve the performance in PEMFC.
The effects of La addition to Ni/CeO2 methane partial oxidation catalysts were investigated. Catalysts were prepared by the impregnation and urea methods. In the preparation of catalysts, La content was changed from 1 wt% to 3wt%. Catalysts that contain 2wt% La showed the highest methane conversion of about 80% and CO selectivity of 84% and H2 selectivity of 70%. This result may be stemmed from that, when La content is 2wt%, a fluorite oxide-type structure is well formed and carbon deposition is also decreased. Among the catalysts, 2.5wt% Ni/Ce(La)Ox showed the highest catalytic activity. From the experiment of changing reaction temperature with 2.5wt% Ni/Ce(La)Ox catalyst, it was found that the optimum reaction temperature is 750℃ and at this temperature methane conversion was about 90%, CO and H2 selectivities were 94 and 80%, respectively.
The electrocatalytic characteristics of oxygen reduction reaction of the PtxM(1-x) (M = Co, Cu, Ni) supported on multi-walled carbon nanotubes (MWNTs) have been evaluated in a Polymer Electrolyte Membrane Fuel Cell (PEMFC). The PtxM(1-x)/MWNTs catalysts with a Pt : M atomic ratio of about 3 : 1 were synthesized and applied to the cathode of PEMFC. The crystalline structure and morphology images of the PtxM(1-x) particles were characterized by X-ray diffraction and transmission electron microscopy, respectively. The results showed that the crystalline structure of the Pt alloy particles in Pt/MWNTs and PtxM(1-x)/MWNTs catalysts are seen as FCC, and synthesized PtxM(1-x) crystals have lattice parameters smaller than the pure Pt crystal. According to the electrochemical surface area (ESA) calculated with cyclic voltammetry analysis, Pt0.77Co0.23/MWNTs catalyst has higher ESA than the other catalysts. The evaluation of a unit cell test using Pt/MWNTs or PtxM(1-x)/MWNTs as the cathode catalysts demonstrated higher cell performance than did a commercial Pt/C catalyst. Among the MWNTs-supported Pt and PtxM(1-x) (M = Co, Cu, Ni) catalysts, the Pt0.77Co0.23/MWNTs shows the highest performance with the cathode catalyst of PEMFC because they had the largest ESA.
Esterification reaction between succinic acid[SA] and 1,4-butanediol [BD was kinetically investigated in the presence of organic metal catalysts (alkyl-silver oxide(ASO),CAT 100E) at 150~190℃. The reaction rates measured by the amount of distilled water from the reaction vessel. The esterification reaction was carried out under the first order kinetics with respect to the concentration of reactants and catalyst, respectively. The overall reaction order was 2nd. From the examination of relationship between apparent reaction rate constants and reciprocal absolute temperature, the activation energy has been calculate as 146.70 kJ/mol with ASO catalyst and 43.04 kJ/mol with CAT 100E catalyst.