• Korean Chemical Engineering Research
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• v.53 no.1
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• pp.11-15
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• 2015

Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for portable proton exchange membrane fuel cells(PEMFCs). Properties of $NaBH_4$ hydrolysis reaction using unsupported Co-B, Co-P-B catalyst were studied. BET surface area of catalyst, yield of hydrogen, effect of $NaBH_4$ concentration and durability of catalyst were measured. The BET surface area of unsupported Co-B catalyst was $75.7m^2/g$ and this value was 18 times higher than that of FeCrAlloy supported Co-B catalyst. The hydrogen yield of $NaBH_4$ hydrolysis reaction by unsupported catalysts using 20~25 wt% $NaBH_4$ solution was 97.6~98.5% in batch reactor. The hydrogen yield decrease to 95.3~97.0% as the concentration of $NaBH_4$ solution increase to 30 wt%. The loss of unsupported catalyst was less than that of FeCrAlloy supported catalyst during $NaBH_4$ hydrolysis reaction and the loss increased with increasing of $NaBH_4$ concentration. In continuous reactor, hydrogen yield of $NaBH_4$ hydrolysis was 90% using 1.2 g of unsupported Co-P-B catalyst with $3{\ell}/min$ hydrogen generation rate.

• Bulletin of the Korean Chemical Society
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• v.19 no.12
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• pp.1342-1346
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• 1998

The dehydrogenation of ethylbenzene with carbon dioxide has been carried out over ZSM-5 zeolite-supported iron oxide catalyst as well as commercial catalyst (K-Fe2O3) and unsupported iron oxide (Fe3O4) for comparison. In the dehydrogenation over the ZSM-5 zeolite-supported iron oxide catalyst, ethylbenzene is predominantly converted to styrene by an oxidative pathway in the presence of excess carbon dioxide. Carbon dioxide in this reaction is found to play a role as an oxidant for promoting catalytic activity as well as coke resistance of catalyst. On the other hand, both of commercial catalyst and unsupported Fe2O4 exhibit considerable decrease in catalytic activity under the same condition. It is suggested that an active phase for the dehydrogenation with carbon dioxide over ZSM-5 zeolite-supported iron oxide catalyst would be rather a reduced and isolated magnetite (Fe3O4)-like phase having oxygen deficiency in the zeolite matrix.

• Korean Chemical Engineering Research
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• v.54 no.5
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• pp.587-592
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• 2016

Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFCs). Properties of $NaBH_4$ hydrolysis reaction using unsupported Co-P-B Co-B, catalyst at high concentration $NaBH_4$ solution were studied. In order to enhance the hydrogen generation yield at high concentration of $NaBH_4$, the effect of catalyst type, $NaBH_4$ concentration and recovery of condensing water on the hydrogen yield were measured. The yield of hydrogen evolution increased as the boron ratio increased in preparation process of Co-P-B catalyst. The hydrogen yield decreased as the concentration increased from 20 wt% to 25 wt% in $NaBH_4$ solution during hydrolysis reaction using 1:5 Co-P-B catalyst. Maximum hydrogen yield of 96.4% obtained by recovery of condensing water and thinning of catalyst pack thickness in reactor using Co-P-B with Co-B catalyst and 25 wt% $NaBH_4$ solution.

• Korean Chemical Engineering Research
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• v.56 no.5
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• pp.641-646
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• 2018

Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFCs). Properties of $NaBH_4$ hydrolysis reaction using activated carbon supported Co-B/C, Co-P-B/C catalyst were studied. BET surface area of catalyst, yield of hydrogen, effect of $NaBH_4$ concentration and durability of catalyst were measured. The BET surface area of carbon supported catalyst was over $500m^2/g$ and this value was 2~3 times higher than that of unsupported catalyst. Hydrogen generation of activated carbon supported catalyst was more stable than that of unsupported catalyst. The activation energy of Co-P-B/C catalyst was 59.4 kJ/mol in 20 wt% $NaBH_4$ and 14% lower than that of Co-P-B/FeCrAlloy catalyst. Catalyst loss on activated carbon supported catalyst was reduced to about 1/3~1/2 compared with unsupported catalyst, therefore durability was improved by supporting catalyst on activated carbon.

• Applied Chemistry for Engineering
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• v.7 no.5
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• pp.913-924
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• 1996

In this study HDS(hydrodesulfurization) of thiophene was researched over nickel catalysts added with small amounts of neodymium which were prepared by different methods such as unsupported coprepricipitated NdNi catalysts, unsupported intermetallic $NdNi_5$ catalysts, and carbon supported NdNi catalyst. The HDS activity was remarkably increased when a small amounts of neodymium was added to unsupported coprecipitated Ni catalysts. Thus it was known that the role of Nd is important in HDS of thiophene of Ni catalysts. For the case of unsupported intermetallic $NdNi_5$, the intermetallic crystallinity was destroyed to oxide and sulfide after calcination and presulfidation respectively. The HDS activity of thiophene can be explained by surface area of unsupported catalysts. And Nd acts like as structural promoter keeping the high surface area of unsupported catalysts. The HDS activity was increased by each ten times based on 1 gr. of nickel in the order of unsupported intermetallic $NdNi_5$, unsupported coprecipitated NdNi, and carbon supported NdNi catalysts according to different preparation method of catalysts.

• Korean Chemical Engineering Research
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• v.55 no.1
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• pp.13-18
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• 2017

Sodium borohydride, $NaBH_4$, shows a number of advantages as hydrogen source for UAV PEMFC (Unmaned Aerial Vehicle Proton Exchange Membrane Fuel Cells). In order to use for UAV, the weight and volume of byproduct should be small after $NaBH_4$ hydrolysis reaction. Therefore, the weight and volume of byproduct were studied after $NaBH_4$ hydrolysis reaction using unsupported catalyst. The effect of catalyst type, concentration of $NaBH_4$, concentration of NaOH and thickness of catalyst pack on the weight and volume of byproduct were studied. Most of byproduct was $NaB(OH)_4$ and superficial volume of byproduct increased due to foam evolved from byproduct. The weight and volume of byproduct were not affected by concentration of NaOH used stabilizer. The weight of byproduct decreased as concentration of $NaBH_4$ solution increased, but maximum volume of byproduct obtained at 23 wt% of $NaBH_4$. Suitable defoaming agent reduced the volume of byproduct.

• 한국신재생에너지학회:학술대회논문집
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• 2006.11a
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• pp.443-446
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• 2006

Carbon-supported Platinum (Pt) is the potential electro-catalyst material for anodic and cathodic reactions in fuel cell. Catalytic activity of the metal strongly depends on the particle shape, size and distribution of the metal in the porous supportive network. Conventional preparation techniques based on wet impregnation and chemical reduction of the metal precursors often do not provide adequate control of particle size and shape. We have proposed a novel route for preparing nano sized Pt colloidal particles in solution by oxidation of ethylene glycol. These Pt nano particles were deposited on large surface area carbon support. The process of nano Pt colloid formation involves the oxidation of solvent ethylene glycol to mainly glycolic acid and the presence of its anion glycolate depends on the solution pH. In the process of colloidal Pt formation glycolate actsas stabilizer for the Pt colloidal particle and prevents the agglomeration of colloidal Pt particles. These mono disperse Pt particles in carbon support are found uniformly distributed in nearly spherical shape and the size distribution was narrow for both supported and unsupported metals. The average diameter of the Pt nano particle was controlled in the range off to 3 nm by optimizing reaction parameters. Transmission electron microscopy, CV and RRDE experiments were used to compliment the results.

• Korean Chemical Engineering Research
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• v.52 no.6
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• pp.695-700
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• 2014

Proton Exchange Membrane Fuel Cells (PEMFC) can generate hydrogen and oxygen from water by electrolysis. But the electrode and polymer electrolyte membrane degrade rapidly during PEM water electrolysis because of high operation voltage over 1.7V. In order to reduce the rate of anode electrode degradation, unsupported $IrO_2$ catalyst was used generally. In this study, Pt/C catalyst for PEMFC was used as a water electrolysis catalyst, and then the degradation of catalyst and membrane were analysed. After water electrolysis reaction in the voltage range from 1.8V to 2.0V, I-V curves, impedance spectra, cyclic voltammograms and linear sweep voltammetry (LSV) were measured at PEMFC operation condition. The degradation rate of electrode and membrane increased as the voltage of water electrolysis increased. The hydrogen yield was 88 % during water electrolysis for 1 min at 2.0V, the performance at 0.6V decreased to 49% due to degradation of membrane and electrode assembly.

• Korean Chemical Engineering Research
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• v.54 no.3
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• pp.419-424
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• 2016

$H_5PMo_{10}V_2O_{40}$ ($PMo_{10}V_2$) catalyst chemically immobilized on sulfur-containing mesoporous carbon (S-MC) was prepared, and it was applied to the benzyl alcohol oxidation reaction. S-MC was synthesized by a templating method using SBA-15 and p-toluenesulfonic acid as a templating agent and a carbon precursor, respectively. S-MC was then modified to have a positive charge, and thus, to provide sites for the immobilization of $PMo_{10}V_2$. By taking advantage of the overall negative charge of $[PMo_{10}V_2O4_{40}]^{5-}$, $PMo_{10}V_2$ catalyst was immobilized on the S-MC support as a charge matching component. It was revealed that $PMo_{10}V_2$ species were finely and molecularly dispersed on the S-MC via chemical immobilization. In the vapor-phase oxidation of benzyl alcohol, $PMo_{10}V_2$/S-MC catalyst showed higher conversion of benzyl alcohol and higher yield for benzaldehyde and benzoic acid than unsupported $PMo_{10}V_2$ catalyst. The enhanced catalytic performance of $PMo_{10}V_2$/S-MC was due to fine dispersion of $PMo_{10}V_2$ species on the S-MC via chemical immobilization.

• Applied Chemistry for Engineering
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• v.27 no.3
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• pp.313-318
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• 2016

In this study, an amorphous silica was functionalized with aminosilane, N-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS) and the late transition metal catalysts including ($(DME)NiBr_2$ and $PdCl_2$(COD)) were subsequently immobilized on the functionalized amorphous silica for norbornene polymerization. Effects of the polymerization temperature, polymerization time, Al/Ni molar ratio, and type of co-catalyst on norbornene polymerization were investigated. Unsupported late transition metal catalysts did not show any activities for norbornene polymerization. However, the $SiO_2$/2NS/Ni catayst with MAO system, with increasing polymerization temperature, increased the polymerization activity and decreased the molecular weight of the polynorbornene (PNB). Furthermore, the catalyst when increasing polymerization temperature caused the decrease in both the polymerization activity and molecular weight of PNB. This confirmed that the stability of $SiO_2$/2NS/Ni at a high temperature was greater than that of $SiO_2$/2NS/Pd. Also the longer polymerization time resulted in the higher conversion of norbornene for both catalysts. When the Al : Ni molar ratio was 1000 : 1, the highest activity (15.3 kg-PNB/($({\mu}mol-Ni^*hr$)) but lowest molecular weight ($M_n$ = 124,000 g/mol) of PNB were achieved. Also $SiO_2$/2NS/Ni catalyst with borate/TEAL resulted in diminishing the polymerization activity and molecular weight of PNB with increasing the polymerization temperature.