• Title/Summary/Keyword: borohydride

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Catalytic Hydrolysis of Sodium Borohydride on LiCoO3 - Supported Pt, Ru Catalysts (LiCoO3에 담지된 Pt, Ru 촉매에 의한 NaBH4 가수분해반응)

  • Ahn, Jong-Gwan;Choi, Seung-Hoon;Lee, Su-Chol
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.13 no.7
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    • pp.3261-3266
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    • 2012
  • Sodium borohydride($NaBH_4$) known as the material of hydrogen generation and storage can produce the hydrogen via catalytic hydrolysis. This protide chemical could be used in the hydrogen supply system for residential and mobile fuel cells, and thus many researches and developments regarding to these chemicals and decomposition reactions have been implemented. We experimented the hydrolysis of $NaBH_4$ alkaline solution by metal oxide-supported PGM(platinum group metal) catalysts and measured the generation rate of hydrogen which is product of decomposition reaction. We compared oxides as catalyst supports, and the precious metals, Pt and Ru for the catalysts and studied the effects of amounts of catalyst added and $NaBH_4$ concentrations on the hydrogen generation rates and patterns.

Heterogeneous Catalysts for Hydrogen Generation Based on Ru-Incorporated Hydroxyapatite

  • Jaworski, Justyn Wayne;Kim, Dae-Hyun;Jung, Kyeong-Mun;Kim, So-Hue;Jeong, Jong-Ok;Jeon, Hyo-Sang;Min, Byoung-Koun;Kwon, Ki-Young
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.319-319
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    • 2011
  • Hydrolysis of sodium borohydride provides a safe and clean approach to hydrogen generation. Having the proper catalytic support for controlling this reaction is therefore a valuable technology. Here we demonstrate the capability of hydroxyapatite as a novel catalytic support material for hydrogen generation. Aside from being inexpensive and durable, we reveal that Ru ion exchange on the HAP surface provides a highly active support for sodium borohydride hydrolysis, exemplifying a high total turnover number of nearly 24,000 mol $H_2$/ mol Ru. Moreover, we observe that the RuHAP support exhibits a high catalytic lifetime of approximately one month upon repeated exposure to $NaBH_4$ solutions. In addition to examining surface area effects, we also identified the role of complex surface morphology in enhancing hydrolysis by the catalytic transition metal covered surface. Particularly, we found that a polycrystalline RuHAP catalytic support exhibits shorter induction times for the initial bubble formation as well as increased hydrogen generation rates as compared to a single crystal supports. The independent factor of a complex surface morphology is believed to provide enhanced sites for gas release during the initial stages of the reaction. By demonstrating the ability to shorten induction time and enhance catalytic activity through changes in surface morphology and Ru content, we find it feasible to further explore this catalyst support in the construction of a practical hydrogen generator.

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The Characterization of New Type of Alkaline Fuel Cell using Hydrogen Storage Alloys (수소저장합금을 이용한 신개념의 알칼라인 연료전지의 특성에 관한 연구)

  • Kim, Jin-Ho;Lee, Ho;Lee, Han-Ho;Lee, Paul S.;Lee, Jal-Young
    • Journal of Hydrogen and New Energy
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    • v.13 no.2
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    • pp.135-142
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    • 2002
  • 본 연구는 Chemical hydride 형태의 수소발생제를 포함한 액체연료를 이용한 신개념의 알칼라인 연료전지의 특성을 분석하였다. Chemical hydride는 연료전지의 수소공급원으로써 사용될 수 있으며, 본 연구팀은 KOH 전해질에 수소발생제인 Sodium Borohydride ($NaBH_4$)를 첨가하여 제조된 액체연료를 알칼라인 연료전지에 공급함으서 상온에서 매운 우수한 전기 화학적 성능결과를 얻을 수 있었다. 이때 음극 찰물질로 $ZrCr_{0.8}Ni_{1.2}$ 수소저장합금이 사용되었으며, 양극은 방수처리된 카본지 위에 분산된 Pt/C 가 사용되었고, air가 latm으로 양극에 공급되었다. 음극에 대한 XRD 분석결과 음극에서의 산화에 의해 Sodium Borohydride ($NaBH_4$)가 분해되어 수소가 발생되며, 연속적으로 액체연료가 주입되어도 전지가 작동하는 것을 확인할 수 있었다. 이때 에너지밀도는 6,000 Ah/kg (for $NaBH_4$ or $KBH_4$)이다.

Exploration of Essential Structure of Malloapelta B for the Inhibitory Activity Against TNF Induced $NF-{\kappa}B$ Activation

  • Luu, Chinh Van;Chau, Minh Van;Lee, Jung-Joon;Jung, Sang-Hun
    • Archives of Pharmacal Research
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    • v.29 no.10
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    • pp.840-844
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    • 2006
  • For the exploration of pharmacophoric moiety of malloapelta B (1) possessing the inhibitory activity of $NF-{\kappa}B$ activation, structural variation of ${\alpha},{\beta}-unsaturated$ carbonyl motif was attempted. 1 was reduced by catalytic hydrogenation, sodium borohydride, and lithium aluminumhydride. Catalytic hydrogenation with 30 psi or 15 psi of $H_2$ gas of 1 generated 8-butyl-5,7-dimethoxy-2,2-dimethylchroman (2) and 1-(5,7-dimethoxy-2,2-dimethylchroman-8-yl)butan-1-one (3), respectively. Reduction with sodium borohydride occurred at the double bond of ${\alpha},{\beta}-unsaturated$ ketone of 1 to give 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)butan-1-one (4). Reduction of 1 with lithium aluminumhydride and then quenched with methanol and water produced unexpected products, 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)-3-methoxy-1-butene (5) and 1-(5,7-dimethoxy-2,2-dimethyl-2H-chromen-8-yl)-3-hydroxy-1-butene (6). These are formed from the isomerization of initial product 9 through the continuous conjugate carbocation intermediate 11. Addition of ethylmagnesium bromide and dimethyl malonate anion to 1 gave the conjugate adducts 7 and 8. Ethylmagesium bromide and sodium borohydride reduction unusually gave the conjugate addition due to steric congestion around carbonyl group of 1. Compound 2 exhibits the reduced inhibitory activity against $NF-{\kappa}B$ activation and the others do not show the activity. Therefore ${\alpha},{\beta}-unsaturated$ carbonyl group of 1 should be important for its inhibitory activity.

Selective Reduction with Lithium Borohydride. Reaction of Lithium Borohydride with Selected Organic Compounds Containing Representative Functional Groups (수소화붕소리튬에 의한 선택환원. 수소화붕소리튬과 대표적 유기화합물과의 반응)

  • Nung Min Yoon;Jin Soon Cha
    • Journal of the Korean Chemical Society
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    • v.21 no.2
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    • pp.108-120
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    • 1977
  • The approximate rates and stoichiometries of the reaction of lithium borohydride, with fifty two selected organic compounds containing representative functional groups under the standard condition (tetrahydrofuran, $0^{\circ}$), were studied.Among the active hydrogen compounds,primary alcohols and compounds containing an acidic proton liberated hydrogen relatively fast, but secondary and tertiary alcohols very sluggishly. All the carbonyl compounds examined were reduced rapidly within one hour. Especially, among the ${\alpha}{\beta}$-unsaturated carbonyl compounds tested, the aldehydes consumed one hydride cleanly, however the cyclic ketones consumed more than one hydride even at $-20^{\circ}$. Carboxylic acids were reduced very slowly, showing about 60% reduction in 6 days at $25^{\circ}$, however acyl chlorides reduced immediately within 30 minutes. On the other hand, the reductions of cyclic anhydrides proceeded moderately to the hydroxy acid stage, however the further reductions were very slow. Aromatic and aliphatic esters, with exception of the relatively moderate reduction of acetate, were reduced very slowly, however lactones were reduced at a moderate rate. Epoxides reacted slowly, but amides and nitriles as well as the nitro compounds were all inert to this reagent. And cyclohexanone oxime and phenyl isocyanate were reduced very sluggishly. Last of all, all sulfur compounds studied were inert to this hydride.

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Yellowing Inhibition of Bagasse Chemimechanical Pulp

  • Andulkhani Ali;Mirshokraie Seyed Ahmad;Latibari Ahmad Jahan;Enayati Ali Akbar
    • Proceedings of the Korea Technical Association of the Pulp and Paper Industry Conference
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    • 2006.06b
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    • pp.337-347
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    • 2006
  • Papers made from unbleached and bleached bagasse chemimechanical pulp were chemically modified by acetylation. The effects of irradiation on unbleached and bleached also reduced papers of bagasse chemimechanical pulp before and after acetylation were investigated in this study. Chemimechanical pulp was prepared from bagasse and then bleached with hydrogen peroxide. Unbleached and hydrogen bleached pulps were reduced by Sodium borohydride in different procedures. Paper sheets were prepared from pulps and then acetylated using a technical grade of acetic anhydride. Accelerated photo-aging was run on the samples using fluorescent lamps to verify photo-stability of paper sheets before and after pretreatments. Brightness reversion (as Post-color number) and other optical properties of the paper sheets were measured. Efficient inhibition of photo-yellowing of papers made from bagasse CMP was achieved by acetylation. The acetylated unbleached CMP was noticeably photo-bleached during irradiation. Sodium borohydride reduction followed by acetylation had the same effect as acetylation alone at the same degree of reaction time and reductive treatment did not affect the yellowing rate to any great extent. The pre-reduced, acetylated unbleached papers were, however, not brightened during irradiation. Calculation done by Kubelka-Munk equation showed that reductive treatment had little effect in reducing the photo-yellowing of paper made from CMP pulp; a small stabilization effect was observed in the case of bleached CMP, while unbleached CMP was slightly more prone to discolor in the later phase of photo-reversion. The improved stability towards light may was closely related to the decrease in the phenolic hydroxyl content as a result of blocking by acetyl groups during treatment with acetic anhydride. The results support the hypothesis that phenolic hydroxyl has an important role in the process of photo-reversion of high-yield pulps. The results obtained in this study demonstrate that the acetylation of paper manufactured from peroxide bleached Bagasse CMP significantly retards light-induced discoloration. The inhibition of yellowing is connected with a decrease in the phenolic hydroxyl content of both unbleached and peroxide bleached papers.

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Saturated- and Unsaturated-Azamacrocyclic Complexes $(M = Co^{3+}, Fe^{3+}$ or $Mn^{3+})$ Catalyzed Oxidation of Hindered Phenols by Molecular Oxygen under Sodium Borohydride (Sodium Borohydride 하에서 산소에 의한 포화- 및 불포화-질소주게 거대고리 착물 $(M=Co^{3+},\;Fe^{3+}$$Mn^{3+})$을 촉매로 한 Hindered Phenols의 산화반응)

  • Yu-Chul Park;Seong-Su Kim;Hun-Gil Na
    • Journal of the Korean Chemical Society
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    • v.37 no.7
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    • pp.648-654
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    • 1993
  • $[M(cyclam)X_2]Y(M=Co^{3+},\;Fe^{3+},\;Mn^{3+}\;:\;X=Cl-^,\;Br^-,\;NCS^-\;:\;Y=Cl^-,\;Br^-,\;NCS^-),\;[Co(trans-14-diene)X_2]Y(X=Cl^-,\;Br^-\;:\;Y=ClO_4^-)\;and\;[Co(trans-14-diene)](ClO_4)_2$ were able to activate an molecular oxygen under sodium borohydride. 2,4-di-tert-butylphenol and 2,6-di-tert-butylphenol reacted with activated molecular oxygen to give 2,4-tert-butyl-1,6-benzoquinone(BQ) and 3,5,3',5'-tetra-tert-butyldiphenoquinone(DPQ). The saturated tetraazamacrocyclic complexes, $[Co(cyclam)X_2]Y$, were more an effective catalyst than $[Co(trans-14-diene)X_2]Y$ the unsaturated complexes in the formation of BQ and DPQ. The mole ratio of $O_2$ vs. catalyst $(O_2/M)$ for $[Co(cyclam)X_2]Y$ and [Co(trans-14-diene)X_2]Y$ was 1/1, while it was 1/2 for $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$. The results suggested that Co(III)-macrocyclic complexes activated molecular oxygen as superoxolike ${O_2}^-$ and $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$ activated that as peroxolike $O_2^{2-}$.

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