• Title/Summary/Keyword: Ruthenium catalyst

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Development of Ruthenium/TEMPO/Nitrate Catalyst System for Efficient Oxidation of Isosorbide (아이소소바이드의 효과적 산화반응을 위한 루테늄/템포/나이트레이트 촉매 시스템 개발)

  • Irshad, Mobina;Yu, Jung-Ah;Oh, Youngtak;Kim, Jung Won
    • Applied Chemistry for Engineering
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    • v.33 no.1
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    • pp.103-108
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    • 2022
  • This research work reports the development of a Ruthenium/2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)/nitrate catalyst system for the highly selective transformation of isosorbide (1,4:3,6-dianhydro-D-glucitol) to isosorbide-diketone (2,6-dioxabicyclo (3,3,0)octan-4,8-one). Isosorbide is a critical platform molecule for future manufacturing processes. TEMPO has been utilized to convert alcohols to carbonyl compounds for a long time. The optimal chemical reaction condition was found to be when using isosorbide (0.5 mmol) with supported Ru (10 mol%), TEMPO (5 mol%), and sodium nitrate (0.03 mmol) in the presence of acetic acid (3 ml) as a solvent at 50 ℃ and 1 atm oxygen pressure. This catalyst system demonstrated good selectivity (> 97%) and yield (87%) with respect to the desired product, in addition to a putative catalytic double oxidation mechanism.

Kinetics and Mechanism of Ruthenium(III) Catalyzed Oxidation of Butanone and Uncatalyzed Oxidation of Cychlohexanone by Cerium(IV) in Acid Sulphate Medium

  • Sharma, Priyamvada;Hemkar, Shalini;Khandelwal, C.L.;Sharma, P.D.
    • Journal of the Korean Chemical Society
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    • v.56 no.1
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    • pp.28-33
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    • 2012
  • The kinetics of ruthenium(III) chloride catalyzed oxidation of butanone and uncatalyzed oxidation of cyclohexanone by cerium(IV) in sulphuric acid medium have been studied. The kinetic rate law(I) in case of butanone conforms to the proposed mechanism. $$-\frac{1}{2}\frac{d[Ce^{IV}]}{dt}=\frac{kK[Ru^{III}][butanone]}{1+K[butanone]}$$ (1). However, oxidation of cyclohexanone in absence of catalyst accounts for the rate eqn. (2). $$-\frac{1}{2}\frac{[Ce^{IV}]}{dt}=\frac{(k_1+k_1K^'[H^+])[Ce^{IV}][Cyclohexanone]}{1+K_3[HSO_4^-]}$$ (2) Kinetics and activation parameters have been evaluated conventionally. Kinetically preferred mode of reaction is via ketonic and not the enolic forms.

Study on the Conversion of Ortho to Para Hydrogen (ORTHO/PARA 수소의 전환에의 연구)

  • Kim, Jong-Pal;Lee, Kwang-Hyun
    • Journal of Hydrogen and New Energy
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    • v.18 no.3
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    • pp.317-324
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    • 2007
  • The conversion reaction of ortho to para hydrogen was studied. The percentage of ortho and para hydrogen is mainly dependent on the equilibrium temperature. Because this reaction is known to be accelerated by the catalyst such as nickel-silicate and ruthenium on silica, we focused in the test and development of the catalysts. We studied metal-silicates because they provide high metal dispersion on support. Nickel-silicate, ruthenium-silicate and mixed-silicate were prepared by the coprecipitation method and used in the reaction at the temperature of liquid nitrogen. The conversion was measured by the difference of thermal conductivity between reference gas and sample gas. The activation condition was important and it affected the activities of the catalysts. Nickel-silicate showed high activities. Ruthenium-silicate also showed relative high activities but mixed-silicate showed poor activities.

Hydropurification of Crude Terephthalic Acid over PdRu/Carbon Composite Catalyst (PdRu/Carbon Composite 촉매를 이용한 테레프탈산의 수소화 정제)

  • Jhung, Sung-Hwa;Park, Youn-Seok
    • Journal of the Korean Chemical Society
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    • v.46 no.1
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    • pp.57-63
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    • 2002
  • The hydropurification reaction of CTA (crude terephthalic acid) was carried out with hydrogen over PdRu/CCM (carbon-carbonaceous composite material) catalyst in a batch reactor at high temperature. The first order kinetics of hydropurification is confirmed with the linear dependence of ln(4-CBA; 4-carboxybenzaldehyde) with reaction time. The reaction condition studied is thought to represent the hydropurification well because of the linear dependence of catalytic activity on the catalyst weight. The p-toluic acid (p-tol) in solid and liquid increases with the conversion of reaction or the decrease of 4-CBA. However, the benzoic acid (BA) concentration does not depend much on the conversion. The AT (alkali transmittance) does not depend on the 4-CBA when the concentration is higher than about 0.2% which shows the 4-CBA, in itself, does not cause the coloring effect. The AT of PTA depends inversely with the concentration of 4-CBA when the 4-CBA is less than about 0.15%. This may show the coloring materials are removed in parallel with the hydrogenation of 4-CBA. The (0.3%Pd-0.2%Ru)/CCM shows larger residual catalytic activity than a commercial catalyst, 0.5%Pd/C, after using in a commercial reactor even though the former has smaller fresh activity than the latter. The palladium and ruthenium in PdRu/CCM show the synergetic effect in activity when the ruthenium concentration is about $0.2{\sim}0.35$ wt%. It may be supposed that the PdRu/CCM catalyst can be a promising candidate to replace the commercial Pd/C catalyst.

Transition Metal-Mediated Living Radical Polymerization toward Precision Functional Polymers via Catalyst Design

  • Sawamoto, Mitsuo;Ouchi, Makoto
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.93-94
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    • 2006
  • This lecture will present an overview of recent advances in our transition metal-mediated living radical polymerization, particularly focused on catalyst design and precision synthesis of functional polymers. Selected topics will include: (A) Design of Transition Metal Complexes: Evolution of Catalysts (B) New Ruthenium and Iron Catalysts: Active and Versatile (C) Functional Methacrylates for Advanced Functional Polymers (D) Functional Star Polymers: Microgel Cores for Metal Catalysts.

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Dynamic Kinetic Resolutions and Asymmetric Transformations by Enzyme-Metal Combo Catalysis

  • Kim, Mahn-Joo;Ahn, Yang-Soo;Park, Jai-Wook
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.515-522
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    • 2005
  • Enzyme-metal combo catalysis is described as a useful methodology for the synthesis of optically active compounds. The key point of the method is the use of enzyme and metal in combination as the catalysts for the complete transformation of racemic substrates to single enantiomeric products through dynamic kinetic resolution (DKR). In this approach, enzyme acts as an enantioselective resolving catalyst and metal does as a racemizing catalyst for the efficient DKR. Three kinds of enzyme-metal combinations - lipase-ruthenium, subtilisin-ruthenium, and lipase-palladium –have been developed as the catalysts for the DKRs of racemic alcohols, esters, and amines. The scope of the combination catalysts can be extended to the asymmetric transformations of ketones, enol acetates, and ketoximes via the DKRs. In most cases studied, enzyme-metal combo catalysis provided enantiomerically-enriched products in high yields.

Highly Active Electrocatalyst based on Ultra-low Loading of Ruthenium Supported on Titanium Carbide for Alkaline Hydrogen Evolution Reaction

  • Junghwan, Kim;Sang-Mun, Jung;Kyu-Su, Kim;Sang-Hoon, You;Byung-Jo, Lee;Yong-Tae, Kim
    • Journal of Electrochemical Science and Technology
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    • v.13 no.4
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    • pp.417-423
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    • 2022
  • With the emerging importance of catalysts for water electrolysis, developing efficient and inexpensive electrocatalysts for water electrolysis plays a vital role in renewable hydrogen energy technology. In this study, a 1nm thickness of TiC-supported Ru catalyst for hydrogen evolution reaction (HER) has been successfully fabricated using an electron (E)-beam evaporator and thermal decomposition of gaseous CH4 in a furnace. The prepared Ru/TiC catalyst exhibited an outstanding performance for alkaline hydrogen evolution reaction with an overpotential of 55 mV at 10 mA cm-2. Furthermore, we demonstrated that the outstanding HER performance of Ru/TiC was attributed to the high surface area of the support and the metal-support interaction.

Tar Reforming for Biomass Gasification by Ru/$Al_2O_3$ catalyst (Ru/$Al_2O_3$ 촉매를 이용한 바이오매스 타르 개질 특성)

  • Park, Yeong-Su;Kim, Woo-Hyun;Keel, Sang-In;Yun, Jin-Han;Min, Tai-Jin;Roh, Seon-Ah
    • 한국신재생에너지학회:학술대회논문집
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    • 2008.05a
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    • pp.247-250
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    • 2008
  • Biomass gasification is a promising technology for producing a fuel gas which is useful for power generation systems. In biomass gasification processes, tar formation often causes some problems such as pipeline plugging. Thus, proper tar treatment is necessary. So far, nickel (Ni)-based catalysts have been intensively studied for the catalytic tar removal. However, the deactivation of Ni-based catalysts takes place because of coke deposition and sintering of Ni metal particles. To overcome these problems, we have been using ruthenium (Ru)-based catalyst for tar removal. It is reported by Okada et al., that a Ru/$Al_2O_3$ catalyst is very effective for preventing the carbon deposition during the steam reforming of hydrocarbons. Also, this catalyst is more active than the Ni-based catalyst at a low steam to carbon ratio (S/C). Benzene was used for the tar model compound because it is the main constituent of biomass tar and also because it represents a stable aromatic structure apparent in tar formed in biomass gasification processes. The steam reforming process transforms hydrocarbons into gaseous mixtures constituted of carbon dioxide ($CO_2$), carbon monoxide (CO), methane ($CH_4$) and hydrogen ($H_2$).

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Activating needle coke to develop anode catalyst for direct methanol fuel cell

  • Park, Young Hun;Im, Ui-Su;Lee, Byung-Rok;Peck, Dong-Hyun;Kim, Sang-Kyung;Rhee, Young Woo;Jung, Doo-Hwan
    • Carbon letters
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    • v.20
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    • pp.47-52
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    • 2016
  • Physical and electrochemical qualities were analyzed after KOH activation of a direct methanol fuel cell using needle coke as anode supporter. The results of research on support loaded with platinum-ruthenium suggest that an activated KOH needle coke container has the lowest onset potential and the highest degree of catalyst activity among all commercial catalysts. Through an analysis of the CO stripping voltammetry, we found that KOH activated catalysis showed a 21% higher electrochemical active surface area (ECSA), with a value of 31.37 m2 /g, than the ECSA of deactivated catalyst (25.82 m2 /g). The latter figure was 15% higher than the value of one specific commercial catalyst (TEC86E86).