• Title/Summary/Keyword: Borohydride Oxidation

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Enhanced Electrocatalytic Activity of Low Ni Content Nano Structured NiPd Electrocatalysts Prepared by Electrodeposition Method for Borohydride Oxidation

  • Zolfaghari, Mahdieh;Arab, Ali;Asghari, Alireza
    • Journal of Electrochemical Science and Technology
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    • v.11 no.3
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    • pp.238-247
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    • 2020
  • Some nano structured bimetallic NiPd electrocatalysts were electrodeposited on glassy carbon electrodes using a double potential step chronoamperometry. The morphology of the electrodeposited samples was investigated by field emission-scanning electron microscopy, while their compositions were evaluated using energy dispersive X-ray spectroscopy. It was observed that the electrodeposited samples contained a low Ni content, in the range of 0.80 - 7.10%. The electrodeposited samples were employed as the anode electro-catalysts for the oxidation of sodium borohydride in NaOH solution (1.0 M) using cyclic voltammetry, chronoamperometry, rotating disk electrode, and impedance spectroscopy. The number of exchanged electrons, charge transfer resistances, apparent rate constants, and double layer capacitances were calculated for the oxidation of borohydride on the prepared catalysts. According to the results obtained, the NiPd-2 sample with the lowest Ni content (0.80%), presented the highest catalytic activity for borohydride oxidation compared with the other NiPd samples as well as the pure Pd sample. The anodic peak current density was obtained to be about 1.3 times higher on the NiPd-2 sample compared with that for the Pd sample.

Preparation of α-Linked 6-Deoxy-D-altro-heptopyranosidic Residues

  • 신영숙;천근호;Shin, E. Nam;Gerald O. Aspinall
    • Bulletin of the Korean Chemical Society
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    • v.16 no.7
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    • pp.625-630
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    • 1995
  • α-Linked D-altropyranosidic derivatives were obtained by configurational change at C-3 of α-D-mannopyranosides as the key step in preparation of allyl and methyl α-D-glycopyranosides of 6-deoxy-D-altro-heptose. The manno-altro conversion was effected by sequential reactions of Swern oxidation and stereoselective borohydride reduction. Allyl 4,6-O-benzylidene-2-O-p-methoxybenzyl-α-D-mannopyranoside was transformed to the corresponding altropyranoside via 3-oxo-arabino-hexopyranoside. Allyl 7-O-benzyl-6-deoxy-3,4-O-isopropylidene-α-D-altro-heptopyranoside has been prepared as a glycosyl acceptor to be coupled with β-D-GlcpNAc-(1→3)-α-D-Galp glycosyl donor for the synthesis of an O-antigen repeating unit of Campylobacter jejuni serotypes O:23 and O:36. Stereoselective borohydride reduction also succeeded in yielding methyl 2,4,7-tri-O-benzyl-6-deoxy-α-D-altro-heptopyranoside from the corresponding 3-oxo-α-D-arabino-heptopyranoside. C-6 Homologation was achieved by sequential reactions of cyanide displacement of 6-sulphonates, reduction of the resulting heptopyranosidurononitrile with diisobutylaluminum hydride, hydrolysis of the imine, and further reduction with sodium borohydride.

DMSO-Oxalyl Chloride for the Oxidation of Carbohydrates (DMSO-Oxalyl Chloride에 의한 당의 산화)

  • 천문우
    • YAKHAK HOEJI
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    • v.27 no.2
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    • pp.181-184
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    • 1983
  • DMSO-oxalyl chloride at low temperature in methylene chloride reacted with isolated secondary hydroxyl groups in some monosaccharides to give alkoxysulfonium salts, convertible to carbonyls in high yields upon addition of triethylamine. And 1, 2:5, 6-di-O-isopropylidene-.alpha.- D-allofuranose which is the key intermediate in the synthesis of 3-O-acetyl-5-O-benzoyl- 2-deoxy-2- fluoro-D-arabinofuranosyl bromide, was also obtained by oxidizing 1, 2:5, 6-di-O-isopropylidene-.alpha.- D-glucofuranose with the oxidizing reagent, followed by reduction with sodium borohydride.

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Nano Electrocatalysis for Fuel Cells

  • Sung, Yung-Eun
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.133-133
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    • 2013
  • For both oxygen reduction (ORR) and hydrogen oxidation reactions (HOR) of proton electrolyte membrane fuel cells (PEMFCs), alloying Pt with another transition metal usually results in a higher activity relative to pure Pt, mainly due to electronic modification of Pt and bifunctional behaviour of alloy surface for ORR and HOR, respectively. However, activity and stability are closely related to the preparation of alloy nanoparticles. Preparation conditions of alloy nanoparticles have strong influence on surface composition, oxidation state, nanoparticle size, shape, and contamination, which result from a large difference in redox priority of metal precursors, intrinsic properties of metals, increasedreactivity of nanocrystallites, and interactions with constituents for the synthesis such as solvent, stabilizer, and reducing agent, etc. Carbon-supported Pt-Ni alloy nanoparticles were prepared by the borohydride reduction method in anhydrous solvent. Pt-Ru alloy nanoparticles supported on carbon black were also prepared by the similar synthetic method to that of Pt-Ni. Since electrocatalytic reactions are strongly dependent on the surface structure of metal catalysts, the atom-leveled design of the surface structure plays a significant role in a high catalytic activity and the utilization of electrocatalysts. Therefore, surface-modified electrocatalysts have attracted much attention due to their unique structure and new electronic and electrocatalytic properties. The carbon-supported Au and Pd nanoparticles were adapted as the substrate and the successive reduction process was used for depositing Pt and PtM (M=Ru, Pd, and Rh) bimetallic elements on the surface of Au and Pd nanoparticles. Distinct features of the overlayers for electrocatalytic activities including methanol oxidation, formic acid oxidation, and oxygen reduction were investigated.

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Color Change Redox Behavior of the 1,3-Squaraine Dyes

  • Jun, Kun;Shin, Seung-Rim;Shin, Jong-Il;Park, Soo-Youl
    • Textile Coloration and Finishing
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    • v.18 no.5 s.90
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    • pp.53-60
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    • 2006
  • The 1,3-bis(4-aminoaryl)squaraines showed color, change behavior, they were found to undergo reduction with sodium borohydride in solution to give colorless leuco compounds, which oxidized readily in air back to the colored squaraine dye. We have shown that initial observations indicated that the derivatives synthesized gave new donor-acceptor chromophores. It is also interesting to note than the oxidation of the leuco squaraines did initially produce a species absorbing about 630-680 wavelengths. The 1,3-squaraines have found many uses as near-infrared absorbers, laser dyes and photoconductive materials. Furthermore their color-change redox behavior has potential in the area of peroxidase-based bioassaysas oxidation sensitive indicator systems were investigated.

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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New Synthetic Approach to Squarylium Near Infrared Dyes

  • Park, Soo-Youl;Oh, Sea-Wha
    • Proceedings of the Korean Society of Dyers and Finishers Conference
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    • 2003.04a
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    • pp.29-31
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    • 2003
  • The 1,3-bis(4-aminoaryl)squaraines showed colour change behaviour, they were found to undergo reduction with sodium borohydride in solution to give colourless leuco compounds, which oxidised readily in air back to the coloured squaraine dye. We have shown that oxidation of the parent leuco-squaraines gives the neutral squaraine system. Initial observations indicated that the derivatives gave new long-wavelength absorbing chromophores, and It is interesting to note that the onidation of the leuco squaraines did initially produce a species absorbing at longer wavelengths than the parent squaraine dye. This colour-change redox behaviour has potential in the area of peroxidase-based bioassays and artificial camouflage.

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