• Title/Summary/Keyword: electrocatalysis

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Electrocatalytic Reduction of Dioxygen at Glassy Carbon Electrodes with Irreversible Self-assembly of N-hexadecyl-N'-methyl Viologen

  • Lee, Chi-Woo;Jang, Jai-Man
    • Bulletin of the Korean Chemical Society
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    • v.15 no.7
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    • pp.563-567
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    • 1994
  • The electroreduction of dioxygen at glassy carbon electrodes with irreversible self-assembly of N-hexadecyl-N'-methyl viologen $(C_{16}VC_1)$ proceeds at potentials more positive than those where the reduction occurs at bare electrodes. The electrocatalyzed reduction takes place at potentials well ahead of those where the catalyst is reduced in the absence of dioxygen and the limiting currents observed at rotating disk electrodes did not deviate from the thoretical Levich line up to 6400 rpm, indicating that the electrocatalysis is extremely rapid. The rate constant for the heterogeneous reaction between $C_{16}V^+C_1$ immobilized on the electrode surface and $O_2$ in solution was estimated to be ca. $10^8\;M^{-1}s^{-1}$. The half-wave potential of dioxygen reduction was independent of solution pH.

Electrochemical Polymerization of Ruthenium(II) Complex and Application to Acetaminophen Analysis

  • Kannan, Sethuraman;Son, Jung-Ik;Yang, Jee-Eun;Shim, Yoon-Bo
    • Bulletin of the Korean Chemical Society
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    • v.32 no.4
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    • pp.1341-1345
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    • 2011
  • A novel ruthenium(II) complex, [$RuCl_2(DMSO)_2$(PhenTPy)] has been synthesized by the condensation of $RuCl_2(DMSO)_4$ with (1-(1,10-phenanthrolinyl)-2,5-di(2-thienyl)-1H-pyrrole)[PhenTPy] in $CHCl_3$ solution. The [$RuCl_2(DMSO)_2$(PhenTPy)] complex modified electrode was fabricated through the electropolymerization of the monomer in a 0.1 M tetrabutylammonium perchlorate (TBAP)/$CH_2Cl_2$ solution, to take advantage of the electronic communication between metal ion center by the conjugated backbone. The UV-visible spectroscopy (UV), mass spectrometry (MS), and cyclic voltammetry (CV) were employed to characterize the [$RuCl_2(DMSO)_2$(PhenTPy)] complex and its polymer (poly-Ru(II)Phen complex). The poly-Ru(II)Phen complex modified electrode exhibited an electrocatalytic activity to the oxidation of acetaminophen and the catalytic property was used for the analysis of acetaminophen at the concentration range between 0.09 and 0.01 mM in a phosphate buffer solution (pH 7.0).

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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Electrochemical Properties of Self-Assembled Viologen Monolayers Using Quartz Crystal Analyzer (QCA를 이용한 자기조립된 Viologen 단분자막의 전기화학적 특성)

  • Lee, Dong-Yun;Park, Sang-Hyun;Shin, Hoon-Kyu;Park, Jae-Chul;Chang, Jeong-Soo;Kwon, Young-Soo
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2004.04b
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    • pp.141-144
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    • 2004
  • Molecular self-assembled of surfactant viologens are recently interesting because they can be from functional electrodes as well as micelle assemblies which can be profitably utilized for display devices, electrochemical studies and electrocatalysis as electron acceptor or electron mediator. The electrochemical behavior of self-assembled viologen monolayer on Au electrode surface has been investigated with QCM which has been known as nano-gram order mass detector. A monolayer of viologen is immobilized on the gold electrode surface and the normal potentials corresponding to the to the successive one-electron transfer processes of the viologen actives are two peaks in 0.1mol/l phosphate buffer solution respectively. These result suggest that the viologen SAMs are stable and well-behaved monolayers.

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Electrochemical Properties of Viologen Self-Assembly Monolayer Using QCM (수정진동자를 이용한 Viologen Self-Assembly 단분자막의 전기화학적 특성)

  • Ock, J.Y.;Song, S.H.;Shin, H.K.;Park, J.C.;Chang, J.S.;Chang, S.M.;Kwon, Y.S.
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2002.11a
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    • pp.403-406
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    • 2002
  • Molecular self-assembled of surfactant viologen are of recent interest because they can from functional electroeds as well as micellar assemblies. which can be profitably utilized for display devices. photoelectrochemical studies and electrocatalysis as electron acceptor or electron mediator[1-3]. Fromherz et al studied the se1f-assembly of thiol and disulfide derivatives of viologens bearing long n-alkyl chains on Au electrode surface[4]. In this study, the electrochemical behavior of self-assembled viologen monolayer has been investigated with QCM, which has been known as nano-gram order mass detector. The self-assembly process of viologen was monitored using resonant frequency$({\Delta}F)$ and resonant resistance(R). The redox process of viologen was observed with resonant frequency$({\Delta}F)$.

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Kinetic Study of the Electrooxidation of Mefenamic Acid and Indomethacin Catalysed on Cobalt Hydroxide Modified Glassy Carbon Electrode

  • Saghatforoush, Lotfali.;Hasanzadeh, Mohammad.;Karim-Nezhad, Ghasem.;Ershad, Sohrab.;Shadjou, Nasrin.;Khalilzadeh, Balal.;Hajjizadeh, Maryam.
    • Bulletin of the Korean Chemical Society
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    • v.30 no.6
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    • pp.1341-1348
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    • 2009
  • Electrocatalytic oxidation of two anti-inflammatory drugs (Mefenamic acid and Indomethacin) was investigated on a cobalt hydroxide modified glassy carbon (CHM-GC) electrode in alkaline solution. The process of oxidation and its kinetics were established by using cyclic voltammetry and chronoamperometry techniques as well as steady state polarization measurements. Voltammetric studies indicated that in the presence of under study drugs, the anodic peak current of low-valence cobalt species increased, followed by a decrease in the corresponding cathodic current. This result indicates that the drugs were oxidized via cobalt hydroxide species immobilized on the electrode surface via an E$\acute{C}$ mechanism. A mechanism based on the electrochemical generation of Co (IV) active sites and their subsequent consumption by the drugs in question was also investigated. The constants rate of the catalytic oxidation of the drugs and the electron-transfer coefficients reported.

An Electrochemical Sensor for Hydrazine Based on In Situ Grown Cobalt Hexacyanoferrate Nanostructured Film

  • Kang, Inhak;Shin, Woo-seung;Manivannan, Shanmugam;Seo, Yeji;Kim, Kyuwon
    • Journal of Electrochemical Science and Technology
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    • v.7 no.4
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    • pp.277-285
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    • 2016
  • There is a growing demand for simple, cost-effective, and accurate analytical tools to determine the concentrations of biological and environmental compounds. In this study, a stable electroactive thin film of cobalt hexacyanoferrate (Cohcf) was prepared as an in situ chemical precipitant using electrostatic adsorption of $Co^{2+}$ on a silicate sol-gel matrix (SSG)-modified indium tin oxide electrode pre-adsorbed with $[Fe(CN)_6]^{3-}$ ions. The modified electrode was characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and electrochemical techniques. Electrocatalytic oxidation of hydrazine on the modified electrode was studied. An electrochemical sensor for hydrazine was constructed on the SSG-Cohcf-modified electrode. The oxidation peak currents showed a linear relationship with the hydrazine concentration. This study provides insight into the in situ growth and stability behavior of Cohcf nanostructures and has implications for the design and development of advanced electrode materials for fuel cells and sensor applications.

Applications of Scanning Electrochemical Microscopy (SECM) Coupled to Atomic Force Microscopy with Sub-Micrometer Spatial Resolution to the Development and Discovery of Electrocatalysts

  • Park, Hyun S.;Jang, Jong Hyun
    • Journal of Electrochemical Science and Technology
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    • v.7 no.4
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    • pp.316-326
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    • 2016
  • Development and discovery of efficient, cost-effective, and robust electrocatalysts are imperative for practical and widespread implementation of water electrolysis and fuel cell techniques in the anticipated hydrogen economy. The electrochemical reactions involved in water electrolysis, i.e., hydrogen and oxygen evolution reactions, are complex inner-sphere reactions with slow multi-electron transfer kinetics. To develop active electrocatalysts for water electrolysis, the physicochemical properties of the electrode surfaces in electrolyte solutions should be investigated and understood in detail. When electrocatalysis is conducted using nanoparticles with large surface areas and active surface states, analytical techniques with sub-nanometer resolution are required, along with material development. Scanning electrochemical microscopy (SECM) is an electrochemical technique for studying the surface reactions and properties of various types of electrodes using a very small tip electrode. Recently, the morphological and chemical characteristics of single nanoparticles and bio-enzymes for catalytic reactions were studied with nanometer resolution by combining SECM with atomic force microscopy (AFM). Herein, SECM techniques are briefly reviewed, including the AFM-SECM technique, to facilitate further development and discovery of highly active, cost-effective, and robust electrode materials for efficient electrolysis and photolysis.

Electrochemical Study of [Ni63-Se)2μ4-Se)3(dppf)3] Cluster and Its Catalytic Activity towards the Electrochemical Reduction of Carbon Dioxide

  • Park, Deog-Su;Jabbar, Md. Abdul;Park, Hyun;Lee, Hak-Myoung;Shin, Sung-Chul;Shim, Yoon-Bo
    • Bulletin of the Korean Chemical Society
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    • v.28 no.11
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    • pp.1996-2002
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    • 2007
  • The redox behavior of a [Ni6(μ3-Se)2(μ4-Se)3(Fe(η 5-C5H4P-Ph2)2)3] (= [Ni-Se-dppf], dppf = 1,1-bis(diphenylphosphino) ferrocene) cluster was studied using platinum (Pt) and glassy carbon electrodes (GCE) in nonaqueous media. The cluster showed electrochemical activity at the potential range between +1.6 and ?1.6 V. In the negative region (0 to ?1.6 V), the cluster exhibited two-step reductions. The first step was one-electron reversible, while the second step was a five-electron quasi-reversible process. On the other hand, in the positive region (0 to +1.6 V), the first step involved one-electron quasi-reversible process. The applicability of the cluster was found towards the electrocatalytic reduction of CO2 and was evaluated by experiments using rotating ring disc electrode (RRDE). RRDE experiments demonstrated that two electrons were involved in the electrocatalytic reduction of CO2 to CO at the Se-Ni-dppf-modified electrode.

High Electrochemical Activity of Pt-Cu Alloy Support on Carbon for Oxygen Reduction Reaction (산소 환원 반응을 위한 탄소기반 Pt-Cu 합금의 높은 전기적 촉매 활성)

  • KIM, HAN SEUL;RYU, SU CHAK;LEE, YOUNG WOOK;SHIN, TAE HO
    • Transactions of the Korean hydrogen and new energy society
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    • v.30 no.6
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    • pp.549-555
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    • 2019
  • Electrocatalysis of oxygen reduction reaction (ORR) using Pt nanoparticles or bimetal on carabon was studied. Currently, the best catalyst is platinum, which is a limited resource and expensive to commercialize. In this paper, we investigated the cheaper and more active electrocatalysts by making Pt nanoparticles and adding 3D transition metal such as copper. Electrocatalysts were obtained by chemical reduction based on ethylene glycol solutions. Elemental analysis and particle size were confirmed by XRD and TEM. The electrochemical surface area (ECSA) and activity of the catalyst were determined by electrochemical techniques such as cyclic voltammetry and linear sweep voltammetry method. The commercialized Pt support on carbon (Pt/C, JM), synthesis Pt/C and synthesis Pt3Cu1 alloy nanoparticles supported on carbon were compared. We confirmed that the synthesized Pt3-Cu1/C has high electrochemical performance than commercial Pt/C. It is expected to develop an electrocatalyst with high activity at low price by increasing the oxygen reduction reaction rate of the fuel cell.