• Journal of Electrochemical Science and Technology
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• v.14 no.2
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• pp.105-119
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• 2023

The electrochemical chlorine evolution reaction (CER) is an important electrochemical reaction and has been widely used in chlor-alkali electrolysis, on-site generation of ClO^-, and Cl₂-mediated electrosynthesis. Although precious metal-based mixed metal oxides (MMOs) have been used as CER catalysts for more than half a century, they intrinsically suffer from a selectivity problem between the CER and parasitic oxygen evolution reaction (OER). Hence, the design of selective CER electrocatalysts is critically important. In this review, we provide an overview of the fundamental issues related to the electrocatalysis of the CER and design strategies for selective CER electrocatalysts. We present experimental and theoretical methods for assessing the active sites of MMO catalysts and the origin of the scaling relationship between the CER and the OER. We discuss kinetic analysis methods to understand the kinetics and mechanisms of CER. Next, we summarize the design strategies for new CER electrocatalysts that can enhance the reactivity of MMO-based catalysts and overcome their scaling relationship, which include the doping of MMO catalysts with foreign metals and the development of non-precious metal-based catalysts and atomically dispersed metal catalysts.

• Korean Journal of Materials Research
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• v.33 no.2
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• pp.29-46
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• 2023

The electrochemical reduction of carbon dioxide (CO₂) to value-added products is a remarkable approach for mitigating CO₂ emissions caused by the excessive consumption of fossil fuels. However, achieving the electrocatalytic reduction of CO₂ still faces some bottlenecks, including the large overpotential, undesirable selectivity, and slow electron transfer kinetics. Various electrocatalysts including metals, metals oxides, alloys, and single-atom catalysts have been widely researched to suppress HER performance, reduce overpotential and enhance the selectivity of CO₂RR over the last few decades. Among them, single-atom catalysts (SACs) have attracted a great deal of interest because of their advantages over traditional electrocatalysts such as maximized atomic utilization, tunable coordination environments and unique electronic structures. Herein, we discuss the mechanisms involved in the electroreduction of CO₂ to carbon monoxide (CO) and the fundamental concepts related to electrocatalysis. Then, we present an overview of recent advances in the design of high-performance noble and non-noble singleatom catalysts for the CO₂ reduction reaction.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1485-1488
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• 2009

A facile, seed-mediated preparation method of trimetallic Au@Pb@Pt core-shell nanoparticles is developed. Au nanoparticles are the template seeds onto which sequentially reduced Pb and Pt are deposited. The trimetallic core-shell structure is confirmed by UV-Vis spectroscopy, TEM and EDS analysis, and cyclic voltammetry. The trimetallic Au@Pb@Pt core-shell nanoparticles show high electrocatalytic activity for formic acid and methanol electrooxidation.

• Bulletin of the Korean Chemical Society
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• v.22 no.8
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• pp.816-820
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• 2001

A new copper hexacyanoferrate modified electrode was constructed by mechanical immobilization. The modified electrode was characterised by cyclic voltammetric experiments. Electrocatalytic oxidation of glutathione was effective at the modified electrode at a significantly reduced overpotential and at broader pH range. The modified electrode shows a stable and linear response in the concentration range of 9 ${\times}$10-5 to 9.9 ${\times}$10-4M with a correlation coefficient of 0.9995. The modified electrode exhibits excellent stability, reproducibility and rapid response and can be used in flow injection analysis for the determination of glutathione.

• Journal of the Korean Electrochemical Society
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• v.15 no.2
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• pp.83-89
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• 2012

We investigate the electrocatalytic activities for oxygen reduction at nanoporous gold (NPG) surfaces fabricated by selective dissolution of Ag from electrodeposited Ag-Au layers on electrode surfaces. The structure of NPG was controlled by changing the concentration ratios of precursor metal complexes during the electrodeposition of Ag-Au layers and the corresponding surface morphology and surface area was examined. NPG structures with Ag/Au ratio of 2.0 exhibited the highest electrocatalytic activity for oxygen reduction, where the nanoporous structure plays a key role, but the surface area does not affect on the electrocatalytic activity. The mechanism of electroreduction of oxygen was investigated by rotating disk electrode techniques. In acidic media, oxygen was first reduced to hydrogen peroxide followed by further reduction to water through 2-step 4-electron mechanism, whereas the oxygen was reduced directly to water by 4-electron mechanism in basic media.

• Applied Chemistry for Engineering
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• v.3 no.1
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• pp.138-147
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• 1992

Chemically-modified electrodes were fabricated and their electrocatalytic behaviors have been investigated. As a modifying layer, poly-[1-methyl-3-(pyrrol-1-ylmethyl) pyridinium] was electropolymerized onto Pt electrodes under constant current. The thickness of the polymer film was controlled by means of total charge consumed during the electropolymerization. SEM was used to measure the thickness. There was a linear relationship between the passed charge and the film thickness. Ferro/ferricyanide, used as an electron mediator in this study, was rapidly ion-exchanged into the polymer layer with its concentration of 1.2~1.3M. It was found that electrooxidation of ascorbic acid is catalyzed by incorporated ferri/ferrocyanide couple. Kinetic parameters for electrooxidation were determined by RDE experiments. The results indicate that the present system corresponds to ER+S case based on the Saveant theory. Improving methods have been proposed to be R+S case which is ideal for electrocatalysis.

• Journal of the Korean Chemical Society
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• v.60 no.5
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• pp.310-316
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• 2016

Oxidation-reduction cycling (ORC) procedures are widely used for cleaning nanoparticle surfaces when investigating their electrocatalytic activities. In this work, the effect of ORC on the surface structures and electrocatalytic oxygen reduction activity of Au electrodes is analyzed. Different structural changes and variations in electrocatalysis are observed depending on the initial structure of the Au electrodes, such as flat bulk, nanoporous, nanoplate, or dendritic Au. In particular, dendritic Au structures lost their sharp-edge morphology during the ORC process, resulting in a significant decrease in its electrocatalytic oxygen reduction activity. The results shown in this paper provide an insight into the pretreatment of nanoparticle-based electrodes during investigation of their electrocatalytic activities.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.16 no.6
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• pp.496-500
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• 2003

Molecular self-assembled of surfactant viologen are of recent interest because they can from functional electrodes as well as micellar assemblies, which can be profitably utilized for display devices, photoelectrochemical studies and electrocatalysis as electron acceptor or electron mediator. Fromherz et al studied the self-assembly of thiol and disulfide derivatives of viologens bearing long n-alkyl chains on Au electrode surface[1]. 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(ΔF) and resonant resistance(R). The redox process of viologen was observed with resonant frequency(ΔF).

• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.2943-2948
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• 2009

Copper-dimethylglyoxime complex (CuDMG) modified Copper electrode (Cu/CuDMG) showed a catalytic activity towards cyclohexanol oxidation in NaOH solution. The modified electrode prepared by the dimethylglyoxime anodic deposition on Cu electrode in the solution contained 0.20 M $NH_4Cl\;+\;NH_4OH\;(pH\;9.50)\;and\;1\;{\times}\;10^{-4}$ M dimethylglyoxime. The modified electrode conditioned by potential recycling in a potential range of -900${\sim}$900 mV vs. Ag/AgCl by cyclic voltammetry in alkaline medium (1 M NaOH). The results show that the CuDMG film on the electrode behaves as an efficient catalyst for the electro-oxidation of cyclohexanol in alkaline medium via Cu (III) species formed on the electrode.

• Bulletin of the Korean Chemical Society
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• v.30 no.4
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• pp.810-816
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• 2009

The interactions between four Keggin-type POMs (${SiW_{12}O_{40}}^{4-},\;{PW_{12}O_{40}}^{3-},\;{SiMo_{12}O_{40}}^{4-},\;and\;{PMo_{12}O_{40}}^{3-}$) and glassy carbon (GC) and highly oriented pyrolytic graphite (HOPG) surfaces are investigated in a systematic way. Electrochemical results show that molibdate series POMs adsorb relatively stronger than tungstate POMs on GC and HOPG surfaces. Adsorption of POMs on HOPG electrode surfaces is relatively stronger than on GC surfaces. ${SiMo_{12}O_{40}}^{4-}$ species exhibits unique adsorption behaviors on HOPG surfaces. Surface-confined ${SiMo_{12}O_{40}}^{4-}$ species on HOPG surfaces exhibit unique adsorption behaviors and inhibit the electron transfer from the solution phase species. The catalytic activity of the surface-confined POMs for hydrogen peroxide electroreduction is also examined, where ${PW_{12}O_{40}}^{3-}$ species adsorbed on GC surfaces exhibits the highest catalytic efficiency among the investigated POM modified electrode systems.