• Title/Summary/Keyword: Chlorine evolution

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Development of templated RuO2 nanorod and nanosheet electrodes to improve the electrocatalytic activities for chlorine evolution (전기적 염소 발생 촉매활성을 위한 성형된 루테늄 산화물 나노로드와 나노시트 전극의 개발)

  • Luu, Tran Le;Kim, Choonsoo;Yoon, Jeyong
    • Journal of Korean Society of Water and Wastewater
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    • v.31 no.5
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    • pp.373-381
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    • 2017
  • $RuO_2$ is a common active component of Dimensionally Stable Anodes (DSAs) for chlorine evolution that can be used in wastewater treatment systems. The recent improvement of chlorine evolution using nanostructures of $RuO_2$ electrodes to increase the treatment efficiency and reduce the energy consumption of this process has received much attention. In this study, $RuO_2$ nanorod and nanosheet electrodes were simply fabricated using the sol-gel method with organic surfactants as the templates. The obtained $RuO_2$ nanorod and nanosheet electrodes exhibit enhanced electrocatalytic activities for chlorine evolution possibly due to the active surface areas, especially the outer active surface areas, which are attributed to the increase in mass transfers compared with a conventional nanograin electrode. The electrocatalytic activities for chlorine evolution were increased up to 20 % in the case of the nanorod electrode and 35% in the case of the nanosheet electrode compared with the nanograin electrode. The $RuO_2$ nanorod 80 nm in length and 20-30 nm in width and the $RuO_2$ nanosheet 40-60 nm in length and 40 nm in width are formed on the surface of Ti substrates. These results support that the templated $RuO_2$ nanorod and nanosheet electrodes are promising anode materials for chlorine evolution in future applications.

A Review of Chlorine Evolution Mechanism on Dimensionally Stable Anode (DSA®) (DSA 전극에서 염소 발생 메커니즘)

  • Kim, Jiye;Kim, Choonsoo;Kim, Seonghwan;Yoon, Jeyong
    • Korean Chemical Engineering Research
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    • v.53 no.5
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    • pp.531-539
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    • 2015
  • Chlor-alkali industry is one of the largest electrochemical processes which annually producing 70 million tons of sodium hydroxide and chlorine from sodium chloride solution. $DSA^{(R)}$ (Dimensionally Stable Anodes) electrodes such as $RuO_2$ and $IrO_2$, which is popular in chlor-alkali process, have been investigated to improve the chlorine generation efficiency. Although DSA electrode has been developed with various researches, understanding of the chlorine evolution mechanism is essential to the development of highly efficient DSA electrode. In this review paper, chlorine generation mechanisms are summarized and that of key factors are identified to systematically understand the chlorine generation mechanism. Rate determining step, effect of pH, reaction intermediate, and electrode crystal structure were intensively overviewed as key factors of the chlorine mechanism.

Electrocatalysis of Selective Chlorine Evolution Reaction: Fundamental Understanding and Catalyst Design

  • Taejung Lim;Jinjong Kim;Sang Hoon Joo
    • 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.

Sonoelectrodeposition of RuO2 electrodes for high chlorine evolution efficiencies (초음파 전기증착법을 활용한 고효율 염소 발생용 루테늄 옥사이드 전극)

  • Luu, Tran Le;Kim, Choonsoo;Yoon, Jeyong
    • Journal of Korean Society of Water and Wastewater
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    • v.31 no.5
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    • pp.397-407
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    • 2017
  • A dimensionally stable anode based on the $RuO_2$ electrocatalyst is an important electrode for generating chlorine. The $RuO_2$ is well-known as an electrode material with high electrocatalytic performance and stability. In this study, sonoelectrodeposition is proposed to synthesize the $RuO_2$ electrodes. The electrode obtained by this novel process shows better electrocatalytic properties and stability for generating chlorine compared to the conventional one. The high roughness and outer surface area of the $RuO_2$ electrode from a new fabrication process leads to increase in the chlorine generation rate. This enhanced performance is attributed to the accelerated mass transport rate of the chloride ions from electrolyte to electrode surface. In addition, the electrode with sonodeposition method showed higher stability than the conventional one, which might be explained by the mass coverage enhancement. The effect of sonodeposition time was also investigated, and the electrode with longer deposition time showed higher electrocatalytic performance and stability.

Effect of Thermally Grown TiO2 Interlayer on Chlorine Evolution Efficiency and Durability of Ti/RuO2-PdO-TiO2 Electrodes (열산화법으로 생성된 TiO2 중간보호층이 Ti/RuO2-PdO-TiO2전극의 염소발생 효율 및 내구성에 미치는 영향)

  • Park, Da Jung;Choi, Sung Mook;Lee, Kyu Hwan
    • Journal of the Korean institute of surface engineering
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    • v.51 no.4
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    • pp.207-213
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    • 2018
  • Not only efficiency of chlorine evolution reaction (CER) but also durability namely service life is very important property in dimensional stable anode for Ballast Water Management System (BWMS) for marine ships. Many researchers have been focused on improving efficiency of CER by controlling composition, phase and surface area for a long time, but the efforts to increase durability was relatively small. In this study, we have investigated the effect of $TiO_2$ protective interlayers on efficiency and durability of DSA electrodes. $TiO_2$ protective interlayers were prepared by thermal oxidation at 500, 600 and $700^{\circ}C$ on Ti substrate. And then the DSA electrodes consisting of $Ti/RuO_2-PdO-TiO_2$ were prepared by thermal decomposition method on $TiO_2$ interlayers. The efficiencies of CER of DSA electrodes without $TiO_2$ interlayer and with $TiO_2$ interlayer grown at 500, 600 and $700^{\circ}C$ were 94.19, 94.45, 84.60 and 76.75% respectively. On the otherhand, durabilities were 30, 55, 90 and 65 hours respectively. In terms of industrial aspect, the performance of DSA is considered high efficiency and durability which can correspond to total production of chlorine. If we considered the performance index of DSA as the product of efficiency and durability, performance indices could be recalculated as 28.26, 50.85, 76.14 and 49.89 respectively. As the thermal oxidation temperature increasing, life time were increased remarkerbly, while efficiency of CER was decreased slightly. As a result, DSA electrode with $TiO_2$ interlayer grown at $600^{\circ}C$ has shown about 2.7 times performace of original DSA electrode without $TiO_2$ interlayer.

The research on static and dynamic mechanical properties of concrete under the environment of sulfate ion and chlorine ion

  • Nie, Liangxue;Xu, Jinyu;Bai, Erlei
    • Computers and Concrete
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    • v.20 no.2
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    • pp.205-214
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    • 2017
  • The Hydraulically driven test system and ${\Phi}100mm$ split Hopkinson pressure bar(SHPB) test device were employed to research the quasi-static and dynamic mechanical properties of concrete specimens which has been immersed for 60 days in sodium sulfate (group S1) and sodium chloride (group S2) solution, the evolution of their mass during corrosive period was explored at the same time, and the mechanism of performances lost was analyzed from the microscopic level by using scanning electron microscope. Results of the experimental indicated that: their law of mass both presents the trend of continuous rising during corrosive period, and it increases rapidly on the early days, the mass growth of group S1 and group S2 in first 7 days are 76.78% and 82.82% of their total increment respectively; during the corrosive period, the quasi-static compressive strength of specimens in two groups are significantly decreased, both of which present the trend of increase first and then decrease, the maximum growth rate of group S1 and group S2 are 7.52% and 12.71% respectively, but they are only 76.23% and 82.84% of specimens which under normal environment (group N) on day 60; after immersed for 60 days, there were different decrease to dynamic compressive strength and specific energy absorption, and so as their strain rate sensitivities. So the high salinity environment has a significant effect of weaken the quasi-static and dynamic mechanical performance of concrete.

A Study on Corrosion Resistance of CA2-Mixed Paste (CA2 혼입 페이스트의 부식저항성에 관한 연구)

  • Kim, Jae-Don;Jang, Il-Young
    • Journal of the Korean Society of Industry Convergence
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    • v.25 no.2_2
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    • pp.289-297
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    • 2022
  • Deterioration in durability of structures due to the steel corrosion is difficult to determine whether or not corrosion is initiated and how much propagated, and moreover, repair and maintenance are not easy to deal with. Therefore, preventive treatments can be the best option to avoid the deterioration. Various methods for preventing corrosion of steel, such as electrochemical treatments, anti-corrosion agents and steel surface coatings, are being developed, but economic and environmental aspects make it difficult to apply them to in-situ field. Thus, the purpose of this study was to improve corrosion resistance by using CA-based clinker that are relatively simple and expected to be economically profitable Existing CA-based clinkers had problems such as flash setting and low strength development during the initial hydration process, but in order to solve this problem, CA clinker with low initial reactivity were used as binder in this study. The cement paste used in the experiments was replaced with CA2 clinker for 0%, 10%, 20%, and 30% in OPC. And the mixture used in the chloride binding test for the extraction of water-soluble chloride was intermixed with Cl- 0.5%, 1%, 2%, and 3% by weight of binder content. To evaluate characteristic of hydration heat evolution, calorimetry analysis was performed and simultaneously chloride binding capacity and acid neutralization capacity were carried out. The identification of hydration products with curing ages was verified by X-ray diffraction analysis. The free chloride extraction test showed that the chlorine ion holding ability improved in order OC 10 > OC 30 > OC 20 > OC 0 and the pH drop resistance test showed that the resistance capability in pH 12 was OC 0 > OA 10 > OA 20 > OA 30. The XRD analyses showed that AFm phase, which can affect the ability to hold chlorine ions, tended to increase when CA2 was mixed, and that in pH12 the content of calcium hydroxide (Ca(OH)2), which indicates pH-low resistance, decreased as CA2 was mixed

The investigations for feasible catalysts that are doped by electrochemical methods onto anodic TiO2 nanotubes and its applications (전기화학적 방법으로 TiO2 나노튜브에 도핑 가능한 촉매제와 그 응용에 관한 연구)

  • Yu, Hyeon-Seok;Choe, Jin-Seop
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2017.05a
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    • pp.99.1-99.1
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    • 2017
  • $TiO_2$는 기계적, 화학적 안정성이 높아 가혹한 화학적 환경 또는 고온 운전 조건에서 훌륭한 내구성을 보여주어 산업적으로 일찍이 널리 이용되어 왔다. 예를 들어, 염소발생 (chlorine evolution reaction) 또는 산소발생반응은 (oxygen evolution reaction) 염소 또는 산소 라디칼에 전극이 지속적으로 노출되기에 강한 내부식성을 지닌 전극재가 요구되었고, 그 결과 $TiO_2$를 골조로 한 불용성전극 (dimensionally stable anode)이 개발되어 이용되고 있다. 그러나, $TiO_2$는 절연성이 높은 금속 산화물 재료이기 때문에 넓은 표면적 획득 및 촉매제 사용을 통해 소재의 단점을 극복해야만 한다. 넓은 반응 표면적 획득의 한 방법으로써 전기화학적 양극산화 (electrochemical anodization)를 통한 $TiO_2$ 나노튜브 제조법은 경제적이면서도 구조 제어도 간편한 방법이다. $TiO_2$ 나노튜브는 100nm 전후의 기공 크기를 가짐과 동시에 매우 높은 종횡비를 지니고 있어 넓은 반응 표면적 획득에 특히 유리하다. 그러나, 이 높은 종횡비는 촉매 도입을 어렵게 하는 저해요소가 되기도 한다. 이러한 문제를 해결하기 위하여 다양한 방법들이 연구되었으나 대부분이 번거롭거나 비싼 후단공정을 필요로 한다. 본 연구에서는 $TiO_2$ 나노튜브에 촉매를 도핑하기 위한 간단한 전기화학적 방법으로, 단일공정 양극산화법 (single-step anodization)과 전압충격법 (potential shock), 그리고 저전압충격법 (under potential shock)을 연구하였으며 이에 적용 가능한 촉매제의 종류를 소개한다. 또한, 촉매의 성질에 따른 응용분야와 그 성능평가 결과를 제시한다.

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Perfluorinated Sulfonic Acid Ionomer Membranes for Valued Chemical Production (과불소계 술폰화 이오노머막을 이용한 고부가가치 화학품 제조)

  • Shim, Jae Goo;Park, In Kee;Lee, Chang Hyun
    • Membrane Journal
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    • v.26 no.2
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    • pp.152-158
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    • 2016
  • The Chlor-alkali (CA) membrane cell is a major electrolysis system to produce valued chemicals such as chlorine gas and sodium hydroxide. The CA membrane process has been attracted in the industries, since it has relatively low energy consumption when compared with other CA processes. The key component in CA process is perfluorinated sulfonic acid ionomer membranes, which provide ion-selectivity and barrier properties to produced gases. Unfortunately, there is limited information to determine which factors should be satisfied for CA applications. In this study, the influences of PFSA membranes on CA performances are disclosed. They include ion transport behaviors, gas evolution capability, and chemical/electrochemical resistances under CA operation conditions.

Regeneration of PCB Etchants and Copper Recovery in a Batch-type Electrolytic Cell (회분식 전해조에서 PCB 식각폐수의 재생 및 구리의 회수)

  • Nam, Sang Cheol;Nam, Chong Woo;Tak, Yongsug;Oh, Seung Mo
    • Applied Chemistry for Engineering
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    • v.8 no.2
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    • pp.161-171
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    • 1997
  • Anodic regeneration of PCB enchant and cathodic deposition of copper using electrochemical method has been studied. Cu(I)/Cu(II) concentration ratio as a function of Cu(I) oxidation at the anode was measured from the potential difference between platinum and Ag/AgCl/4M KCl electrodes. Chlorine gas evolution was minimized by maintaining Cu(I) concentration above a specific concentration and using non-porous graphite electrode. Dendritic copper deposition was observed at the cathode and the optimum conditions for Cu deposition was identified as the current density of $360mA/cm^2$, and copper concentration of 12 g/l. Titanium was the most effective cathode material which showed a higher current efficiency and copper recovery. The current efficiency decreased with increasing temperature, but the highest power efficiency was achieved at $50^{\circ}C$.

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