• 상하수도학회지
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• 제31권5호
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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.

• Korean Chemical Engineering Research
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• 제53권5호
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• pp.531-539
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• 2015

클로로알카리 산업은 염화나트륨 수용액의 전기분해로 연간 약 7천만 톤의 가성소다 및 염소를 생산하는 전 세계적으로 가장 큰 전기화학 공정 중 하나이다. 클로로알카리 공정에서는 DSA(Dimensionally Stable Anodes) 전극인 $RuO_2$ 및 $IrO_2$를 주로 사용하여 염소를 생산하며 상업적으로 사용되고 있는 전극에 비하여 염소 발생 효율이 높은 전극을 개발하려는 연구가 계속되고 있다. 그러나 보다 염소 발생 효율이 좋은 전극을 개발하기 위해서는 DSA 전극에서의 염소 발생 메커니즘에 대한 이해가 뒷받침되어야 한다. 따라서 본 글에서는 기존 연구를 중심으로 DSA 전극에서 염소 발생 메커니즘 연구가 현재까지 어떻게 발전되어 왔는지 검토하고 염소 발생 메커니즘의 핵심적인 요인들을 분석 및 정리하여 DSA 전극에서 염소 발생을 체계적으로 이해하는데 도움이 되고자 한다.

• Journal of Electrochemical Science and Technology
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• 제14권2호
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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.

• 상하수도학회지
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• 제31권5호
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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.

• 한국표면공학회지
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• 제51권4호
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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.

• Computers and Concrete
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• 제20권2호
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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.

• 한국산업융합학회 논문집
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• 제25권2_2호
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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

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2017년도 춘계학술대회 논문집
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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.

• 멤브레인
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• 제26권2호
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• pp.152-158
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• 2016

클로알칼리(CA) 멤브레인 셀은 대표적인 염수전해 시스템으로서 가성소다와 염소를 생산하는 염수전기분해 프로세스이다. CA 멤브레인 프로세스는 타 공정에 비해 낮은 에너지 소모량을 가져 CA산업에서 가장 선호되는 공정이다. CA프로세스에 사용되는 과불소계 술폰화 이오노머막은 CA프로세스의 핵심구성 요소이며, 양이온을 선택적으로 이동시키는 역할 및 배리어적인 역할을 제공한다. 하지만, CA 구동을 위해 충족되어야 하는 요소들에 대한 정보가 제한적이기 때문에 알맞은 CA분리막 적용을 위한 제품 간의 연구가 필요하다. 본 연구에서는 실제 셀 구동을 바탕으로 하여 상용 고불소계 분리막의 이온전도경향 및 전기화학적 성능 등을 평가하였다.

• 공업화학
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• 제8권2호
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• pp.161-171
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• 1997

인쇄회로기판의 식각폐수를 전기화학적 방법을 이용하여 양극에서 이를 재생하고, 음극에서 구리를 석출하기 위한 실험을 행하였다. 양극에서의 Cu(I)의 산화에 따른 Cu(I)/Cu(II) 변화는 Pt와 Ag/AgCl/4M KCl 전극사이의 전위차를 이용하여 측정하였으며, 반응의 진행에 따른 양극에서의 염소기체 발생은 용액내에 Cu(I)의 농도를 일정치 이상으로 유지시키고, 비다공성 흑연전극을 이용하여 억제할 수 있었다. 그리고, 음극에서의 구리석출은 전류밀도 $360mA/cm^2$, 구리이온농도 12g/l 일때 가장 효율적이며 석출된 구리는 dendrite구조임을 알 수 있었다. 또한 석출효율과 회수방법을 고려할 때 음극으로서 Ti전극을 사용할 경우 가장 우수한 효율을 얻을 수 있었다. 전해온도가 증가함에 따라서 전류효율은 낮아졌으며, 전력효율은 $50^{\circ}C$에서 최대값을 나타내었다.