• 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.

• 전기화학회지
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• 제23권1호
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• pp.1-10
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• 2020

불용성 산화 전극(Dimensionally Stable Anode, DSA)은 물리적, 열적, 전기화학적으로 안정적인 산화 전극이며, 주로 Ru, Ir, Ta 등의 금속 산화물이 Ti 기판에 코팅되어 사용된다. DSA 전극의 우수한 물성을 바탕으로 chlor-alkali, 전기화학적 수처리, 수전해 등의 여러 분야에 활용되고 있다. 이에 본 총설은 DSA 전극의 여러 분야의 적용과 관련된 최근 5년 자료를 정리 요약한 것이다. 이를 통해 DSA 전극의 다양한 적용을 위해서 전극 물질의 스크리닝, 구조 설계 및 경제적인 제조법에 대한 연구가 필요하다는 것을 알 수 있었다. 이러한 연구를 통하여 다양한 분야에 적용할 수 있는 DSA 전극 개발에 기여할 수 있을 것으로 기대된다. 또한, DSA 전극 개발을 통하여 전기화학적 공정을 적용할 수 있는 응용 분야를 넓힐 수 있을 것으로 예상한다.

• 상하수도학회지
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• 제33권1호
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• pp.31-41
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• 2019

Volatile organic compounds(VOCs) are toxic carcinogenic compounds found in wastewater. VOCs require rapid removal because they are easily volatilized during wastewater treatment. Electrochemical advanced oxidation processes(EAOPs) are considered efficient for VOC removal, based on their fast and versatile anodic electrochemical oxidation of pollutants. Many studies have reported the efficiency of removal of various types of pollutants using different anodes, but few studies have examined volatilization of VOCs during EAOPs. This study examined the removal efficiency for VOCs (chloroform, benzene, trichloroethylene and toluene) by oxidization and volatilization under a static stirred, aerated condition and an EAOP to compare the volatility of each compound. The removal efficiency of the optimum anode was determined by comparing the smallest volatilization ratio and the largest oxidization ratio for four different dimensionally stable anodes(DSA): Pt/Ti, $IrO_2/Ti$, $IrO_2/Ti$, and $IrO_2-Ru-Pd/Ti$. EAOP was operated under same current density ($25mA/cm^2$) and electrolyte concentration (0.05 M, as NaCl). The high volatility of the VOCs resulted in removal of more than 90% within 30 min under aerated conditions. For EAOP, the $IrO_2-Ru/Ti$ anode exhibited the highest VOC removal efficiency, at over 98% in 1 h, and the lowest VOC volatilization (less than 5%). Chloroform was the most recalcitrant VOC due to its high volatility and chemical stability, but it was oxidized 99.2% by $IrO_2-Ru/Ti$, 90.2% by $IrO_2-Ru-Pd/Ti$, 78% by $IrO_2/Ti$, and 75.4% by Pt/Ti anodes The oxidation and volatilization ratios of the VOCs indicate that the $IrO_2-Ru/Ti$ anode has superior electrochemical properties for VOC treatment due to its rapid oxidation process and its prevention of bubbling and volatilization of VOCs.

• Corrosion Science and Technology
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• 제5권2호
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• pp.45-51
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• 2006

Properties of the anode for cathodic protection need low overvoltage for oxygen evolution and high corrosion resistance. It is well known that DSA (Dimensionally Stable Anode) has been the best anode ever since. DSA is mainly composed of $RuO_2$, $IrO_2$, $ZrO_2$, $Co_2O_3$, and also $Ta_2O_5$, $TiO_2$, $MnO_2$ are added to DSA for better corrosion resistance. The lifetime of DSA for cathodic protection is also one of the very important factors. $RuO_2$, $IrO_2$, $RhO_2$, $ZrO_2$ are well used for life extension, and many researches are focused on life extension by lowering oxygen evolution potential and minimizing dissolution of oxide coatings. This work aims to evaluate the influence of constituents of MMO and coating cycles and $ZrO_2$ coating on the electrochemical properties and lifetime of DSA electrodes. From the results of lifetime assessment in the anodes coated with single component, $RuO_2$ coating was more effective and showed longer lifetime than $IrO_2$ coating. Also, an increased coating cycle and an electrochemically coated $ZrO_2$ could enhance the lifetime of a DSA.

• 상하수도학회지
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• 제32권4호
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• pp.349-355
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• 2018

This study interrogated multi-layer heterojunction anodes were interrogated for potential applications to water treatment. The multi-layer anodes with outer layers of $SnO_2/Bi_2O_3$ and/or $TiO_2/Bi_2O_3$ onto $IrO_2/Ta_2O_5$ electrodes were prepared by thermal decomposition and characterized in terms of reactive chlorine species (RCS) generation in 50 mM NaCl solutions. The $IrO_2/Ta_2O_5$ layer on Ti substrate (Anode 1) primarily served as an electron shuttle. The current efficiency (CE) and energy efficiency (EE) for RCS generation were significantly enhanced by the further coating of $SnO_2/Bi_2O_3$ (Anode 2) and $TiO_2/Bi_2O_3$ (Anode 3) layers onto the Anode 1, despite moderate losses in electrical conductivity and active surface area. The CE of the Anode 3 was found to show the highest RCS generation rate, whereas the multi-junction architecture (Anode 4, sequential coating of $IrO_2/Ta_2O_5$, $SnO_2/Bi_2O_3$, and $TiO_2/Bi_2O_3$) showed marginal improvement. The microscopic observations indicated that the outer $TiO_2/Bi_2O_3$ could form a crack-free layer by an incorporation of anatase $TiO_2$ particles, potentially increasing the service life of the anode. The results of this study are expected to broaden the usage of dimensionally stable anodes in water treatment with an enhanced RCS generation and lifetime.

• Corrosion Science and Technology
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• 제6권2호
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• pp.44-49
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• 2007

Dimensionally stable anodes have been widely used to cathodically protect the metallic materials in corrosive environments including concrete structure as the insoluble anode. Lifespan of the anode for concrete construction can be determined by NACE TM0294-94 method. Lifespan of conductive oxide electrode would be affected by thermal treatment condition in the process of sol-gel coatings. This work aims to evaluate the effect of thermal treatment temperature on the lifespan of the $RuO_{2}$ electrode. $450^{\circ}C$ treated conductive oxide electrode showed the excellent properties and its lifespan was evaluated to be over 88 years in 3% NaCl, 4% NaOH, and simulated pore water. This behavior was related to the formation of $RuO_{2}$.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 추계학술발표대회
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• pp.29.2-29.2
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• 2011

수용액 상에서 유기물이나 무기물의 전해산화에는 높은 산소과전압과 그 화학종에 대한 화학적, 물리적 안정성이 요구되며, 이러한 요구 조건을 만족하는 소재로써 백금족의 원소가 통상 사용되고 있으나, 가격이 매우 비싸다는 단점을 가지고 있다. 특히 고전류밀도 폐수처리 불용성 전극은 수용액을 전기분해할 때 높은 전류밀도를 낼 수 있으며, 폐수에 혼합되어 있는 각종 화학적 성분에 대한 화학적, 물리적 내구성이 있는 전극으로서, 현재 기존의 수처리용 전극은 금속 Ti을 기판으로 하여 그 위에 불용성 촉매로써 전도성 금속염을 도포, 열처리를 반복하여 산화물의 형태로 수 ${\mu}m$의 두께로 코팅하는 이른바, DSA (Dimensionally Stable Anodes) 전극을 사용하고 있는데, 이는 제조 단가의 상승과 금속 Ti 기판 상에 코팅된 전도성 금속산화물의 미약한 접착력으로 인한 탈리로 전극 전체의 성능 저하 및 수명 단축을 초래하는 문제점이 있다. 본 연구에서는 상기의 문제점을 개선하고자 대표적 불용성 촉매 물질인 백금을 RF magnetron 스퍼터링방식으로 100~300 nm 두께로 성막하여 Ti 기판에 대한 불용성 촉매 물질의 부착력과 내구성 및 모의 해수에 대한 해수전해 특성 등을 평가하였다.

• 한국재료학회지
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• 제22권2호
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• pp.86-90
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• 2012

Insoluble catalytic electrodes were fabricated by RF magnetron sputtering of Pt on Ti substrates and the performance of seawater electrolysis was compared in these electrodes to that is DSA electrodes. The Pt-sputtered insoluble catalytic electrodes were nearly 150 nm-thick with a roughness of $0.18{\mu}m$, which is 1/660 and 1/12 of these values for the DSA (dimensionally stable anodes) electrodes. The seawater electrolysis performance levels were determined through measurements of the NaOCl concentration, which was the main reaction product after electrolysis using artificial seawater. The NaOCl concentration after 2 h of electrolysis with artificial seawater, which has 3.5% NaCl normally, at current densities of 50, 80 and 140 mA/$cm^2$ were 0.76%, 1.06%, and 2.03%, respectively. A higher current density applied through the electrodes led to higher electrolysis efficiency. The efficiency reached nearly 58% in the Pt-sputtered samples after 2 h of electrolysis. The reaction efficiency of DSA showed higher values than that of the Pt-sputtered insoluble catalytic electrodes. One plausible reason for this is the higher specific surface area of the DSA electrodes; the surface cracks of the DSAs resulted in a higher specific surface area and higher reaction sites. Upon the electrolysis process, some Mg- and Ca-hydroxides, which were minor components in the artificial seawater, were deposited onto the surface of the electrodes, resulting in an increase in the electrical resistances of the electrodes. However, the extent of the increase ranged from 4% to 7% within an electrolysis time of 720 h.

• 한국환경보건학회지
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• 제40권2호
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• pp.137-146
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• 2014

Objectives: Feasibility of electrochemical oxidation of the aqueous non-biodegradable wastewater such as cationic dye Rhodamine B (RhB) has been investigated in an electrochemical reactor with solid polymer electrolyte (SPE). Methods: Nafion 117 cationic exchange membrane as SPE has been used. Anode/Nafion/cathode sandwiches were constructed by sandwiching Nafion between two dimensionally stable anodes (JP202 electrode). Experiments were conducted to examine the effects of applied current (0.5~2.0 A), supporting electrolyte type (0.2 N NaCl, $Na_2SO_4$, and 1.0 g/L NaCl), initial RhB concentration (2.5~30.0 mg/L) on RhB and COD degradation and $UV_{254}$ absorbance. Results: Experimental results showed that an increase of applied current in electrolysis reaction with solid polymer electrolyte has resulted in the increase of RhB and $UV_{254}$ degradation. Performance for RhB degradation by electrolyte type was best with NaCl 0.2 N followed by SPE, and $Na_2SO_4$. However, the decrease of $UV_{254}$ absorbance of RhB was different from RhB degradation: SPE > NaCl 0.2 N > $Na_2SO_4$. RhB and $UV_{254}$ absorbance decreased linearly with time regardless of the initial concentration. The initial RhB and COD degradation in electrolysis reaction using SPE showed a pseudo-first order kinetics and rate constants were 0.0617 ($R^2=0.9843$) and 0.0216 ($R^2=0.9776$), respectively. Conclusions: Degradation of RhB in the electrochemical reactor with SPE can be achieved applying electrochemical oxidation. Supporting electrolyte has no positive effect on the final $UV_{254}$ absorbance and COD degradation. Mineralization of COD may take a relatively longer time than that of the RhB degradation.

• 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.