Acrylonitrile-butadiene rubber를 포함한 균질계 음이온교환 복합막의 제조 및 전기화학적 특성

송푸름,문혜진,홍성권,김정훈,장봉준,Song, Pu Reum,Mun, Hye Jin,Hong, Sung Kwon,Kim, Jeoung Hoon,Chang, Bong Jun 한국막학회 2014 멤브레인 Vol.24 No.6

폴리스티렌계 음이온교환막은 제조가 쉽고 공정이 간단한 장점을 갖고 있으나 막의 취성이 높아 내구성이 떨어지는 단점을 가지고 있다. 이를 보완하여 유연하고 우수한 내구성을 갖는 막을 만들기 위해 acrylonitrile-butadiene rubber를 첨가제로 사용하여 음이온교환막을 제조하였다. 다양한 조성의 vinylbenzylchloride와 styrene, divinylbenzene, acrylonitrile-butadiene rubber 그리고 benzoyl peroxide로 이루어진 단량체 용액을 지지체인 직물 형태의 지지체인 poly(propylene)위에 캐스팅 후 열중합 가교시킨 다음 trimethylamine과 acetone을 이용하여 음이온 교환기($-N+(CH_3)_3$)를 함유하는 복합막을 제조하였다. 음이온 교환막 제조시 첨가제의 함량에 따른 막의 성능을 평가하여 최적화 비율을 찾고, 단량체의 함량을 변화하여 함수율, 이온교환용량(IEC) 및 전기저항 값을 측정하였다. 그 결과 최적화 비율로 제조된 막들은 아스톰사의 상용화 음이온 교환막(AMX)보다 높은 IEC와 낮은 전기저항 값을 나타내는 동시에 유연성과 내구성이 우수한 막이 만들어진 것을 확인할 수 있었다. While poly(styrene)-based anion exchange membranes have the advantage like easy and simple manufacturing process, they also possess the disadvantage of poor durability due to their brittleness. Acrylonitrile-butadiene rubber was used here as an additive to make the membranes have improved flexibility and durability. For the preparation of the anion exchange membranes, a PP mesh substrate was immersed into monomer solutions with vinylbenzyl chloride, styrene, divinylbenzene and benzoyl peroxide, then thermally polymerized & crosslinked. The prepared membranes were subsequently post-aminated using trimethylamine to result in $-N+(CH_3)_3$ group-containing composite membranes. Various contents of vinylbenzyl chloride and acrylonitrile-butadiene rubber were investigated to optimize the membrane properties and the prepared membranes were evaluated in terms of water content, ion exchange capacity and electric resistance. It was found that the optimized composite membranes showed higher IEC and lower electric resistance than a commercial anion exchange membrane(AMX) and have excellent flexibility and durability.

Non-cryogenic structure of a chloride pump provides crucial clues to temperature-dependent channel transport efficiency

Yun, Ji-Hye,Li, Xuanxuan,Park, Jae-Hyun,Wang, Yang,Ohki, Mio,Jin, Zeyu,Lee, Wonbin,Park, Sam-Yong,Hu, Hao,Li, Chufeng,Zatsepin, Nadia,Hunter, Mark S.,Sierra, Raymond G.,Koralek, Jake,Yoon, Chun Hong,C American Society for Biochemistry and Molecular Bi 2019 The Journal of biological chemistry Vol.294 No.3

<P>Non-cryogenic protein structures determined at ambient temperature may disclose significant information about protein activity. Chloride-pumping rhodopsin (ClR) exhibits a trend to hyperactivity induced by a change in the photoreaction rate because of a gradual decrease in temperature. Here, to track the structural changes that explain the differences in CIR activity resulting from these temperature changes, we used serial femtosecond crystallography (SFX) with an X-ray free electron laser (XFEL) to determine the non-cryogenic structure of ClR at a resolution of 1.85 Å, and compared this structure with a cryogenic ClR structure obtained with synchrotron X-ray crystallography. The XFEL-derived ClR structure revealed that the all-<I>trans</I> retinal (ATR) region and positions of two coordinated chloride ions slightly differed from those of the synchrotron-derived structure. Moreover, the XFEL structure enabled identification of one additional water molecule forming a hydrogen bond network with a chloride ion. Analysis of the channel cavity and a difference distance matrix plot (DDMP) clearly revealed additional structural differences. B-factor information obtained from the non-cryogenic structure supported a motility change on the residual main and side chains as well as of chloride and water molecules because of temperature effects. Our results indicate that non-cryogenic structures and time-resolved XFEL experiments could contribute to a better understanding of the chloride-pumping mechanism of ClR and other ion pumps.</P>

아민형 PP-g-VBC의 NO<SUB>3</SUB>-N과 PO<SUB>4</SUB>-P 흡착특성

이용재(Yong-Jae Lee),송재준(Jee-June Song),나춘기(Choon-Ki Na) 대한환경공학회 2016 대한환경공학회지 Vol.38 No.10

비닐벤질클로라이드(VBC)를 PP부직포에 광그라프트 중합시키고 에칠렌디아민을 이용한 아민반응을 통해 음이온 교환기능기를 갖는 아민형 PP-g-VBC-EDA 흡착제를 제조하고, 회분식 흡착실험을 통해 음이온 영양염에 대한 흡착특성을 평가하였다. 흡착평형은 랭뮤어 흡착등온식과 잘 일치하였으며, 그로부터 계산한 단일층 최대흡착량은 NO3-N이 59.9 mg/g, PO4-P가 111.4 mg/g이었다. 흡착에너지는 8 kJ/mol 이상으로 이온교환이 주된 흡착메커니즘임을 나타내었다. 흡착속도는 이차흡착속도모델식과 일치하였으며 9.8-36.7 kJ/mol의 흡착활성화에너지를 나타내어 화학적 흡착과정에 의해 지배되었음을 시사하였다. 흡착에 대한 열역학 함수 ΔG<SUP>o</SUP>, ΔH<SUP>o</SUP>와 ΔS<SUP>o</SUP>는 음이온 영양염에 대한 PP-g-VBC-EDA의 흡착이 자발적이고 발열적으로 일어남을 나타내었다. PP-g-VBC-EDA 흡착제는 0.1 N HCl 용액을 이용한 세척과정을 통해 재생할 수 있었다. Amine-type PP-g-VBC-EDA adsorbent, which possesses anionic exchangeable function, was prepared through photoinduced graft polymerization of vinylbenzyl chloride (VBC) onto polypropylene non-woven fabric and subsequent amination reaction using ethylenediamine (EDA). Adsorption characteristics of anionic nutrients on the PP-g-VBC-EDA adsorbent have been studied by batch adsorption experiments. The equilibrium data well fitted the Langmuir isotherm model, and the maximum monolayer sorption capacity was found to be 59.9 mg/g for NO3-N and 111.4 mg/g for PO4-P. The adsorption energies were higher than 8 kJ/mol indicating anion-exchange process as the primary adsorption mechanism. The pseudo-second order kinetic model described well the kinetic data and resulted in the activation energy of 9.8-36.7 kJ/mol suggesting that the overall rates of NO3-N and PO4-P adsorption are controlled by the chemical process. Thermodynamic parameters such as ΔG<SUP>o</SUP>, ΔH<SUP>o</SUP> and ΔS<SUP>o</SUP> indicated that the adsorption nature of PP-g-VBC-EDA for anionic nutrients is spontaneous and exothermic. The PP-g-VBC-EDA could be regenerated by washing with 0.1 N HCl.

Effects of chloride and other anions on electrochemical chlorine evolution over self-doped TiO2 nanotube array

이태영,김성수,최준영,이창하,김춘수,윤제용 한국화학공학회 2021 Korean Journal of Chemical Engineering Vol.38 No.4

Electrochemically reduced TiO2 nanotube arrays (r-TiO2 NTA) have emerged as an alternative that can replace the dimensionally stable anode (DSA®) due to comparable performance for chlorine evolution reaction (ClER). However, previous studies have reported applications of r-TiO2 NTA for ClER only under limited conditions (concentrated NaCl solution without other anions). Thus, the potential of r-TiO2 NTA for CIER has not yet been fully demonstrated. Therefore, this study focused on investigating ClER of r-TiO2 NTA under various parameters such chloride concentration (5-1,000mM) and the presence of other anions (i.e., SO4 2, HPO4 2, and CO3 2). The results suggest that, at low chloride concentration (5-50mM NaCl), the r-TiO2 NTA exhibited higher performance for CIER (production rate of 3.35-9.82mg l1 min1, current efficiency of 14.43-42.04%, energy consumption of 69.24-11.02Wh g(Cl2)1) than RuO2 (2.55-7.88mg l1 min1, 11.07-33.85% and 77.29-6.84Wh g(Cl2)1, respectively). Additionally, other anions did not affect the ClER of r-TiO2 NTA more than RuO2. These can be explained by the indirect pathway of ClER in r- TiO2 NTA while the direct pathway of RuO2 was negatively affected by dilute chloride and other anions.

음이온교환수지 혼입 시멘트 모르타르의 압축강도 및 염소이온 침투 저항성에 관한 실험적 연구

정도현 ( Jung Do-hyun ),이윤수 ( Lee Yun-su ),이한승 ( Lee Han-seung ) 한국건축시공학회 2018 한국건축시공학회 학술발표대회 논문집 Vol.18 No.2

Reinforced concrete is a building material that is generally used in modern society. Also, reinforced concrete structures in high salinity environments have low durability due to corrosion of reinforcing bars due to infiltrated chlorine ions. Anion exchange resins have an ability to immobilize chlorine ions in the resin while releasing their anions. As a material, it has already been shown that it is possible to fix the chloride ion inside the cementitious material through the cement mortar experiment. The purpose of this study is to confirm the compressive strength of cement mortar using powdered anion exchange resin after powdering an anion exchange resin. In order to confirm the chloride ion fixation ability of the powder anion exchange resin, chlorine ion penetration resistance test was carried out.

Poly(vinylbenzyl chloride-glycidyl methacrylate)/Polyethylene Composite Anion Exchange Membranes for Vanadium Redox Battery Application

Min-A Park,심준목,Se-Kook Park,전재덕,진창수,이기봉,신경희 대한화학회 2013 Bulletin of the Korean Chemical Society Vol.34 No.6

Anion exchange membranes for a vanadium redox flow battery (VRB) were prepared by pore-filling on a PE substrate with the copolymerization of vinylbenzyl chloride (VBC) and glycidyl methacrylate (GMA). The ion exchange capacity, water uptake and weight gain ratio were increased with a similar tendency up to 65% of GMA content, indicating that the monomer improved the pore-filling degree and membrane properties. The vanadium ion permeability and open-circuit voltage were also investigated. The permeability of the VG65 membrane was only 1.23 × 10−7 cm2 min−1 compared to 17.9 × 10−7 cm2 min−1 for Nafion 117 and 1.8 × 10−7 cm2 min−1 for AMV. Consequently, a VRB single cell using the prepared membrane showed higher energy efficiency (over 80%) of up to 100 cycles compared to the commercial membranes, Nafion 117 (ca. 58%) and AMV (ca. 70%).

가교결합을 기반으로 한 1,4-dimethylpiperazinum chloride을 가교제로서 가진 비수계 바나듐 레독스 흐름 전지용 음이온 교환 membrane의 개발

신성수,최성호 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.0

최근 몇 년 동안 바나늄 레독스 흐름 전지(Vanadium Redox Flow Battery, VRFB)는 전해용액의 재사용 기능과 설계의 유연성 때문에 에너지 저장 시스템로서 많은 관심을 가져왔다. 현재 사용되는 VRFB는 수계 용매를 사용하여 제한된 전위창을 갖고, 또한, 황산을 사용하기 때문에 전극 및 membrane에 손상을 주어전지의 수명을 짧게 하는 요인이 된다. 이러한 문제점을 해결하기 위하여 비수계 VRFB가 제시되었고 VRFFB의 주요 구성요소 중 하나로써, membrane은 양극, 음극 사이의 separtor로써 기능한다. 몇몇의 상업 음이온 교환 membrane은 유기용매에서 용해되는 성질을 가지고 있기 때문에, 유기용매 상에서 낮은 화학적, 물리적 안정성을 가지고 있다. 그러므로, 이번 연구에서, 비수계 VRFB용 membrane으로 사용하기 위해 poly(vinyl chloride)을 기반으로 한 1,4-dimethylpiperazinum chloride을 가교제로서 비수계 VRFB용 membrane을 제조하였다. 제조된 음이온 교환 membrane은 FT-IR, SEM, XPS, contact angle, and thermal analysis (TGA)을 통해 화학적 구조 및 열적 안정성을 확인하였다. 또한, 제조된 음이온 교환 막은 VRFB에 적용하기 위하여 물리적, 화학적 그리고 전기화학적 특성을 평가하였다.

Poly(vinylbenzyl chloride-glycidyl methacrylate)/Polyethylene Composite Anion Exchange Membranes for Vanadium Redox Battery Application

Park, Min-A,Shim, Joonmok,Park, Se-Kook,Jeon, Jae-Deok,Jin, Chang-Soo,Lee, Ki Bong,Shin, Kyoung-Hee Korean Chemical Society 2013 Bulletin of the Korean Chemical Society Vol.34 No.6

Anion exchange membranes for a vanadium redox flow battery (VRB) were prepared by pore-filling on a PE substrate with the copolymerization of vinylbenzyl chloride (VBC) and glycidyl methacrylate (GMA). The ion exchange capacity, water uptake and weight gain ratio were increased with a similar tendency up to 65% of GMA content, indicating that the monomer improved the pore-filling degree and membrane properties. The vanadium ion permeability and open-circuit voltage were also investigated. The permeability of the VG65 membrane was only $1.23{\times}10^{-7}\;cm^2\;min^{-1}$ compared to $17.9{\times}10^{-7}\;cm^2\;min^{-1}$ for Nafion 117 and $1.8{\times}10^{-7}\;cm^2\;min^{-1}$ for AMV. Consequently, a VRB single cell using the prepared membrane showed higher energy efficiency (over 80%) of up to 100 cycles compared to the commercial membranes, Nafion 117 (ca. 58%) and AMV (ca. 70%).

음이온교환수지 분말이 치환된 포틀랜드 시멘트 모르타르의 염소이온 침투 특성

이윤수 ( Lee Yun-su ),임승민 ( Lim Seung-min ),박장현 ( Park Jang-hyun ),정도현 ( Jung Do-hyun ),이한승 ( Lee Han-seung ) 한국건축시공학회 2020 한국건축시공학회지 Vol.20 No.1

Chloride ion, which penetrates into the cement composites from the outside, generally diffuses by the concentration gradient. Chloride ions are adsorbed by the chemical reaction with cement hydrates. Recent studies have shown that anion exchange resin (AER) powder can effectively adsorb the chloride ion in the cement composites, and thus, the cement composites containing AER have a high chloride adsorption capacity and a good resistance for chloride penetration. In this study, the chloride adsorption ability of the AER powder was investigated under the conditions of distilled water and calcium hydroxide saturated solution to determine if the AER powder is less effective to increase the chloride adsorption ability after grinding process. The chloride adsorption ability of AER powder was compared with the previous research about the chloride adsorption of AER bead. In addition, the compressive strength, chloride diffusion coefficient (using NT Build 492 method), and the chloride profile of cement mortar substituted with AER powder were investigated. There was no decrease in the chloride adsorption capacity of AER powder but increase in the kinetic property for chloride adsorption after the grinding process. The AER powder could absorb the chloride ion in the mortar quickly, and showed better chloride ion adsorption ability than the cement hydrates.

Removal of cadmium from phosphoric acid in the presence of chloride ions using commercially available anion exchange resins

Marta Marszałek,Ewa Knapik,Marcin Piotrowski,Katarzyna Chruszcz-Lipska 한국공업화학회 2023 Journal of Industrial and Engineering Chemistry Vol.118 No.-

The production of cadmium-free phosphoric acid is crucial for the manufacturing of environmentallyfriendly fertilizers. One of the most promising methods for purification of phosphoric acid is ionexchange/adsorption. The article presents studies on the adsorption of cadmium from a 40 % phosphoricacid solution in the presence of chloride ions with the use of commercially available anion exchangeresins. Five borderline cases were examined in a batch system, as well as kinetic studies were performed. The effect of chloride (0.2–2.2 wt%) and cadmium (5–2500 mg/kg) concentration on adsorption with theuse of two best resins was studied in depth. The Amberlite PWA5 resin was selected for column tests andfor experiments with wet process phosphoric acid simulated solution (WPPA-SS) to prove the concept ofpractical application of the resin. The obtained results indicate that PWA5 has a number of advantagesover the resins tested so far, e.g., the resin is characterized by high cadmium adsorption efficiency(89 % in batch experiments with WPPA-SS and 95.5 % in column tests), the resin effectively adsorbs cadmiumin the presence of low chloride concentrations (0.2–0.5 wt%), and the column with this resin canwork properly even at high flow rates (40 BV/h).