• Proceedings of the Korea Water Resources Association Conference
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• 2019.05a
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• pp.198-198
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• 2019

2011년 동일본 지역에서 발생한 지진으로 인하여 후쿠시마 다이이치에 위치한 원자력 발전소에서 다양한 방사성 물질들이 바다, 하천 그리고 대기와 같은 자연환경 속으로 유출되었다. 방사성 세슘(Cesuim, $Cs^{137}$)은 다양한 방사성 물질들 가운데 반감기(Half-life)가 30.17년으로 가장 긴 물질이다. 방사성 세슘이 환경 생태계로 한번 유출될 경우 긴 반감기과 널리 퍼지는 성질로 인하여 오랜 시간동안 넓은 지역에 막심한 피해를 초래하므로 효과적인 처리방법을 통해 안전하게 처리하는 것이 아주 중요하다. 세슘을 제거하기 위하여 물리적, 화학적, 생물학적 등 다양한 방법들을 통해 연구를 진행하고 있으며, 특히 세슘을 제거하는 아주 효과적인 방법 중 하나인 프러시안 블루(Prussian Blue, PB) 흡착제를 적용하는 방법이 많이 주목받고 있다. 그러나 프러시안 블루는 미세한 분말입자로서 수처리에 사용하게 되면 처리 후 발생되는 슬러지들을 수중으로 부터 분리하기 어려운 한계점을 가지고 있다. 최근 연구에서는 프러시안 블루의 적용 한계점를 극복하기 위하여 자성체(Magnetic substance)를 물리적 지지체로 이용하여 외부 자기장을 통해 수중으로 분리하는 방법들이 연구되고 있다. 자성체란 외부 자기장이 주어지게 되면 입자들 표면에 자성력을 띄는 물질들을 말한다. 본 연구에서는 자성체 종류들 가운데 가장 높은 자성력을 지닌 강자성체(Ferromagnetic Substance)를 물리적 지지체로 하여 산화과정, 실란과정, 합성과정을 거쳐 강자성체 입자의 표면에 프러시안 블루를 합성한 새로운 형태에 합성체를 제조하고, 제조된 합성체를 이용하여 수중에 존재하는 세슘 제거 능력을 평가하였다. 제조된 합성체의 물리적 특성을 분석하기 위하여 SEM, XRD를 이용하여 합성체 입자의 표면 분석을 진행하였다. 합성체의 세슘 제거 능력을 평가하기 위하여 임의 제조된 0.5mg/L의 세슘 농도를 가진 원수 100ml에 제조된 새로운 형태의 합성체 1g을 투입한 뒤 1분간의 반응시간 동안 반응한 이후 잔류 세슘을 측정한 결과 수중의 존재하는 세슘에 대해 99.9%의 세슘 제거율을 기록하였다. 자가분리(Magnetic Seperate)의 원리를 이용하여 수중으로부터 회수율을 측정한 결과, 99%의 합성체 회수율을 얻었다. 실험결과를 통해 외부자기장이 주어지게 되면 수중으로부터 합성체를 대부분 분리하여 회수할 수 있다고 판단된다. 본 연구를 통해 개발된 새로운 형태의 합성체는 수중의 세슘 처리 공정에서 사용자가 직접 접촉하지 않고 세슘제거 및 외부자기장을 통해 수중으로부터 분리가 가능한 합성체라고 판단된다.

• Korean Chemical Engineering Research
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• v.62 no.2
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• pp.181-190
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• 2024

Here, we develop a centrifugal microfluidic reactor with simple, fast, and high-throughput manner for the generation of magnetic Janus micro-adsorbents (MAs). By using the multi-micronozzle consisting of two separate aligned needles and centrifugal tubes, we have synthesized highly monodispersed Prussian blue- and magnetic nanoparticle-laden micro-adsorbents (PB-MNP-MAs). The enhanced cesium (Cs⁺) adsorption was demonstrated by conducting the adsorption isotherm and kinetics experiment which can be contributed to the porous nature of the Ca-alginate networks with a high surface area of embedded PB nanoparticles, resulting to perform rapid adsorption activity within 10 min. After Cs⁺ adsorption process, the as-synthesized PB-MNP-MAs were successfully harvested by introducing the external magnetic fields. Therefore, we believe that our findings can be provided new direction towards the development of advanced functional adsorbents in biological and environmental fields.

• Journal of the Korean Magnetics Society
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• v.22 no.4
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• pp.125-129
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• 2012

By employing soft x-ray absorption spectroscopy (XAS) and soft x-ray magnetic circular dichroism (XMCD), the electronic structures of molecule-based nano bioparticles, such as Helicobacter pylori ferritin (H. pylori ferritin), Heme, $NaM[Fe(CN)_6]{\cdot}H_2O$-type Prussian Blue (M=Co, Ni) analogue, have been investigated. The measured Fe 2p XAS spectra reveal that Fe ions are trivalent ($Fe^{3+}$) in H. pylori ferritins, while they are in the $Fe^{2+}-Fe^{3+}$ mixed-valent states in $NaM[Fe(CN)_6]{\cdot}H_2O$ Prussian Blue analogues (M=Co, Ni). According to the Fe 2p XMCD spectrum of high-state H. pylori ferritin, all the $Fe^{3+}$ ions have the same local symmetry and their magnetic moments are aligned in the same direction. It is also found that the Fe 3d orbitals in $NaM[Fe(CN)_6]{\cdot}H_2O$ have a strong covalent bonding to $(CN)^-$ ligands, but with a very weak bonding to the 2p orbitals of O ligands.

• Journal of Korean Society of Water and Wastewater
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• v.38 no.2
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• pp.95-107
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• 2024

This study proposes the use of a cobalt-based Prussian blue analogue (Co-PBA; potassium cobalt hexacyanoferrate), as an adsorbent for the cost-effective recovery of aqueous ammonium ions. The characterization of Co-PBA involved various techniques, including Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, nitrogen adsorption-desorption analysis, and zeta potential. The prepared Co-PBA reached an adsorption equilibrium for ammonium ions within approximately 480 min, which involved both surface adsorption and subsequent diffusion into the interior. The isotherm experiment revealed a maximum adsorption capacity of 37.29 mg/g, with the Langmuir model indicating a predominance of chemical monolayer adsorption. Furthermore, the material consistently demonstrated adsorption efficiency across a range of pH conditions. Notably, adsorption was observed even when competing cations were present. Co-PBA emerges as a readily synthesized adsorbent, underscoring its efficacy in ammonium removal and selectivity toward ammonium.

• Journal of Korean Society of Water and Wastewater
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• v.32 no.5
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• pp.399-409
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• 2018

Prussian blue is known as a superior material for selective adsorption of radioactive cesium ions; however, the separation of Prussian blue from aqueous suspension, due to particle size of around several tens of nanometers, is a hurdle that must be overcome. Therefore, this study aims to develop granule type adsorbent material containing Prussian blue in order to selectively adsorb and remove radioactive cesium in water. The surface of granular activated carbon was grafted using a covalent organic polymer (COP-19) in order to enhance Prussian blue immobilization. To maximize the degree of immobilization and minimize subsequent detachment of Prussian blue, several immobilization pathways were evaluated. As a result, the highest cesium adsorption performance was achieved when Prussian blue was synthesized in-situ without solid-liquid separation step during synthesis. The sample obtained under optimal conditions was further analyzed by scanning electron microscope-energy dispersive spectrometry, and it was confirmed that Prussian blue, which is about 9.7% of the total weight, was fixed on the surface of the activated carbon; this level of fixing represented a two-fold improvement compared to before COP-19 modification. In addition, an elution test was carried out to evaluate the stability of Prussian blue. Leaching of Prussian blue and cesium decreased by 1/2 and 1/3, respectively, compared to those levels before modification, showing increased stability due to COP-19 grafting. The Prussian blue based adsorbent material developed in this study is expected to be useful as a decontamination material to mitigate the release of radioactive materials.

• Journal of the Korean Electrochemical Society
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• v.22 no.1
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• pp.13-21
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• 2019

Prussian blue analogues(PBAs) are comprised of cyano-bridged transition metal ions. The wide and unique open-framework structures of the PBAs enable reversible intercalation and deintercalation of various ions such as $Na^+$, $K^+$, $Mg^{2+}$, $Zn^{2+}$, etc. In addition, since PBAs are synthesized through coprecipitation reaction in aqueous solution at room temperature, they are produced economically and environmentally friendly. However, the formation of crystals proceeds rapidly, and defects such as vacancy and crystal water tend to be present in the crystals, thereby affecting key battery performance. Therefore, significant efforts to inhibit defects in PBAs have been made. In the case of vacancy, the reaction rate was controlled at the synthesis stage to reduce the formation of vacancy, and the crystal water was removed by heat treatment under vacuum. In addition, by adding transition metals that do not react within the structure of PBA, the structural instability during the electrochemical reaction was largely alleviated.

• Journal of the Korean Applied Science and Technology
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• v.33 no.1
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• pp.67-74
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• 2016

The Prussian Blue Analogue(PBA) has three dimensional structure and the metal - organic framework material, and it has a variety configurations depending on the type of organic ligands. PBA has been receving an attention in the fields of biosensors, optical, catalytic, and hydrogen storage device. Also, it is an environmental friendly substance with a chemical stability. In addition, PBA is widely used in the filed of adsorption art since we can adjust the size of the fine pores. In this study, we synthesized $Mn_3[Fe(CN)_6]_2$, an organometallic framework chains by using a hydrothermal synthesis method. We used $K_4[Fe(CN)_6]$ and $MnCl_2$ as precursors. We also produced a manganese iron oxide, by baking the synthesized material. The effect of the size and shape of the particles was examined by controling pH of the precursor solution, the molar concentration of the precursor, and reaction time as the experimental variables. Synthesized absorbent was analyzed by XRD, SEM, FT-IR, UV-Vis, and TG / DTA to evaluate the adsorption properties of several dyes.

• Journal of Radiation Industry
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• v.9 no.3
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• pp.127-130
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• 2015

Since the accident at the Fukushima Daiichi power plant, Prussian blue (PB) has attracted increasing attention as a material for use in decontaminating the environment. We have focused the fundamental mechanism of specific $Cs^+$ adsorption into PB in order to develop high-performance PB-based $Cs^+$ adsorbents. The ability of PB to adsorb Cs varies considerably according to its origin such as what synthesis method was used, and under what conditions the PB was prepared. It has been commonly accepted that the exclusive abilities of PB to adsorb hydrated $Cs^+$ ions are caused by regular lattice spaces surrounded by cyanido-bridged metals. $Cs^+$ ions are trapped by simple physical adsorption in the regular lattice spaces of PB. $Cs^+$ ions are exclusively trapped by chemical adsorption via the hydrophilic lattice defect sites with proton-exchange from the coordination water. Prussian blue are believed to hold great promise for the clean-up of $^{137}Cs$ contaminated water around nuclear facilities and/or after nuclear accidents.

• Journal of the Korean Society of Safety
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• v.36 no.1
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• pp.80-85
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• 2021

Radionuclides, particularly radioactive cesium (Cs), are a concern of human health in some nuclear power accidents. It could lead to a high level of intracellular accumulation due to its high radioactivity and long half-life. Therefore, it is imperative to develop a method to remove Cs from wastewater. Herein, we synthesized activated carbon fibers (ACFs) doped with Prussian blue (PB) via in situ methods. We classified samples by their preparation method as either physical (PB-ACF-A) or physicochemical (PB-ACF-B) syntheses for comparison. The PB-ACF-B sample showed a significant surface loss compared to PB-ACF-A but a better ¹³³Cs adsorption capacity. All samples fit well to Langmuir isotherms and the values of qmax were directly correlated to the amount of PB on the surface of the ACFs. Adsorption characteristics were further confirmed by the calculated free energy, enthalpy, and entropy.

• Korean Journal of Materials Research
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• v.33 no.4
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• pp.151-158
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• 2023

In this study, a new type of composite material combined with carbonyl iron, a relatively strong ferromagnetic material, was prepared to overcome the current application limitations of Prussian blue, which is effective in removing radioactive cesium. The surface of the prepared composite was analyzed using SEM and XRD, and it was confirmed that nano-sized Prussian Blue was synthesized on the particle surface. In order to evaluate the cesium removal ability, 0.2 g of the composite prepared for raw cesium aquatic solution at a concentration of 5 ㎍ was added and reacted, resulting in a cesium removal rate of 99.5 %. The complex follows Langmuir's adsorption model and has a maximum adsorption amount (q_e) of 79.3 mg/g. The Central Composite Design (CCD) of the Response Surface Method (RSM) was used to derive the optimal application conditions of the prepared composite. The optimal application conditions achieved using Response optimization appeared at a stirring speed of pH 7, 17.6 RPM. The composite manufactured through this research is a material that overcomes the Prussian Blue limit in powder form and is considered to be excellent economically and environmentally when applied to a cesium removal site.