The structure and magnetic properties of composite powders prepared by ball milling a mixture of Fe2O3 ‧ (0.4-1.0)Fe were investigated. Hysteresis loops and differential scanning calorimetry (DSC) curves are used to characterize the materials and to examine the effect of the solid state reaction induced by ball milling. The results showed that a solid state reaction in Fe2O3 ‧ (0.4-1.0)Fe clearly proceeds after only 1 h of ball milling. The system is characterized by a positive reaction heat of +2.23 kcal/mole. The diffraction lines related to Fe2O3 and Fe disappeared after 1 h of ball milling and, instead, diffraction lines of the intermediate phase of Fe3O4 plus FeO formed. The magnetization and coercivity of the Fe2O3 ‧ 0.8Fe powders were changed by the solid state reaction process of Fe2O3 by Fe during ball milling. The coercivity of the Fe2O3 ‧ 0.8Fe powders increased with increasing milling time and reached a maximum value of 340 Oe after 5 h of ball milling. This indicates the grain size of Fe3O4 was clearly reduced during ball milling. The magnetic properties of the annealed powders depend on the amount of magnetic Fe and Fe3O4 phases.
Metal–organic frameworks (MOFs) are widely used as supports for single-atom catalysts (SACs) owing to their high specific surface area, porosity, and ordered metal–ligand structure. Their activity can be increased by increasing the number of electrochemically accessible active sites via the formation of atomically dispersed metal catalysts (M–Nx) that coordinate with nitrogen atoms on the MOF. Herein, we introduce the relationship between the size of the MOF as a starting material and the catalytic activity for the oxygen reduction reaction in alkaline media. The morphology and features of the MOFs are critically dependent on their size. Remarkably, cage-like MOFs below 33 nm are converted into collapsed structures and are connected between each MOF, even carbon fiber- or tube-like features, after carbonization. SACs derived from medium-sized MOFs exhibit excellent activity and are comparable to commercial Pt/C catalysts owing to their porous structure. Therefore, we believed that controlling the size of MOFs containing active atoms is an effective method of modulating the morphological properties of the support and even the number of active sites that are closely related to the activity.
In this study, we compared the MZVI (Microscale Zero-Valent Iron) and NZVI (Nanoscale Zero-Valent Iron) for reactivity and mobility in a column to reduce nitrate, which is a major pollutant in Korea, and investigated the effect of operational parameters on the NZVI filled column. For the comparison of MZVI and NZVI, samples were collected for 990 minutes using fractionator in the similar operation conditions (MZVI 10g, NZVI 2g). The nitrate reduction efficiency of NZVI was about 5 times higher than that of MZVI, which was about 7.45% and 38.75% when using MZVI and NZVI, respectively. In the mobility experiment, the MZVI descended due to gravity while NZVI moved up with water flow due to its small size. Furthermore, the optimum condition of NZVI filled column was determined by changing the flow rate and pH. The amount of Fe ions was increased as the pH of the nitrate solution was lowered, and the nitrate removal rate was similar due to the higher yield of hydroxyl groups. The removal rate of nitrate nitrogen was stable while flow rate was increased from 0.5 mL/min to 2.0 mL/min (empty bed contact time: 2.26 min to 0.57 min). NZVI has a high reduction rate of nitrate, but it also has a high mobility, so both of reactivity and mobility need to be considered when NZVI is applied for drinking water treatment.
In this study, the reduction kinetics and behaviors of oxides in the water-atomized iron powder have been evaluated as a function of temperature ranging 850-1000˚C in hydrogen environment, and compared to the reduction behaviors of individual iron oxides including Fe2O3, Fe3O4 and FeO. The water-atomized iron powder contained a significant amount of iron oxides, mainly Fe3O4 and FeO, which were formed as a partially-continuous surface layer and an inner inclusion. During hydrogen reduction, a significant weight loss in the iron powder occurred in the initial stage of 10 min by the reduction of surface oxides, and then further reduction underwent slowly with increasing time. A higher temperature in the hydrogen reduction promoted a high purity of iron powder, but no significant change in the reduction occurred above 950˚C. Sequence reduction process by an alternating environment of hydrogen and inert gases effectively removed the oxide scale in the iron powder, which lowered reduction temperature and/or shortened reduction time.
The synthesis of silver coated iron base alloy (Sendust : Fe-Si-Al) powder having the both effects of shielding and suppressing of electromagnetic wave was studied. Depending on thickness of silver coating layer, the electromagnetic properties of the dispersed particles complexed with organic binder were examined. It is proposed that the silver coated sendust flake powders with controlled electrical properties and thickness can be used as thin microwave absorbers in quasi-microwave frequency band.
This paper compares the effect of using different types of iron powders for the preparation of by calciothermic reduction-diffusion (CRD). Three types of iron powder were used: carbonyl, sponge and water atomized. The results show that, when immediately nitrogenated after the CRD process, prepared from sponge and water atomized iron powders yield -magnets with a high degree of texture. However, after a suitable treatment with hydrogen followed by nitrogenation, -powders made from Carbonyl iron produce magnets with the best quality regarding coercivity, remanence and degree of texture.
Synthesis of iron nanopowder by room-temperature electrochemical reduction process of nanopowder was investigated in terms of phase evolution and microstructure. As process variables, reduction time and applied voltage were changed in the range of h and V, respectively. From XRD analyses, it was found that volume of Fe phase increased with increasing reduction time and applied voltage, respectively. The crystallite size of Fe phase in all powder samples was less than 30 nm, implying that particle growth was inhibited by the reaction at room temperature. Based on the distinct equilibrium shape of crystalline particle, phase composition of nanoparticles was identified by TEM observation.
염화철(Ferrous Choloride) 증기의 고온 수소환원 반응을 통한 미립질 철분말의 생성속도에 대한 이론적인 해석돠 실험을 수행하였다. 철분말의 생성기구는 염화철이 증발하여 생성된 증기와 운반가스인 알곤을 혼합하여 반응부로 유입시키고 수소에 의한 고온환원반을을 통하여 철분말과 함께 부산물인 염화수소(HCI) 가스를 얻게 된다. 생성된 반응부 후미에 설치한 유기용매 포집기를 이용하여 회수하였으며, 염화수소는 가성소다 수용액에 흡수시키고 이를 적정함으로써 초기 반응물인 염화철의 전환율을 계산하였다. 반응속도식의 반응물에 대하여 1차반응(1st-order reaction)이고 염화철 증가와 운반체인 알곤가스가 평형상태일 때의 속도상수는 k=7,879exp(-53,840/RT)dm3/mole.sec으로 표시되며, 이때의 활성화에너지는 53.84kJ/mole이었다. 철분말의 TEM 사진에 의하면 입도범위는 0.1~1.0μm이며, 반응온도 및 가스유량에는 크게 영향을 받지 않는것으로 나타났다.
In this study, the reductive dechlorination of triclosan using zero-valent iron (ZVI, Fe0) and modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium-coated iron (Pd/Fe)) was experimentally investigated, and the reduction characteristics were evaluated by analyzing the reaction kinetics. Triclosan could be reductively decomposed using zero-valent iron. The degradation rates of triclosan were about 50% and 67% when Fe0 and Aw/Fe were used as reductants, respectively, after 8 h of reaction. For the Pd/Fe system, the degradation rate was about 57% after 1 h of reaction. Thus, Pd/Fe exhibited remarkable performance in the reductive degradation of triclosan. Several dechlorinated intermediates were predicted by GC-MS spectrum, and 2-phenoxyphenol was detected as the by-product of the decomposition reaction of triclosan, indicating that reductive dechlorination occurred continuously. As the reaction proceeded, the pH of the solution increased steadily; the pH increase for the Pd/Fe system was smaller than that for the Fe0 and Aw/Fe system. Further, zero-order, first-order, and second-order kinetic models were used to analyze the reaction kinetics. The first-order kinetic model was found to be the best with good correlation for the Fe0 and Aw/Fe system. However, for the Pd/Fe system, the experimental data were evaluated to be well fitted to the second-order kinetic model. The reaction rate constants (k) were in the order of Pd/Fe > Aw/Fe > Fe0, with the rate constant of Pd/Fe being much higher than that of the other two reductants.
This study examined the treatment characteristics of hard-to-degrade pollutants such as TCE which are found in organic solvent and cleaning wastewater by nZVI that have excellent oxidation and reduction characteristics. In addition, this study tried to find out the degradation characteristics of TCE by Fenton-like process, in which H2O2 is dosed additionally.
In this study, different ratios of nZVI and H2O2, such as 1.0 mM : 0.5 mM, 1.0 mM : 1.0 mM, and 1.0 mM : 2.0 mM were used. When 1.0 mM of nZVI was dosed with 1.0 mM of H2O2, the removal efficiency of TOC was the highest and the first order rate constant was also the highest. When 1mM of nZVI was dosed with 0.5 mM of H2O2, the first order rate constant and removal efficiency were the lowest. The size of first order rate constant and removal efficiency was in the order of nZVI 1.0 mM : H2O2 1.0 mM > nZVI 1.0 mM : H2O2 2.0 mM > nZVI 1.0 mM : H2O2 0.5 mM > H2O2 1.0 mM > nZVI 1.0 mM. It is estimated that when 1.0 mM of nZVI is dosed with 1.0 mM of H2O2, Fe2+ ion generated by nZVI and H2O2 react in the stoichiometric molar ratio of 1:1, thus the first order rate constant and removal efficiency are the highest. And when 1.0 mM of nZVI is dosed with 2.0 mM of H2O2, excessive H2O2 work as a scavenger of OH radicals and excessive H2O2 reduce Fe3+ into Fe2+.
As for the removal efficiency of TOC in TCE by simultaneous dose and sequential dose of nZVI and H2O2, sequential dose showed higher first order reaction rate and removal efficiency than simultaneous dose. It is estimated that when nZVI is dosed 30 minutes in advance, pre-treatment occurs and nanoscale Fe0 is oxidized to Fe2+ and TCE is pre-reduced and becomes easier to degrade. When H2O2 is dosed at this time, OH radicals are generated and degrade TCE actively.
The use of support materials on the nanoparticle synthesis and applications has advantages in many aspects; resisting the aggregation and gelation of nanoparticles, providing more active sites by dispersing over the supports, and facilitating a filtering process. In order to elucidate the influence of the supports on the nitrate reduction reactivity, the supported iron nanoparticles were prepared by borohydride reduction of an aqueous iron salt in the presence of supports such as activated carbon, silica and polyethylene. The reactivity for nitrate reduction decreased in the order of unsupported Fe(0) > activated carbon(AC) supported Fe(0) > polyethylene(PE) supported Fe(0) ≥ silica supported Fe(0). Rate constants decrease with increasing initial nitrate concentration implying that the reaction is limited by the surface reaction kinetics.