• Journal of Electrochemical Science and Technology
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• v.12 no.1
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• pp.137-145
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• 2021

Among the non-precious metal catalysts, iron-nitrogen doped carbon (Fe-N/C) catalysts have been recognized as the most promising candidates for an alternative to Pt-based catalysts for the oxygen reduction reaction (ORR) under alkaline and acidic conditions. In this study, the nano replication method using mesoporous silica, which features tunable primary particle sizes and shape, is employed to prepare the mesoporous Fe-N/C catalysts with different shapes. Platelet SBA-15, irregular KIT-6, and spherical silica particle (SSP) were selected as a template to generate three different kinds of shapes of the mesoporous Fe-N/C catalyst. Physicochemical properties of mesoporous Fe-N/C catalysts are characterized by using small-angle X-ray diffraction, nitrogen adsorption-desorption isotherms, and scanning electron microscopy images. According to the electrochemical evaluation, there is no morphological preference of mesoporous Fe-N/C catalysts toward the ORR activity with half-cell configuration under alkaline electrolyte. By implementing X-ray photoelectron spectroscopy analysis of Fe and N atoms in the mesoporous Fe-N/C catalysts, it is possible to verify that the activity towards ORR highly depends on the portions of "Fe-N" species in the catalysts regardless of the shape of catalysts. It was suggested that active site distribution in the Fe-N/C is one important factor towards ORR activity.

• Bulletin of the Korean Chemical Society
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• v.16 no.5
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• pp.398-400
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• 1995

Selective oxidation of cyclohexane in acetone solution has been studied using iron catalysts with hydrogen peroxide in-situ produced by palladium catalyst. Iron tetraphenylporphyrin chloride shows the highest activity among the tested chlorides and porphyrin complexes of some metals of the first transiton series. Iron chloride and iron tetraphenylporphyrin chloride were supported on four kinds of 4-vinylpyridine copolymer with styrene or divinyl-benzene. Nitrogen 1s photoelectron spectra give the evidence that pyridyl nitrogens of the 4-vinyl pyridine copolymer act as ligands to bind iron species. The copolymer with styrene is the most efficient support for the binding because its solubility in catalyst preparation solvent (methylene chloride) gives the pyridyl group advantage to contact with the iron catalysts. However, better catalytic activity per iron atom could be obtained with a rigid crosslinked polymer due to active site isolation.

• Journal of Environmental Science International
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• v.30 no.3
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• pp.195-206
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• 2021

Contaminated marine sediment is a secondary pollution source in the coastal areas, which can result in increased nutrients concentrations in the overlying water. We analyzed the nutrients release characteristics into overlying water from sediments and the interaction among benthic circulation of nitrogen, phosphorus, iron, and sulfur were investigated in a preset sediment/water column. Profiles of pH, ORP, sulfur, iron, nitrogen, phosphorus pools were determined in the sediment and three different layers of overlying water. Variety types of sulfur in the sediments plays a significant role on nutrients transfer into overlying water. Dissimilatory nitrate reduction and various sulfur species interaction are predominantly embodied by the enhancing effects of sulfide on nitrogen reduction. Contaminant sediment take on high organic matter, which is decomposed by bacteria, as a result promote bacterial sulfate reduction and generate sulfide in the sediment. The sulfur and iron interactions had also influence on phosphorus cycling and released from sediment into overlying water may ensue over the dissolution of ferric iron intercede by iron-reducing bacteria. The nutrients release rate was calculated followed by release rate equation. The results showed that the sediments released large-scale quantity of ammonium nitrogen and phosphate, which are main inner source of overlying water pollution. A mechanical migration of key nutrients such as ammonia and inorganic phosphate was depicted numerically with Fick's diffusion law, which showed a fair agreement to most of the experimental data.

• Journal of the Korean Applied Science and Technology
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• v.22 no.4
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• pp.349-354
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• 2005

It is interesting to discover the reaction kinetics of the newly developed molybdenum containing catalysts. The dissociation/adsorption of nitrogen on molybdenum surface is known to be structure sensitive, which is similar to that of nitrogen on iron surface. The rates over molybdenum nitride catalysts are increased with the increase of total pressure. This tendency is the same as that for iron catalyst, but is quite different from that for ruthenium catalyst. The activation energies of the molybdenum nitride catalysts are almost on the same level, although the activity is changed by the addition of the second component. The reaction rate is expressed as a function of the concentration of reactants and products. The surface nature of $CO_3Mo_3N$ is drastically changed by the addition of alkali, changing the main adsorbed species from $NH_2$ to NH on the surface. The strength of $NH_x$ adsorption is found to be changed by alkali dopping.

• Advances in environmental research
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• v.3 no.2
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• pp.107-116
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• 2014

This study aimed to synthesize dispersed and reactive nanoscale zero-valent iron (nZVI) with poly(1-vinylpyrrolidone-co-vinyl acetate) (PVP/VA), nontoxic and biodegradable stabilizer. The nZVI used for the experiments was prepared by reduction of ferric solution in the presence of PVP/VA with specific weight ratios to iron contents. Colloidal stability was investigated based on the rate of sedimentation, hydrodynamic radius and zeta potential measurement. The characteristic time, which demonstrated dispersivity of particles resisting aggregation, increased from 21.2 min (bare nZVI) to 97.8 min with increasing amount of PVP/VA (the ratios of 2). For the most stable nZVI coated by PVP/VA, its reactivity was examined by nitrate reduction in a closed batch system. The pseudo-first-order kinetic rate constants for the nitrate reduction by the nanoparticles with PVP/VA ratios of 0 and 2 were 0.1633 and $0.1395min^{-1}$ respectively. A nitrogen mass balance, established by quantitative analysis of aqueous nitrogen species, showed that the addition of PVP/VA to nZVI can change the reduction capacity of the nanoparticles.

• Environmental Engineering Research
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• v.25 no.3
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• pp.274-280
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• 2020

The marine sediment sustains from the anoxic condition due to increased nutrients of external sources. The nutrients are liberated from the sediment, which acts as an internal source. In hypoxic environments, anaerobic respiration results in the formation of several reduced matters, such as N₂ and NH₄⁺, N₂O, Fe²⁺, H₂S, etc. The experimental results have shown that nitrogen and sulfur played an influential, notable role in this biogeochemical cycle with expected chemical reductions and a 'diffusive' release of present nutrient components trapped in pore water inside sediment toward the bulk water. Nitate/ammonium, sulfate/sulfides, and ferrous/ferric irons are found to be the key players in these sediment-waters mutual interactions. Organonitrogen and nitrate in the sediment were likely to be converted to a form of ammonium. Reductive nitrogen is called dissimilatory nitrate reduction to ammonium and denitrification. The steady accumulation in the sediment and surplus increases in the overlying waters of ammonium strongly support this hypothesis as well as a diffusive action of the involved chemical species. Sulfate would serve as an essential electron acceptor so as to form acid volatile sulfides in present of Fe³⁺, which ended up as the Fe²⁺ positively with an aid of the residential microbial community.

• Journal of Soil and Groundwater Environment
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• v.10 no.1
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• pp.1-5
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• 2005

Nitrate reduction with zero valent iron $(Fe^0)$ has been extensively studied, but the proper treatment for ammonium byproduct has not been reported yet. In groundwater, however, ammonium is regarded as contaminant species, and particularly, its acceptable level is regulated to 0.5 mg-N/L. for drinking water. This study is focused on developing new material to reduce nitrate and properly remove ammonium by-products. A new material, Fe-loaded zeolite, is derived from zeolite modified by Fe(II) chloride followed by reduction with sodium borohydride. Batch experiments were performed without buffer at two different pH to evaluate the removal efficiency of Fe-loaded zeolite. After 80 hr reaction time, Fe loaded zeolite showed about $60\%$ nitrate removal at initial pH of 3.3 and $40\%$ at pH of 6 with no ammonium release. Although iron filing showed higher removal efficiency than Fe-loaded zeolite at each pH, it released a considerable amount of ammonium stoichiometrically equivalent to that of reduced nitrate. In terms of nitrogen species including $NO_3-N$ and $NH_4^+-N$, Fe-loaded zeolite removed about $60\%\;and\;40\%$ of nitrogen in residual solution at initial pH of 3.3 and 6, respectively, while the removal efficiency of iron filing was negligible.

• Carbon letters
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• v.17 no.1
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• pp.53-64
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• 2016

Nitrogen (N)-doped ordered mesoporous carbons (OMCs) with a dual transition metal system were synthesized as non-Pt catalysts for the ORR. The highly nitrogen doped OMCs were prepared by the precursor of ionic liquid (3-methyl-1-butylpyridine dicyanamide) for N/C species and a mesoporous silica template for the physical structure. Mostly, N-doped carbons are promoted by a single transition metal to improve catalytic activity for ORR in PEMFCs. In this study, our N-doped mesoporous carbons were promoted by the dual transition metals of iron and cobalt (Fe, Co), which were incorporated into the N-doped carbons lattice by subsequently heat treatments. All the prepared carbons were characterized by via transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). To evaluate the activities of synthesized doped carbons, linear sweep was recorded in an acidic solution to compare the ORR catalytic activities values for the use in the PEMFC system. The dual transition metal promotion improved the ORR activity compared with the single transition metal promotion, due to the increase in the quaternary nitrogen species from the structural change by the dual metals. The effect of different ratio of the dual metals into the N doped carbon were examined to evaluate the activities of the oxygen reduction reaction.

• Bulletin of the Korean Chemical Society
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• v.21 no.6
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• pp.588-594
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• 2000

Structural changes of an iron phthalocyanine (FePC) monolayer induced by adsorption and externally applied potential on high area carbon surface have been investigated in situ by iron K-edge X-ray absorption fine structure (XAFS) in 0.5 M $H_2S0_4.$ Fine structures shown in the X-ray absorption near edge structure (XANES) for microcrystalline FePC decreased upon adsorption and further diminished under electrochemical conditions. Fe(II)PC(-2) showed a 1s ${\rightarrow}$ 4p transition as poorly resolved shoulder to the main absorption edge rather than a distinct peak and a weak 1s ${\rightarrow}$ 3d transition. The absorption edge position measured at half maximum was shifted from 7121.8 eV for Fe(lI)PC(-2) to 7124.8 eV for $[Fe(III)PC(-2)]^+$ as well as the 1s ${\rightarrow}$ 3d pre-edge peak being slightly enhanced. However, essentially no absorption edge shift was observed by the 1-electron reduction of Fe(Il)PC(-2), indicating that the species formed is $[Fe(II)PC(-3)]^-$. Structural parameters were obtained by analyzing extended X-ray absorption fine structure (EXAFS) oscillations with theoretical phases and amplitudes calculated from FEFF 6.01 using multiple-scattering theory. When applied to the powder FePC, the average iron-to-phthalocyanine nitrogen distance, d(Fe-$N_p$) and the coordination number were found to be 1.933 $\AA$ and 3.2, respectively, and these values are the same, within experimental error, as those reported ( $1.927\AA$ and 4). Virtually no structural changes were found upon adsorption except for the increased Debye-Wailer factor of $0.005\AA^2$ from $0.003\AA^2.$ Oxidation of Fe(II)PC(-2) to $[Fe(III)PC(-2)]^+$ yielded an increased d(Fe-Np) (1 $.98\AA)$ and Debye-Wailer factor $(0.005\AA^2).$ The formation of $[Fe(II)PC(-3)]^-$, however, produced a shorter d(Fe-$N_p$) of $1.91\AA$ the same as that of crystalline FePC within experimental error, and about the same DebyeWaller $factor(0.006\AA^2)$.

• The Korean Journal of Ecology
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• v.19 no.3
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• pp.209-216
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• 1996

In order to identify the habitat characteristics of water shield (Brasenia schreberi), water quality and sediment characters were investigated. Water shield had peculial habitats such as old reservoir, developed basin-like reservior, a water depth within 1.5 m, constant water level, and thick sediment layer at the bottom. The species had very dense populations under the favorable growing conditions and occasionally grew together with Utricularia japonica. When water shield decreased, Nelumbo nucifera, Nuphar japonicum and Zizania latifolia increased. Natural populations of water shield need protection because it is endangered by the human activities and their harvest. The optimal conditions for the growth of water shield was near neutral pH. low conductivity and low turbidity. Therefore the input of pollutants should be controlled for its growth. The inorganic ion contents such as K, Mg, and Na were higher in the water shield growing area. Especially iron content of the sediments in the reservoirs with water shield was nearly five times as high as that in the reservoirs without water shield. thus iron might be one of the major limiting factors for the growth. It was considered that molybdenum can be another major factor because water shield is a nitrogen fixing plant.