Enhanced activation of peroxymonosulfate by Fe/N co-doped ordered mesoporous carbon with dual active sites for efficient removal of m-cresol

The novel Fe-N co-doped ordered mesoporous carbon with high catalytic activity in m-cresol removal was prepared by urea-assisted impregnation and simple pyrolysis method.During the preparation of the Fe-NC catalyst,the complexation of N elements in urea could anchor Fe,and the formation of C3N4during urea pyrolysis could also prevent migration and aggregation of Fe species,which jointly improve the dispersion and stability of Fe.The FeN4sites and highly dispersed Fe nanoparticles synergistically trigger the dual-site peroxymonosulfate (PMS) activation for highly efficient m-cresol degradation,while the ordered mesoporous structure of the catalyst could improve the mass transfer rate of the catalytic process,which together promote catalytic degradation of m-cresol by PMS activation.Reactive oxygen species (ROS) analytic experiments demonstrate that the system degrades m-cresol by free radical pathway mainly based on SO_(4)^(-)·and·OH,and partially based on·OH as the active components,and a possible PMS activation mechanism by 5Fe-50 for m-cresol degradation was proposed.This study can provide theoretical guidance for the preparation of efficient and stable catalysts for the degradation of organic pollutants by activated PMS.

Dissimilatory reduction of Fe^III (EDTA) with microorganisms in the system of nitric oxide removal from the flue gas by metal chelate absorption

In the system of nitric oxide removal from the flue gas by metal chelate absorption, it is an obstacle that ferrous absorbents are easily oxidized by oxygen in the flue gas to ferric counterparts, which are not capable of binding NO. By adding iron metal or electrochemical method, Fe III (EDTA) can be reduced to Fe II (EDTA). However, there are various drawbacks associated with these techniques. The dissimilatory reduction of Fe III (EDTA) with microorganisms in the system of nitric oxide removal by metal chelate absorption was investigated. Ammonium salt instead of nitrate was used as the nitrogen source, as nitrates inhibited the reduction of Fe III due to the competition between the two electron acceptors. Supplemental glucose and lactate stimulated the formation of Fe II more than ethanol as the carbon sources. The microorganisms cultured at 50℃ were not very sensitive to the other experimental temperature, the reduction percentage of Fe III varied little with the temperature range of 30—50℃. Concentrated Na 2CO 3 solution was added to adjust the solution pH to an optimal pH range of 6—7 The overall results revealed that the dissimilatory ferric reducing microorganisms present in the mix culture are probably neutrophilic, moderately thermophilic Fe III reducers.

Experimental study on the inhibition of biological reduction of Fe(III)EDTA in NO_x absorption solution

Scrubbing of NOx from the gas phase with Fe(II)EDTA has been shown to be highly effective. A new biological method can be used to convert NO to N2 and regenerate the chelating agent Fe(II)EDTA for continuous NO absorption. The core of this biological regeneration is how to effectively simultaneous reduce Fe(III)EDTA and Fe(II)EDTA-NO, two mainly products in the ferrous chelate absorption solution. The biological reduction rate of Fe(III)EDTA plays a main role for the NOx removal efficiency. In this paper, a bacterial strain identified as Klebsiella Trevisan sp. was used to demonstrate an inhibition of Fe(III)EDTA reduction in the presence of Fe(II)EDTA-NO. The competitive inhibition experiments indicted that Fe(II)EDTA-NO inhibited not only the growth rate of the iron-reduction bacterial strain but also the Fe(III)EDTA reduction rate. Cell growth rate and Fe(III)EDTA reduction rate decreased with increasing Fe(II)EDTA-NO concentration in the solution.

Photooxidation of Methacrolein in Fe(III)-Oxalate Aqueous System and Its Atmospheric Implication

Iron and oxalic acids are widely distributed in the atmosphere and easily form ferric oxalate complex(Fe(III)-Ox).The tropospheric aqueous-phase could provide a medium to enable the photo-Fenton reaction with Fe(III)-Ox under solar irradiation.Although the photolysis mechanisms of Fe(III)-Ox have been investigated extensively,information about the oxidation of volatile organic compounds(VOC),specifically the potential for Secondary Organic Aerosol(SOA)formation in the Fe(III)-Ox system,is lacking.In this study,a ubiquitous VOC methacrolein(MACR)is chosen as a model VOC,and the oxidation of MACR with Fe(III)-Ox is investigated under typical atmospheric water conditions.The effects of oxalate concentration,Fe(III)concentration,MACR concentration,and pH on the oxidation of MACR are studied in detail.Results show that the oxidation rate of MACR greatly accelerates in the presence of oxalate when compared with only Fe(III).The oxidation rate of MACR also accelerates with increasing concentration of oxalate.The effect of Fe(III)is found to be more complicated.The oxidation rate of MACR first increases and then decreases with increasing Fe(III)concentration.The oxidation rate of MACR increases monotonically with decreasing pH in the common atmospheric water pH range or with decreasing MACR concentration.The production of ferrous and hydrogen peroxide,pH,and aqueous absorbance are monitored throughout the reaction process.The quenching experiments verify that·OH and O_(2)^(+)are both responsible for the oxidation of MACR.MACR is found to rapidly oxidize into small organic acids with higher boiling points and oligomers with higher molecular weight,which contributes to the yield of SOA.These results suggest that Fe(III)-Ox plays an important role in atmospheric oxidation.

电化学系统内Feammox/NDFO耦合工艺脱氮效能和机理

针对目前Feammox/NDFO耦合工艺启动慢、脱氮效能不理想等缺陷,提出基于电化学原理强化Feammox/NDFO耦合工艺的策略.实验室内搭建生物电化学系统(BES)序批式厌氧反应器(B组),同时以不加电化学系统的普通厌氧反应器(A组)为对照组.A、B两组反应器共运行100d,分析了两反应器Feammox/NDFO耦合工艺启动过程中的脱氮效能、脱氮路径验证及种群结构组成,并探讨了BES系统Feammox/NDFO强化脱氮的机理.结果表明,实验组(B组)内NH_(4)^(+)-N去除率显著提高,第76d去除率趋于100%,TN去除率达65.83%;而对照组(A组)在第100d时,对NH_(4)^(+)-N和TN的去除率分别为50.22%和43.01%.脱氮路径验证实验结果表明,A、B组反应器内均有Feammox、NDFO、Anammox反应发生;并且B组反应器内反硝化速率明显大于A组.高通量测序结果表明,B组中铁循环脱氮功能菌中Desulfobacterota菌门的相对丰度较A组提高了2.34%;Thiobacillus和Denitratisoma丰度较A组分别提高了1.13%和0.87%.BES反应体系加速富集铁循环脱氮功能菌群,并可通过BES电极进行胞外电子转移,从而达到增强脱氮效能.

CRYSTAL STRUCTURE OF A 2D SHEET－LIKE μ－CYANIDO－OXAMIDATO BRIDGED Fe（III）－Cu（II） HETERNUCLEAR COMPLEX

The synthesis is and crystal structure are reported for the sheet-like compourd [CU2(oxpn)Fe(CN )5(NO)]. there oxpn is the dianion of M, M'-bis(3-aminopropyl)oxamide. This compound crustallizes in the orthogonal space group Puma. with a=11 .413(4), b=22.242(5), c=7.736(2) A, and Z=4.The structure was refined to conventionat discrepancy factors R=0.047 and Pw=0.054. The Cu(II ) and Fe(III)centers are bridged by oxpn and cyanide, the formal behaves as a his-terdentate tigand bound to cooper(II)ion to form (II) dimers. whereas the latter bridges Cu(II) and Fe(III) centers in both symmetric and asymetric end- to-end bis-monodentate fashions, spreading out along be plane to form a 20 network. The Structure is made up of CuFe unit with Cu(II) and Fe(III) ions locating in a distorted square-based pyramid and a compressed octahedron, respectively.

Adsorption of Fe(III) from Aqueous Solution by Linde Type-A Zeolite

Linde Type-A (LTA) zeolite was prepared from sodium aluminate and sodium metasilicate by hydrothermal process precursors. Sodium metasilicate prepared from molten NaOH and SiO2. The zeolite was characterized by FTIR, XRD, XRF and SEM. The adsorption of Fe(III) from aqueous solution by zeolite A was studied. Different parameters like contact time, pH and concentration of iron were investigated. The results show that at contact time of 60 min and pH of 6 maximum adsorption of iron onto zeolite was observed. The kinetic data was analyzed using pseudo-first-order and pseudo-second-order kinetic models. The adsorption kinetics of Fe(III) were fitted well with the pseudo-second-order kinetic model.

伯胺(N1923)-正辛烷在硫酸体系中萃取和反萃Fe(III)机理的研究

对伯胺—正辛烷萃取体系在萃取和反萃过程中有机相组成和水含量的变化用FTIR和光子相关谱进行分析研究。结果表明:伯胺与水相酸作用生成了阳离子型表面活性剂的结构,在有机相中易生成反相胶团。其萃取和反萃过程的实质是反相胶团内外的阳离子交换过程。Fe(Ⅲ)以水合形式萃取入有机相中,Fe(Ⅲ)的水解可能发生在反相胶团的微环境中。

水杨醛缩三乙烯四胺Schiff碱Fe(III)配合物的合成、结构和光谱性质

合成水杨醛缩三乙烯四胺Schiff碱Fe(Ⅲ)配合物[(saltrien)Fe]Cl.2H2O。采用元素分析、红外光谱、电子光谱对其结构进行了表征,晶体结构通过X-射线衍射法测定。该化合物的化学计量式为:20H29ClFeN4O4,晶体属单斜晶系,其空间群为P21/c。晶胞参数:a = 18.517(4), b = 9.985(2), c = 12.035(2) , b = 103.43(2)o, V = 2164.3(7) 3, Z = 4, F(000) = 1008, r = 1.475 g/cm3, Mr = 480.77, m (MoKa) = 0.855 cm-1。结构偏离因子R1 = 0.0345, wR2 = 0.0469。共收集到4566个独立衍射点,其中I>2 (I)的可观测点为3730个。

双水杨醛邻苯二胺与Fe(III)的显色反应研究及应用

研究了双水杨醛邻苯二胺(SALOPHEN)与Fe(III)的显色反应,试验表明,在pH=2.21的氨基乙酸-盐酸缓冲介质中,在阴离子表面活性剂十二烷基磺酸钠(SDS)存在下,Fe(III)与双水杨醛邻苯二胺(SALOPHEN)形成1:1稳定的棕色配合物。其最大吸收峰位于462nm处,表观摩尔吸光系数为4.1'104。铁浓度在0-4.5mg/ml范围内符合比尔定律。方法具有较高的灵敏度和选择性。应用于食品样品中微量铁的测定,结果满意。

Flow injection spectrophotometric determination of vitamin E in pharmaceuticals,milk powder and blood serum using potassium ferricyanide-Fe(Ⅲ) detection system

A simple and sensitive flow injection spectrophotometric method is reported for the determination of vitamin E using potassium ferricyanide-Fe(Ⅲ) detection system.In the presence of vitamin E,Fe(Ⅲ)/ferricyanide reduces.The in situ reduced ions are then reacted with unreduced portion of ferricyanide/Fe(Ⅲ) to make soluble Prussian blue,which is monitored at absorption wavelength of 735 nm.Linear calibration graph was obtained in the concentration range of 0.1-40μg mL^(-1).The relative standard deviations (n=4) were in the range of 1.1-3.6%,with limits of detection(3 s blank) of 0.04μg mL^(-1).The proposed method allowed 12 injections h^(-1).The method is applied to determine vitamin E in pharmaceuticals,infant milk and blood serum samples using hexane extraction with the recoveries in the range of 93±3 to 97.5±4%.The method is validated using certified reference materials SRM 968c for blood serum samples.

Silicon isotope fractionation during the precipitation of quartz and the adsorption of H_4SiO_(4(aq))on Fe(Ⅲ)-oxyhydroxide surfaces

Equilibrium Si isotope fractionation factors among orthosilicic acid(i.e.,H4 Si O4(aq)), quartz and the adsorption complexes of H4 Si O4(aq)on Fe(III)-oxyhydroxide surface were calculated using the full-electron wave-function quantum chemistry methods [i.e., B3LYP/6-311G(2df,p)]with a new cluster-model-based treatment. Solvation effects were carefully included in our calculations via water-droplet method combined with implicit solvent models(e.g., PCM).The results revealed that, if it is under equilibrium conditions,heavy Si isotopes would be significantly enriched in quartz in comparison to H4 Si O4(aq). However, most of the field observations suggested that quartz would have identical or even depleted d30 Si values compared to that of H4 Si O4(aq). To explain this discrepancy between the equilibrium calculation results and the field observations, the kinetic isotope effect(KIE) associated with the formation of amorphous silica,which usually is the precursor of crystalline quartz, was investigated using quantum chemistry methods. The KIE results showed that amorphous silica would be significantly enriched in light Si isotopes during its formation. Our equilibrium fractionation results, however, matched a special type of quartz(i.e., Herkimer ‘‘diamond'') very well, due to its nearly equilibrated precipitation condition. Opposite to the case of precipitated quartz, a large equilibrium Si isotope fractionation(i.e.,-3.0 %) was found between the absorbed bidentate Si surface complexes(i.e.,2C [ Fe2O2Si(OH)2) and H4 Si O4(aq). This calculated equilibrium Si isotope fractionation factor largely differed from a previous experimental result(ca.-1.08 %). We found that the formation of transient or temporary surface complexes [e.g.,1V [ Fe2OSi(OH)3] may have accounted for the smaller net fractionation observed.With the equilibrium and kinetic Si isotope fractionation factors provided here, the distributions and changes of Si isotope compositions in the Earth's surface systems can be better understood.

基于柔性配体5-[N-乙酸根(4-吡啶基)]四唑(a4-pytz)与Fe(II)和Sm(III)两个配合物的合成与表征

5-[N-乙酸根(4-吡啶基)]四唑钾盐(简写为Ka4-pytz)与(NH4)2Fe(SO4)2和SmCl3·6H2O在水-甲醇体系中反应,得到两个新的配合物,[Fe(a4-pytz)2·2H2O]·2H2O (1)和[Sm4(a4-pytz)8(H2O)18]Cl3·10H2O (2)。通过元素分析,红外光谱分析及X-射线单晶衍射对两个配合物进行结构表征。单晶衍射结果显示了配合物1和2都具有一维链状结构。但不同的是,配合物1的一维链是通过a4-pytz作为双齿配体,经四唑环上的氮原子和羧基的一个氧原子与Fe(II)相连而成的;而配合物2的结构形成源于羧基的桥联作用,氮原子未配位。通过氢键作用,配合物1和2形成了三维结构。室温下研究了配合物1和2的荧光性质。

石煤含氟酸浸液中V(Ⅴ)-Fe(Ⅲ)-F-H_(2)O系钒铁分离热力学研究

针对石煤含氟酸浸液中钒铁分离问题,计算并绘制298.15 K下V(Ⅴ)-Fe(Ⅲ)-F-H_(2)O系热力学平衡图,分析含钒离子、含铁离子随总钒浓度、总铁浓度、总氟浓度的变化规律。研究结果表明,随着pH由0升高至3.00,由于氟离子与VO_(2)^(+)、Fe^(3+)的配位作用,含钒物种由阳离子转变为阴离子,含铁物种由阳离子转变为中性分子,此时可实现钒铁有效分离。定义pH_(50%)为含钒阴离子摩尔分数50%时的pH,溶液中总钒浓度升高、总铁浓度升高,均导致pH50%升高,总氟浓度升高,pH_(50%)则降低。采用N235阴离子萃取剂分离含氟溶液中的钒铁,当溶液中总钒浓度为0.05 mol/L、总铁浓度为0.05 mol/L、总氟浓度为0.50 mol/L时,溶液萃取pH升高,钒铁分离系数βV/Fe增加,当pH为1.97时,钒铁分离系数β_(V/Fe)可达122.86,钒铁达到有效分离,与热力学分析结果一致。

MECHANISM OF EXTRACTION AND STRIPPING OF Fe(Ⅲ) WITH PRIMARY AMINE N1923 AS EXTRACTANT AND n-OCTANE AS DILUENT

Mechanism of extraction of Fe (III) from sulphate solution by primary amine N1923 and stripping of Fe loaded organic phase with dilute H_2SO_4 was investigated. The organic phase was characterized by FT-IR and photon correlation spectroscopy. The composition of extracted species as well as the content of H_2O in organic phase were determined. The dependence of both the rate of extraction and stripping on the formation of reverse micelle in primary amine (N1923)system has been confirmed. It is shown that the extraction of Fe(III) by primary amine sulphate may be related to the adduct formation or cation exchange reaction under different concentrations of H_2SO_4 in aqueous solution.

An Efficient FeCl₃Catalyzed Synthesis of N,N’-Diarylformamidines

An efficient FeCl3 catalyzed synthesis of N,N’-diarylformamidines using triethylorthoformate (1 equivalent) and primary aryl amines (2 equivalents) at ambient temperature has been described. This methodology provides an eco-friendly and simple procedure without using any hazardous and expensive chemicals.

异化Fe(Ⅲ)还原微生物研究进展

铁是地壳中含量第四丰富的元素,微生物介导的异化铁还原是自然界中Fe(Ⅲ)还原的主要途径。介绍了Fe(Ⅲ)还原菌的分类及多样性,总结了Fe(Ⅲ)还原菌还原铁氧化物机制及其产能代谢机制,概述了Fe(Ⅲ)还原菌的生态环境意义,并对未来Fe(Ⅲ)还原菌的分子生态学研究方向提出了探索性的建议。

东山湾海水中Fe(Ⅱ)和Fe(Ⅲ)相互转化围隔实验研究

根据2008年8月与11月在东山湾海域获得的调查资料对表层水中溶解态Fe(II)和Fe(III)含量、浮游植物叶绿素a、营养元素及其浓度等环境参数进行分析。结果表明,夏、秋季海水中Fe(II)浓度及其在总溶解铁中所占比例均与浮游植物叶绿素a呈正相关,其相关系数分别为0.7959、0.9219。现场围隔实验表明,海水中总溶解态Fe含量在24 h内有较大的变化,最大减少量达到17.4%。DS2站点海水中Fe(II)浓度及其在总溶解铁中所占比例随光照强度增加而增加。最高值与初始值相比较,叶绿素a较高的DS2站点海水中Fe(II)浓度增加较叶绿素a较低的DS5号站点高0.053μg/L。Fe(II)和Fe(III)加富实验研究了溶解态的Fe(II)和Fe(III)在海水中相互转化。高浓度的Fe(II)在海水中被氧化成Fe(III),海水中浮游植物也会引发光还原作用使Fe(III)还原成Fe(II)。

吗啉二硫代氨基甲酸铁(Ⅲ)配合物Fe(S_2CNC_4H_8O)_3的合成、表征及晶体结构

合成了标题化合物Fe(S_2CNC_4H_8O)_3,得到黑色柱状晶体。晶体属三斜晶系,空间群为P-1,晶胞参数a=0.9300(2)nm,b=1.0490(2)nm,c=1.3710(3)nm,a=100.60(3)°,β=95.4O(3)°,γ=106.60(3)°,V=1.2445(4)nm^3,M_r=542.58,Z=2.中心Fe原子分别与来自三个吗啉二硫代氨基甲酸的六个硫原子配位形成八面体构型,由于四元螯合环的环张力,导致该八面体严重变形,六个Fe-S键的键长范围在0.2423(5)～0.2458(2)nm。热分析表明标题化合物在791.80℃完全分解。