四甲基二硅桥连双(四甲基环戊二烯基)四羰基二铁的反应性

标题化合物1与HgCl2反应,除生成希望的产物2外,还分离到2的歧化产物3和4。1经Na-Hg还原,生成Fe-Fe键断裂的双铁负离子5,5分别与多种氯化物反应,生成在铁原子上引入取代基的衍生物6,7和8。以元素分析,IR及1H NMR谱表征了化合物2～4及6～8的分子结构。

三维氢键超分子化合物[H_3cth][Fe(CN)_6]·3H_2O的合成与结构

用内消旋５，７，７，１２，１４，１４－六甲基－１，４，８，１１－四氮杂环十四烷（ｃｔｈ）和Ｋ_３［Ｆｅ（ＣＮ）_６〕合成了氢键连接的超分子化合物［Ｈ_３ｃｔｈ］［Ｆｅ（ＣＮ）_３］·３Ｈ_２Ｏ．该化合物的晶体属三斜晶系，Ｐ－１空间群，晶胞参数ａ＝０．９３０ ９７（９）ｎｍ，ｂ＝１．０５１ ６０（１１）ｎｍ，ｃ＝１．６３８ ４７（１７）ｎｍ，ａ＝１０１．０７７（２）°，β＝９０．８６０（２）°，γ＝１１１．６７１（２）°， Ｖ＝１．４５６ ４（３） ｎｍ３， Ｚ＝２， Ｒ＝０．０４１５．晶体中质子化的大环四胺与六氰合铁（Ⅱ ）离子之间通过氢键连接成二维层状结构，而水分子所形成的氢键使化合物呈现三维超分子网络．

高温分解法合成Fe_3O_4磁性纳米微粒

以油酸为表面活性剂,高温分解铁有机物,合成Fe3O4磁性纳米微粒,并对其进行了TEM、XRD分析,结果表明,Fe3O4磁性纳米微粒为规则的立方体,平均粒径为10nm,且粒径分布均匀。

Negative effects of dissolved organic compounds on settling performance of goethite in Bayer red mud

Goethite, a typical iron-containing monomineral in red mud, was synthesized under the simulated Bayer digestion condition during the alumina production. The effects of dissolved organic compounds including sodium formate, sodium acetate, sodium oxalate, sodium salicylate and disodium phthalate on the settling performance of goethite slurries were studied. The settling performance of the slurries was also investigated with the addition of self-made hydroxamated polyacrylamide flocculant （HCPAM）. The adsorption mechanism of dissolved organic compounds on the goethite surfaces was studied by FT-IR and XPS, respectively. The results show that the addition of organic compounds lowers the settling performance of the slurries and a deterioration in settling performance is observed in the order of sodium oxalate 〉 sodium salicylate （~ disodium phthalate） 〉 sodium formate 〉 sodium acetate. Moreover, HCPAM can efficiently eliminate the negative effects of sodium formate, sodium acetate and sodium oxalate on the settling performance of the goethite slurries, but it can only partially improve the settling performance of the goethite slurries containing sodium salicylate or disodium phthalate. FT-IR and XPS results show that these organic compounds are chemically adsorbed on the goethite surface.

Iron Arene Salts as Initiators for Thermal Curing of Epoxides by Photo-catalysis

[Cyclopentadien-Fe-naphthalene]BF4(CFN) and [cyclopentadien-Fe-anisole]BF4(CFA) as thermal cationic initiators for the curing of epoxide E44 and GGE were investigated. CFN brought out the curing of E44 at 89.1℃ and that of GGE at 148.7℃. However, CFA had much less thermal initiating activity under 300℃. Under UV radiation for short time, the thermal initiating activities of CFN and CFA were enhanced obviously. It was observed that the initiating onset temperature decreased and the evolved heat of the curing increased. Both CFN and CFA can carry out the polymerization of E44 and GGE near 85℃ and 112℃ by UV radiation.

Effect of Soil Moisture on Release of Low-Molecular Weight Organic Acids in Root Exudates and the Accu-mulation of Iron in Root Apoplasm of Peanut

A three-compartments rhizobox was designed and used to study the low-molecular-weight organic acids in root exudates and the root apoplastic iron of "lime-induced chlorosis" peanut grown on a calcareous soil in relation to different soil moisture conditions. Results showed that chlorosis of peanuts developed under condition of high soil moisture level (250 g kg-1), while peanuts grew well and chlorosis did not develop when soil moisture was managed to a normal level (150 g kg-1). The malic acid, maleic acid and succinic acid contents of chlorotic peanut increased by 108.723, 0.029 and 22.446 ig cm-2, respectively, compared with healthy peanuts. The content of citric acid and fumaric acid also increased in root exudates of chlorotic peanuts. On Days 28 and 42 of peanut growth, the accumulation of root apoplastic iron in chlorotic peanuts was higher than that of healthy peanuts. From Day 28 to Day 42, the mobilization percentages of chlorotic peanuts and healthy peanuts to root apoplastic iron were almost the same, being 52.4% and 52.8%, respectively, indicating that the chlorosis might be caused by the inactivation of iron within peanut plant grown on a calcareous soil under high soil moisture conditions.

Ferrocenyl building block constructing porous organic polymer for gas capture and methyl violet adsorption

Ferrocene-based porous organic polymer(FcPOP) was constructed with ferrocene and porphyrin derivatives as building blocks via Schiff-base coupling. FcPOP was well characterized, and exhibited good thermal stability, high porosity, microporous structure, and homogeneous pore size distribution. Ferrocene blocks with highly electron-rich characteristics endowed Fc POP with excellent adsorption capacity of CO2 and methyl violet. The kinetic study indicated adsorption of methyl violet onto FcPOP mainly complied with pesudo-second order model. The maximum adsorption capacity of FcPOP derived from Langmuir isotherm model reached up to 516 mg/g. More importantly, FcPOP could be easily regenerated and repeatedly employed for removal of methyl violet with high efficiency. Overall, FcPOP in the present study highlighted prospective applications in the field of gas capture and dyeing wastewater treatment.

Mechanism of Photo-Fenton Degradation of Ethanol and PVA

Contrast degradation experiments between ethanol and polyvinyl alcohol (PVA) were conducted during H2O2, UV/H2O2, Fenton, and Photo-Fenton processes in this study. UV/VIS spectra showed' that complexes between Fe(Ⅲ) and organics were easily formed and degraded within reaction time. Compared with ,the degradation of complex, hydroxyl radicals acted weakly in Fenton or Photo-Fenton process. Hydroxyl radi'cals involved in Photo-Fenton process were deemed to be generated from the split decomposition of H2O2, photolysis of Fe_aq^3+, and degradation of hydrated Fe(Ⅳ)-complex but not traditional Fenton reaction. Experimental evidence to support this point was presented in this paper.

Synthesis and Structure Characterization of [HgCl(η~5-C_5H_3C(CH_3)=N-3- C_5H_4N)Fe(η~5-C_5H_5)]·(1/2)CH_2Cl_2

S A new cyclomercurated ferrocenylketimine containing pyridyl ring ([HgCl(5- C5H3C(CH3)=N-3-C5H4N)Fe(5-C5H5)]紺H2Cl2, Mr = 581.66) was synthesized and its molecular structure has been confirmed by IR, elemental analysis, 1H-NMR and X-ray crystal structure analysis. It is of monoclinic system, space group P21/c with a = 9.213(2), b = 17.479(4), c = 11.510(2) ? b = 100.32(3)o, V = 1823.7(6) 3, Z = 4, C17.5H16Cl2FeHgN2, Dc = 2.119 g/cm3, m = 9.497 mm-1, F(000) = 1100, R = 0.0436 and wR = 0.0987. The independent reflections are 3527, of which 3153 with I ≥ 2s(I) were observed. The compound contains a five-membered metallocycle. The mercury atom is bonded with the 2-position of substituted cyclopentadienyl ring (Cp), and coordinated weakly to the N atom of imino group. The pyridyl ring is almost perpendicular to the substituted Cp which is nearly coplanar with the metallocycle. The Hg(1)C(1) and Hg(1)Cl(1) bond lengths are 2.050(8) and 2.321(2) ? respectively.

Distribution of Organic Matter,Iron,Mangenese in Surface Sediments in the Nansha Islands Sea Area,South China Sea

Concentrations of organic matter, iron and manganese in the deep sea surface sediments in the Nansha Islands sea area, South China Sea are measured. Horizontal and vertical distributions of iron and manganese are discussed. The vertical distribution of iron and manganese in the sediments results from reduction, diffusion, and redeposition of manganese (or iron) oxide and hydroxide in the sediment. There are the maxima of iron and manganese in solid phase in the top of the sediment, which is caused by the penetration of O2 and the upward flux of Mn2+ ( or Fe2+ ). Manganese bacteria play a very important role in the cycle of solid-phase iron and manganese in the ocean environment. Manganese bacteria oxidize Mn2+ ( or Fe2+ ) in dissolved state to Mn4+ ( or Fe3+ ) in oxidized state under the aerobic condition, whereas they reduce iron and manganese in anaerobic conditions.

Influence of Long-Term Fertilization on Selenium Accumulation in Soil and Uptake by Crops

Continuous applications of organic and inorganic fertilizers can affect soil and food quality with respect to selenium （Se） concen- trations. A long-term （over 20 years） experimental field study, started in 1989, was conducted to investigate the changes in soil Se fractions and its uptake by crops, as affected by different fertilizer practices, in the North China Plain with an annual crop rotation of winter wheat and summer maize. The long-term experiment was arranged in a complete randomized block design consisting of 4 replications with 7 fertilizer treatments： 1） organic compost （OC）, 2） half organic compost plus half N-P-K chemical fertilizers （OC ＋ NPK）, 3） N-P-K fertilizers （NPK）, 4） N-P fertilizers （NP）, 5） P-K fertilizers （PK）, 6） N-K fertilizers （NK）, and 7） an un-amended control. Soil samples from the surface （20 cm） were collected in 1989, 1994, 1999, 2004 and 2009 to characterize Se and other soil properties. In 2009, the average soil Se concentrations in the treatments （149 ± 8 beg kg-1） were higher than those in the soil samples collected in 1989 at the beginning of the experiment （112 4- 4 beg kg-1）, and decreased in the order of OC 〉 OC ＋ NPK 〉 NPK NP 〉 PK NK 〉 control. Sequential extraction showed the oxidizable fraction （50.06%± 3.94%） was the dominant form of Se in the soil, followed by the residual fraction （24.12% ± 2.89%）, exchangeable fraction （15.09% ± 4.34%） and Fe-Mn oxides fraction （10.73%±4.04%）. With an increase of soil K, the exchangeable Se concentrations in the soil increased. The Se concentrations in the soil tillage layer （0-20 cm） were mainly related to soil organic carbon （SOC）, although different contributions came from atmospheric deposition, irrigation and fertilizers. With the accumulation of SOC, the uptakes of soil Se by two crops were inhibited. For the OC and OC ＋ NPK treatments, Se concentrations in wheat grains were lower than the critical standard of Se in stable food （100 μg kg·1]. Additionallv. Se concentrations in grains were also decreased by the deficiencies of major soil nutrients, especially P.

Chromium Adsorption in Different Mineralogical Fractions from Subtropical Soils

Safe application of chromium （Cr）-containing organic industrial wastes to soil requires considering the ability of the soil to adsorb Cr. In this study, the maximum Cr adsorption capacity was assessed for the bulk samples and their clay and iron-free clay fractions of four subtropical soils differing in mineralogy. To this end, the samples were supplied with Cr（Ⅲ） nitrate solutions at pH 4.5 or 5.5. The results of Cr（Ⅲ） adsorption fitted to a Freundlich equation and the adsorption capacity was positively correlated with soil organic matter and iron oxide contents. The clay fractions adsorbed more Cr per unit mass than the bulk soils and the iron-free clay fractions. The Cr（Ⅲ） adsorption capacity increased with increasing soil pH due to more charges on adsorbing surfaces. Our results suggest that the soils rich in organic matter and iron oxides and having a pH above 4.5 are suitable for application of Cr（Ⅲ）-loaded industrial wastes.

Iron Mobilization and Mineralogical Alterations Induced by Iron-Deficient Cucumber Plants (Cucumis sativus L.) in a Calcareous Soil

Dicotyledons cope with ion(Fe) shortage by releasing low-molecular-weight organic compounds into the rhizosphere to mobilize Fe through reduction and complexation mechanisms. The effects induced by these root exudates on soil mineralogy and the connections between Fe mobilization and mineral weathering processes have not been completely clarified. In a batch experiment, we tested two different kinds of organic compounds commonly exuded by Fe-deficient plants, i.e., three organic acids(citrate, malate, and oxalate)and three flavonoids(rutin, quercetin, and genistein), alone or in combination, for their ability to mobilize Fe from a calcareous soil and modify its mineralogy. The effect of root exudates on soil mineralogy was assessed in vivo by cultivating Fe-deficient and Fe-sufficient cucumber plants(Cucumis sativus L.) in a RHIZOtest device. Mineralogical analyses were performed by X-ray powder diffraction. The batch experiment showed that citrate and, particularly, rutin(alone or combined with organic acids or genistein)promoted Fe mobilization from the soil. The combinations of rutin and organic acids modified the soil mineralogy by dissolving the amorphous fractions and promoting the formation of illite. These mineralogical alterations were significantly correlated with the amount of Fe mobilized from the soil. The RHIZOtest experiment revealed a drastic dissolution of amorphous components in the rhizosphere soil of Fe-deficient plants, possibly caused by the intense release of phenolics, amino acids, and organic acids, but without any formation of illite. Both batch and RHIZOtest experiments proved that exudates released by cucumber under Fe deficiency concurred to the rapid modification(on a day-scale) of the mineralogy of a calcareous soil.

First-principles Study on the Magnetic,Half-metal and Thermoelectric Transport Properties of Inorganic-Organic Hybrid Compounds [C_4N_2H_(12)][Fe_4~Ⅱ(HPO_3)_2(C_2O_4)_3]

The electronic structure, magnetic and half-metal properties of inorganic-organic hybrid compound [C4N2H12][FeoI （HP03）2 （（72 04）3] are investigated by using the full-potential linearized augmented plane wave （FPLAPW） method within density-functional theory （DFT） calculations. The density of states （DOS）, the total energy of the cell and the spontaneous magnetic moment of [C4N2H12][FeII （HP03）2 （C2 04）3] are calculated. The calculation results reveal that the low-temperature phase of [C4N2H12][FeII （HP03）2（C204）3] exhibits a stable ferromagnetic （FM） ground state, and we find that this organic compound is a half-metal in FM state. In addition, we have calculated antiferromagnetically coupled interactions, revealing the existence of antiferromagnetic （AFM）, which is in agreement with the experiment. We have also found that [C4N2HI2][Fe4II （HP03）2（C204）3] is a semiconductor in the AFM state with a band gap of about 0.40 eV. Subsequently, the transport properties for potential thermoelectric applications have been studied in detail based on the Boltzmann transport theory.