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。

一水合碱式苯甲酸铁(Ⅲ)的流变相法合成及热分解研究

The complex of iron（Ⅲ）hydroxide benzoate monohydrate,[Fe3（C6H5COO）7（OH）2]·H2O was synthesized with rheological phase reaction.The complex was characterized by elemental analysis and IR.The mechanism of thermal decomposition for iron（Ⅲ）hydroxide benzoate monohydrate in O2 and N2 was studied by using TG,DTG,DTA,IR and FABMS.The solid product of thermal decomposition of iron（Ⅲ）hydroxide benzoate monohydrate in O2 was Fe2O3.Iron（Ⅲ）hydroxide benzoate monohydrate in N2 decomposted to form Fe3O4 and organic compounds.The organic compounds obtained from decomposition reaction are mainly benzophenone,benzoate acid,triphenylmethane and so on.

二乙基二硫代氨基甲酸铁的溶剂热合成、晶体结构及电化学性质

溶剂热法合成了二乙基二硫代氨基甲酸铁配合物[(C5H10NS2)3Fe(III)],并用X射线衍射法测定了其晶体结构。该化合物属于单斜晶系,C2/c空间群,晶胞参数为a=1.425 2(3)nm,b=1.039 5(2)nm,c=1.719 2(3)nm,z=4,Dc=1.404 g.cm-3,μ=1.170 mm-1,F(000)=1 052,最终结构偏离因子R=0.049 1,wR=0.121 7,S=1.036。循环伏安研究表明该化合物具有电化学活性。

光降解剂二乙基二硫代氨基甲酸铁的合成及应用

合成了二乙基二硫代氨基甲酸铁（ＦｅＤＥＣ），通过人工加速老化和户外铺膜试验，考察了该光降解剂应用于聚乙烯薄膜时的光降解情况。试验证明：ＦｅＤＥＣ是一种具有加速聚乙烯薄膜的光氧化作用，且在光照射初期具有抗氧剂性能，而在光照射后期具有光活性剂性能的光降解剂。

二乙基二硫代氨基甲酸铁对聚乙烯光降解性能的影响

借助人工加速光老化试验，通过测定含二乙基二硫代氨基甲酸铁（ＦｅＤＥＣ）聚乙烯薄膜的断裂伸长率、熔体流动速率、凝胶含量、羰基含量和脆化时间等指标，考察了ＦｅＤＥＣ对聚乙烯光降解性能的影响，证实ＦｅＤＥＣ在光氧化初期起抗氧剂作用，抑制了光氧化交联反应，使聚乙烯出现一个光降解诱导期；而在光氧化后期起光活性剂作用，加速断链反应，从而促进了聚乙烯的光降解，两种作用均与ＦｅＤＥＣ浓度成正比，通过调整ＦｅＤＥＣ用量，可以改变聚乙烯的光降解速度。

N，N－二乙基二硫代氨基甲酸铁的合成及其光敏化效果的研究

本文研究了Ｎ，Ｎ－二乙基二硫代氨基甲酸铁（ＦｅＤＥＣ）的合成、分子结构、热分解温度、紫外吸收及其对光氧化低密度聚乙烯（ＬＤＰＥ）薄膜的物理性能、羰基指数和桔均分子量的影响，并探讨了它的作用机理。结果表明，在ＬＤＰＥ膜中加入０．１０～０．３０ｗｔ％ＦｅＤＥＣ，即可控ＬＤＰＥ膜的使用寿命。

(4-环戊二烯基苯甲酸-铁-甲苯)六氟磷酸盐键合硅胶固定相的制备及色谱性能

基于二茂铁独特的分子结构及其作为新型液相色谱分离基质的潜质,制备了新型(4-环戊二烯基苯甲酸-铁-甲苯)六氟磷酸盐键合硅胶固定相,利用红外光谱、元素分析、热重分析等手段对其进行了表征。分别选取多环芳烃、萘胺位置异构体、硝基苯胺位置异构体、硝基咪唑类化合物和有机磷化合物溶质作为探针,对其色谱性能进行了评价。结果表明,该色谱固定相能提供π-电子转移、π-π作用、偶极-偶极作用及与底物的静电相互作用等多种作用力,并探讨了可能的分离机理。

对氨基苯甲酸——铁络合物催化氢波的研究

作者研究了对氨基苯甲酸——铁络合物在生理食盐水底液中的极谱催化氢波,观察了当固定铁或络合剂浓度时改变络合剂或铁浓度催化电流的变化情况,推导了催化电流与络合剂浓度的关系式,并测定了络合物形成常数和络合物组成;通过表面活性剂、温度和循环伏安法等实验证明催化氢波主要是受扩散控制的不可逆过程。

Binding interactions of pefloxacin mesylate with bovine lactoferrin and human serum albumin

The binding of pefloxacin mesylate （PFLX） to bovine lactoferrin （BLf） and human serum albumin （HSA） in dilute aqueous solution was studied using fluorescence spectra and absorbance spectra. The binding constant K and the binding sites n were obtained by fluorescence quenching method. The binding distance r and energy-transfer efficiency E between pefloxacin mesylate and bovine lactoferrin as well as human serum albumin were also obtained according to the mechanism of Forster-type dipole-dipole nonradiative energy-transfer. The effects of pefloxacin mesylate on the conformations of bovine lactoferrin and human serum albumin were also analyzed using synchronous fluorescence spectroscopy.

Methanol oxidation over shell-core MOx/Fe2O3（M = Mo, V, Nb） catalysts

We present a comparison of Mo, V and Nb oxides as shell materials atop haematite cores used for selective methanol oxidation. While Mo and V both yield high selectivity to formaldehyde, Nb does not. Very different reactivity patterns are seen for Nb, which mainly shows dehydrogenation (to CO) and dehydration (to DME), indicating the lack of a complete shell, while Raman spectroscopy shows that the Mo and V formation process is not followed by NbOx. We suggest this is due to the large differences in mobility within the solid materials during formation, NbOx requiring significantly higher (and deleterious) calcination temperatures to allow sufficient mobility for shell completion.

FeOx Coating on Pd/C Catalyst by Atomic Layer Deposition Enhances the Catalytic Activity in Dehydrogenation of Formic Acid

Hydrogen generation from formic acid （FA） has received significant attention. The challenge is to obtain a highly active catalyst under mild conditions for practical applications. Here atomic layer deposition （ALD） of FeOx was performed to deposit an ultrathin oxide coating layer to a Pd/C catalyst, therein the FeOx coverage was precisely controlled by ALD cycles. Transmission electron microscopy and powder X-ray diffraction measurements suggest that the FeOx coating layer improved the thermal stability of Pd nanoparticles （NPs）. X-ray photoelectron spectroscopy measurement showed that deposition of FeOx on the Pd NPs caused a positive shift of Pd3d binding energy. In the FA dehydrogenation reaction, the ultrathin FeOx layer on the Pd/C could considerably improve the catalytic activity, and Pd/C coated with 8 cycles of FeOx showed an optimized activity with turnover frequency being about 2 times higher than the uncoated one. shape as a function of the number of FeOx ALD The improved activities were in a volcanocycles, indicating the coverage of FeOx is critical for the optimized activity. In summary, simultaneous improvements of activity and thermal stability of Pd/C catalyst by ultra-thin FeOx overlayer suggest to be an effective way to design active catalysts for the FA dehydrogenation reaction.

Perovskite LaFeO_3 supported bi-metal catalyst for syngas methanation

LaFeO3 perovskite supported Ni and Ni-Fe catalysts were prepared and applied to methanation reaction of syngas. Two preparation methods were employed. One was one-step citrate complexing method, and the other was a two step method using citrate complexing method to produce LaFeO3 and followed by loading nickel oxide on it with impregnation. The structure evolution of the sample as prepared was investigated by XRD, TPR and TEM techniques. For the former, the chemical composites of the calcined sample are NiO-Fe2O3/LaFe1-xNixO3. After reduction and reaction of CO methanation, its composites convert to Fe-Ni@Ni/LaFeO3-La2O2CO3, in which Fe-Ni@Ni is metal particles in nano-size composed of nickel core and Fe-Ni alloy shell. For the latter, the chemical composites of the calcined sample are NiO/LaFeO3; and after reduction and reaction of CO methanation, its chemical composites change to Ni/LaFeO3. Ni/LaFeO3 catalyst is a little more active, while Fe-Ni@Ni/LaFeO3-La2O2CO3 is much more stable and shows very good resistance to carbon deposition. In this work it is aimed to show that the structure and composites of the catalysts can be tailored using perovskite-type oxide as precursor with different preparing method or preparing condition. Therefore, it is a promising route to prepare supported bi-metal catalysts in nano-size for a lot of metals with desired catalytic performances.

Synthesis of novel thionocarbamate for copper-sulfur flotation separation and its adsorption mechanism

As a novel collector, O-isopropyl-N,N-diethyl thionocarbamate(IPDTC) was designed and synthesized for copper-sulfur flotation separation. Density functional theory calculations were performed to investigate the electronic structures of IPDTC. The results showed that IPDTC had higher energy of the highest occupied molecular orbital but lower electronegativity than O-isopropyl-N-ethyl thionocarbamate(Z-200). It was predicted that IPDTC had strong collection ability according to the reaction energy criteria. Flotation results demonstrated that the collecting ability of IPDTC to chalcopyrite and pyrite was stronger than that of Z-200. Then, the flotation mechanism was analyzed by measurements of surface tension, adsorption capacity, XPS, FTIR and zeta potential. These results indicated that IPDTC could reduce the solution surface tension. The adsorption capacity of IPDTC on chalcopyrite was higher than that on pyrite, consistent with the results of the flotation tests. FTIR, zeta potential and XPS results also demonstrated that IPDTC was strongly absorbed on the chalcopyrite surface by formation of Cu—S—C bonds, but showed a weak affinity on the pyrite surface.

Microencapsulation of stearic acid with polymethylmethacrylate using iron(Ⅲ) chloride as photo-initiator for thermal energy storage

Aiming to identify the validity of fabricating microencapsulated phase change material(PCM) with polymethylmethacrylate(PMMA) by ultraviolet curing emulsion polymerization method using iron(III) chloride as photoinitiator,SA/PMMA microcapsules were prepared and various techniques were employed to determine the ignition mechanism,structural characteristics and thermal properties of the composite.The results shown that the microcapsules containing SA with maximum percentage of 52.20 wt% formed by radical mechanism and only physical interactions existed in the components both in the prepared process and subsequent use.The phase change temperatures and latent heats of the microencapsulated SA were measured as 55.3 °C and 102.1 J·g^(-1) for melting,and 48.8 °C and 102.8 J·g^(-1) for freezing,respectively.Thermal gravimetric analysis revealed that SA/PMMA has good thermal durability in working temperature range.The results of accelerated thermal cycling test are all shown that the SA/PMMA have excellent thermal reliability and chemical stability although they were subjected 1000 melting/freezing cycles.In summary,the comparable thermal storage ability and good thermal reliability facilitated SA/PMMA to be considered as a viable candidate for thermal energy storage.The successful fabrication of SA/PMMA capsules indicates that ferric chloride is a prominent candidate for synthesizing PMMA containing PCM composite.

Study on the Magnetic Properties of MoFe_3S_4 Single Cubane-like Clusters Containing R_2dtc Ligands

Both cubane-like clusters MoFe_3S_4 (Me_2dtc)_5·2CH_2Cl_2 (1) and MoFe_3S_4(C_4H_8dtc)_5·2EtCN (2) were used to study the temperature-dependent behavior of the molar magnetic susceptibility. A spin coupling model was suggested and the fitting results agree with the model and structural and spectroscopic parameters.