Kinetics and Mechanism of Iridium（Ⅲ）-Catalyzed Oxidation of Ethanol Amine by Cerium（ Ⅳ ） in Sulfuric Acid Media

In this study, the kinetics and mechanism of the iridium(Ⅲ)-catalyzed oxidation of ethanol amine(EAN) by cerium(Ⅳ) in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298—313 K. It was found that the reaction is of first order with respect to Ce(Ⅳ) and Ir(Ⅲ), and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order([EAN][Ce(Ⅳ)]) rate constant kobs decreases with the increase of [H ] and [HSO-4]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of kobs on the concentration of hydrogen sulfate, Ce(SO4)2 was found to be the kinetically active species. The rate constants of the rate-determining step together with the activation parameters were evaluated.     

S-M（M=Al,Co）复合掺杂LiMn2O4的结构稳定性

应用量子化学电荷自洽离散变分Xα(SCC-DV-Xα)方法,研究了S-Al、S-Co复合掺杂增强尖晶石结构锂锰氧化物稳定性的作用机制.计算结果表明, S-Al复合掺杂锂锰尖晶石和S-Co复合掺杂锂锰尖晶石中的共价键强度均比未掺杂尖晶石LiMn2O4中的强,且与MnO2中的共价键强度相近; S-Al, S-Co复合掺杂尖晶石中Mn的电荷也与MnO2模型[Mn6O26]28－中十分接近. Mn原子的电荷密度次序是MnO2≈掺硫铝后锰锂尖晶石≈掺硫钴后的锂锰尖晶石< 锰锂尖晶石.即[LixMn3Co3O20S6]n－和[LixMn3Al3O20S6]n－中Mn的状态与MnO2中的Mn相似.上述结果揭示了S和非Jahn-Teller效应阳离子（Al3＋,Co3＋）复合掺杂尖晶石结构锂锰氧化物在电化学过程中不会发生Jahn-Teller畸变的内在原因.     

Synthesis,Characterization and Catalytic Activity of Salen Co(Ⅲ)Cl in Alternating Copolymerization of CO2 and Propylene Oxide

The title complex Salen Co(Ⅲ)Cl(Salen = 6,6’-((1E,1’E)-(cyclohexane-1,2-diylbis(azaneylylidene))bis(methaneylylidene))bis(2,4-di-tert-butylphenol)) was synthesized and characterized by elemental analysis, IR spectroscopy, 1H NMR and UV-Vis. The complex can be used as catalyst for the propylene oxide(PO)/CO2 copolymerization in different conditions of reaction time, reaction temperature, carbon dioxide pressure and monomer concentration, and the optimum conditions for copolymerization were obtained.     

Synthesis and Crystal Structure of a Novel Three-dimensional Complex Ni（Iz）2（Bdc）（H2O）2 （Iz = Imidazole, Bdc = 1,4-Benzenedicarboxylate）

1 INTRODUCTION Inorganic-organic hybrid materials constructed by self-assembly processes have been developed at a tre- mendous rate recently because of their expansion by potential magnetic, optical, electronic and catalytic applications[1~6]. The apparent structural diversity observed for these topologies is due to selecting proper metal ions and polydentate ligands. Organic polydentate ligands containing N- or O-donors in the framework offer great potential for chemical and structural d…     

Photocatalytic Activities for Water Splitting of RuO_2-loaded MGa_2O_4（M=Zn,Ni） with d~（10） Configuration

MGa2O4(M=Zn,Ni) rods with similar crystallinity and BET surface area were prepared via a facile template-engaged reaction.The photocatalytic activities for water splitting of RuO2-loaded MGa2O4(M=Zn,Ni) were investigated under high-pressure Hg lamp.RuO2-loaded ZnGa2O4 catalyst exhibited much higher photocatalytic activity than RuO2-loaded NiGa2O4.Factors affecting the photocatalytic activities of RuO2-loaded MGa2O4(M=Zn,Ni) were discussed.It was suggested that the electronic structure of oxide semiconductor was a predominant factor of the photocatalytic behavior for RuO2-loaded MGa2O4(M=Zn,Ni).     

Synthesis,Characterization, and DNA Binding Properties of Dinuclear Copper（Ⅱ） Complex [Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2O

A dinuclear copper（Ⅱ） complex[Cu2（TATP）2（L-Leu）2（CIO4）2]2·2H2Owas synthesized and characterized, where, TATP=1,4,8,9-tetraazatriphenylene, and L-Leu=L-leucinate. The complex was crystallized in the triclinic space group P1, with two independent molecules in a unit cell. Two Cu（Ⅱ） ions in each complex [Cu2（TATP）2（L-Leu）2（CIO4）2] molecule were found to be in different coordination geometries, i.e., Cu2 or Cu4 of a distorted square-pyramidal geometry coordinated with two nitrogens of TATP, the amino nitrogen and one carboxylate oxygen of L-Leu and one oxygen of perchlorate, and Cul or Cu3 with an octahedral geometry coordinated with the above stated similar coordinated atoms, and another carboxylate oxygen of L-Leu coordinating to Cu2 or Cu4. The complex can interact with CT-DNA by an intercalative mode and cleave pBR322 DNA in the presence of ascorbate.     

Bending modes of the water molecules and the MO stretching modes in the series MF2 · 4H2O (M = Fe,Co, Ni,Zn)

The infrared spectra of the series MF₂·4X₂O (M = Fe, Co, Ni, Zn; X = H, D) are reported in the frequency ranges of the bending vibrations of the water molecules (ν₂) at 296 and ∼100 K and the MO lattice vibrations (ν_MO) at 296 K. Four ν_MO vibrations consisting of two doublets are identified using deuterium substitution. The various ν_ZnO vibrations correlate well with the metal-oxygen distances R(ZnO), and this correlation is further used to calculate R(MO)'s of the remainder of the series and to refine R(ZnO). Four ν₂(H₂O, HDO, D₂O) vibrations, consisting of two sharp overlapping bands flanked by two broad shoulders, are identified. The number of ν₂(H₂O) components, the sequence of ν₂ in the series and the correlation with R(MO) suggest that the ν₂ frequencies are mainly determined by R(MO). Using this assignment the two types of ν₂ bands are assigned to the two types of crystallographically distinct water molecules found in the MF₂·4H₂O structure.     

MF2 vibrations and librations of water molecules in the series MF2·4H2O (M = Fe,Co, Ni or Zn)

The infrared absorption spectra of the series MF₂·4H₂O (M = Fe, Co, Ni or Zn) and of the respective deuterates were recorded at 296 and ∼ 100 K in the 1200-400 cm⁻¹ wavenumber region. Using the known ZnF₂·4H₂O structure as a model, the number of i.r. active librations and MF₂ vibrations was predicted with the aid of a group theoretical treatment. The librations were distinguished from the MF₂ and MO vibrations and assigned, using isotopic ratios and correlations between the unit cell volumes, the uncoupled OH and OD stretch vibrations of HDO and the twisting libration. The six librations are assigned to two types of water molecules with low symmetry and with different hydrogen bond strengths, and are compatible with an orthorhombic Pca2₁ structure. The v₁ and v₃ intramolecular MF₂ vibrations are assigned, using ZnF₂·4H₂O crystal data and matrix-isolated v₁ and v₃ (v_1.3) values as guide. Shifts of v_1.3 and v₁/v₃ relative to the matrix-isolated values suggest smaller MF bond lengths. The shifts in the values of v_1.3 and v₁/v₃ upon deuteration and lowering of the temperature indicate smaller MF bond lengths and FMF angles.     

一维[M（tmp）]2ReO4（M=Ni,Cu,Pd）聚合物的能带结构

用紧束缚ＥＨＴ晶体轨道方法对一维［Ｍ（ｔｍｐ）２］２ＲｅＯ４（＝Ｎｉ，Ｃｕ，Ｐｄ）聚合物进行了能带计算，利用键向量近似方法对能带的结构及组成进行了讨论。结果表明，该类型了事物具有不同的导电机理，并进一步研究了环平面间的成键性质及转角改变对聚合物导电性能的影响。     

Preparation and Crystal Structures of LaCl_3（12－crown－4）（MeOH）and［LaCl_3（phen）_2（H_2O）］·MeOH

Ｐｒｅｐａｒａｔｉｏｎ　ａｎｄ　Ｃｒｙｓｔａｌ　Ｓｔｒｕｃｔｕｒｅｓ　ｏｆ　ＬａＣｌ_３（１２－ｃｒｏｗｎ－４）（ＭｅＯＨ）ａｎｄ［ＬａＣｌ_３（ｐｈｅｎ）_２（Ｈ_２Ｏ）］·ＭｅＯＨＭａｏＪｉａｎｇ－Ｇａｏ（ＦｕｊｉａｎＩｎｓｔｉｔｕｔｅｏｆＲｅｓｅａ...     

Ru/ZrO2-CeO2催化剂催化湿式氧化乙酸和苯酚的研究

采用共沉淀法制备了ZrO2-CeO2颗粒载体,利用浸渍法制备了Ru/ZrO2-CeO2颗粒催化剂,采用BET、XRD、SEM、TEM等方法对其进行了结构表征,测定了其催化湿式氧化乙酸的活性,并以苯酚为模型物进行了动态试验.结果表明,Zr的添加抑制了CeO2晶粒的长大,增加了催化剂的抗热性能.当催化剂Zr、Ce摩尔比为1∶9,焙烧温度为300℃时催化剂活性最高,在200℃和4 MPa下,催化湿式氧化乙酸反应120 m in后,COD去除率可达99%.动态实验100 h内,苯酚与COD的去除率都保持在90%以上,催化剂具有很好的活性和稳定性.     

以乙酸为模型反应物的Ti-Ce复合氧化物湿式氧化催化剂的研制

催化湿式氧化(catalytic wet air oxidation, CWAO)为高浓度难降解有机废水提供了一种有效可行的处理技术[1～8],它可使难降解有机物分子在相对较低的反应温与压力下降解矿化或生成易生物处理的小分子有机物.     

含钯类水滑石衍生复合氧化物Pd/M3AlO(M=Mg,Co, Ni,Cu, Zn)催化剂上氯苯的催化氧化

采用共沉淀法制备了系列含Pd类水滑石材料, 类水滑石基体为M3Al-HT (M=Mg, Co, Ni, Cu, Zn), 经焙烧制备出含Pd类水滑石衍生复合氧化物催化剂. 通过X射线衍射(XRD), 热重-差热分析(TG-DTG), H2程序升温还原(H2-TPR), O2程序升温脱附(O2-TPD)和N2吸脱附等表征技术手段研究了不同二价金属元素对含Pd类水滑石衍生复合氧化物催化剂物理化学性质及其对挥发性有机污染物氯苯催化氧化性能的影响. XRD和TG-DTG结果表明, 不同二价金属元素, 除Cu外, 都能形成类水滑石层状结构, Pd在不同类水滑石前驱物中均能良好分散. 不同的二价金属元素对催化剂性能的影响不同, 其中Pd/Co3AlO催化剂表现出最高的氯苯催化氧化活性, 其起燃温度和全转化温度分别为182和283 ℃. H2-TPR和O2-TPD测试表明, Pd和类水滑石衍生复合氧化物存在着协同作用, Pd的引入促进了复合氧化物的还原, 从而影响氧化物的氧化还原性能. Pd/M3AlO系列催化剂的活性主要受催化剂的氧化还原性能及其表面活性氧物种的影响.     

TiO2-CeO2催化剂湿式氧化苯酚的活性研究

采用共沉淀法制备了湿式氧化降解苯酚的TiO2-CeO2催化剂，测定了反应过程中不同反应时间的COD去除率，结果表明，当Ti、Ce摩尔比为3：1时，在150℃、总压5MPa（其中氧分压4．5MPa）时，所制备的催化剂活性最高，反应90分钟COD去除率可以达到71％．对催化剂进行了比表面积、XRD和XPS测试，结果表明，高效的催化剂具有较多的活性位、催化剂粉末体系Ce的变价特性以及大量的表面吸附氧．     

TiO_2-CeO_2催化剂湿式氧化苯酚的活性研究

采用共沉淀法制备了湿式氧化降解苯酚的TiO2-CeO2催化剂,测定了反应过程中不同反应时间的COD去除率,结果表明,当Ti、Ce摩尔比为3∶1时,在150℃、总压5MPa(其中氧分压4.5MPa)时,所制备的催化剂活性最高,反应90分钟COD去除率可以达到71%.对催化剂进行了比表面积、XRD和XPS测试,结果表明,高效的催化剂具有较多的活性位、催化剂粉末体系Ce的变价特性以及大量的表面吸附氧.     

ZrxCe1－xO2催化剂催化湿式氧化乙酸的活性研究

采用共沉淀法制备了Zr_xCe_1－xO₂催化剂, 利用BET, XRD和XPS对其进行了表征, 并研究了催化剂催化湿式氧化乙酸的活性. 结果表明: Zr和Ce摩尔比为1∶9的催化剂催化湿式氧化乙酸时具有最好的活性, 当乙酸溶液的初始化学需氧量(COD)为5000 mg/L, 反应温度为230 ℃, 压力为5 MPa时, 120 min后, COD的去除率为76% . 催化剂具有良好的活性是因为在CeO₂中加入Zr能够增大催化剂的比表面积和表面缺陷氧的含量, 并最终加快了HO₂•自由基的产生, 从而提高了催化剂的活性.     

Ru/Mn-Ce/TiO2催化剂催化湿式氧化丁二酸的反应活性和动力学研究

在二氧化钛载体中通过掺杂Ru，Mn，Ce制备了一系列用于催化湿式氧化的催化剂，利用XRD，TEM，BET等手段对催化剂进行了表征．在反应温度T=210～270℃，氧分压Po2=2．1MPa条件下，在间歇式高压反应釜中对丁二酸进行了降解实验．催化剂在反应中有很高的催化活性．催化剂在30min内对丁二酸降解的COD去除率为54．4～98．3％．Ru及Mn，Ce的氧化物对催化活性都有促进作用．建立了丁二酸催化湿式氧化的一级分段动力学模型．基于COD的一段及二段反应的活化能分别为43．74kJ／mol和54．28kJ／mol．     

Application of Catalytic Wet Air Oxidation to Treatment of Landfill Leachate on Co／Bi Catalyst

Catalytic wet air oxidation(CWAO) was employed to reduce the organic compounds in landfill leachate and the effects of temperature, oxygen pressure, catalyst dosage, and concentration of the organic compounds on the TOC and CODcr removal rates were studied. The degradation kinetics of landfill leachate was also investigated and an exponential experiential model consisting of four influential factors was established to describe the reduction of the organic compounds in the landfill leachate. Meanwhile, the GC-MS technique was used to detect the components of the organic intermediates for the inference of the decomposition mechanisms of the organic compounds in landfill leachate. The results reveal that the reaction temperature and the catalyst dosage are the most important factors affecting the degradation reaction of the organic compounds and that the principal intermediates confirmed by GC-MS are organic acids at a percentage of more than 88% with no aldehydes or alcohols detected. The decomposition mechanisms of the organic compounds in landfill leachate were inferred based on the GC-MS information as follows;the activated gas phase O2 captured the hydrogen of the organic pollutants to produce free radicals, which then initiated the catalytic reaction. So most of the organic compounds were oxidized into CO2 and H2O ultimately. In general, catalytic wet air oxidation over catalyst Co3O4/Bi2O3 was a very promising technique for the treatment of landfill leachate.     

催化湿式氧化中铜基催化剂的流失与控制

 制备了催化湿式氧化处理有机废水用铜基催化剂，并用XRD，XRF和TG－DTG等手段对催化剂进行了表征，对催化剂及其前驱体的组成和结构进行了分析鉴定．结果表明，由类水滑石结构的前驱体焙烧得到的催化剂Cu－Al－Zn－O，其活性组分铜的流失得到了控制；在氧化降解苯酚、十二烷基苯磺酸钠和磺基水杨酸时，在初始氧分压0．5MPa和160～220℃的反应条件下，催化剂活性组分铜的流失量小于0．3mg／L．对催化剂活性组分不易流失的原因进行了理论解释和计算．     

湿式氧化工艺中颗粒Ru催化剂的活性和稳定性

分别采用传统成型法和新的成型法制备了一系列以CeO2为主要成分的载体,将贵金属Ru浸渍在这些载体上制备了不同的催化剂.对催化剂的比表面积和机械强度进行了表征,并通过湿式氧化乙酸的静态实验和湿式氧化苯酚的动态实验分别考察了催化剂的活性和稳定性.结果表明,Ru负载在采用新方法成型的载体上制得的催化剂具有更大的比表面积.向CeO2中掺杂Zr能增大载体的比表面积.新方法制备的催化剂Ru/ZrO2-CeO2催化湿式氧化乙酸具有良好的活性,化学需氧量(COD)去除率为98%.在110h的催化湿式氧化苯酚反应中,苯酚和COD的去除率维持在96%左右,反应过程中活性组分的溶出浓度很小,催化剂表面有少量的积炭,但积炭在300℃能够被完全氧化.因而催化剂具有较好的稳定性和工业应用可能性.