胶束溶液中金属卟啉Fe(TEPyP)催化H2O2氧化降解2,4,6-三氯苯酚的动力学研究

合成了四(4-N-乙基吡啶基)卟啉铁（Fe(TEPyP)）,并用紫外-可见分光光度法研究了Fe(TEPyP)分别与表面活性剂LSS、CTAB和Brij35形成的金属胶束催化H2O2氧化2,4,6-三氯苯酚(TCP)反应的动力学,探讨了体系酸度、H2O2/催化剂摩尔比、温度对催化降解反应速率的影响,提出了催化氧化机理,建立了反应的动力学数学模型。研究结果表明：Fe(TEPyP)和胶束形成的金属胶束表现出过氧化物酶的催化氧化特性,其中阴离子表面活性剂LSS形成的金属胶束的催化作用最显著。     

水溶性四(p-磺酸钠苯基)金属卟啉配合物的合成、光谱性质及催化三氯苯酚的氧化脱氯反应

通过四苯基卟啉(H2TPP)和浓硫酸发生磺化反应及其金属化, 控制反应体系pH并利用透析法纯化, 高效合成了水溶性四(对磺酸钠苯基)卟啉(H2TPPS)及其金属配合物(FeTPPS和ZnTPPS); 采用UV-Vis、荧光、1H NMR和FTIR等光谱手段表征及研究了水溶性卟啉的结构及性质. 结果表明, 磺酸根离子的存在增强了卟啉分子间的π-π作用, 从而使H2TPPS及其金属配合物的分子间聚合作用增强. 研究了FeTPPS对2,4,6-三氯苯酚(TCP)催化氧化脱氯反应, 结果表明, FeTPPS/H2O2催化体系对TCP具备很好的催化氧化脱氯性能, 2,6-二氯对苯醌的转化数达到了766.     

氨基羧酸铁(III)配合物催化分解过氧化氢

用碘量法研究了[Fe（EDTA],[FeⅢ(DCTA)],[FeⅢ(EGTA)]催化分解H2O2反应，提出了反应动力学方程为-d[H2O2]/dt=k[FE(Ⅲ)][H2O2][H ]^-1，认为氨基羧酸铁（Ⅲ）配合物催化分解H2O2反应为键式自由基反应，反应中间体包括过氧铁（Ⅲ）配合物，氨基羧酸铁（Ⅱ）和HO-，HO2-自由基。     

Fe2O3/CNT催化湿法H2O2氧化苯酚

通过化学沉积法和热处理得到多壁碳纳米管负载Fe2O3催化剂 Fe2O3/CNT, Fe2O3的负载质量分数约为15.1%,XRD表征显示,负载的Fe2O3存在α和γ这2种晶型。考察了Fe2O3/CNT催化湿式H2O2氧化去除废水中苯酚催化性能,通过苯酚的去除率及反应过程中催化剂活性组分的溶出总量,研究了催化剂制备过程中添加聚乙烯醇对催化剂性能的影响。在苯酚和H2O2初始浓度分别为350和1 500 mg/L、催化剂投加量为1.0 g/L、温度80 ℃条件下,经过240 min的反应,苯酚去除率达100％,COD去除率为86.1％。     

胶束溶液中四(4-N-乙基吡啶基)卟啉铁催化H_2O_2氧化降解2,4,6-三氯苯酚的动力学研究

合成了四(4-N-乙基吡啶基)卟啉铁[Fe(TEPyP)],并用紫外-可见分光光度法研究了Fe(TEPyP)分别与表面活性剂正月桂酸肌氨酸钠(LSS)、十六烷基三甲基溴化铵(CTAB)和聚氧乙烯(23)十二烷基醚(Brij35)形成的金属胶束催化H2O2氧化2,4,6-三氯苯酚(TCP)反应的动力学,探讨了体系酸度、H2O2与催化剂的摩尔比以及温度对催化降解反应速率的影响,提出了催化氧化机理,建立了反应的动力学数学模型。结果表明,Fe(TEPyP)和胶束形成的金属胶束表现出过氧化物酶的催化氧化特性,其中阴离子表面活性剂LSS形成的金属胶束的催化作用最显著。     

咪唑衍生物金属胶束模拟过氧化物酶研究

咪唑衍生物铜配合物Cu(biap)·Cl2及其与胶束形成的金属胶束模拟过氧化物酶成功地用于催化H2O2氧化苯酚反应,反应遵循酶催化的动力学规律.过氧化氢/催化剂物质的量比和酸度对反应的影响符合生物催化剂条件影响的一般规律.讨论了不同类型表面活性剂胶束对该氧化反应的影响.     

硒钼杂多配合物及其稀土盐的合成及催化苯酚羟化反应的研究

合成了杂多配合物(NH4)6[Se2Mo8O31]·5H2O,在此基础上合成了其稀土盐Ln2[Se2Mo8O31]·xH2O(Ln=La3+,Ce3+,Nd3+,Sm3+),探讨了这些杂多配合物在苯酚羟化反应中的催化作用,发现稀土盐的催化效果低于配合物(NH4)6[Se2Mo8O31]·5H2O的催化效果;在溶剂丙酮中苯酚的转化率大于在乙腈中的转化率。通过正交法研究了反应温度、原料比、反应时间和催化剂用量对苯酚转化率、产品分布和过氧化有效转化率的影响,找到了最佳反应条件,即在苯酚/H2O2(摩尔比)为1,催化剂用量10g·mol-1,反应温度70℃,反应时间4h时,得到苯酚转化率29.65%,产品选择率77.2%。     

Schiff碱铜配合物模拟过氧化物酶的研究

两种Schiff碱铜配合物首次作为过氧化物酶的模拟物用于催化过氧化氢氧化苯酚的反应;分析了配合物的特征光谱;研究了Schiff碱铜配合物的催化氧化机理,建立了催化氧化反应动力学数学模型;讨论了过氧化氢／催化剂摩尔比、体系温度、体系pH和胶束微环境对催化反应速率的影响．结果表明：这两种Schiff碱铜配合物在不同的反应条件下均表现出过氧化物酶催化的特征．     

金属铜(Ⅱ)配合物催化2,6-二甲基苯酚氧化偶合反应的动力学研究

 合成了四种金属铜(Ⅱ)-四氮配合物,并用初始速率法研究了25 ℃时四种配合物催化H2O2氧化偶合2,6-二甲基苯酚生成3,3′,5,5′-四甲基联苯二醌反应的动力学. 结果表明此偶合反应符合Michaelis-Menten酶催化动力学,并由此获得了反应在不同配合物和不同pH值情况下的动力学参数k2和Km. 研究还发现不同的铜配合物其催化活性有不同的最适pH,具有较好电子共轭效应和合适刚柔性结构的铜配合物更有利于反应的进行. 对此催化反应的动力学机理研究发现,铜配合物的一级酸式电离中间物种是反应的主要催化活性物种. 质谱分析表明,此类铜配合物都能催化2,6-二甲基苯酚进行C-O偶合反应生成不同聚合度的高分子.     

Schiff碱配合物催化过氧化氢氧化苯酚的动力学研究

按照文献方法合成了钴(Ⅱ)和铁(Ⅱ)Schiff碱配合物,研究了它们作为模拟过氧化物酶在缓冲溶液中以及在三种不同的表面活性剂(CTAB,Brij35,LSS)胶束中催化过氧化氢氧化苯酚的反应,结果表明：过氧化氢／配合物物质的量比和胶束微环境对金属配合物催化过氧化氢氧化苯酚的反应有明显的影响;本文所提出的Schiff碱金属配合物催化苯酚氧化反应的机理和动力学数学模型是合理的。     

Studies on Phenol Oxidation with H2O2 Catalyzed by Schiff Base Cobalt(II) Complexes in Micellar Solution

The two Schiff base cobalt(II) complexes, CoL¹ and CoL², were synthesized and characterized. The metallomicelle made up of the cobalt(II) complexes and surfactants (CTAB, LSS and Brij35), as mimic peroxidase metalloenzyme, were used in the catalytic oxidation of phenol by H₂O₂. The mechanism and a kinetic mathematic model of the phenol catalytic oxidation were studied. The acid effect of reaction system, structural effect of the complexes, and effect of temperature on the rate of the phenol oxidation catalyzed by the mimetic peroxidases have been discussed. The results showed that the schiff base cobalt(II) complexes and their metallomicelles as peroxidase mimics exhibit good catalytic activity and similar catalytic character to natural enzyme.     

Studies on the Phenol Oxidation by H2O2 Catalyzed by Metallomicelle Made from Crowned Schiff Base Co(II) Complexes Containing Benzoaza-15-crown-5

Three novel cobalt(II) complexes of the benzoaza-15-crown-5 Schiff base, CoL¹, CoL², and CoL³ were synthesized and characterized. Metallomicelles made from CoL and surfactants (CTAB, LSS, and Brij35) were used as mimetic peroxidase in the catalytic oxidation of phenol by H₂O₂. For comparison, the catalytic activity of the complexes (CoL¹, CoL², and CoL³) were also investigated. The mechanism and a kinetic mathematic model of the phenol catalytic oxidation were studied. The acid effect of reaction system, structural effect of the complexes, and effect of temperature on the rate of the phenol catalytic oxidation by the mimetic peroxidase were discussed. The results show that the Schiff base cobalt(II) complexes and their metallomicelles as peroxidase mimics exhibit good catalytic activity and similar catalytic character to natural enzyme.     

Study on the Phenolic Oxidation by H2O2 Using Metallomicelles Composed of Dinuclear Copper(II) Complex as Synthetic Peroxidases

A dinuclear copper(II) complex [Cu₂(oxheel)] was synthesized and its structure was analyzed. This compound was then mixed with a surfactant (Brij35 or LSS) to form a metallomicelle, which would catalyze the phenol oxidation with the hydrogen peroxide (H₂O₂). The reaction mechanism and the mathematic model for the kinetics of this reaction were proposed, and the effect of the molar ratio between H₂O₂ and catalyst, of the temperature and of the pH levels on the rate of catalytic reaction were studied.     

FeZSM-5/N2O催化氧化苯制苯酚

苯一步氧化制苯酚，是有机物氧化合成中富有挑战性的研究课题之一。该文着重论述了在FeZSM-5及其一系列沸石催化剂上，应用氧化亚氮作为氧化剂使苯直接氧化制苯酚的研究进展。这一系列催化剂体系的特殊之处在于通过氧化亚氮在沸石分子筛上的分解获得具有催化活性的a－氧。详细讨论了在沸石分子筛上形成特殊结构的铁氧化物作为催化活性中心这一观点。由于这种催化体系对苯直接氧化制苯酚的反应有着很高的选择性，因此，这种比较经济和安全的制备苯酚的方法引起了人们的广泛关注。     

新的聚苯乙烯负载锌化合物:高效苯酚氧化催化剂(英文)

The novel recyclable free –ONNO– tetradentate Schiff base ligand N,N′‐bis(2‐hydroxy‐3‐ methox‐ybenzaldehyde)4‐methylbenzene‐1,2‐diamine (3‐MOBdMBn) was synthesized. Complexation of this ligand with zinc(3‐MOBdMBn‐Zn) was performed, and the catalytic activity of the complex was evaluated. The polymer‐supported analog of this complex(P‐3‐MOBdMBn‐Zn) was synthesized, and its catalytic activity was studied. These free and polymer‐anchored zinc complexes were prepared by the reactions of metal solutions with one molar equivalent of unsupported 3‐MOBdMBn or P‐3‐MOBdMBn in methanol under nitrogen. The catalytic activity of 3‐MOBdMBn‐Zn and P‐3‐MOBdMBn‐Zn was evaluated in phenol oxidation. The activity of P‐3‐MOBdMBn‐Zn was signif‐icantly affected by the polymer support, and the rate of phenol conversion was around 50% for polystyrene‐supported 3‐MOBdMBn. The experimental results indicated that the reaction rate was affected by the polymer support, and the rate of phenol conversion was 1.64 μmol/(L·s) in the presence of polystyrene‐supported 3‐MOBdMBn.     

A Kinetic Study of Phenolic Oxidation by H2O2 Using the Schiff Base Complexes As Mimetic Peroxidases

The Schiff base complexes containing a transition metal ion, Co^II and Cu^II, were used as mimetic peroxidase in the catalytic oxidation of phenol by H₂O₂. The characteristic spectra of the Schiff base complexes in H₂O₂-buffered solution were recorded and analyzed, respectively. The mechanism and the kinetic mathematic model of the phenol catalytic oxidation were studied. The results showed that the Schiff base complexes containing the transition metal ion, Co^II and Cu^II, as peroxidase mimics exhibited good catalytic activity and the character of the peroxidase in the catalytic oxidation of phenol by H₂O₂ under different conditions.     

Oxidation of phenol by hydrogen peroxide catalyzed by metal-containing poly(amidoxime) grafted starch

Polyamidoxime chelating resin was obtained from polyacrylonitrile (PAN) grafted starch. The nitrile groups of the starch-grafted polyacrylonitrile (St-g-PAN) were converted into amidoximes by reaction with hydroxylamine under basic conditions. The synthesized graft copolymer and polyamidoxime were characterized by FTIR, TGA and elemental microanalysis. Metal chelation of the polyamidoxime resin with iron, copper and zinc has been studied. The produced metal-polyamidoxime polymer complexes were used as catalysts for the oxidation of phenol using H(2)O(2) as oxidizing agent. The oxidation of phenol depends on the central metal ion present in the polyamidoxime complex. Reuse of M-polyamidoxime catalyst/H(2)O(2) system showed a slight decrease in catalytic activities for all M-polyamidoxime catalysts.