双核金属酞菁的制备及其对二苯并噻吩的催化氧化性能

采用微波法合成了双核酞菁钴,并采用红外光谱、紫外可见光谱、热重分析对其进行表征。以二苯并噻吩(DBT)为反应底物,考察双核酞菁钴对DBT催化氧化性能,筛选出较优催化剂,并进行脱硫反应工艺条件优化。结果表明,双核酞菁钴具有较好的催化性能,在室温下、双核酞菁钴用量为0.01 g(cat)/5 m L、空气流量为80 m L/min、反应温度为40℃、反应1 h,DBT脱硫率达到97.17%。催化剂重复使用5次,催化效果无明显下降。氧化产物经红外光谱、质谱分析为DBTO2。对芳香烃及烯烃进行了催化氧化实验,发现该工艺对油品的质量基本无影响。     

新型钴酞菁接枝温敏聚合物的制备及性能

采用2,4,6-三氯-1,3,5-三嗪对四氨基钴酞菁进行改性,并以共价键接枝到聚N-异丙基丙烯酰胺上制得一种新型温敏性高分子催化剂——钴酞菁接枝温敏聚合物,并采用UV-Vis、TG等对其进行表征.对钴酞菁接枝温敏聚合物、温敏聚合物和小分子金属酞菁进行溶解性测试,结果表明与四氨基钴酞菁相比,所合成的钴酞菁接枝温敏聚合物能溶解于水和大多数有机溶剂,且该聚合物水溶液具有良好的温敏性,其最低临界溶解温度(LCST)为34.5℃.采用浊度法考察了不同比例的混合溶剂(乙醇/水、DMF/水)对LCST的影响,结果表明随着有机溶剂含量的增加,LCST先下降后升高,而当有机溶剂增加到一定程度时温敏性消失.本文还考察了钴酞菁接枝温敏聚合物对2-巯基乙醇的催化活性,结果表明随着温度升高,催化活性也不断提高,而当温度超过LCST时催化活性急剧下降,聚合物从溶液中析出.基于这些特性,该温敏聚合物负载酞菁作为一种新型的催化剂可实现均相催化、异相分离.     

金属酞菁催化巯基乙醇氧化的研究

研究了２，９，１６，２３－四羧基铁（Ⅲ），钴（Ⅱ）酞菁及固载在硅胶上的２，９，１６，２３－四甲酰胺基铁（Ⅲ），钴（Ⅱ）酞菁，在水溶液中催化硫醇氧化的反应，比较了几种催化剂的性能，考察了反应条件对硫醇氧化反应的影响，提出了反应机理，结果表明，当硫醇浓度较高地，固载后的酞菁铁，其催化性能优于或接近未固载的酞菁铁；当而硫醇浓度较低时，固载后的金属酞菁显示出更接近实际的优越性，而两种金属酞菁固载后仍具有良     

轻质油品中硫醇的催化氧化脱除

二次加工得到的轻质油品常常由于含有较多硫醇而造成质量低下。Merox脱硫醇(即脱臭)法虽已成熟,但作为催化剂的磺化酞菁钴或聚酞菁钴,不仅合成与制备条件苛刻,而且其催化氧化活性对这些条件又十分敏感。本文考察了一组金属离子插入交换蒙脱石的催化氧化脱臭性能。结果表明,C_0~(2+)蒙脱石不仅制备简便,而且具有与磺化酞菁钴极相近的脱臭性能。     

碳纳米纤维增强钴酞菁催化氧化染料的性能研究

将氨基钴酞菁（CoTAPc）以共价键的形式负载到碳纳米纤维（CNF）上制备碳纳米纤维负载钴酞菁催化剂（CoTAPc-CNF）,利用原子吸收光谱、紫外-可见光吸收光谱、衰减全反射-红外光谱等方法对CoTAPc-CNF进行表征.选用具有氧杂蒽结构的罗丹明6G（Rh6G）为主要研究对象,研究CoTAPc-CNF对Rh6G的催化氧化性能,考察了温度、pH、NaCl、异丙醇等对CoTAPc-CNF催化性能的影响.结果表明,CoTAPc-CNF在常温中性条件下能有效催化氧化Rh6G;随着温度和pH的增加,CoTAPc-CNF催化氧化Rh6G速率逐渐提高;NaCl和异丙醇的加入,没有抑制催化氧化反应的进行,相反大大提高了Rh6G的降解速率,这与一般羟基自由基占主导的高级氧化体系完全不同;进一步采用电子顺磁共振波谱法证实CoTAPc-CNF/H2O2体系确实为非羟基自由基催化机理.另外,研究发现CoTAPc-CNF还能有效催化氧化其他共轭结构的染料,如偶氮染料酸性橙7（AO7）、三芳甲烷染料碱性绿1（BG1）.因此,本文探索的CoTAPc-CNF/H2O2非羟基自由基催化反应体系在处理成分复杂的实际印染废水中具有较好的应用前景.     

钴(II)酞菁与巯基乙醇轴向配位反应的动力学

用停流法研究了2,9,16,23-四羧基钴（Ⅱ）酞菁与2-巯基乙醇轴向配位的快速反应动力学,提出了较为合理的反应机理,用非线性及线性拟合的方法求得了各基元步骤的动力学参数,探讨了温度、pH等因素对反应的影响．     

四羧基金属酞菁负载纤维素纤维的制备及其消臭性能研究

合成了四羧基铁酞菁(Fe-CPc)和四羧基钴酞菁(Co-CPc),并对其进行了元素分析和红外光谱表征.在酸性条件下,将四羧基金属酞菁负载到改性纤维素纤维上,制备得到消臭纤维.实验结果表明,在室温条件下,四羧基铁酞菁消臭纤维(FePcF)、四羧基钴酞菁消臭纤维(CoPcF)和混合金属酞菁消臭纤维(CoFePcF)3种功能性纤维都能有效去除甲硫醇、硫化氢、氨气和三甲胺,甲硫醇和硫化氢按催化氧化机理除去,而氨气和三甲胺按酸碱中和机理除去;3种消臭纤维对甲硫醇和硫化氢的消臭效果为CoFePcF>CoPcF>FePcF.     

负载离子对型酞菁钴双功能硫醇氧化催化剂

将分别带有正、负电荷基团的季铵盐酞菁钴CoPc[N(CH3 ) 3 I]4 和磺酸盐酞菁钴CoPc(SO3 Na) 4溶解在一起 ,负载在由水滑石热分解而成的MgAl复合氧化物碱性载体上 ,制成负载离子对型酞菁钴催化剂 ,其所具有的碱性、氧化性双功能的特征能够有效地催化 1 辛硫醇氧化 .当这两种酞菁钴配合物的摩尔比为 1时 ,催化活性最高 ,并且稳定性也有较明显的改善 .这种双功能催化剂体系具有酶催化的特点 ,即遵循双底物 ( 1 C8H17SH和O2 )Michaelis Menten动力学规律 ;表观活化能Ea=5 0 .4kJ·mol-1.在一定范围内提高二元酞菁钴混合物的负载量 ,单位酞菁钴中心的活性基本保持恒定 ,表明形成的二聚体络合物可在一定程度上抑制酞菁钴分子的聚集 ,改善催化剂的性能 .同时 ,增大Mg(Al)O载体量即碱中心数 ,有利于催化剂活性和稳定性的提高 .这类新型双功能催化剂具有工业应用的前景 .     

平面双核铜酞菁催化氧化硫醇

采用苯酐-尿素路线合成了八羧基铜酞菁(CuPc)和十二羧基双核铜酞菁(Cu₂Pc₂), 研究了两种铜酞菁对巯基乙醇的催化活性, 推测出了双核铜酞菁的催化机理, 并考察了pH值、催化剂浓度和温度对双核铜酞菁催化氧化巯基乙醇的影响. 实验发现, 单核铜酞菁对巯基乙醇无催化活性, 而双核铜酞菁对巯基乙醇有较高的催化活性; 双核铜酞菁的催化活性在pH=11时最大; 催化活性随催化剂浓度和温度升高而提高; 此催化反应为吸热反应.     

酞菁钴液相催化氧化羰基硫(COS)的研究

本文首次报道在液相中，用金属酞菁催化氧化脱除羰基硫（COS）。发现COS先被水解成HS~－，HS~-再被氧化成S，酞菁钴（CoPC）的活性高于其它金属酞菁（MPC），酞菁苯环上推电子基因使酞菁的催化活性提高，双核酞菁钴的活性高子单核酞菁钴。D296树脂负载的酞菁钴的催化活性高于均相酞菁钴的活性。     

Catalytic properties of cobalt complexes with tetrapyrazino porphyrazine and phthalocyanine derivatives

The catalytic activity of cobalt complexes with octaphenyltetrapyrazinoporphyrazine and phthalocyanine derivatives containing branched peripheral substituents is studied in heterogeneous catalysis of the oxidation of sodium diethyldithiocarbamate (SDC) with atmospheric oxygen. Cobalt phthalocyanines are shown to display higher catalytic activity than cobalt complexes with octaphenyltetrapyrazinoporphyrazine. The highest efficiency of heterogeneous catalysts is attained at temperatures of 298–303 K.     

Oxidation of benzyl alcohol by novel peripherally and non-peripherally modular C2-symmetric diol substituted cobalt (II) phthalocyanines

In this study, a modular ligand structure was designed by altering the binding position of the phenyl group at backbone of hydrobenzoin. A series of regio isomeric substituted phthalonitriles derived from this modular C₂-symmetric ligand was synthesized and characterized. Then, eight cobalt (II) phthalocyanines (CoPc) were obtained from the reaction of phthalonitrile derivatives with cobalt (II) chloride. The catalytic activities of synthesized cobalt (II) phthalocyanines were tested for benzyl alcohol oxidation in acetonitrile using tert-butylhydroperoxide as the oxygen source and in the presence of N-bromosuccinimide as an additive at 80 °C for 5 hr of the reaction. In this sense, the effect of substrate to catalyst ratio and oxidant to catalyst ratio have been studied in detail for getting the highest benzaldehyde selectivity (up to 83%). The effect of structural design of substituents at peripheral or non-peripheral positions of phthalocyanine skeleton on the catalytic activity performance of cobalt (II) phthalocyanines in benzyl alcohol oxidation was also clarified. All newly synthesized compounds are characterized by FT-IR, ¹H NMR, IR, UV–Vis and MALDI-TOF MS spectral data.     

Complexes of Copper(I) with Dimercapto Compounds as Catalysts for Oxidation of Mercaptans and Hydrogen Sulfide with Molecular Oxygen in Aqueous Solutions

The conditions for formation of complexes of copper(I) with mercapto compounds in aqueous- alkaline solutions and the catalytic activity of these complexes in oxidation of mercaptans and hydrogen sulfide was studied. The kinetic characteristics of these catalysts were compared with those of catalysts based on cobalt phthalocyanines. A method was proposed for suppressing formation of the thiosulfate ion in oxidation of H₂S to elemental sulfur.     

无机膜反应器用于正丁烷氧化制顺丁烯二酐的研究(英文)

通过浸渍法在中孔γ－Ａｌ２Ｏ３膜上制备出Ｖ－Ｐ－Ｃｏ－Ｃｅ－Ｏ多组分金属氧化物催化膜,将之应用于非燃料电池型催化膜反应器并研究其可行性及正丁烷制顺丁烯二酐的反应特性。考察了反应温度、空速和吹好气流速对催化活性的影响,对膜反应器的稳定性也进行了简单的测试。实验证明,与固定床相比,膜反应器具有更高的反应转化率和选择性。     

Electrocatalytic activity of cobalt phthalocyanine CoPc adsorbed on a graphite electrode for the oxidation of reduced L-glutathione (GSH) and the reduction of its disulfide (GSSG) at physiological pH

Modified electrodes coated by adsorbed cobalt phthalocyanines are known to show substantial electrocatalytic activity for the electro-oxidation of several thiols in alkaline aqueous solution. In this context, we explore in this study the electrocatalytic activity of adsorbed cobalt phthalocyanine (CoPc) on ordinary pyrolytic graphite electrode for the oxidation of reduced L-glutathione GSH and the reduction of its disulfide GSSG at physiological pH. To do so, cyclic and rotating disk voltammetries were performed and the amperometric results show that a stable electrochemical sensing material, with good reproducibility and sensitivity (in accordance with the concentrations of GSH expected in biological media), can be easily achieved. This opens the way for the design of an electrochemical sensor able to detect these two analytes in biologically relevant experimental conditions (in terms of pH).     

正丁烷氧化制顺酐Ce基复合氧化物VPO催化剂研制

在用共沉淀方法制备的Ｃｅ－Ｆｅ复合氧化物中,加入ＶＰＯ化剂制备复合ＶＰＯ催化剂;井测试结构、氧化还原性能以及催化性能。实验结果表明,Ｃｅ－Ｆｅ复合氧化物的组成和数量均对复合ＶＰＯ催化剂的结构产生较大的影响,Ｃｅ－Ｆｅ复合氧化物的加入,提高了复合ＶＰＯ催化剂表面低温氧物种的活性,降低了品格氧物种的ＴＰＲ出峰温度,无论在有无气相氧条件下,复合ＶＰＯ催化剂的晶格氧均有良好的反应催化性能。     

室温下钯-金属酞菁/分子筛复合催化剂催化甲烷选择氧化制甲醇

 在交换了 Fe2+, Co2+或 Cu2+的 Y 型分子筛上, 采用苯酐-尿素固相合成法制备了组装在 Y 型分子筛超笼中的金属酞菁类催化剂. 以 H2O2 为氧化剂, 考察了该金属酞菁/分子筛复合物上甲烷选择氧化制甲醇反应的性能, 并优化了反应条件. 结果表明, 在室温下, 金属酞菁/分子筛复合催化剂 FePc/Y, CoPc/Y 和 CuPc/Y 对 H2O2 氧化甲烷反应均有催化作用. 在这些复合物上进一步担载可催化 H2O2 原位生成的 Pd, Au 或 PdAu 贵金属, 并考察了其催化分子氧选择氧化甲烷反应的性能. 贵金属与金属酞菁/分子筛复合催化剂的偶合实现了室温下分子氧对甲烷的活化. 其中, Pd 与 CuPc/Y 间的协同效应使得室温下甲烷选择氧化反应活性有了较大提高.     

Cobalt Sulfate as a Recyclable Catalyst for Chemoselective Synthesis of Diacetates from Aldehydes

A mild and efficient method for diacetylation reaction was developed,by which diacetate could be achieved through the reaction of aldehyde with acetic anhydride,in the presence of cobalt sulfate,with an admirable yield,at room temperature,without solvent.The catalyst could be recycled six times without a distinct loss of activity.     

Multinuclear cobalt–salen complexes with phenylene linker for epoxide polymerizations

Di‐ and trinuclear cobalt (Co)–salen complexes with a benzene ring as a rigid linker were explored for epoxide polymerizations. The dinuclear Co–salen complex with a 1,2‐phenylene linker showed higher catalytic activity than the dinuclear Co–salen complex with a 1,3‐phenylene linker and the trinuclear Co–salen complex with a 1,3,5‐benzenetriyl linker for the copolymerization of propylene oxide (PO) with carbon dioxide. A combination of the absolute configuration of the two Co–salen moieties was found to affect its catalytic activity. The optimized dinuclear Co–salen complex with a heterochiral combination demonstrated highest activity and maintained its catalytic activity under a low catalyst concentration. The heterochiral dinuclear Co–salen complex also showed high activity for the copolymerization of PO with cyclic anhydride. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2150–2159