李延斌,高保娇,杜瑞奎

• 1:中北大学化学工程系

摘要(Abstract)：

利用接枝于微米级硅胶表面的聚乙烯亚胺(PEI)与氯乙酸反应,制备了亚胺乙酸(IAA)型复合螯合微粒IAA-PEI/SiO2,再使之与铜(Ⅱ)盐配位螯合,形成固载化亚胺乙酸-铜配合物Cu(Ⅱ)-IAA-PEI/SiO2。将微粒Cu(Ⅱ)-IAA-PEI/SiO2用作非均相催化剂,用于分子氧氧化乙苯与苯甲醇的氧化反应,研究了催化活性与催化氧化机理。研究结果表明,固载化亚胺乙酸-铜配合物Cu(Ⅱ)-IAA-PEI/SiO2可有效地催化分子氧氧化乙苯的过程,主产物为苯乙酮,在适宜的温度(130℃)与适宜的催化剂用量条件下,苯乙酮的得率为40%。Cu(Ⅱ)-IAA-PEI/SiO2与2,2,6,6-四甲基哌啶氧自由基(TEMPO)所构成的复合催化剂,可高效地催化分子氧氧化苯甲醇的氧化反应,产物为苯甲醛,在温和条件下(常压下的氧气、80℃),苯甲醇的转化率可达75%。

关键词(KeyWords)： 亚胺乙酸-铜配合物;2,2,6,6-四甲基哌啶氧自由基;氧化催化;分子氧;乙苯;苯甲醇

Abstract:

Keywords:

基金项目(Foundation): 山西省自然科学基金资助项目(201002100843)

作者(Author): 李延斌,高保娇,杜瑞奎

参考文献(References)：

• [1]Navarro M,Escobar A,Landaeta V R,et al.Catalytic oxidation of tetralin by biologically active copper and palladium complexes[J].Applied Catalysis A:General,2009,363(1-2):27-31.
• [2]BiswasA N,Das P,Agarwala A,et al.Selective hydroxylation of alkanes catalyzed by iron(IV)corrole[J].Journal of MolecularCatalysis A:Chemical,2010,326(1-2):94-98.
• [3]Anisia K S,Kumar A.Oxidation of cyclohexane with molecular oxygen in presence of characterized macrocyclic heteronuclearFeCu complex catalyst ionically bonded to zirconium pillared montmorillonite clay[J].Journal of Molecular Catalysis A:Chemical,2007,271(1-2):164-179.
• [4]Yoshihiko Moro-oka.Reactivities of active oxygen species and their roles in the catalytic oxidation of inactive hydrocarbon[J].Catalysis Today,1998,45(1-4):3-12.
• [5]Akita M,Yoshihiko Moro-oka.Reductive activation of dioxygen:A new concept for the catalytic oxidation[J].Catalysis Today,1998,44(1-4):183-188.
• [6]Suzuki M,Ishikawa T,Harada A,et al.Chemical mechanism of dioxygen activation by manganese(III)Schiff base compound in thepresence of aliphatic aldehydes[J].Polyhedron,1997,16(15):2553-2561.
• [7]Manzur J,García A M,Vega A,et al.Synthesis and structure of copper(II)complexes with L–OH(L–OH=2,6-bis-[N-(2-pyridylethyl)-formidoyl]-4-methyl-phenol)[J].Polyhedron,2007,26(1-2):115-122.
• [8]Singh A,Patra S,Lee J-A,et al.An artificial enzyme-based assay:DNA detection using a peroxidase-like copper–creatininecomplex[J].Biosensors and Bioelectronics,2011,26(12):4798-4803.
• [9]Figiel P J,Kirillov A M,Karabach Y Y,et al.Mild aerobic oxidation of benzyl alcohols to benzaldehydes in water catalyzed byaqua-soluble multicopper(II)triethanolaminate compounds[J].Journal of Molecular Catalysis A:Chemical,2009,305(1-2):178-182.
• [10]Ahmad J U,Figiel P J,R is nen M T,et al.Aerobic oxidation of benzylic alcohols with bis(3,5-di-tert-butylsalicylaldimi-ne)copper(II)complexes[J].Applied Catalysis A:General,2009,371(1-2):17-21.
• [11]Ratnasamy P,Srinivas D.Selective oxidations over zeolite-and mesoporous silica-based catalysts:Selected examples[J].CatalysisToday,2009,141(1-2):3-11.
• [12]Gupta K C,Sutar A K,Lin C-C.Polymer-supported Schiff base complexes in oxidation reactions[J].Coordination ChemistryReviews,2009,253(13-14):1926-1946.
• [13]Jana1 S,Bhunia S,Dutta B,et al.Anchoring of copper(II)complexes onto the organically modified MCM-41:Preparation,characterization and catalytic epoxidation[J].Applied Catalysis A:General,2011,392(1-2):225-232.
• [14]LI Yan-bin(李延斌),GAO Bao-jiao(高保娇),WANG Rui-xing(王瑞欣).Preparation of imido-acetic acid-type compositechelationg adsorption material IAA-PEI/SiO2based on PEI and preliminarily exploring chelating adsorption property(基于PEI的亚氨乙酸型复合螯合吸附材料IAA-PEI/SiO2的制备及其螯合吸附特性初探)[J].Journal of Function Polymers(功能高分子学报),2010,23(3):236-243.
• [15]LI Yan-bin(李延斌),GAO Bao-jiao(高保娇),DU Rui-kui(杜瑞奎).Chelating adsorption behaviour and adsorptionthermodynamics of imido-acetic acid-type composite chelating adsorption material IAA-PEI/SiO2for heavy metal Ions(亚氨乙酸型复合螯合吸附材料IAA-PEI/SiO2对重金属离子的螯合吸附行为与吸附热力学研究)[J].The Chinese Journal of ProcessEngineering(过程工程学报),2011,11(2):221-226.
• [16]Qin J W,Fu Z H,Liu Y C,et al.Aerobic oxidation of ethylbenzene Co-catalyzed by N-hydroxyphthalimide and oxobis(8-quinolinolato)vanadium(IV)complexes[J].Chinese Journal of Catalysis,2011,32(6-8):1342-1348.