后修饰法合成介孔钴金属有机框架及其催化烯烃环氧化

doi:10.3724/SP.J.1095.2014.30511

摘要/Abstract

摘要： 通过后修饰水热合成法制备了新型Co2+配位的金属有机框架材料，并采用红外、电感耦合等离子分析和N2吸附等技术手段对其进行了表征。在氧气/异丁醛反应体系中，介孔钴金属有机框架对烯烃环氧化反应表现出较高的活性。其中，环辛烯的转化率及环氧环辛烷的选择性分别达到了94%和91%,转化频率(TOF)值为509 h-1。催化剂循环使用5次之后，其结构和活性无明显变化。

关键词: 金属有机框架, 后修饰, 烯烃环氧化, 分子氧

Abstract: A newly Co²⁺ coordinated metal-organic framework had been successfully synthesized via one-step post-functionalization hydrothermal method and characterized through Fourier Transform Infrared Spectrometer, N₂ adsorption and Inductively Coupled Plasma. Using O₂ as oxidant, mesoporous cobalt metal-organic framework was investigated as a good performed heterogeneous catalytic material for various olefins epoxidation. Among them, the conversion of cyclooctene and selectivity of epoxycyclooctane were 94% and 91%, respectively, the turnover frequency was 509 h^-1. The PCN-100(Co) exhibited excellent stabilities in 5 recycles without any loss of its catalytic performance.

Key words: metal-organic framework, post-functionalization, olefins epoxidation, molecular oxygen

中图分类号:

O643.3

沙莎, 李军, 庄长福, 刘术侠, 高爽. 后修饰法合成介孔钴金属有机框架及其催化烯烃环氧化[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30511.

SHA Sha1,2, LI Jun2, ZHUANG Changfu2, LIU Shuxia1*, GAO Shuang2*. A New Mesoporous Cobalt Metal-organic Framework was Synthesized by Post-functionalization and Its Application for the Epoxidation of Olefins[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30511.

参考文献

[1] Arnold U,Habicht W,Doring M. Metal-doped Epoxy Resins-new Catalysts for the Epoxidation of Alkenes with High Long-term Activities[J]. Adv Synth Catal,2006，348:142-150.

[2] Vaz A D,McGinnity D F,Coon M J. Epoxidation of Olefins by Cytochrome P450:Evidence from Site-specific Mutagenesis for Hydroperoxo-iron as an Electrophilic Oxidant[J]. Natl Acad Sci,1998，95:3555-3560.

[3] Dhakshinamoorthy A,Alvaro M,Garcia H. Aerobic Oxidation of Cycloalkenes Catalyzed by Iron Metal Organic Framework Containing N-Hydroxyphthalimide[J]. J Catal,2012，289:259-265.

[4] Kamata K,Yonehara K,Sumida Y,et al. Efficient Epoxidation of Olefins with ≥ 99% Selectivity and Use of Hydrogen Peroxide[J]. Science,2003，300:964-966.

[5] Tonigold M,Lu Y,Bredenkotter B,et al. Heterogeneous Catalytic Oxidation by MFU-1:A Cobalt(Ⅱ)-containing Metal-organic Framework[J]. Angew Chem Int Ed,2009，48:7546-7550.

[6] Zuwei X,Ning Z,Yu S,et al. Reaction-controlled Phase-transfer Catalysis for Propylene Epoxidation to Propylene Oxide[J]. Science,2001，292:1139-1141.

[7] Hill C L,Brown R B. Sustained Epoxidation of Olefins by Oxygen Donors Catalyzed by Transition Metal-substituted Polyoxometalates, Oxidatively Resistant Inorganic Analogs of Metalloporphyrins[J]. J Am Chem Soc,1986，108:536-538.

[8] Katsuki T. Catalytic Asymmetric Oxidations Using Optically Active (salen)Manganese(Ⅲ) Complexes as Catalysts[J]. Coord Chem Rev,1995，140:189-214.

[9] Monnier J R. The Direct Epoxidation of Higher Olefins Using Molecular Oxygen[J]. Appl Catal A General,2001，221:73-91.

[10] Cheetham A K,Ferey G,Loiseau T. Open-framework Inorganic Materials[J]. Angew Chem Int Ed,1999，38:3268-3292.

[11] Kitagawa S,Kitaura R,Noro S I. Functional Porous Coordination Polymers[J]. Angew Chem Int Ed,2004，43:2334-2375.

[12] LI Linqing,LV Ying,LI Jun,et al. Application of Metal-organic Frameworks in Olefin Oxidation[J]. Prog Chem,2012，24:747-756(in Chinese).

黎林清,吕迎,李军,等. 金属-有机骨架材料在烯烃氧化中的应用[J]. 化学进展,2012，24:747-756.

[13] Latroche M,Surble S,Serre C,et al. Hydrogen Storage in the Giant-pore Metal-organic Frameworks MIL-100 and MIL-101[J]. Angew Chem Int Ed,2006，45:8227-8231.

[14] Zhao D,Timmons D J,Yuan D,et al. Tuning the Topology and Functionality of Metal-organic Frameworks by Ligand Design[J]. Acc Chem Res,2010，44:123-133.

[15] Fang Q R,Yuan D Q,Sculley J,et al. Functional Mesoporous Metal-organic Frameworks for the Capture of Heavy Metal Ions and Size-selective Catalysis[J]. Inorg Chem,2010，49:11637-11642.

[16] Rowsell J L,Yaghi O M. Strategies for Hydrogen Storage in Metal-organic Frameworks[J]. Angew Chem Int Ed,2005，44:4670-4679.

[17] Beier M J,Kleist W,Wharmby M T,et al. Aerobic Epoxidation of Olefins Catalyzed by the Cobalt-based Metal-organic Framework STA-12(Co)[J]. Chem Eur J,2012，18:887-898.

[18] Zhang J,Biradar A V,Pramanik S,et al. A New Layered Metal-organic Framework as A Promising Heterogeneous Catalyst for Olefin Epoxidation Reactions[J]. Chem Commun,2012，48:6541-6543.

[19] Kang Z,Zhang G,Li H,et al. A Cobalt-based 3D Porous Framework with Excellent Catalytic Ability for the Selective Oxidation of cis-Cyclooctene[J]. Dalton Trans,2013，42:9423-9427.

[20] Zhang A,Li L,Li J,et al. Epoxidation of Olefins with O2 and Isobutyraldehyde Catalyzed by Cobalt(Ⅱ)-containing Zeolitic Imidazolate Framework Material[J]. Catal Commun,2011，12:1183-1187.

[21] Annis D A,Jacobsen E N. Polymer-supported Chiral Co(salen) Complexes:Synthetic Applications and Mechanistic Investigations in the Hydrolytic Kinetic Resolution of Terminal Epoxides[J]. J Am Chem Soc,1999，121:4147-4154.

[22] Wang X S,Ma S,Sun D,et al. A Mesoporous Metal-organic Framework with Permanent Porosity[J]. J Am Chem Soc,2006，128:16474-16475.

[23] Brown K,Zolezzi S,Aguirre P,et al. [Cu(H2btec)(bipy)]∞:A Novel Metal Organic Framework(MOF) as Heterogeneous Catalyst for the Oxidation of Olefins[J]. Dalton Trans,2009:1422-1427.

[24] W entzel B B,Alsters P L,Feiters M C,et al. Mechanistic Studies on the Mukaiyama Epoxidation[J]. J Org Chem,2004，69:3453-3464.