多金属氧酸盐催化苯甲醇的选择性氧化：一个绿色可循环的高效催化氧化体系

doi:10.3724/SP.J.1095.2014.30534

摘要/Abstract

摘要： 以Keggin结构的几类杂多酸和三乙胺（TEA）为原料，通过简单的酸碱反应合成了相应杂多酸的TEA盐。并以它们作为催化剂，30％H2O2作氧化剂，在不使用长链相转移剂的条件下，研究了它们催化苯甲醇选择氧化制备苯甲醛的反应性能。结果表明，该类催化剂在苯甲醇的选择氧化反应中具有比相应杂多酸更高的催化活性或选择性。其中[TEAH]H2PW12O40为最佳催化剂，在适宜的反应条件下，该催化剂上苯甲醇转化率可达99.5％以上，苯甲醛选择性达~100％。催化剂可以被分离和循环使用多次，活性、选择性基本不变。用水作溶剂，避免了有机溶剂的使用，是一个高效、绿色的苯甲醛选择氧化体系。

关键词: 苯甲醇, 选择氧化, 多金属氧酸盐, 催化

Abstract: Several triethylamine(TEA) salts of heteropolyacids were synthesized by acidbase reaction using Keggin-type heteropolyacids and TEA as raw materials. These salts were used to catalyze the oxidation of benzyl alcohol to benzaldehyde in water with 30% aqueous hydrogen peroxide as oxidant without employment of phase transfer catalyst with long chain. These salts possess higher catalytic activities or selectivities than the corresponding acids. [TEAH]H2PW12O40 exhibits the best performance of all catalysts. Under the optimum reaction conditions, the conversion of benzyl alcohol and the selectivity of benzaldehyde is over 99.5% and ~100%, respectively, over [TEAH]H2PW12O40. After the reaction, the catalyst can be isolated and used for next oxidation cycle, and the activity and selectivity are maintained in recycle. In view of the fact that water is used as reaction medium instead of organic solvent, this system is effective and green for selective oxidation of benzyl alcohol.

Key words: benzyl alcohol, selective oxidation, polyoxometalates, catalysis

中图分类号:

O643.3

苏浩, 杨春. 多金属氧酸盐催化苯甲醇的选择性氧化：一个绿色可循环的高效催化氧化体系[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30534.

SU Hao, YANG Chun*. Selective Oxidation of Benzyl Alcohol Catalyzed by Polyoxometalates:A Green Recyclable Catalytic System with High Performance[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30534.

参考文献

[1] FAN Chunling,LIU Wenming. Advancements on Research of Selective Oxidation of Toluene to Benzaldehyde[J]. Chem Ind Times,2008,22(9):61-67(in Chinese).

樊春玲,刘文明. 甲苯选择氧化制苯甲醛的研究进展[J]. 化工时刊,2008,22(9):61-67.

[2] WU Xingan,YIN Juanjuan,HU Zaijun. Progress in Benzaldehyde Synthesis[J]. Spec Petrochem,2002,(4):57-63(in Chinese).

吴鑫干,尹娟娟，胡在君. 苯甲醛的合成进展[J]. 精细石油化工,2002,(4):57-63.

[3] Ishii Y,Yamawaki K,Ura T,et al. Hydrogen Peroxide Oxidation Catalyzed by Heteropoly Acids Combined with Cetylpyridinium Chloride:Epoxidation of Olefins and Allylic Alcohols,Ketonization of Alcohols and Diols, and Oxidative Cleavage of 1,2-Diols and Olefins[J]. J Org Chem,1988,53(15):3587-3593.

[4] Zhang S J,Zhao G D,Gao S,et al. Secondary Alcohols Oxidation with Hydrogen Peroxide Catalyzed by [n-C16H33N(CH3)3]3PW12O40:Transform-and-retransform Process Between Catalytic Precursor and Catalytic Activity Species[J]. J Mol Catal A:Chem,2008,289(1/2):22-27.

[5] Zhang F M,Guo M P,Ge H Q,et al. Hydroxylation of Benzene with Hydrogen Peroxide over Highly Efficient Molybdovanadophosphoric Heteropoly Acid Catalysts[J]. Chinese J Chem Eng,2007,15(6):895-898.

[6] Yadav G D,Mistry C K. Oxidation of Benzyl Alcohol under a Synergism of Phase Transfer Catalysis and Heteropolyacids[J]. J Mol Catal A:Chem,2001,172(1/2):135-149.

[7] LI Guixian,WANG Jianmin,HU Dongcheng,et al. Study of Selective Oxidation of Benzyl Alcohol to Benzaldehyde over Dawson-type Cetyltrimethylammonium Molybdovanadophosphate[J]. J Mol Catal(China),2005,19(3):182-187(in Chinese).

李贵贤，王建民，胡东成,等. Dawson-型磷钼钒杂多酸盐相转移选择催化氧化苯甲醇合成苯甲醛反应研究[J]. 分子催化,2005,19(3):182-187.

[8] Weng Z H,Wang J Y,Zhang S H,et al. Synthesis and Characterization of a Polymer-supported Heteropolytungstate Catalyst for Oxidation of Benzyl Alcohol[J]. Catal Commun,2008,10(2):125-128.

[9] Manyar H G,Chaure G S,Kumar A. Supported Polyperoxometallates:Highly Selective Catalyst for Oxidation of Alcohols to Aldehydes[J]. J Mol Catal A:Chem,2006,243(2):244-252.

[10] Weng Z H,Liao G X,Wang J Y,et al. Selective Oxidation of Benzyl Alcohol with Hydrogen Peroxide over Reaction-Controlled Phase-Transfer Catalyst[J]. Catal Commun,2007,8(10):1493-1496.

[11] Weng Z H,Wang J Y,Jian X G. A Reusable and Active Lacunary Derivative [PW11O39]7- as Benzyl Alcohol Oxidation Catalyst with Hydrogen Peroxide[J]. Catal Commun,2008,9(8):1688-1691.

[12] Ma B C,Zhang Y S,Ding Y,et al. A Water-Soluble Dilacunary Silicotungstate as an Effective Catalyst for Oxidation Alcohols in Water with Hydrogen Peroxide[J]. Catal Commun,2010,11(9):853-857.

[13] Zhao W,Ding Y,Ma B C,et al. Lacunary Derivative [HPW9O34]8- as Reusable and Active Catalyst for Alcohol Oxidation in Water[J]. Synth Commun,2012,42(4):554-562.

[14] ZHANG Fumin,GUO Maiping,GE Hanqing,et al. A New Method for Synthesis of Molybdovanadophosphoric Heterpoly Acids and Their Catalytic Activities[J]. Chem Ind Eng Prog,2006,25(10):1171-1174(in Chinese).

张富民，郭麦平，葛汉青,等. 合成钼钒磷杂多酸的新方法及其催化性能[J]. 化工进展，2006,25(10):1171-1174.

[15] Zhao W,Zhang Y S,Ma B C,et al. Oxidation of Alcohols with Hydrogen Peroxide in Water Catalyzed by Recyclable Keggin-type Tungstoborate Catalyst[J]. Catal Commun,2010,11(6):527-531.

[16] Wang J M,Yan L,Li G X,et al. Mono-Substituted Keggin-Polyoxometalate Complexes as Effective and Recyclable Catalyst for the Oxidation of Alcohols with Hydrogen Peroxide in Biphasic System[J]. Tetrahedron Lett,2005,46(41):7023-7027.

[17] Sloboda-Rozner D,Alsters P L,Neumann R. A Water-Soluble and “Self-Assembled” Polyoxometalate as a Recyclable Catalyst for Oxidation of Alcohols in Water with Hydrogen Peroxide[J]. J Am Chem Soc,2003,125(18):5280-5281.

[18] HU Dongcheng,LI Guixian,WANG Xiaoning,et al. Study of Selective Oxidation of Benzyl Alcohol to Benzaldehyde over Metal-substituted the Lacunary Dawson-type Molybdotungstophosphoric Compounds[J]. J Mol Catal,2007,21(4):324-328(in Chinese).

胡东成，李贵贤，王晓宁,等. 金属取代Dawson型磷钼钨杂多化合物催化氧化苯甲醇合成苯甲醛反应研究[J]. 分子催化,2007,21(4):324-328.

[19] LI Guixian,YU Hua,TENG Zhijun,et al. Oxidation of Benzyl Alcohol to Benzaldehyde over Keggin Type Multicomponent Heteropoly Compounds[J]. Chem Ind Eng Prog,2010,29(1):71-75 (in Chinese).

李贵贤，余华，滕志君,等. Keggin型多元杂多化合物催化氧化苯甲醇制苯甲醛[J]. 化工进展,2010,29(1):71-75.

[20] Duncan D C,Chambers R C,Hecht E,et al. Mechanism and Dynamics in the H3[PW12O40]-Catalyzed Selective Epoxidation of Terminal Olefins by H2O2. Formation, Reactivity, and Stability of {PO4[WO(O2)2]4}3-[J]. J Am Chem Soc,1995,117(2):681-691.

[21] Aubry C,Chottard G,Platzer N,et al. Reinvestigation of Epoxidation Using Tungsten-Based Precursors and Hydrogen Peroxide in a Biphase Medium[J]. Inorg Chem,1991,30(23):4409-4415.

[22] Salles L,Aubry C,Thouvenot R,et al. 31P and 183W NMR Spectroscopic Evidence for Novel Peroxo Species in the “H3[PW12O40]·yH2O/H2O2” System. Synthesis and X-ray Structure of Tetrabutylammonium (μ-Hydrogen phosphato)bis(μ-peroxo)bis(oxoperoxotungstate)(2-):A Catalyst of Olefin Epoxidation in a Biphase Medium[J]. Inorg Chem,1994,33(5):871-878.

[23] Dengel A C,Griffith W P,Parkin B C. Studies on Polyoxo- and Polyperoxo-metalates.Part 1.Tetrameric Heteropolyperoxotungstates and Heteropolyperoxomolybdates[J]. J Chem Soc Dalton Trans,1993:2683-2688.

[24] MA Huimin,HAN Furong,XU Bo,et al. On the Catalytic Behaviour of 12-Molybdophosphoric Acid in the Decomposition Reaction of H2O2[J]. Chinese J Appl Chem,1986,3(1):36-40(in Chinese).

马惠敏,韩富荣,胥勃,等. 十二钼磷酸(盐)在H2O2分解反应中的催化作用[J]. 应用化学,1986,3(1):36-40.