固载化阳离子金属卟啉/杂多阴离子复合催化剂在分子氧氧化乙苯过程中的催化特性

doi:10.3866/PKU.WHXB201210266

摘要/Abstract

摘要：

以交联聚苯乙烯微球(CPS)为基质载体, 采用同步合成与固载的方法, 简捷地制得了固载化阳离子苯基卟啉, 继而通过与钴盐的配合反应, 制备了固载化阳离子钴卟啉. 在此基础上, 以Keggin 型杂多酸磷钨酸(HPW)及磷钼酸(HPMo)为试剂, 凭借阳离子钴卟啉(CoP)与杂多阴离子之间的静电相互作用, 制备与表征了固载化的由阳离子钴卟啉与杂多阴离子复合而成的固体催化剂CoPPW-CPS和CoPPMo-CPS. 将两种复合催化剂用于分子氧氧化乙苯的氧化反应, 考察研究了催化特性. 结果表明: 在分子氧氧化乙苯的氧化反应中, 复合催化剂具有很高的催化活性, 可使乙苯高选择性地转化为苯乙酮, 反应12 h, 苯乙酮的产率达30.1%; 复合催化剂的催化活性比单纯的固载化钴卟啉高75%; CoPPW-CPS的催化活性高于CoPPMo-CPS. 在复合催化剂结构组分中, 固载化的杂多阴离子并无催化活性, 起催化作用的组分是钴卟啉; 但是, 杂多阴离子可有效保护钴卟啉, 使其免于被氧化失活, 从而使其保持稳定的高催化活性. 复合催化剂具有最适宜的投加量, 过量催化剂的加入, 会抑制钴卟啉的催化活性. 复合催化剂还具有良好的循环使用性能.

关键词: 阳离子金属卟啉, 杂多酸, 复合催化剂, 固载化, 乙苯氧化, 分子氧

Abstract:

An immobilized cationic phenyl porphyrin was prepared with crosslinked polystyrene (CPS) microspheres as carriers via synthesis and immobilization. A kind of immobilized cationic cobalt porphyrin was obtained through a coordination reaction between the immobilized cationic phenyl porphyrin and the cobalt salt. In the composite reactions, phosphotungstic acid (HPW) and phosphomolybdic acid (HPMo) with Keggin structures were used as reagents, respectively, and the combination of the cationic cobalt porphyrin (CoP) with the heteropoly anions by electrostatic interaction led to the formation of the immobilized composite catalysts of CoPPW-CPS and CoPPMo-CPS. We then characterized these immobilized composite catalysts. The immobilized composite catalysts were used in the oxidation of ethylbenzene by molecular oxygen, and their catalytic characters were investigated. The results show that the immobilized composite catalysts possess high catalyst activity. They can transform ethyl benzene into acetophenone with high selectivity, and the yield of acetophenone after 12 h reaches 30.1%. The catalytic activity of the immobilized composite catalysts is 75% higher than that of the immobilized cobalt porphyrin. The catalytic activity of CoPPW-CPS is higher than that of CoPPMo-CPS. The cobalt porphyrin in the composite is the catalyst component as the heteropoly has no catalytic activity. However, the heteropoly anion has a protective effect on the metalloporphyrin against its deactivation during the catalytic reaction. In the oxidation reaction, there is an optimum addition for catalyst, and adding excessive catalyst inhibits its activity. The composite catalysts show good recycle properties.

Key words: Cationic metalloporphyrin, Heteropolyacid, Composite catalyst, Immobilization, Ethylbenzene oxidation, Molecular oxygen

顾来沅, 高保娇, 房晓琳. 固载化阳离子金属卟啉/杂多阴离子复合催化剂在分子氧氧化乙苯过程中的催化特性[J]. 物理化学学报, 2013, 29(01), 191-198. doi: 10.3866/PKU.WHXB201210266

GU Lai-Yuan, GAO Bao-Jiao, FANG Xiao-Lin. Characterization of Immobilized Composite Catalysts of Cationic Metalloporphyrin and Heteropoly Anion in Oxidation of Ethyl Benzene by Molecular Oxygen[J]. Acta Phys. -Chim. Sin. 2013, 29(01), 191-198. doi: 10.3866/PKU.WHXB201210266

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201210266

https://www.whxb.pku.edu.cn/CN/Y2013/V29/I01/191

参考文献

(1) Rahiman, A. K.; Bharathi, K. S.; Sreedaran, S.; Rajesh, K.;Narayanan, V. Inorg. Chim. Acta 2009, 362, 1810. doi: 10.1016/j.ica.2008.08.019
(2) Ma, J. J.;Wu, J.; Gu, J.; Liu, L.; Zhang, D. G.; Xu, X. Y.; Yang,X. J.; Tong, Z.W. J. Mol. Catal. A: Chem. 2012, 357, 95. doi: 10.1016/j.molcata.2012.01.025
(3) Rahiman, A. K.; Rajesh, K.; Bharathi, K. S.; Sreedaran, S.;Narayanan, V. Appl. Catal. A: Gen. 2006, 314, 216. doi: 10.1016/j.apcata.2006.08.018
(4) Machado, G. S.; Castro, K. A. D. F.;Wypych, F.; Nakagaki, S.J. Mol. Catal. A: Chem. 2008, 283, 99. doi: 10.1016/j.molcata.2007.12.009
(5) Zhao, P.; Huang, J.W.; Ji, L. N. Spectrochim. Acta Part A 2012,88, 130. doi: 10.1016/j.saa.2011.12.017
(6) Serwicka, E. M.; Poltowicz, J.; Bahranowski, K.; Olejniczak,Z.; Jones,W. Appl. Catal. A: Gen. 2004, 275, 9. doi: 10.1016/j.apcata.2004.07.005
(7) Ye, T. X.; Ye, S. L.; Chen, D. M.; Chen, Q. A.; Qiu, B.; Chen, X.Spectrochim. Acta Part A 2012, 86, 467. doi: 10.1016/j.saa.2011.10.070
(8) Moghadam, M.; Tangestaninejad, S.; Mirkhani, V.;Mohammadpoor-Baltork, I.; Moosavifaret, M. J. Mol. Catal. A: Chem. 2009, 302, 68. doi: 10.1016/j.molcata.2008.11.036
(9) Rahiman, A. K.; Rajesh, K.; Bharathi, K. S.; Sreedaran, S.;Narayananet, V. Inorg. Chim. Acta 2009, 362, 1491. doi: 10.1016/j.ica.2008.07.011
(10) Poltowicz, J.; Serwicka, E. M.; Bastardo-Gonzalez, E.; Jones,W.; Mokaya, R. Appl. Catal. A: Gen. 2001, 218, 211. doi: 10.1016/S0926-860X(01)00647-0
(11) Vinhado, F. S.; Prado-Manso, C. M. C.; Sacco, H. C.; Iamamoto,Y. J. Mol. Catal. A: Chem. 2001, 174, 279. doi: 10.1016/S1381-1169(01)00200-X
(12) Huang, G.; Guo, C. C.; Tang, S. S. J. Mol. Catal. A: Chem.2007, 261, 125. doi: 10.1016/j.molcata.2006.08.014
(13) Mirkhani, V.; Moghadam, M.; Tangestaninejad, S.; Bahramian,B. Appl. Catal. A: Gen. 2006, 311, 43. doi: 10.1016/j.apcata.2006.05.043
(14) Poltowicz, J.; Pamin, K.; Haber, J. J. Mol. Catal. A: Chem.2006, 257, 154. doi: 10.1016/j.molcata.2006.04.070
(15) Halma, M.; Bail, A.;Wypych, F.; Nakagaki, S. J. Mol. Catal. A: Chem. 2006, 243, 44. doi: 10.1016/j.molcata.2005.08.019
(16) Nakagaki, S.; Halma, M.; Bail, A.; Arízaga, G. G. C.;Wypych,F. J. Colloid Interface Sci. 2005, 281, 417. doi: 10.1016/j.jcis.2004.08.098
(17) Kim, H.; Jung, J. C.; Park, D. R.; Baeck, S. H.; Song, I. K. Appl. Catal. A: Gen. 2007, 320, 159. doi: 10.1016/j.apcata.2007.01.034
(18) Yuan, C. Y.; Chen, J. Chin. J. Catal. 2011, 32, 1191. doi: 10.1016/S1872-2067(10)60236-7
(19) Gao, S. Y.; Cao, R.; Yan, C. P. J. Colloid Interface Sci. 2008,324, 156. doi: 10.1016/j.jcis.2008.05.011
(20) Souza, A. L.; Marques, L. A.; Eberlin, M. N.; Nascente, P. A. P.;Junior, P. S. P. H.; Leite, F. L.; Rodrigues-Filho, U. P. Thin Solid Films 2012, 520, 3574. doi: 10.1016/j.tsf.2011.12.069
(21) Gu, L. Y.; Gao, B. J.; Fang, X. L. Chemistry 2012, 75 (12),1114. [顾来沅, 高保娇, 房晓琳. 化学通报, 2012, 75 (12),1114.]
(22) Santos, I. C. M. S.; Rebelo, S. L. H.; Balula, M. S. S.; Martins,R. R. L.; Pereira, M. M. M. S.; Simões, M. M. Q.; Neves, M. G.P. M. S.; Cavaleiro, J. A. S.; Cavaleiro, A. M. V. J. Mol. Catal. A: Chem. 2005, 231, 35. doi: 10.1016/j.molcata.2004.12.021
(23) Haber, J.; Pamin, K.; Poltowicz, J. J. Mol. Catal. A: Chem.2004, 224, 153. doi: 10.1016/j.molcata.2004.07.031
(24) Guo, C. C.; Chu, M. F.; Liu, Q.; Liu, Y.; Guo, D. C.; Liu, X. Q.Appl. Catal. A: Gen. 2003, 246, 303. doi: 10.1016/S0926-860X(03)00061-9
(25) Tang, H.; Shen, C. G.; Lin, M. R.; Sen, A. Inorg. Chim. Acta2000, 300-302, 1109.
(26) Kharat, A. N.; Pendleton, P.; Badalyan, A.; Abedini, M.; Amini,M. M. J. Mol. Catal. A: Chem. 2001, 175, 277. doi: 10.1016/S1381-1169(01)00234-5
(27) Guo, C. C.; Liu, X. Q.; Liu, Y.; Liu, Q.; Chu, M. F.; Zhang, X.B. J. Mol. Catal. A: Chem. 2003, 192, 289. doi: 10.1016/S1381-1169(02)00449-1
(28) Chen, Y. J.; Gao, B. J.; Tian, P.; Ma, Y. X. Acta Chim. Sin. 2011,69, 1337. [陈英军, 高保娇, 田鹏, 马云霞. 化学学报, 2011,69, 1337.]
(29) Huang, G.; Luo, J.; Deng, C. C.; Guo, Y. A.; Zhao, S. K.; Zhou,H.;Wei, S. Appl. Catal. A: Gen. 2008, 338, 83. doi: 10.1016/j.apcata.2007.12.027

[1]	李峥嵘, 申涛, 胡冶州, 陈科, 陆贇, 王得丽. 有序金属间化合物电催化剂在燃料电池中的应用进展[J]. 物理化学学报, 2021, 37(9): 2010029 - .
[2]	袁明明,李迪帆,赵秀阁,马文保,孔康,倪文秀,顾青雯,侯震山. 二氧化硅包覆的杂多酸在双氧水存在条件下催化氧化甘油[J]. 物理化学学报, 2018, 34(8): 886 -895 .
[3]	马青,童金辉,宿玲弟,王文慧,马文梅,薄丽丽. 杂多酸/离子液体杂化材料催化苯的高选择性羟基化[J]. 物理化学学报, 2016, 32(12): 2961 -2967 .
[4]	吴昱,罗键. 原位生长Pd/Ni(OH)₂/NF复合催化剂及其析氢性能[J]. 物理化学学报, 2016, 32(11): 2745 -2752 .
[5]	郭丽梅, 匡元江, 杨晓丹, 于彦龙, 姚江宏, 曹亚安. 偏硼酸锶/碳酸锶复合催化剂光催化还原CO₂生成CH₄的研究[J]. 物理化学学报, 2013, 29(07): 1558 -1565 .
[6]	张坡, 黄明, 储伟, 罗仕忠, 李通. 银含量对二氧化硅固载磷钨酸银催化四氢呋喃聚合反应性能的影响[J]. 物理化学学报, 2013, 29(04): 770 -776 .
[7]	郑宁, 朱春梅, 孙斌, 施祖进, 刘岩, 王远. 高耐甲醇性和稳定性的纳米复合阴极催化剂[J]. 物理化学学报, 2012, 28(10): 2263 -2268 .
[8]	徐玲, 沈晓旭, 肖强, 钟依均, 叶素芳, 叶向荣, 朱伟东. Pd/Fe₃O₄-MCNT磁性催化剂的制备、表征及催化性能[J]. 物理化学学报, 2011, 27(08): 1956 -1960 .
[9]	梁丽萍, 朱晴, 赵永祥, 刘滇生. 热处理过程中磷钨杂多酸修饰ZrO₂气凝胶固体酸的结构及性能演变[J]. 物理化学学报, 2011, 27(08): 1933 -1940 .
[10]	朱晴, 梁丽萍, 贾志奇, 高春光, 赵永祥. 多钨酸盐修饰ZrO₂气凝胶催化四氢呋喃开环聚合[J]. 物理化学学报, 2011, 27(02): 491 -498 .
[11]	刘鼎, 许宜铭. 杂多酸存在下X3B染料光降解和Cr(VI)光还原的协同反应机理[J]. 物理化学学报, 2008, 24(09): 1584 -1588 .
[12]	刘百军;蔡天锡. 杂多酸盐在Raney Ni和Raney Co表面上的状态[J]. 物理化学学报, 2004, 20(07): 727 -730 .
[13]	王升富;杜丹;邹其超. 磷钼钨杂多酸-L-半胱氨酸自组装膜电极的电化学性质[J]. 物理化学学报, 2001, 17(12): 1102 -1106 .
[14]	赵振波, 孙闻东, 杨向光, 叶兴凯, 吴越. 异丁烷-丁烯烷基化杂多酸-醋酸催化机理[J]. 物理化学学报, 2000, 16(07): 613 -620 .
[15]	王新平,叶兴凯,吴越. 杂多酸在活性炭表面含氧基团上的化学键合作用[J]. 物理化学学报, 1995, 11(12): 1105 -1109 .