Citation: 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 Physico-Chimica Sinica, ;2013, 29(01): 191-198. doi: 10.3866/PKU.WHXB201210266 shu

Characterization of Immobilized Composite Catalysts of Cationic Metalloporphyrin and Heteropoly Anion in Oxidation of Ethyl Benzene by Molecular Oxygen

1.
Department of Chemical Engineering, North University of China, Taiyuan 030051, P. R. China

Received Date: 18 September 2012
Available Online: 26 October 2012
Fund Project: 山西省自然科学基金(2010021008-4)资助项目 (2010021008-4)

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 od recycle properties.
- Cationic metalloporphyrin,
- Heteropolyacid,
- Composite catalyst,
- Immobilization,
- Ethylbenzene oxidation,
- Molecular oxygen
1. [1]
  
  (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. [2]
  (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. [3]
  (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. [4]
  (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. [5]
  (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. [6]
  (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. [7]
  (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. [8]
  (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. [9]
  (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. [10]
  (10) Poltowicz, J.; Serwicka, E. M.; Bastardo- nzalez, E.; Jones,W.; Mokaya, R. Appl. Catal. A: Gen. 2001, 218, 211. doi: 10.1016/S0926-860X(01)00647-0
11. [11]
  (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. [12]
  (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. [13]
  (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. [14]
  (14) Poltowicz, J.; Pamin, K.; Haber, J. J. Mol. Catal. A: Chem.2006, 257, 154. doi: 10.1016/j.molcata.2006.04.070
15. [15]
  (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. [16]
  (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. [17]
  (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. [18]
  (18) Yuan, C. Y.; Chen, J. Chin. J. Catal. 2011, 32, 1191. doi: 10.1016/S1872-2067(10)60236-7
19. [19]
  (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. [20]
  (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. [21]
  (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. [22]
  (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. [23]
  (23) Haber, J.; Pamin, K.; Poltowicz, J. J. Mol. Catal. A: Chem.2004, 224, 153. doi: 10.1016/j.molcata.2004.07.031
24. [24]
  (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. [25]
  (25) Tang, H.; Shen, C. G.; Lin, M. R.; Sen, A. Inorg. Chim. Acta2000, 300-302, 1109.
26. [26]
  (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. [27]
  (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. [28]
  (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. [29]
  (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. [1]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . Effect of Interlayer Anions in Layered Double Hydroxides on the Photothermocatalytic CO₂ Methanation of Derived Ni-Al₂O₃ Catalysts. Acta Physico-Chimica Sinica, 2025, 41(1): 100002-0. doi: 10.3866/PKU.WHXB202309002
2. [2]
  Hailang JIA , Pengcheng JI , Hongcheng LI . Preparation and performance of nickel doped ruthenium dioxide electrocatalyst for oxygen evolution. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1632-1640. doi: 10.11862/CJIC.20240398
3. [3]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
4. [4]
  Ran Yu , Chen Hu , Ruili Guo , Ruonan Liu , Lixing Xia , Cenyu Yang , Jianglan Shui . Catalytic Effect of H₃PW₁₂O₄₀ on Hydrogen Storage of MgH₂. Acta Physico-Chimica Sinica, 2025, 41(1): 100001-0. doi: 10.3866/PKU.WHXB202308032
5. [5]
  Wang Wang , Yucheng Liu , Shengli Chen . Use of NiFe Layered Double Hydroxide as Electrocatalyst in Oxygen Evolution Reaction: Catalytic Mechanisms, Electrode Design, and Durability. Acta Physico-Chimica Sinica, 2024, 40(2): 2303059-0. doi: 10.3866/PKU.WHXB202303059
6. [6]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201
7. [7]
  Shijie Ren , Mingze Gao , Rui-Ting Gao , Lei Wang . Bimetallic Oxyhydroxide Cocatalyst Derived from CoFe MOF for Stable Solar Water Splitting. Acta Physico-Chimica Sinica, 2024, 40(7): 2307040-0. doi: 10.3866/PKU.WHXB202307040
8. [8]
  Wentao Xu , Xuyan Mo , Yang Zhou , Zuxian Weng , Kunling Mo , Yanhua Wu , Xinlin Jiang , Dan Li , Tangqi Lan , Huan Wen , Fuqin Zheng , Youjun Fan , Wei Chen . Bimetal Leaching Induced Reconstruction of Water Oxidation Electrocatalyst for Enhanced Activity and Stability. Acta Physico-Chimica Sinica, 2024, 40(8): 2308003-0. doi: 10.3866/PKU.WHXB202308003
9. [9]
  Wenjun Yang , Qiaoling Tan , Wenjiao Xie , Xiaoyu Pan , Youyong Yuan . Construction and Characterization of Calcium Alginate Microparticle Drug Delivery System: A Novel Design and Teaching Practice in Polymer Experiments. University Chemistry, 2025, 40(3): 371-380. doi: 10.12461/PKU.DXHX202405150
10. [10]
  Ke Li , Chuang Liu , Jingping Li , Guohong Wang , Kai Wang . Architecting Inorganic/Organic S-Scheme Heterojunction of Bi₄Ti₃O₁₂ Coupling with g-C₃N₄ for Photocatalytic H₂O₂ Production from Pure Water. Acta Physico-Chimica Sinica, 2024, 40(11): 2403009-0. doi: 10.3866/PKU.WHXB202403009
11. [11]
  Yang WANG , Xiaoqin ZHENG , Yang LIU , Kai ZHANG , Jiahui KOU , Linbing SUN . Mn single-atom catalysts based on confined space: Fabrication and the electrocatalytic oxygen evolution reaction performance. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2175-2185. doi: 10.11862/CJIC.20240165
12. [12]
  Yuchen Zhou , Huanmin Liu , Hongxing Li , Xinyu Song , Yonghua Tang , Peng Zhou . Designing thermodynamically stable noble metal single-atom photocatalysts for highly efficient non-oxidative conversion of ethanol into high-purity hydrogen and value-added acetaldehyde. Acta Physico-Chimica Sinica, 2025, 41(6): 100067-0. doi: 10.1016/j.actphy.2025.100067
13. [13]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Liu Fei . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 2408004-0. doi: 10.3866/PKU.WHXB202408004
14. [14]
  Wenjuan Tan , Yong Ye , Xiujuan Sun , Bei Liu , Jiajia Zhou , Hailong Liao , Xiulin Wu , Rui Ding , Enhui Liu , Ping Gao . Building P-Poor Ni₂P and P-Rich CoP₃ Heterojunction Structure with Cation Vacancy for Enhanced Electrocatalytic Hydrazine and Urea Oxidation. Acta Physico-Chimica Sinica, 2024, 40(6): 2306054-0. doi: 10.3866/PKU.WHXB202306054
15. [15]
  Xichen YAO , Shuxian WANG , Yun WANG , Cheng WANG , Chuang ZHANG . Oxygen reduction performance of self?supported Fe/N/C three-dimensional aerogel catalyst layers. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1387-1396. doi: 10.11862/CJIC.20240384
16. [16]
  Zongfei YANG , Xiaosen ZHAO , Jing LI , Wenchang ZHUANG . Research advances in heteropolyoxoniobates. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 465-480. doi: 10.11862/CJIC.20230306
17. [17]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
18. [18]
  Huiwei Ding , Bo Peng , Zhihao Wang , Qiaofeng Han . Advances in Metal or Nonmetal Modification of Bismuth-Based Photocatalysts. Acta Physico-Chimica Sinica, 2024, 40(4): 2305048-0. doi: 10.3866/PKU.WHXB202305048
19. [19]
  Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039
20. [20]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-Based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-0. doi: 10.3866/PKU.WHXB202406029

Get Citation

PDF

XML

Metrics

PDF Downloads(661)
Abstract views(1724)
HTML views(21)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142