English

Catalytic Oxidation of Toluene Over Potassium Modified Mn/Ce_0.65Zr_0.35O₂ Catalyst

• Lai Xiaoxiao ^1, ,
• Feng Jie ^2, ,
• Zhou Xiaoying ^1, ,
• Hou Zhongyan ^1, ,
• Lin Tao ^{1, ,} ,
• Chen Yaoqiang ^{1,3, ,}

• 1.

  College of Chemistry, Sichuan University, Chengdu 610064, P. R. China

• 2.

  College of Chemical Engineering, Sichuan University, Chengdu 610064, P. R. China

• 3.

  Sichuan Provincial Environmental Catalytic Material Engineering Technology Center, Chengdu 610064, P. R. China

Corresponding author: Lin Tao, lintaochem@scu.edu.cn Chen Yaoqiang, chenyaoqiang@scu.edu.cn

• Received Date: 13 May 2019
  Accepted Date: 02 July 2019
  Revised Date: 27 June 2019
  Available Online: 15 August 2020
• Fund Project:

  The research was supported by National Key Research and Development Program of China (2016YFC0204901)

Abstract: Volatile organic compounds (VOCs) are both harmful to human health and the environment; however, catalytic combustion offers a promising method for VOC purification because of its high efficiency without secondary pollution. Although manganese-based catalysts have been well studied for VOC catalytic oxidation, their catalytic activity at low temperature must be improved. Alkali metals as promoters have the potential to modulate the electronic and structural properties of the catalysts, improving their catalytic activity. Herein, a Ce_0.65Zr_0.35O₂ support was prepared by co-precipitation and MnO_x/Ce_0.65Zr_0.35O₂ catalysts were obtained through the incipient-wetness impregnation method. The catalytic properties of K-modified MnO_x/Ce_0.65Zr_0.35O₂ for toluene oxidation with different molar ratios of K/Mn were investigated. In addition, the catalysts were characterized by XRD, UV/visible Raman, Hydrogen temperature program reduction (H₂-TPR), Oxygen temperature programmed desorption (O₂-TPD), X-ray photoelectron spectroscopy (XPS) and in situ diffuse reflectance FTIR spectroscopy (DRIFTS) experiments. The results showed that alkali metal doping with K significantly improved the catalytic activity. In particular, when the molar ratio of K/Mn was 0.2, the monolith catalyst Mn/Ce_0.65Zr_0.35O₂-K-0.2 exhibited the best performance with the lowest complete conversion temperature T₉₀ of 242 ℃ at a GHSV of 12000 h⁻¹. The XRD results suggested that MnO_x was uniformly distributed on the surface of the catalyst and that Mn⁴⁺ partially reduced to Mn³⁺ on the addition of K. The Raman spectrum demonstrated that with increasing K content, both the β- and α-MnO₂ phases coexisted on the Mn/Ce_0.65Zr_0.35O₂-K-0.2 catalyst, increasing the number of surface defect sites. The H₂-TPR experiment results confirmed that Mn/Ce_0.65Zr_0.35O₂-K-0.2 exhibited the lowest reduction temperature and good reducibility. From the O₂-TPD experiments, it was clear that Mn/Ce_0.65Zr_0.35O₂-K-0.2 contained the most surface adsorbed oxygen species and excellent lattice oxygen mobility, which benefitted the toluene oxidation activity. In addition, the XPS results suggested that the content of surface adsorbed oxygen species of the Mn/Ce_0.65Zr_0.35O₂-K-0.2 catalyst was the highest among all the tested samples. In addition, toluene-TPSR in N₂ as measured by in situ DRIFTs analysis demonstrated that available lattice oxygen was present in the Mn/Ce_0.65Zr_0.35O₂-K-0.2 catalyst. Therefore, the Mn/Ce_0.65Zr_0.35O₂-K-0.2 catalyst exhibited the best redox properties and oxygen mobility of the prepared samples and showed excellent activity toward toluene oxidation. Therefore, it was concluded that the addition of an appropriate amount of K improved the redox performance of the catalyst and increased the number of surface defect sites and mobility of the lattice oxygen of the catalyst as well as the concentration of the surface active oxygen species, thereby significantly improving catalytic ability.

Key words:
• Toluene
•  /  Catalytic oxidation
•  /  Potassium
•  /  Ce_0.65Zr_0.35O₂
•  /  Manganese oxide

• 1. [1]

     He, C.; Cheng, J.; Zhang, X.; Douthwaite, M.; Pattisson, S.; Hao, Z. Chem. Rev. 2019, doi: 10.1021/acs.chemrev.8b00408

  2. [2]

     Kim, S. C.; Shim, W. G. Appl. Catal. B 2010, 98 (3–4), 180. doi: 10.1016/j.apcatb.2010.05.027

  3. [3]

     Parmar, G. R.; Rao, N. N. Crit. Rev. Environ. Sci. Technol. 2008, 39 (1), 41. doi: 10.1080/10643380701413658

  4. [4]

     Tidahy, H.; Siffert, S.; Lamonier, J.; Zhilinskaya, E.; Aboukais, A.; Yuan, Z.; Vantomme, A.; Su, B.; Canet, X.; Deweireld, G. Appl. Catal. A 2006, 310, 61. doi: 10.1016/j.apcata.2006.05.020

  5. [5]

     Scirè, S. Appl. Catal. B 2003, 45 (2), 117. doi: 10.1016/s0926-3373(03)00122-x

  6. [6]

     Genuino, H. C.; Dharmarathna, S.; Njagi, E. C.; Mei, M. C.; Suib, S. L. J. Phys. Chem. C 2012, 116 (22), 12066. doi: 10.1021/jp301342f

  7. [7]

     Yang, J. S.; Jung, W. Y.; Lee, G. D.; Park, S. S.; Jeong, E. D.; Kim, H. G.; Hong, S. S. J. Ind. Eng. Chem. 2008, 14 (6), 779. doi: 10.1016/j.jiec.2008.05.008

  8. [8]

     Li, H.; Qi, G.; Tana; Zhang, X.; Huang, X.; Li, W.; Shen, W. Appl. Catal. B 2011, 103 (1–2), 54. doi: 10.1016/j.apcatb.2011.01.008

  9. [9]

     Wu, M.; Wang, X.; Dai, Q.; Gu, Y.; Li, D. Catal. Today 2010, 158 (3–4), 336. doi: 10.1016/j.cattod.2010.04.006

  10. [10]

      Zhao, F.; Zhang, G.; Zeng, P.; Yang, X.; Ji, S. Chin. J. Catal. 2011, 32 (5), 821. doi: 10.1016/s1872-2067(10)60184-2

  11. [11]

      Zhang, C.; Guo, Y.; Guo, Y.; Lu, G.; Boreave, A.; Retailleau, L.; Baylet, A.; Giroir-Fendler, A. Appl. Catal. B 2014, 148–149, 490. doi: 10.1016/j.apcatb.2013.11.030

  12. [12]

      Lahousse, C.; Bernier, A.; Grange, P.; Delmon, B.; Papaefthimiou, P.; Ioannides, T.; Verykios, X. J. Catal. 1998, 178, 214. doi.org/10.1006/jcat.1998.2148 doi: 10.1006/jcat.1998.2148

  13. [13]

      Raciulete, M.; Afanasiev, P. Appl. Catal. A 2009, 368 (1–2), 79. doi: 10.1016/j.apcata.2009.08.012

  14. [14]

      Aguero, F. N.; Barbero, B. P.; Gambaro, L.; Cadús, L. E. Appl. Catal. B 2009, 91 (1–2), 108. doi: 10.1016/j.apcatb.2009.05.012

  15. [15]

      Piumetti, M.; Fino, D.; Russo, N. Appl. Catal. B 2015, 163, 277. doi: 10.1016/j.apcatb.2014.08.012

  16. [16]

      Huang, N.; Qu, Z.; Dong, C.; Qin, Y.; Duan, X. Appl. Catal. A 2018, 560, 195. doi: 10.1016/j.apcata.2018.05.001

  17. [17]

      Wang, H.; Lu, Y.; Han, Y.; Lu, C.; Wan, H.; Xu, Z.; Zheng, S. Appl. Surf. Sci. 2017, 420, 260. doi: 10.1016/j.apsusc.2017.05.133

  18. [18]

      Shen, B.; Wang, Y.; Wang, F.; Liu, T. Chem. Eng. J. 2014, 236, 171. doi: 10.1016/j.cej.2013.09.085

  19. [19]

      Ferrandon, M.; Mawdsley, J.; Krause, T. Appl. Catal. A 2008, 342 (1–2), 69. doi: 10.1016/j.apcata.2008.03.001

  20. [20]

      Pasha, N.; Lingaiah, N.; Siva Sankar Reddy, P.; Sai Prasad, P. S. Catal. Lett. 2007, 118 (1–2), 64. doi: 10.1007/s10562-007-9146-1

  21. [21]

      Tang, Q.; Liu, T.; Yang, Y. Catal. Commun. 2008, 9 (15), 2570. doi: 10.1016/j.catcom.2008.07.013

  22. [22]

      Panagiotopoulou, P.; Kondarides, D. I. J. Catal. 2008, 260 (1), 141. doi: 10.1016/j.jcat.2008.09.014

  23. [23]

      Li, X.; Hong, H.; Chang, L.; Changbin, Z.; Bo, Z. Environ. Sci. Technol. 2009, 43, 890. doi: 10.1021/es801867y

  24. [24]

      Bai, B.; Li, J. ACS Catal. 2014, 4 (8), 2753. doi: 10.1021/cs5006663

  25. [25]

      Tang, Q.; Huang, X.; Wu, C.; Zhao, P.; Chen, Y.; Yang, Y. J. Mol. Catal. A: Chem. 2009, 306 (1–2), 48. doi: 10.1016/j.molcata.2009.02.020

  26. [26]

      Jirátová, K.; Mikulová, J.; Klempa, J.; Grygar, T.; Bastl, Z.; Kovanda, F. Appl. Catal. A 2009, 361 (1–2), 106. doi: 10.1016/j.apcata.2009.04.004

  27. [27]

      Hou, Z.; Feng, J.; Lin, T.; Zhang, H.; Zhou, X.; Chen, Y. Appl. Surf. Sci. 2018, 434, 82. doi: 10.1016/j.apsusc.2017.09.048

  28. [28]

      Feng, J.; Hou, Z.; Zhou, X.; Zhang, H.; Cheng, T.; Lin, T.; Chen, Y. Chem. Pap. 2017, 72 (1), 161. doi: 10.1007/s11696-017-0267-8

  29. [29]

      Saqer, S. M.; Kondarides, D. I.; Verykios, X. E. Appl. Catal. B 2011, 103 (3–4), 275. doi: 10.1016/j.apcatb.2011.01.001

  30. [30]

      Tang, W.; Wu, X.; Li, S.; Li, W.; Chen, Y. Catal. Commun. 2014, 56, 134. doi: 10.1016/j.catcom.2014.07.023

  31. [31]

      Chiou, J. Y. Z.; Lai, C. L.; Yu, S.W.; Huang, H. H.; Chuang, C. L.; Wang, C. B. Int. J. Hydrog. Energy 2014, 39 (35), 20689. doi: 10.1016/j.ijhydene.2014.07.141

  32. [32]

      Gandía, L. M.; Gil, A.; Korili, S. A. Appl. Catal. B 2001, 33, 1. doi: org/10.1016/S0926-3373 (01)00155-2

  33. [33]

      He, H.; Lin, X.; Li, S.; Wu, Z.; Gao, J.; Wu, J.; Wen, W.; Ye, D.; Fu, M. Appl. Catal. B 2018, 223, 134. doi: 10.1016/j.apcatb.2017.08.084

  34. [34]

      Deng, J.; Zhou, Y.; Cui, Y.; Lan, L.; Wang, J.; Yuan, S.; Chen, Y. J. Mater. Sci. 2017, 52 (9), 5242. doi: 10.1007/s10853-017-0765-7

  35. [35]

      Hong, W. J.; Iwamoto, S.; Hosokawa, S.; Wada, K.; Kanai, H.; Inoue, M. J. Catal. 2011, 277 (2), 208. doi: 10.1016/j.jcat.2010.11.007

  36. [36]

      Zhou, G.; He, X.; Liu, S.; Xie, H.; Fu, M. J. Ind. Eng. Chem. 2015, 21, 932. doi: 10.1016/j.jiec.2014.04.035

  37. [37]

      Natile, M. M.; Giovanni, B.; Antonella, G. Chem. Mater. 2005, 17, 6272. doi: 10.1021/cm051352d

  38. [38]

      Azalim, S.; Franco, M.; Brahmi, R.; Giraudon, J. M.; Lamonier, J. F. J. Hazard. Mater. 2011, 188 (1–3), 422. doi: 10.1016/j.jhazmat.2011.01.135

  39. [39]

      Zhou, K.; Wang, X.; Sun, X.; Peng, Q.; Li, Y. J. Catal. 2005, 229 (1), 206. doi: 10.1016/j.jcat.2004.11.004

  40. [40]

      Wu, Y.; Liu, M.; Ma, Z.; Xing, S. T. Catal. Today 2011, 175 (1), 196. doi: 10.1016/j.cattod.2011.04.023

  41. [41]

      Liao, Y.; Fu, M.; Chen, L.; Wu, J.; Huang, B.; Ye, D. Catal. Today 2013, 216, 220. doi: 10.1016/j.cattod.2013.06.017

  42. [42]

      Levasseur, B.; Kaliaguine, S. Appl. Catal. B 2009, 88 (3–4), 305. doi: 10.1016/j.apcatb.2008.11.007

  43. [43]

      Cellier, C.; Ruaux, V.; Lahousse, C.; Grange, P.; Gaigneaux, E. Catal. Today 2006, 117 (1–3), 350. doi: 10.1016/j.cattod.2006.05.033

  44. [44]

      Atribak, I.; Bueno-Lopez, A.; Garcia-Garcia, A.; Azambre, B. Phys. Chem. Chem. Phys. 2010, 12 (41), 13770. doi: 10.1039/c0cp00540a

  45. [45]

      Wang, X.; Kang, Q.; Li, D. Appl. Catal. B 2009, 86 (3–4), 166. doi: 10.1016/j.apcatb.2008.08.009

  46. [46]

      Tang, W.; Wu, X.; Li, S.; Shan, X.; Liu, G.; Chen, Y. Appl. Catal. B 2015, 162, 110. doi: 10.1016/j.apcatb.2014.06.030

  47. [47]

      Wang, X.; Du, L. Y.; Du, M.; Ma, C.; Zeng, J.; Jia, C. J.; Si, R. Phys. Chem. Chem. Phys. 2017, 19 (22), 14533. doi: 10.1039/c7cp02004j

  48. [48]

      Muroyama, H.; Asajima, H.; Hano, S.; Matsui, T.; Eguchi, K. Appl. Catal. A 2015, 489, 235. doi: 10.1016/j.apcata.2014.10.039

  49. [49]

      Einaga, H.; Mochiduki, K.; Teraoka, Y. Catalysts 2013, 3 (1), 219. doi: 10.3390/catal3010219

  50. [50]

      Sun, H.; Liu, Z.; Chen, S.; Quan, X. Chem. Eng. J. 2015, 270, 58. doi: 10.1016/j.cej.2015.02.017

  51. [51]

      Lichtenberger, J.; Hargroveleak, S.; Amiridis, M. J. Catal. 2006, 238 (1), 165. doi: 10.1016/j.jcat.2005.12.007

  52. [52]

      Du, J.; Qu, Z.; Dong, C.; Song, L.; Qin, Y.; Huang, N. Appl. Surf. Sci. 2018, 433, 1025. doi: 10.1016/j.apsusc.2017.10.116

•