English

Hollow Nitrogen-Rich Carbon Nanoworms with High Activity for Metal-Free Selective Aerobic Oxidation of Benzyl Alcohol

• Ping An ^{1, †,} ,
• Yu Fu ^{2, †,} ,
• Danlei Wei ^1, ,
• Yanglong Guo ^2, ,
• Wangcheng Zhan ^{2, ,} ,
• Jinshui Zhang ^{1, ,}

• 1.

  State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350108, China

• 2.

  Key Laboratory for Advanced Materials and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

• ^†These authors contributed equally to this work.

Corresponding author: Wangcheng Zhan, jinshui.zhang@fzu.edu.cn Jinshui Zhang, zhanwc@ecust.edu.cn

• Received Date: 07 January 2020
  Revised Date: 10 February 2020
  Available Online: 15 October 2021
• Fund Project:

Abstract: Carbon materials have become one of the research hotspots in the field of catalysis as a typical representative of non-metallic catalytic materials. Herein, a facile synthetic strategy is developed to fabricate a series of hollow carbon nanoworms (h-NCNWs) that contain nitrogen up to 9.83 wt% by employing graphitic carbon nitride (g-C₃N₄) as the sacrificing template and solid nitrogen source. The h-NCNWs catalysts were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), N₂ adsorption-desorption, Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric (TG), Raman spectra, and X-ray photoelectron spectroscopies (XPS). The catalytic activities of the h-NCNWs catalysts for selective oxidation of benzyl alcohol with O₂ were also evaluated. The characterization results revealed that the h-NCNWs catalysts displayed a unique hollow worm-like nanostructure with turbostratic carbon shells. The nitrogen content and shell thickness can be tuned by varying the relative ratio of resorcinol to g-C₃N₄ during the preparation process. Furthermore, nitrogen is incorporated to the carbon network in the form of graphite (predominantly) and pyridine, which is critical for the enhancement of the catalytic activity of carbon catalysts for the selective oxidation of benzyl alcohol. At a reaction temperature of 120 ℃, a 24.9% conversion of benzyl alcohol with > 99% selectivity to benzaldehyde can be achieved on the h-NCNWs catalyst prepared with a mass ratio of resorcinol to g-C₃N₄ of 0.5. However, the catalytic activities of the h-NCNWs catalysts were dependent on the amount of N dopants, in particular graphitic nitrogen species. The conversion of benzyl alcohol markedly decreased to 13.1% on the h-NCNWs catalyst prepared with a mass ratio of resorcinol to g-C₃N₄ of 1.5. Moreover, the h-NCNWs catalyst showed excellent stability during the reaction process. The conversion of benzyl alcohol and the high selectivity to aldehyde can be kept within five catalytic runs over the h-NCNWs0.5 catalyst. These results indicate that rationally designed carbon materials have great potential as highly efficient heterogeneous catalysts for oxidation reactions.

Key words:
• Hollow nanostructure
•  /  Nitrogen doping
•  /  Metal-free catalyst
•  /  Selective oxidation
•  /  Benzyl alcohol

• 1. [1]

     Allen, M. J.; Tung, V. C.; Kaner, R. B. Chem. Rev. 2010, 110, 132. doi: 10.1021/cr900070d

  2. [2]

     Dresselhaus, M. S. ACS Nano 2010, 4, 4344. doi: 10.1021/nn101845f

  3. [3]

     Dreyer, D. R.; Bielawski, C. W. Chem. Sci. 2011, 2, 1233. doi: 10.1039/C1SC00035G

  4. [4]

     Su, D. S.; Perathoner, S.; Centi, G. Chem. Rev. 2013, 113, 5782. doi: 10.1021/cr300367d

  5. [5]

     Navalon, S.; Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H. Chem. Rev. 2014, 114, 6179. doi: 10.1021/cr4007347

  6. [6]

     张树辰, 张娜, 张锦.物理化学学报, 2020, 36, 1907021. doi: 10.3866/PKU.WHXB201907021Zhang, S. C.; Zhang, N.; Zhang, J. Acta Phys. -Chim. Sin. 2020, 36, 1907021. doi: 10.3866/PKU.WHXB201907021

  7. [7]

     Primo, A.; Neatu, F.; Florea, M.; Parvulescu, V.; Garcia, H. Nat. Commun. 2014, 5, 5291. doi: 10.1038/ncomms6291

  8. [8]

     Trandafir, M. M.; Florea, M.; Neaţu, F.; Primo, A.; Parvulescu, V. I.; García H. ChemSusChem 2016, 9, 1565. doi: 10.1002/cssc.201600197

  9. [9]

     Su, C. L.; Acik, M.; Takai, K.; Lu, J.; Hao, S. J.; Zheng, Y.; Wu, P. P.; Bao, Q. L.; Enoki, T.; Chabal, Y. J.; et al. Nat. Commun. 2012, 3, 1298. doi: 10.1038/ncomms2315

  10. [10]

      Sedrpoushan, A.; Heidari, M.; Akhavan, O. Chin. J. Catal. 2017, 38, 745. doi: 10.1016/S1872-2067(17)62776-1

  11. [11]

      Li, X. Y.; Pan, X. L.; Yu, L.; Ren, P. J.; Wu, X.; Sun, L. T.; Jiao, F.; Bao, X. H. Nat. Commun. 2014, 5, 3688. doi: 10.1038/ncomms4688

  12. [12]

      Tang, P.; Hu, G.; Li, M. Z.; Ma, D. ACS Catal. 2016, 6, 6948. doi: 10.1021/acscatal.6b01668

  13. [13]

      Wang, D. W.; Su, D. S. Energy Environ. Sci. 2014, 7, 576. doi: 10.1039/C3EE43463J

  14. [14]

      Hu, C. G.; Dai, L. M. Angew. Chem. Int. Ed. 2016, 55, 11736. doi: 10.1002/anie.201509982

  15. [15]

      Tang, C.; Zhang, Q. Adv. Mater. 2017, 29, 1604103. doi: 10.1002/adma.201604103

  16. [16]

      Zheng, Y.; Jiao, Y.; Jaroniec, M.; Jin, Y. G.; Qiao, S. Z. Small 2012, 8, 3550. doi: 10.1002/smll.201200861

  17. [17]

      Liu, Z. W.; Peng, F.; Wang, H. J.; Yu, H.; Zheng, W. X.; Yang, J. A. Angew. Chem. Int. Ed. 2011, 50, 3257. doi: 10.1002/anie.201006768

  18. [18]

      Yang, L. J.; Jiang, S. J.; Zhao, Y.; Zhu, L.; Chen, S.; Wang, X. Z.; Wu, Q.; Ma, J.; Ma, Y. W.; Hu, Z. Angew. Chem. Int. Ed. 2011, 50, 7132. doi: 10.1002/anie.201101287

  19. [19]

      Gong, K. P.; Du, F.; Xia, Z. H.; Durstock, M.; Dai, L. M. Science 2009, 323, 760. doi: 10.1126/science.1168049

  20. [20]

      Tang, P.; Gao, Y. J.; Yang, J. H.; Li, W. J.; Zhao, H. B.; Ma, D. Chin. J. Catal. 2014, 35, 922. doi: 10.1016/S1872-2067(14)60150-9

  21. [21]

      Zhang, J. S.; Schott, J. A.; Li, Y. C.; Zhan, W. C.; Mahurin, S. M.; Nelson, K.; Sun, X. G.; Paranthaman, M. P.; Dai, S. Adv. Mater. 2017, 29, 1603797. doi: 10.1002/adma.201603797

  22. [22]

      Lu, A. H.; Li, W. C.; Hao, G. P.; Spliethoff, B.; Bongard, H. J.; Schaack, B. B.; Schüth, F. Angew. Chem. Int. Ed. 2010, 49, 1615. doi: 10.1002/anie.200906445

  23. [23]

      Yang, S. B.; Feng, X. L.; Zhi, L. J.; Cao, Q.; Maier, J.; Müllen, K. Adv. Mater. 2010, 22, 838. doi: 10.1002/adma.200902795

  24. [24]

      Wang, Y.; Su, F.; Lee, J. Y.; Zhao, X. S. Chem. Mater. 2006, 18, 1347. doi: 10.1021/cm052219o

  25. [25]

      Wang, G. H.; Hilgert, J.; Richter, F. H.; Wang, F.; Bongard, H. J.; Spliethoff, B.; Weidenthaler, C.; Schüth, F. Nat. Mater. 2014, 13, 293. doi: 10.1038/nmat3872

  26. [26]

      Titirici, M. M.; Antonietti, M. Chem. Soc. Rev. 2010, 39, 103. doi: 10.1039/B819318P

  27. [27]

      Liu, R.; Mahurin, S. M.; Li, C.; Unocic, R. R.; Idrobo, J. C.; Gao, H. J.; Pennycook, S. J.; Dai, S. Angew. Chem. Int. Ed. 2011, 50, 6799. doi: 10.1002/anie.201102070

  28. [28]

      White, R. J.; Tauer, K.; Antonietti, M.; Titirici, M. M. J. Am. Chem. Soc. 2010, 132, 17360. doi: 10.1021/ja107697s

  29. [29]

      Zheng, G. Y.; Lee, S. W.; Liang, Z.; Lee, H. W.; Yan, K.; Yao, H. B.; Wang, H. T.; Li, W. Y.; Chu, S.; Cui, Y. Nat. Nanotechnol. 2014, 9, 618. doi: 10.1038/nnano.2014.152

  30. [30]

      Wang, X. C.; Maeda, K.; Thomas, A.; Takanabe, K.; Xin, G.; Carlsson, J. M.; Domen, K.; Antonietti, M. Nat. Mater. 2009, 8, 76. doi: 10.1038/nmat2317

  31. [31]

      王亦清, 沈少华.物理化学学报, 2020, 36, 1905080. doi: 10.3866/PKU.WHXB201905080Wang, Y.Q.; Sheng, S. H. Acta Phys. -Chim. Sin. 2020, 36, 1905080. doi: 10.3866/PKU.WHXB201905080

  32. [32]

      Groen, J. C.; Peffer, L. A. A.; Pérez-Ramírez J. Microporous Mesoporous Mat. 2003, 60, 1. doi: 10.1016/S1387-1811(03)00339-1

  33. [33]

      Wang, X. C.; Maeda, K.; Chen, X. F.; Takanabe, K.; Domen, K.; Hou, Y. D.; Fu, X. Z.; Antonietti, M. J. Am. Chem. Soc. 2009, 131, 1680. doi: 10.1021/ja809307s

  34. [34]

      Goettmann, F.; Fischer, A.; Antonietti, M.; Thomas, A. Angew. Chem. Int. Ed. 2006, 45, 4467. doi: 10.1002/anie.200600412

  35. [35]

      Ghosh, K.; Kumar, M.; Maruyama, T.; Ando, Y. Carbon 2009, 47, 1565. doi: 10.1016/j.carbon.2009.02.007

  36. [36]

      Wang, Z. J.; Jia, R. R.; Zheng, J. F.; Zhao, J. H.; Li, L.; Song, J. L.; Zhu, Z. P. ACS Nano 2011, 5, 1677. doi: 10.1021/nn1030127

  37. [37]

      Chen, Y. Z.; Wang, Z.; Mao, S. J.; Wang, Y. Chin. J. Catal. 2019, 40, 917. doi: 10.1016/S1872-2067(19)63342-5

  38. [38]

      Watanabe, H.; Asano, S.; Fujita, S. I.; Yoshida, H.; Arai, M. ACS Catal. 2015, 5, 2886. doi: 10.1021/acscatal.5b00375

  39. [39]

      Zhang, P. F.; Deng, J.; Mao, H. R.; Li, H. R.; Wang, Y. Chin. J. Catal. 2015, 36, 1580. doi: 10.1016/S1872-2067(15)60871-3

  40. [40]

      Gong, Y. T.; Li, M. M.; Li, H. R.; Wang, R. Green Chem. 2015, 17, 715. doi: 10.1039/C4GC01847H

  41. [41]

      Zhang, P. F.; Gong, Y. T.; Li, H. R.; Chen, Z. R.; Wang, Y. Nat. Commun. 2013, 4, 1593. doi: 10.1038/ncomms2586

  42. [42]

      Li, M. M.; Xu, F.; Li, H. R.; Wang, Y. Catal. Sci. Technol. 2016, 6, 3670. doi: 10.1039/C6CY00544F

•