Citation: Ping An, Yu Fu, Danlei Wei, Yanglong Guo, Wangcheng Zhan, Jinshui Zhang. Hollow Nitrogen-Rich Carbon Nanoworms with High Activity for Metal-Free Selective Aerobic Oxidation of Benzyl Alcohol[J]. Acta Physico-Chimica Sinica, ;2021, 37(10): 200102. doi: 10.3866/PKU.WHXB202001025 shu

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

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

^†

Received Date: 7 January 2020
Revised Date: 10 February 2020
Available Online: 28 February 2020
Fund Project: the National Natural Science Foundation of China 21972022the National Natural Science Foundation of China U1805255the 111 Project D16008Natural Science Foundation of Fujian Province, China 2018J01681the Independent Research Project of State Key Laboratory of Photocatalysis on Energy and Environment SKLPEE-2017A03

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.
- 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 doi: 10.1021/cr900070d
2. [2]
  Dresselhaus, M. S. ACS Nano 2010, 4, 4344. doi: 10.1021/nn101845f doi: 10.1021/nn101845f
3. [3]
  Dreyer, D. R.; Bielawski, C. W. Chem. Sci. 2011, 2, 1233. doi: 10.1039/C1SC00035G doi: 10.1039/C1SC00035G
4. [4]
  Su, D. S.; Perathoner, S.; Centi, G. Chem. Rev. 2013, 113, 5782. doi: 10.1021/cr300367d doi: 10.1021/cr300367d
5. [5]
  Navalon, S.; Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H. Chem. Rev. 2014, 114, 6179. doi: 10.1021/cr4007347 doi: 10.1021/cr4007347
6. [6]
  Zhang, 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 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 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 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 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 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 doi: 10.1021/acscatal.6b01668
13. [13]
  Wang, D. W.; Su, D. S. Energy Environ. Sci. 2014, 7, 576. doi: 10.1039/C3EE43463J doi: 10.1039/C3EE43463J
14. [14]
  Hu, C. G.; Dai, L. M. Angew. Chem. Int. Ed. 2016, 55, 11736. doi: 10.1002/anie.201509982 doi: 10.1002/anie.201509982
15. [15]
  Tang, C.; Zhang, Q. Adv. Mater. 2017, 29, 1604103. doi: 10.1002/adma.201604103 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 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 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 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 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 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 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 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 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 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 doi: 10.1038/nmat3872
26. [26]
  Titirici, M. M.; Antonietti, M. Chem. Soc. Rev. 2010, 39, 103. doi: 10.1039/B819318P 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 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 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 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 doi: 10.1038/nmat2317
31. [31]
  Wang, 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 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 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 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 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 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 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 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 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 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 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 doi: 10.1039/C6CY00544F
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