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
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