Hierarchical Carbon Nanocages as Efficient Catalysts for Oxidative Coupling of Benzylamine to N-Benzylidene Benzylamine

doi:10.6023/A20110527

Acta Chimica Sinica ›› 2021, Vol. 79 ›› Issue (4): 539-544.DOI: 10.6023/A20110527 Previous Articles

Article

分级结构碳纳米笼高效催化苄胺氧化偶联制N-苄烯丁胺

曾誉¹, 吕品¹, 蔡跃进¹, 高福杰¹, 卓欧¹, 吴强¹^,^*(), 杨立军¹, 王喜章¹^,^*(), 胡征¹

1 南京大学化学化工学院介观化学教育部重点实验室南京 210023

投稿日期:2020-11-17 发布日期:2021-02-05
通讯作者: 吴强, 王喜章
基金资助:
国家重点研发计划(2018YFA0209100); 国家重点研发计划(2017YFA0206500); 国家自然科学基金(21773111); 国家自然科学基金(21972061); 国家自然科学基金(21832003); 国家自然科学基金(52071174)

Hierarchical Carbon Nanocages as Efficient Catalysts for Oxidative Coupling of Benzylamine to N-Benzylidene Benzylamine

Yu Zeng¹, Pin Lyu¹, Yuejin Cai¹, Fujie Gao¹, Ou Zhuo¹, Qiang Wu¹^,^*(), Lijun Yang¹, Xizhang Wang¹^,^*(), Zheng Hu¹

1 Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China

Received:2020-11-17 Published:2021-02-05
Contact: Qiang Wu, Xizhang Wang
About author:
* E-mail: wqchem@nju.edu.cn;
E-mail: wangxzh@nju.edu.cn; Tel.: 0086-025-89681910
Supported by:
National Key Research and Development Program of China(2018YFA0209100); National Key Research and Development Program of China(2017YFA0206500); National Natural Science Foundation of China(21773111); National Natural Science Foundation of China(21972061); National Natural Science Foundation of China(21832003); National Natural Science Foundation of China(52071174)

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Abstract

N-Benzylidene benzylamine is an important pharmaceutical intermediate and industrial chemical. Traditionally, it is synthesized via the reaction between benzylamine and benzaldehyde by using Lewis acid catalysts, which usually suffers from the difficulty of product separation and environmental unfriendliness. An alternative approach is the oxidative coupling of benzylamine catalyzed by metal-based catalysts, which is also beset by the contamination of metallic impurities. Thus, the development of green, metal-free and reusable heterogeneous catalysts is highly attractive. Herein, we report an efficient metal-free catalyst, hierarchical carbon nanocages (hCNCs) synthesized by the in-situ magnesium oxide template method with benzene precursor at different temperatures (700, 800 and 900 ℃), for the oxidative coupling of benzylamine to N-benzylidene benzylamine. The hCNCs feature multi-scale hierarchical pore structure, high specific surface area and abundant surface defects. The hCNC700 exhibits excellent catalytic performance for the solvent-free oxidative coupling of benzylamine to N-benzylidene benzylamine under mild conditions (100 ℃, atmospheric O₂). Specifically, after reacting for 8 h, both benzylamine conversion and N-benzylidene benzylamine selectivity are larger than 98%, far better than the counterparts of carbon nanotubes, reduced graphene oxide and activated carbon, as well as the reported mesoporous carbon and graphene oxide. The hCNC700 also presents high mass activity, significantly better than the reported carbon-based catalysts. Its catalytic performance is almost unattenuated after 6 times of recycling, exhibiting good stability. By comparison experiments, the catalytic activity of hCNCs results from the intrinsic defects of carbon, and the excellent performance of hCNC700 is mainly attributed to the following aspects: (i) its ultra-high specific surface area can provide abundant surface active sites (defects), (ii) the unique hierarchical pore structure is very conducive to mass transfer in the reaction process, enabling the full utilization of these active sites. In addition, hCNC700 shows good catalytic performance for different substrates, with high catalytic activity (>90% conversion rate for 12 h reaction) and high selectivity (>95%) for oxidative coupling of aromatic methylene amines. This study provides a new avenue for the development of cheap and efficient carbon-based metal-free catalysts.

Key words: hierarchical carbon nanocage, metal-free catalyst, defect catalysis, benzylamine, N-benzylidene benzylamine

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Yu Zeng, Pin Lyu, Yuejin Cai, Fujie Gao, Ou Zhuo, Qiang Wu, Lijun Yang, Xizhang Wang, Zheng Hu. Hierarchical Carbon Nanocages as Efficient Catalysts for Oxidative Coupling of Benzylamine to N-Benzylidene Benzylamine[J]. Acta Chimica Sinica, 2021, 79(4): 539-544.

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Fig. & Tab. 5

Figure 1. SEM and TEM characterizations of hCNCs. (a) Typical SEM image; (b~d) TEM images of hCNC700, hCNC800 and hCNC900, respectively. Insets are high-resolution TEM images.

Figure 2. Raman characterizations of hCNCs. (a) Raman spectra; (b, d) ID/IG versus synthesis and annealing temperatures of hCNCs, respectively; (c, e) FWHMs of D- and G-band versus synthesis and annealing temperatures of hCNCs, respectively.

Figure 3. Comparison of catalytic performance of hCNCs for the oxidative coupling of benzylamine. (a) Comparison of the turnover frequency (TOF) of benzylamine for hCNC700 and several typical carbon-based materials (rGO, CNT, XC-72 and AC). The data for the carbon-based metal-free catalysts from Refs [14⇓⇓-17] are also listed for reference; (b) cycling stability of hCNC700; (c) benzylamine conversions of hCNC700, hCNC800, hCNC900 and hCNC700-C after reacting for 8 h; (d) benzylamine conversions of the as-prepared hCNC700 and the annealed hCNC700 at different temperatures versus time. Inset is the curve of k versus ID/IG, here k is the linearly-fitted slope in the fast reaction period marked in (d).

Catalyst	Conversion/ %	Selectivity/ %	S_BET^b/ (m²•g^–1)	S_total^c/ m²	Mass/ mg
Blank	0	—	—	—	—
hCNC700	98	>98	2300	46.0	20.0
rGO	70	>95	2000	40.0	20.0
CNT	22	>98	230	46.0	200
XC-72	20	>98	300	42.0	140
AC	8	>98	150	42.0	280

Table 1. Comparison of catalytic performance of hCNC700 and other typical carbon-based metal-free catalysts for the oxidative coupling of benzylamine to N-benzylidene benzylamine

底物	产物	转化率/%
		98
		96
		97
		95
		90
		40
		15

Table 2. Catalytic performance of selective oxidation of substituted methylene amine with hCNC700

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分级结构碳纳米笼高效催化苄胺氧化偶联制N-苄烯丁胺

Hierarchical Carbon Nanocages as Efficient Catalysts for Oxidative Coupling of Benzylamine to N-Benzylidene Benzylamine

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