掺杂多孔碳材料催化硝基苯还原反应的研究进展

doi:10.16085/j.issn.1000-6613.2020-0609

摘要/Abstract

摘要：

苯胺是重要的化工原料和合成中间体，通过硝基苯的催化还原反应可以方便地制备苯胺类化合物。多孔碳材料因其高比表面积、发达的孔隙结构和容易回收等特点在催化领域越来越受到重视，然而其应用受到自身活性位点缺乏和化学惰性的限制。杂原子掺杂可以增强碳材料的表面极性，调节电子结构，改善其催化性能，可作为硝基苯催化还原反应的有效催化剂。本文对近年来掺杂多孔碳材料在硝基苯催化还原反应中的研究进展进行了总结。本文概述了氮掺杂型多孔碳材料、共掺杂型多孔碳材料、负载贵金属的掺杂多孔碳材料和负载廉价金属的掺杂多孔碳材料这4种主要的掺杂多孔碳材料的制备方法，并详细介绍了不同掺杂多孔碳材料在催化硝基苯催化还原反应时的催化性能、可能的催化活性位点以及催化机理。最后，指出目前掺杂多孔碳材料催化硝基苯还原还需要解决反应选择性、催化剂催化活性和生产成本等问题，以生物质为前体，开发共掺杂型和二元双金属负载的掺杂多孔碳材料是未来的重要发展方向之一。

关键词: 多孔碳材料, 催化剂, 硝基苯, 还原, 掺杂, 载体

Abstract:

As an industrially important raw material and synthetic intermediate, aniline can be directly prepared by catalytic reduction of nitrobenzene. More and more attention has been paid to the application of porous carbon materials in catalysis due to their high specific surface area, well-developed pore structure and recyclability. However, the application of porous carbon materials directly as catalyst is limited by their inadequate active sites and chemical inertness. Heteroatomic doping can enhance the surface polarity, adjust the electronic structure and improve the catalytic performance of the porous carbon materials. Therefore, the doped porous carbon materials can be used as effective catalysts for the reduction of nitrobenzene. This review summarizes the recent research progress of doped porous carbon materials in the catalytic reduction of nitrobenzene. The preparation methods for the nitrogen-doped and co-doped porous carbon materials, as well as the doped porous carbon materials loading noble and non-noble metals are presented. Special attention is given to the catalytic performance, possible catalytic active sites and the catalytic mechanism of the doped porous carbon materials. Finally, the problems of reaction selectivity, catalytic activity and production cost are still needed to be solved in the reduction of nitrobenzene catalyzed by doped porous carbon materials. Using biomass as the precursor to develop co-doped porous carbon materials and doped porous carbon materials loading bimetals is one of the important directions in the future.

Key words: porous carbon materials, catalysis, nitrobenzene, reduction, doping, support

中图分类号:

TQ24

卢贝丽, 刘杏, 尹铸, 黄彪. 掺杂多孔碳材料催化硝基苯还原反应的研究进展[J]. 化工进展, 2021, 40(2): 778-788.

Beili LU, Xing LIU, Zhu YIN, Biao HUANG. Recent development on doped porous carbon materials for catalytic reduction of nitrobenzene[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 778-788.

图/表 10

图1 N原子在碳骨架中的存在形式示意[14]1—吡啶氮；2—吡咯氮；3—石墨氮；4—氧化氮；5—胺基

图2 含氮金属-有机框架材料热解制备氮掺杂介孔碳材料[16]

图3 可能的反应机理示意图[18]

表1 不同碳材料催化硝基苯的还原制备苯胺

催化剂	第一步HNO₃	第二步KOH	第三步H₂O₂	转化率/%	选择性/%
non-C	no	no	no	42.1	100
PC	no	活化（1h）	no	62.7	100
OPC	no	活化（1h）	24	83.2	100
ONPC	氧化（16h）	活化（1h）^①	no	100	100

表2 4-硝基苯酚还原反应中共掺杂原子的协同效应

催化剂	4-硝基苯酚的转化率 /%	(N/B) /%	表观活化能 /kJ·mol^-1
NPC	16	11.3/0	48.2
B-NPC-800	32	8.5/0	39.1
B-NPC-1000	77	4.2/0.9	30.2
B-NPC-1200	94	1.9/1.5	27.0

图4 对氯硝基苯选择性催化加氢生成对氯苯胺的机理[27]

表3 Pt/NOMC催化带有不同取代基的硝基苯的氢化反应

反应时间/h	转化率/%	选择性/%
0.5	100	99.5
0.5	100	98.8
0.5	100	95.5
2	100	100
2	100	99.2
2	100	100
2	100	100
2	100	85.4
2	100	70

图5 氮、硫共掺杂多孔碳材料的合成

图6 CoOx@NC-800催化不同类型硝基苯的氢化及其可能的机理[36]

图7 γ-Fe2O3/MC催化卤素取代硝基苯还原的反应机理[38]

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