多孔碳纳米球及其负载金属催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2018-1911

摘要/Abstract

摘要：

多孔碳纳米球由于可实现尺寸、形貌、孔结构以及表面基团等的可控合成制备，其负载/镶嵌的金属粒子又兼具高活性和高热稳定性等，在多相催化领域中受到越来越多的关注。本文追溯了多孔碳纳米球形貌调控的发展历程及其负载金属催化剂在催化反应领域中的应用。归纳了不同形貌的多孔碳纳米球及其制备方法和原理，详细对比了各个方法的优缺点；阐述了多孔碳纳米球负载金属催化剂的性能和碳球结构与形貌之间的构效关系；总结了目前碳球作为催化剂载体亟需解决的问题是碳球的多孔结构及其负载尺寸可控和空间匀称分布的金属粒子的可控合成，并展望了其发展方向是进一步研究和探索结构可调、经济可行的碳纳米球制备方法，真正实现工业化应用。

关键词: 碳纳米球, 形貌, 纳米结构, 催化剂载体, 多相反应

Abstract:

Porous carbon nanospheres have attracted intensive and increasing attention worldwide in heterogeneous catalysis due to the controllable size, morphology, pore structure and surface groups in their synthesis and excellent catalytic performance as catalyst support materials. This review outlines the development of morphology regulation of porous carbon nanospheres and their application as the supports of metal catalysts. The methods for the preparation of carbon nanospheres with various morphologies as well as the formation mechanisms involved are summarized and compared. The relationship between morphology and performance of porous carbon nanospheres supported metal catalysts is discussed. Based on the above discussion, it is suggested that the synthesis of porous carbon nanospheres with size-controlled and spatially symmetric disposition of metal particles is the current main challenge of carbon spheres as catalyst support. And it is also proposed that the structure-controlled and economic preparation method of porous carbon nanospheres will be an important direction of future developments.

Key words: carbon nanospheres, morphologies, nanostructure, catalyst support, multiphase reaction

中图分类号:

TQ127.1

季豪克, 张雪洁, 王昊, 朱倩文, 周烨彬, 卢春山, 李小年. 多孔碳纳米球及其负载金属催化剂的研究进展[J]. 化工进展, 2019, 38(07): 3143-3152.

Haoke JI, Xuejie ZHANG, Hao WANG, Qianwen ZHU, Yebin ZHOU, Chunshan LU, Xiaonian LI. Research progress of the porous carbon nanospheres and their supported metal catalysts[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3143-3152.

图/表 11

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催化剂结构	催化剂名称	催化剂组成	催化性能	参考文献
多孔实心碳纳米球载金属催化剂	Pd/CSs	Pd颗粒（粒径约5.4nm）均匀分布在碳球（约120nm）外表面	温和反应条件下催化硝基芳香化合物加氢反应的转化率以及选择性均为100%	[55]
	M/N-MCNSs	金属颗粒M（Au、 Pt、Rh、Ru、 Ag、 Pd 和 Ir）均匀分布在氮掺杂碳球的表面和孔道	室温或较高的温度下催化苯甲醛加氢反应中，羰基还原的选择性为100%	[56]
多孔中空碳纳米球载金属催化剂	Pd/CSs	Pd颗粒（粒径4～15nm）均匀分布在碳球外表面	在硝基苯液相催化还原反应中表现出高活性	[57]
	Pt/N-HCNSs	Pt颗粒（粒径约2.8 nm）均匀分布在中空碳球的内和外表面，碳壳厚度约为50nm	肉桂醛催化加氢的选择性为99.9%，转化率在催化剂循环套用12次后未下降	[12]
	Pd/B-HCSs	Pd颗粒（粒径约4.7 nm）均匀分布在中空碳球的内和外表面	催化苯甲醇无溶剂氧化反应，转化率为100%，选择性为99%	[58]
多孔核壳碳纳米球载金属催化剂	Pd@C	Pd颗粒（粒径约10.6nm）表面包裹碳层的实心核壳结构	室温下催化硝基苯液相还原反应中表现高转化率	[59]
	Au@C	Au颗粒（粒径约15nm）在中空碳球（约为150nm）内部自由活动，碳壳厚度约为18nm	在2-硝基苯酚液相催化还原反应中表现出高活性和高稳定性	[60]

催化剂结构	催化剂名称	催化剂组成	催化性能	参考文献
多孔实心碳纳米球载金属催化剂	Pd/CSs	Pd颗粒（粒径约5.4nm）均匀分布在碳球（约120nm）外表面	温和反应条件下催化硝基芳香化合物加氢反应的转化率以及选择性均为100%	[55]
	M/N-MCNSs	金属颗粒M（Au、 Pt、Rh、Ru、 Ag、 Pd 和 Ir）均匀分布在氮掺杂碳球的表面和孔道	室温或较高的温度下催化苯甲醛加氢反应中，羰基还原的选择性为100%	[56]
多孔中空碳纳米球载金属催化剂	Pd/CSs	Pd颗粒（粒径4～15nm）均匀分布在碳球外表面	在硝基苯液相催化还原反应中表现出高活性	[57]
	Pt/N-HCNSs	Pt颗粒（粒径约2.8 nm）均匀分布在中空碳球的内和外表面，碳壳厚度约为50nm	肉桂醛催化加氢的选择性为99.9%，转化率在催化剂循环套用12次后未下降	[12]
	Pd/B-HCSs	Pd颗粒（粒径约4.7 nm）均匀分布在中空碳球的内和外表面	催化苯甲醇无溶剂氧化反应，转化率为100%，选择性为99%	[58]
多孔核壳碳纳米球载金属催化剂	Pd@C	Pd颗粒（粒径约10.6nm）表面包裹碳层的实心核壳结构	室温下催化硝基苯液相还原反应中表现高转化率	[59]
	Au@C	Au颗粒（粒径约15nm）在中空碳球（约为150nm）内部自由活动，碳壳厚度约为18nm	在2-硝基苯酚液相催化还原反应中表现出高活性和高稳定性	[60]

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