单分散氮掺杂的碳纳米球负载钯催化氯代硝基苯加氢反应

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摘要高效钯炭催化剂的研制是卤代硝基苯选择性加氢还原制备卤代苯胺工艺取得突破的关键。以单分散氮掺杂的碳纳米球为载体、钯为活性组分,采用浸渍法制备出负载型的Pd/CN-x(x代表碳基载体的焙烧温度),并对其催化氯代硝基苯加氢制备氯代苯胺反应的性能进行了研究。分别采用傅里叶变换红外光谱(FT-IR)、X射线衍射光谱(XRD)、透射电子显微镜(TEM)、场发射扫描电镜(SEM)以及X射线光电子能谱(XPS)技术对Pd/CN-x催化剂的形貌、结构及表面化学性质进行了表征分析。考察了不同温度下制备出的碳氮材料负载钯催化剂对氯代硝基苯选择性加氢还原反应活性和选择性的影响。研究结果表明,以单分散氮掺杂的碳纳米球为载体能够实现金属Pd颗粒的均匀分散,因而催化剂表现出优异的催化加氢性能。其中,Pd/CN-600催化剂表现出100%的3-氯硝基苯转化率,同时对3-氯苯胺的选择性高达76.9%。此外,载体表面含氮官能团影响活性Pd组分的有效分散,进而影响3-氯苯胺的选择性。

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	于芳
	祖荣艳
	吕云鹏
	韩兴华
	王志鹏
	李裕
	宋健

关键词：单分散氮掺杂碳球催化加氢负载型Pd催化剂 3-氯硝基苯 3-氯苯胺

Abstract： The preparation of efficient Pd/C catalysts for selective hydrogenation of halogenated nitrobenzene to halogenated aniline is the key to get a breakthrough in this process. Here, supported Pd/CN-x(x represents the carbonization temperature of carbon-based support) catalysts were prepared via an impregnation method with monodispersed nitrogen-doped carbon nanospheres as the support and metallic palladium as the active component, and their catalytic performances for the hydrogenation of chlorinated nitrobenzene to chlorinated aniline were studied. The morphology, structure and surface chemical properties of obtained catalysts were characterized by Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The effect of nitrogen-doped carbon support prepared at different temperatures on the activity and selectivity of selective hydrogenation of chloronitrobenzene for supported palladium catalysts were investigated. Experimental results revealed that the monodispersed nitrogen-doped carbon nanospheres as support could achieve uniform dispersion of Pd nanoparticles, and endow the obtained samples with excellent catalytic properties. In particular, the Pd/CN-600 catalyst exhibits 100% conversion of 3-chloronitrobenzene with a selectivity of 76.9% for 3-chloroaniline. In addition, it was indicated that the nitrogen-containing functional groups on the surface of the carbon nanospheres could influence the effective dispersion of the active Pd component and thus the selectivity of 3-chloroaniline.

Keywords： monodispersed nitrogen-doped carbon nanospheres catalytic hydrogenation supported Pd catalysts 3-chloronitrobenzene 3-chloroaniline

Received 2023-03-17;

Fund:国家自然科学基金资助项目(22002143,22202185);山西省自然科学基金资助项目(22202185)。

Corresponding Authors: 韩兴华,讲师,E-mail:hxh@nuc.edu.cn;宋健,副教授,E-mail:songj@nuc.edu.cn。 Email: hxh@nuc.edu.cn;songj@nuc.edu.cn

About author: 于芳(1998-),女,硕士研究生,主要从事绿色催化及应用研究。

引用本文:

于芳, 祖荣艳, 吕云鹏, 韩兴华, 王志鹏, 李裕, 宋健.单分散氮掺杂的碳纳米球负载钯催化氯代硝基苯加氢反应[J]. 化学工业与工程, 2023,40(6): 45-52

YU Fang, ZU Rongyan, LYU Yunpeng, HAN Xinghua, WANG Zhipeng, LI Yu, SONG Jian.Hydrogenation of chlorinated nitrobenzene by Pd supported on monodispersed nitrogen-doped carbon nanospheres[J]. Chemcial Industry and Engineering, 2023,40(6): 45-52

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