Pd-CuO@mSiO<sub>2</sub>催化剂的制备及其选择性催化取代硝基芳烃加氢制取代芳胺

陈敏婷; 于洪波; 张守超; 尹宏峰

doi:10.12434/j.issn.2097-2547.20240120

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Pd-CuO@mSiO₂催化剂的制备及其选择性催化取代硝基芳烃加氢制取代芳胺

低碳分子转化合成

- Pd-CuO@mSiO₂催化剂的制备及其选择性催化取代硝基芳烃加氢制取代芳胺
- Preparation of Pd-CuO@mSiO₂ catalyst and its selective catalytic hydrogenation of substituted nitroaromatics to substituted aromatic amines
- 低碳化学与化工 2024, 49(12): 39-46.
- 作者机构：
  
  1.天津城建大学理学院，天津 300384
  2.中国科学院宁波材料技术与工程研究所，浙江宁波 315201
  3.宁波工程学院材料与化学工程学院，浙江宁波 315211
- 作者简介：
  
  陈敏婷（1999—），硕士研究生，研究方向为催化材料，E-mail：chenminting@nimte.ac.cn。
  于洪波（1984—），博士后，副研究员，研究方向为纳米催化，E-mail：hongboyu@nbut.edu.cn；
  张守超（1982—），博士，副教授，研究方向为晶体缺陷及其应用，E-mail：zhshch@tcu.edu.cn；
  尹宏峰（1977—），博士后，研究员，研究方向为纳米材料合成及其在催化反应中的应用与机理分析， E-mail：yinhf@nimte.ac.cn。
- 基金信息：
  
  国家自然科学基金(22072171);天津市研究生科研创新项目(2022SKYZ135)
- DOI：10.12434/j.issn.2097-2547.20240120
  中图分类号： TQ426
- 纸质出版日期：2024-12-25，
  
  收稿日期：2024-03-24，
  
  修回日期：2024-05-05，
- 稿件说明：
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陈敏婷,于洪波,张守超等.Pd-CuO@mSiO₂催化剂的制备及其选择性催化取代硝基芳烃加氢制取代芳胺[J].低碳化学与化工,2024,49(12):39-46.

CHEN Minting,YU Hongbo,ZHANG Shouchao,et al.Preparation of Pd-CuO@mSiO₂ catalyst and its selective catalytic hydrogenation of substituted nitroaromatics to substituted aromatic amines[J].Low-carbon Chemistry and Chemical Engineering,2024,49(12):39-46.
陈敏婷,于洪波,张守超等.Pd-CuO@mSiO₂催化剂的制备及其选择性催化取代硝基芳烃加氢制取代芳胺[J].低碳化学与化工,2024,49(12):39-46. DOI： 10.12434/j.issn.2097-2547.20240120.

CHEN Minting,YU Hongbo,ZHANG Shouchao,et al.Preparation of Pd-CuO@mSiO₂ catalyst and its selective catalytic hydrogenation of substituted nitroaromatics to substituted aromatic amines[J].Low-carbon Chemistry and Chemical Engineering,2024,49(12):39-46. DOI： 10.12434/j.issn.2097-2547.20240120.

摘要

取代硝基芳烃选择性催化加氢是制备取代芳胺的有效方法，精确调控贵金属催化剂在该反应中的反应位点和增强其催化稳定性是亟待解决的难题。采用溶胶-凝胶法制备了含PdCu合金的SiO

核壳型前体（PdCu@SiO

），进而制备了含PdO-CuO的介孔核壳SiO

催化剂（PdO-CuO@mSiO

）、含Pd-CuO的介孔核壳SiO

催化剂（Pd-CuO@mSiO

）和含PdCu合金的介孔核壳SiO

催化剂（PdCu@mSiO

）。采用TEM、XRD和TG等对催化剂进行了表征，并研究了催化剂对4-硝基氯苯选择性催化加氢制4-氨基氯苯的催化性能。结果表明，在最优条件（0.5 mmol 4-硝基氯苯、12.0 mL乙醇、80 ℃和1.0 MPa）下反应4.0 h，相比Pd@mSiO

和PdCu@mSiO

，Pd-CuO@mSiO

具有更好的催化性能，其4-硝基氯苯转化率为96.5%，4-氨基氯苯选择性为99.6%。Pd-CuO@mSiO

的良好催化性能与其结构中Pd与CuO之间的强相互作用有关。同时Pd-CuO@mSiO

在间氯硝基苯、对硝基苯乙酮和4-硝基苯甲酸乙酯的催化加氢反应中也表现出了较好的催化性能。此外，Pd-CuO@mSiO

在最优反应条件下经过5次循环后，其4-硝基氯苯转化率和4-氨基氯苯选择性分别维持在96.4%和95.7%。

Abstract

Selective catalytic hydrogenation of substituted nitroaromatic hydrocarbons is an effective method to prepare substituted aromatic amines. It is an urgent problem to precisely regulate the reaction site of precious metal catalyst and enhance its catalytic stability in this reaction. The SiO

core-shell precursor containing PdCu alloy (PdCu@SiO

) was prepared by sol-gel method. Then the mesoporous core-shell SiO

catalyst containing PdO-CuO (PdO-CuO@mSiO

)

the mesoporous core-shell SiO

catalyst containing Pd-CuO (Pd-CuO@mSiO

) and the mesoporous core-shell SiO

catalyst containing PdCu alloy (PdCu@mSiO

) were prepared. The catalysts were characterized by TEM

XRD and TG

etc.

and their catalytic performances for selective catalytic hydrogenation of 4-nitrochlorobenzene to 4-aminochlorobenzene were studied. The results show that reaction under the optimal conditions (0.5 mmol 4-nitrochlorobenzene

12.0 mL ethanol

80 ℃ and 1.0 MPa) for 4.0 h

Pd-CuO@mSiO

has better catalytic performance than Pd@mSiO

and PdCu@mSi

with 4-nitrochlorobenzene conversion rate of 96.5% and 4-amino-chlorobenzene selectivity of 99.6%. The good catalytic performance of Pd-CuO@mSiO

is related to the strong interaction between Pd and CuO in the structure. Pd-CuO@mSiO

also shows good catalytic performance for the catalytic hydrogenation of

-chloronitrobenzene

-nitroacetophenone and 4-nitrobenzoate. In addition

cycling under the optimal reaction conditions for five times

the 4-nitrochlorobenzene conversion rate and 4-amino-chlorobenzene selectivity of Pd-CuO@mSiO

maintain at 96.4% and 95.7%

respectively.

关键词

取代硝基芳烃Pd基核壳型催化剂选择性加氢取代芳胺

Keywords

substituted nitroaromaticsPd-based core-shell catalystsselective hydrogenationsubstituted aromatic amines

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Pd-CuO@mSiO2催化剂的制备及其选择性催化取代硝基芳烃加氢制取代芳胺

Preparation of Pd-CuO@mSiO2 catalyst and its selective catalytic hydrogenation of substituted nitroaromatics to substituted aromatic amines

DOI：10.12434/j.issn.2097-2547.20240120

摘要

Abstract

关键词

Keywords

references

Pd-CuO@mSiO₂催化剂的制备及其选择性催化取代硝基芳烃加氢制取代芳胺

Preparation of Pd-CuO@mSiO₂ catalyst and its selective catalytic hydrogenation of substituted nitroaromatics to substituted aromatic amines