1,5-Dinitronaphthalene hydrogenation to 1,5-diaminonaphthalene over carbon nanotube supported non-noble metal catalysts under mild conditions

doi:10.1016/j.apcata.2016.01.018

Applied Catalysis A: General

Volume 514, 25 March 2016, Pages 126-134

https://doi.org/10.1016/j.apcata.2016.01.018 Get rights and content

Highlights

•
A new system of 1,5-dinitronaphthalene hydrogenation to 1,5-diaminonaphthalene catalyzed by non-noble metal supported catalysts.
•
Surface modifications of CNTs improve the catalytic properties effectively.
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Non-noble Ni/CNTs gives the best result of 100% conversion of 1,5-dinitronaphthalene and 92.04% selectivity to 1,5-diaminonaphthalene under mild conditions.
•
Such non-noble metal hydrogenation catalysts are expected to replace the present supported palladium or platinum noble catalysts in industry.

Abstract

Carbon nanotubes (CNTs) were firstly thermal treated and then acid treated in HNO₃ or mixture of HNO₃ and H₂SO₄. The treated carbon nanotubes were used as support to load nickel to prepare non-noble metal hydrogenation catalysts. These catalysts were characterized and applied in 1,5-dinitronaphthalene hydrogenation. The characterization results indicate that acid modified carbon nanotubes not only possess a more hydrophilic surface by introducing a variety of oxygen-containing functional groups, but also improve the nickel dispersion, hydrogen uptake quantity and metallic surface area. The Ni/CNTs catalysts show good catalytic activity in 1,5-dinitronaphthalene hydrogenation under mild reaction conditions, and the Ni/CNTs-4 gives the best result of 100% conversion of 1,5-dinitronaphthalene and 92.04% selectivity to 1,5-diaminonaphthalene under 0.6 MPa and 393 K. The influences of reaction conditions and metal loading amount are discussed, and a possible reaction routes of 1,5-dinitronaphthalene hydrogenation is proposed. Such non-noble metal hydrogenation catalysts are expected to replace the present supported palladium or platinum noble catalysts in industry.

Graphical abstract

Introduction

Active carbon supported palladium or platinum noble metal catalysts are widely used in hydrogenation, especially in fine chemicals hydrogenation process. 1,5-diaminonaphthalene can be used in the manufacture of dyestuff, pesticide, rubber chemicals, resin and photographic materials [1]. Particularly, it is the critical material to produce 1,5-diisocyanatonaphthalene, which is an advanced polyurethane for large machinery production, the shock absorption and noise reduction of railway transportation equipments, the composite materials of wind power equipment vane, new membrane materials of solar cell module and so on [2], [3], [4], [5]. The traditional technology of 1,5-diaminonaphthalene production suffers from many disadvantages such as the complex routes, the generation of large quantities of organic wastes and lower yield [5], [6], [7], [8]. Hence, many researchers have tried to develop novel methods for the production of 1,5-diaminonaphthalene. In industry, the higher cost of 1,5-dinitronaphthalene hydrogenation to 1,5-diaminonaphthalene lies in the use of noble metal catalysts such as Pt/C or Pd/C [9], [10]. Therefore, non-noble metal catalysts have obtained more and more attention in the hydrogenation processes [11], [12], [13], [14]. Carbon nanotubes (CNTs) have been reported to be excellent catalyst supports based on their intrinsic properties such as high surface area, unique electronic properties and chemical inertness, thermal stability and high mechanical strength [15], [16], [17], [18], [19], [20]. And carbon nanotubes supported metal catalysts exhibited high activity in hydrogenation processes [21], [22], [23], it has been assumed that the phenomenon of Hydrogen Spillover on the catalysts plays an important role. Quite a few literature are concerned with the using of modified carbon nanotubes as catalyst support [24], [25], [26], [27], [28], [29], [30], [31], [32].

In this paper, carbon nanotubes supported non-noble nickel catalysts were prepared and applied in 1,5-dinitronaphthalene hydrogenation to 1,5-diaminonaphthalene. It has been found that modified carbon nanotubes supported non-noble metal catalysts show good catalytic activity and selectivity to 1,5-diaminonaphthalene under mild conditions.

Section snippets

Materials

The CNTs with a diameter of 10–20 nm were purchased from Shenzhen Nanotech Port Co., Ltd., China. 1,5-dinitronaphthalene was purchased from Shanghai Jingchun Reagent Co., Ltd. Nickel nitrate (Ni(NO₃)₂·6H₂O) was purchased from Shanghai Aibi Chemistry Reagent Co., Ltd. And all the other reagents were analytical grade. The 1,5-diaminonaphthalene (97 wt.%) standard sample was purchased from Alfa Aesar-A Johnson Matthey Company.

Catalyst preparation

The raw CNTs material were denoted as CNTs-1. The raw CNTs underwent acid

Characterization of catalysts

Boehm titration results of the supports are presented in Table 1. The results indicate that there are a small quantity of carboxylic and phenolic groups on the surface of CNTs-1. Surface modification with various oxidants leads to the increment of acidic groups [34], [35]. Hence, the modified samples show significant difference in their chemical nature. CNTs-2 oxidized with 65 wt.% HNO₃ at 303 K exhibits the presence of the lactonic groups and a small quantity of carboxylic groups, and the number

Conclusions

In conclusion, nickel was supported on the modified carbon nanotubes to prepare non-noble metal catalysts by impregnation method. The characterization results indicate that carbon nanotubes undergo acid treatment were introduced a variety of oxygen-containing functional groups, which is help to improve the metal dispersion, hydrogen uptake quantity and metallic surface area. It shows that 20 wt.% Ni/CNTs-4 gives the best catalytic performance of 100% conversion of 1,5-dinitronaphthalene and

Acknowledgments

This work was supported by NSFC (21276218, 21306160), Specialized Research Fund for the Doctoral Program of Higher Education (20124301110007), General project of Hunan Provincial Education Department (14C1093) and the Project of Xiangtan University (2015SEP04, 2015SEP05)

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1,5-Dinitronaphthalene hydrogenation to 1,5-diaminonaphthalene over carbon nanotube supported non-noble metal catalysts under mild conditions

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Catalyst preparation

Characterization of catalysts

Conclusions

Acknowledgments

Opt. Mater.

Catal. Commun.

Appl. Catal. A: Gen.

Appl. Catal. A: Gen.

J. Mol. Catal. A: Chem.

Carbon

Appl. Catal. A: Gen.

Appl. Catal. B: Environ.

Chem. Eng. J.

Catal. Today

Chem. Eng. J.

Mater. Chem. Phys.

J. Colloid Interface Sci.

J. Colloid Interface Sci.

Carbon

Water Res.

Carbon

Chem. Eng. J.

Advance in NDI Elastoner Chemisty, Poly Urethanes Wdrld Congr. 91. USA

J. Elastomers Plast.

Macromolecules

Chin. J. Org. Chem.

US Pat.