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Acta Metall Sin  2024, Vol. 60 Issue (8): 1141-1149    DOI: 10.11900/0412.1961.2024.00079
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Hydrogenation of Nitrobenzene Catalyzed by Pt Supported on Carbon Coated Nickel Magnetic Supports
WU Yi1, SI Yang1, HUANG Yanmin2, DIAO Jiangyong1, MENG Fanjing2, LIU Zeng2, LIU Hongyang1()
1 Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2 Technology Innovation Center of Modified Isocyanate of Hebei Province, Cangzhou Dahua Co. Ltd., Cangzhou 061000, China
Cite this article: 

WU Yi, SI Yang, HUANG Yanmin, DIAO Jiangyong, MENG Fanjing, LIU Zeng, LIU Hongyang. Hydrogenation of Nitrobenzene Catalyzed by Pt Supported on Carbon Coated Nickel Magnetic Supports. Acta Metall Sin, 2024, 60(8): 1141-1149.

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Abstract  

Aniline is an important chemical raw material widely used in various industries, including medicine, dye manufacturing, and rubber production. Catalytic liquid-phase dhydrogenation of nitrobenzene is a main industrial production method for aniline. However, the separation and recovery of the catalyst from the liquid hydrogenation system remain challenging. Graphene-encapsulated transition-metal nanoparticles (TM@G, where TM = Fe, Co, and Ni) exhibit magnetic separability and electron transfer effects, making them widely applicable in heterogeneous catalysis. In this study, a magnetically separable catalyst support, comprising graphene-encapsulated Ni nanoparticles (Ni@NG), was developed. This support was then loaded with a Pt metal catalyst for efficient catalytic hydrogenation of nitrobenzene to aniline. To fabricate the catalyst support, ethylenediaminetetraacetic acid and Ni(OH)2 were uniformly mixed in deionized water until the solution turned blue at 90°C. The resulting blue solid precursor was then dried and annealed at 600°C in argon to yield the magnetic support (Ni@NG). The support was then characterized using Raman spectroscopy, TEM, XRD, and XPS. TEM results revealed that the Ni@NG support exhibited a typical core-shell structure (with nanoscale Ni particles as the core and 2-5 layers of graphene as the shell). The Raman spectrum of the Ni@NG support exhibited the characteristic D and G bands of graphene at 1341 and 1604 cm-1, respectively. Moreover, the XRD spectrum of this support exhibited distinct peaks corresponding to Ni and graphene, while its XPS analysis confirmed the presence of an approximate nitrogen atom concentration of 3.64% in the nitrogen-doped graphene shell. Furthermore, the deposition-precipitation method was employed to synthesize a Pt-loaded Ni@NG catalyst (Pt/Ni@NG), which was later used in the catalytic hydrogenation of nitrobenzene in a liquid-phase reaction. Results revealed that increasing the Pt weight loading (mass fraction) from 0.1% to 0.5% altered the Pt dispersion state from single atoms to clusters and then to particles. In particular, at a Pt weight loading of 0.3%, the Pt/Ni@NG catalyst dominated by Pt clusters exhibited the highest activity for the hydrogenation of nitrobenzene. At this Pt weight loading, the catalyst achieved a turnover frequency of 27239.2 h-1 at 1 MPa reaction pressure under 30°C, completely converting nitrobenzene to aniline within 60 min. Furthermore, the Pt/Ni@NG catalyst maintained its activity over five testing cycles, attributed to its excellent liquid-phase magnetic separability.

Key words:  core-shell structure      nitrobenzene hydrogenation      magnetic separability      nitrogen-doped carbon material     
Received:  11 March 2024     
ZTFLH:  O643.38  
Fund: National Natural Science Foundation of China(22072162);National Natural Science Foundation of China(U21B2092);Institutionalization Research Platform Project by Chinese Academy of Sciences, and Science and Technology Achievement Transfer Projec by Hebei Province and Chinese Academy of Sciences(23291401Z)
Corresponding Authors:  LIU Hongyang, professor, Tel: (024)83970027, E-mail: liuhy@imr.ac.cn

URL: 

https://www.ams.org.cn/EN/10.11900/0412.1961.2024.00079     OR     https://www.ams.org.cn/EN/Y2024/V60/I8/1141

Fig.1  HRTEM images of Ni@NG support with different magnifications (a-d), high angle annular dark field (HAADF) STEM image of Ni@NG support (e), and size distributions of Ni nanoparticles in Ni@NG support (f) (Inset in Fig.1d shows the selected area electron diffraction pattern, d—lattice spacing)
Fig.2  XPS results of the Ni@NG support
(a) N1s (b) C1s (c) Ni2p (d) O1s
Fig.3  Raman spectrum (a) and thermogravimetric (TG) curves (b) of the as-prepared Ni@NG support (ID / IG—intensity ratio)
Fig.4  Schematics of the Ni@NG support with magnetic separability under the hydrogenation system
(a) the as-prepared Ni@NG sample was dispersed into the solvent
(b) then a magnet is placed on one side for 1 min
Fig.5  Low (a, c, e) and high (b, d, f) magnified HAADF STEM images of 0.1%Pt1/Ni@NG (a, b), 0.3%Ptn/Ni@NG (c, d), and 0.5%Ptp/Ni@NG (e, f) catalysts (White labels indicate Pt single atoms, blue labels indicate Pt nanoparticles, and red labels indicate Pt clusters)
Fig.6  XRD spectra of Ni@NG support and 0.1%Pt1/Ni@NG, 0.3%Ptn/Ni@NG, and 0.5%Ptp/Ni@NG catalysts
Fig.7  N2 adsorption/desorption isotherms (a, b) and pore size distribution curves (c, d) of Ni@NG support (a, c) and 0.3%Ptn/Ni@NG catalyst (b, d) (Vads—N2 adsorption volume, D—pore size)
Fig.8  Turnover frequency (TOF) for 0.1%Pt1/Ni@NG, 0.3%Ptn/Ni@NG, and 0.5%Ptp/Ni@NG catalysts (a); nitrobenzene hydrogenation kinetic curves (b), time-nitrobenzene conversion rates and aniline yield curve (c), and hydrogenation stability (d) of 0.3%Ptn/Ni@NG catalyst (T—absolute temperature; r—reaction rate constant at temperature T; Ea—experimental activation energy)
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