MIL-53 (Al) derived single-atom Rh catalyst for the selective hydrogenation of m-chloronitrobenzene into m-chloroaniline

doi:10.1016/S1872-2067(20)63697-X

Chinese Journal of Catalysis ›› 2021, Vol. 42 ›› Issue (5): 824-834.DOI: 10.1016/S1872-2067(20)63697-X

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MIL-53 (Al) derived single-atom Rh catalyst for the selective hydrogenation of m-chloronitrobenzene into m-chloroaniline

Weiyin Wang^a^,^b, Lu Lin^b, Haifeng Qi^b^,^c, Wenxiu Cao^d, Zhi Li^e, Shaohua Chen^f, Xiaoxuan Zou^a^,^#(), Tiehong Chen^f, Nanfang Tang^b, Weiyu Song^e, Aiqin Wang^b^,^g, Wenhao Luo^b^,^*()

^aCollege of Chemistry, Xiangtan University, Xiangtan 411105, Hunan, China
^bCAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^cUniversity of Chinese Academy of Sciences, Beijing 100049, China
^dCollege of Chemistry and Chemical Engineering, Jishou University, Jishou 416000, Hunan, China
^eState Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
^fInstitute of New Catalytic Materials Science, School of Materials Science and Engineering, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University, Tianjin 300350, China
^gState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2020-05-08 Accepted:2020-05-08 Online:2021-05-18 Published:2021-01-29
Contact: Xiaoxuan Zou,Wenhao Luo
About author:^# E-mail: zouxiaoxuan@xtu.edu.cn
^* Tel: +86-411-84379738; Fax: +86-411-84685940; E-mail: w.luo@dicp.ac.cn;
First author contact:
^† Contributed equally to this work.
Supported by:
Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020100);National Natural Science Foundation of China(21703238);National Natural Science Foundation of China(21690084);National Natural Science Foundation of China(21802134);Educational Commission of Hunan Province(19B463);Collaborative Innovation Center of Manganese-Zinc-Vanadium Industrial Technology(MXF202001);Research Startup Foundation of Jishou University(21)

Abstract

Abstract:

The catalytic hydrogenation of halonitroarenes to haloanilines is a green and sustainable process for the production of key nitrogen-containing intermediates in fine chemical industry. Chemoselective hydrogenation poses a significant challenge, which requires the rational design of the catalysts with proper hydrogenation ability for nitro group and simultaneously preventing dehalogenation of halogen group. Herein, a highly effective Rh@Al₂O₃@C single-atom catalyst (SAC) was developed for the hydrogenation of m-chloronitrobenzene (m-CNB) to m-chloroaniline (m-CAN), through an in-situ grafting of metal during the assembly of MIL-53 (Al), followed by confined pyrolysis. Extensive characterizations reveal an exquisite structure of the Rh@Al₂O₃@C, containing atomically dispersed Rh sites onto Al₂O₃ confined by the amorphous carbon. The five-coordinated aluminum (Al^V) species are essential for achieving the atomic dispersion of Rh atoms, providing the unsaturated coordinative sites for metal. Compared to the benchmark Rh/γ-Al₂O₃ and Rh/C nanocatalysts, the Rh@Al₂O₃@C SAC affords an excellent turnover frequency of 2317 mol_m_-CNB·mol_Rh^-1·h^-1, the highest value to date in heterogeneous catalyst systems for the hydrogenation of m-CNB at 313 K and 20 bar H₂, together with a sustained selectivity to m-CAN (~98%) during five consecutive runs. The superior catalytic performance of the Rh@Al₂O₃@C is attributed to a proper modulation of electronic structure of hydrogenation metal by forming SAC, together with an enhanced accessibility of acid function sites.

Key words: Single-atom catalyst, Rhodium, Metal-organic framework, Hydrogenation, Chemoselectivity

Weiyin Wang, Lu Lin, Haifeng Qi, Wenxiu Cao, Zhi Li, Shaohua Chen, Xiaoxuan Zou, Tiehong Chen, Nanfang Tang, Weiyu Song, Aiqin Wang, Wenhao Luo. MIL-53 (Al) derived single-atom Rh catalyst for the selective hydrogenation of m-chloronitrobenzene into m-chloroaniline[J]. Chinese Journal of Catalysis, 2021, 42(5): 824-834.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63697-X

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Figures/Tables 11

Scheme 1. Schematic illustration for the synthesis of the Rh@Al2O3@C.

Fig. 1. XRD patterns of the MIL-53 (Al), the Rh@MIL-53 (Al), the Al2O3@C and the Rh@Al2O3@C.

Fig. 2. N2 adsorption-desorption isotherms (a) and pore size distributions (b) of the MIL-53 (Al), the Rh@MIL-53 (Al) and the Rh@Al2O3@C.

Table 1 Physicochemical properties of different samples under study.

Catalysts	BET surface area (m²·g^-1)	Micropore surface area ^a (m²·g^-1)	External surface area^a (m²·g^-1)	Micropore volume^a (cm³·g^-1)	Rh loading (wt%)
MIL-53 (Al)	1451	1001	450	0.498	—
Rh@MIL-53 (Al)	1109	770	338	0.402	—
Rh@Al₂O₃@C	219	78	141	0.040	0.1 ^d
Rh@Al₂O₃@C (spent) ^b	180	58	122	0.031	0.1^d
Rh/γ-Al₂O₃	174	— ^c	178	— ^c	0.1^d
Rh/C	1472	598	875	0.309	0.1^d

Fig. 3. STEM images of the Rh@MIL-53 (Al) (a,b) and the Rh@Al2O3@C (c-f).

Fig. 4. AC-HAADF-STEM images of the Rh@Al2O3@C in grey (a,b) and in color (c,d).

Fig. 5. (a) FT-IR spectra of CO adsorption over the Rh@Al2O3; (b) 27Al MAS NMR spectra of the Rh@Al2O3@C.

Fig. 6. (a) The migration energetic diagram of single Rh atoms on the γ-Al2O3(100) surface; (b) nucleation energies Enuc of the aggregation from Rh1 to Rh4 on the γ-Al2O3(100) surface. Red, pink and dark cyan balls represent O, Al, and Rh atoms, respectively.

Fig. 7. Time profiles of selective hydrogenation of m-chloronitrobenzene using the Rh@Al2O3@C (a), the Rh/γ-Al2O3 (b) and the Rh/C (c) as the catalysts; (d) catalytic routes of selective hydrogenation of m-chloronitrobenzene to m-chloroaniline. Reaction conditions: T = 313 K, PH2 = 20 bar, 30 mg catalyst, 0.5 mmol m-chloronitrobenzene, 2 mL toluene.

Fig. 8. Rh 3d XPS spectra of the Rh/C, the Rh/γ-Al2O3 and the Rh@Al2O3@C.

Fig. 9. (a) The recycling experiments of the Rh@Al2O3@C; (b-d) STEM images of the spent Rh@Al2O3@C after five consecutive runs. Reaction conditions: T = 313 K, PH2 = 20 bar, t = 12 h, 30 mg catalyst, 0.5 mmol m-chloronitrobenzene, 2 mL toluene.

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MIL-53 (Al) derived single-atom Rh catalyst for the selective hydrogenation of m-chloronitrobenzene into m-chloroaniline

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