MIL-53 (Al)衍生的Rh单原子催化剂在间氯硝基苯选择性加氢制间氯苯胺反应中的应用

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

催化学报 ›› 2021, Vol. 42 ›› Issue (5): 824-834.DOI: 10.1016/S1872-2067(20)63697-X

MIL-53 (Al)衍生的Rh单原子催化剂在间氯硝基苯选择性加氢制间氯苯胺反应中的应用

王伟银^a^,^b, 林露^b, 齐海峰^b^,^c, 曹文秀^d, 李志^e, 陈少华^f, 邹晓轩^a^,^#(), 陈铁红^f, 唐南方^b, 宋卫余^e, 王爱琴^b^,^g, 罗文豪^b^,^*()

^a湘潭大学化学学院, 湖南湘潭411105
^b中国科学院大连化学物理研究所, 中国科学院航天催化材料重点实验室, 辽宁大连116023
^c中国科学院大学, 北京100049
^d吉首大学化学与化工学院, 湖南吉首416000
^e中国石油大学重质油加工国家重点实验室, 北京102249
^f南开大学材料科学与工程学院高级能源材料重点实验室, 新催化材料科学研究所, 天津300350
^g中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连116023

收稿日期:2020-05-08 接受日期:2020-05-08 出版日期:2021-05-18 发布日期:2021-01-29
通讯作者: 邹晓轩,罗文豪
作者简介:第一联系人：
^†共同第一作者.
基金资助:
中国科学院战略性先导科技专项(XDB17020100);国家自然科学基金(21703238);国家自然科学基金(21690084);国家自然科学基金(21802134);湖南省教育厅优秀青年项目(19B463);锰锌钒产业技术湖南省2011协同创新中心(MXF202001);吉首大学人才启动基金(21)

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)

摘要/Abstract

摘要：

卤代苯胺是化学工业中重要的中间体, 主要用于制造药物、聚合物、染料等含氮化学品, 用多相金属催化剂催化卤代硝基芳烃加氢制备卤代苯胺是一种高效, 绿色和可持续发展的生产工艺. 该过程需要选择性加氢硝基基团, 同时避免卤素基团的脱卤副反应发生. 然而, 化学选择性加氢存在巨大的挑战, 难点在于催化剂的精准设计, 一方面要求具备对硝基基团合适的加氢能力, 另一方面要阻止对卤素基团的脱卤副反应发生. 基于此, 研制高效多相金属催化剂用于卤代硝基芳烃选择性加氢制备卤代苯胺反应引起了高度关注. 近年来, 单原子金属催化剂受到越来越多的关注, 并在卤代硝基芳烃选择性加氢制备卤代苯胺反应中显现出极大的潜力. 本文通过在金属有机骨架材料MIL-53 (Al)自组装的过程中将金属Rh原位嫁接其骨架结构中, 继而通过限域热解的方法制备了Rh@Al₂O₃@C单原子催化剂, 其在间氯硝基苯(m-CNB)加氢制间氯苯胺(m-CAN)反应中显现了高效催化选择性. 球差校正高角度环形暗场模式的透射电镜, CO作为探针分子的红外光谱和X射线光电子能谱等结果发现, Rh是以单原子的形式均匀的分布在Al₂O₃上并被无定型碳包覆, 且Rh化学价态呈正价. 而²⁷Al固体核磁共振与密度泛函理论计算的结果则进一步确定Al₂O₃@C载体中存在的五配位的Al物种(Al ^V)是锚定Rh单原子的主要位点, Al^V的不饱和的配位结构可以有效地稳定Rh单原子, 对形成Rh位点的单原子分散至关重要. 在间氯硝基苯选择性加氢制间氯苯胺反应中, 与等体积浸渍法制备的Rh/C和Rh/γ-Al₂O₃纳米催化剂相比, Rh@Al₂O₃@C单原子催化剂表现出优异催化性能:其在313 K, 氢气压力为20 bar的温和条件下转换频率(TOF)高达2317 mol_m_-CNB·mol_Rh^-1·h^-1, 优于已报道的多相金属催化剂, 是目前的最高值. 此外, 该催化剂展现出极佳的稳定性能, 经过五次循环后, 该催化剂对m-CAN的选择性仍旧保持在98%左右. Rh@Al₂O₃@C单原子催化剂的优异催化性能源自于金属单原子结构的形成对于金属位点电子结构的有效调节, 进而调控催化剂加氢性能并实现对加氢脱卤副反应的抑制; 与此同时, Rh@Al₂O₃@C催化剂增进了酸位点的可及性, 从而促进了其串联步骤中包含的脱水反应的发生, 进而有效提高催化剂的反应活性.

关键词: 单原子催化剂, 铑, 金属有机骨架, 加氢反应, 化学选择性

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

王伟银, 林露, 齐海峰, 曹文秀, 李志, 陈少华, 邹晓轩, 陈铁红, 唐南方, 宋卫余, 王爱琴, 罗文豪. MIL-53 (Al)衍生的Rh单原子催化剂在间氯硝基苯选择性加氢制间氯苯胺反应中的应用[J]. 催化学报, 2021, 42(5): 824-834.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63697-X

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图/表 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)衍生的Rh单原子催化剂在间氯硝基苯选择性加氢制间氯苯胺反应中的应用

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

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