Controllable synthesis of novel nanoporous manganese oxide catalysts for the direct synthesis of imines from alcohols and amines

doi:10.1016/j.cjche.2019.01.038

中国化学工程学报 ›› 2019, Vol. 27 ›› Issue (10): 2438-2446.DOI: 10.1016/j.cjche.2019.01.038

Controllable synthesis of novel nanoporous manganese oxide catalysts for the direct synthesis of imines from alcohols and amines

Fushan Chen^1,2, Songlin Zhao^1,3, Tao Yang², Taotao Jiang¹, Jun Ni¹, Houfeng Xiong², Qunfeng Zhang¹, Xiaonian Li¹

1 Industrial Catalysis Institute of Zhejiang University of Technology, Hangzhou 310014, China;
2 Jiangxi Province Engineering Research Center of Ecological Chemical Industry, Jiujiang University, Jiujiang 332005, China;
3 School of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 318000, China

收稿日期:2018-12-15 修回日期:2019-01-21 出版日期:2019-10-28 发布日期:2020-01-17
通讯作者: Qunfeng Zhang
基金资助:
Supported by the National Natural Science Foundation of China (21776258, 21476207, 91534113, 21406199, 21566013, 21875220), Education Science Planning Project of Jiangxi Province (No.18YB243), the Program from Science and Technology Department of Zhejiang Province (2015C31042).

Controllable synthesis of novel nanoporous manganese oxide catalysts for the direct synthesis of imines from alcohols and amines

Fushan Chen^1,2, Songlin Zhao^1,3, Tao Yang², Taotao Jiang¹, Jun Ni¹, Houfeng Xiong², Qunfeng Zhang¹, Xiaonian Li¹

1 Industrial Catalysis Institute of Zhejiang University of Technology, Hangzhou 310014, China;
2 Jiangxi Province Engineering Research Center of Ecological Chemical Industry, Jiujiang University, Jiujiang 332005, China;
3 School of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 318000, China

Received:2018-12-15 Revised:2019-01-21 Online:2019-10-28 Published:2020-01-17
Contact: Qunfeng Zhang
Supported by:
Supported by the National Natural Science Foundation of China (21776258, 21476207, 91534113, 21406199, 21566013, 21875220), Education Science Planning Project of Jiangxi Province (No.18YB243), the Program from Science and Technology Department of Zhejiang Province (2015C31042).

摘要/Abstract

摘要： A novel template-free oxalate route was applied to synthesize different mesoporous manganese oxides (amorphous manganese oxide (AMO), Mn₅O₈, Mn₃O₄, MnO₂) in the narrow temperature range from 350℃ to 400℃ by controlling the calcination conditions, which were employed as the efficient catalysts for the oxidative coupling of alcohols with amines to imines. The chemical and structural properties of the manganese oxides were characterized by the methods of thermogravimetry analysis and heat flow (TG-DSC), X-ray diffraction (XRD), nitrogen sorption, scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), H₂ temperature-programmed reduction (H₂-TPR), and inductively coupled plasma optical emission spectrometry (ICP-OES) techniques. The structures of different manganese oxides were confirmed by characterization. The M-350 (AMO) presented the maximum surface area, amorphous nature, the lowest reduction temperature, the higher (Mn³⁺ + Mn⁴⁺)/Mn²⁺ ratio, and the higher adsorbed oxygen species compared to other samples. Among the catalysts, M-350 showed the best catalytic performance using air as an oxidant, and the conversion of benzyl alcohol (BA) and the selectivity of N-benzylideneaniline (NBA) reached as high as 100% and 97.1% respectively at the lower reaction temperature (80℃) for 1 h. M-350 had also the highest TOF value (0.0100 mmol·mg^-1·h^-1) compared to the other manganese oxide catalysts. The catalyst was reusable and gave 95.8% conversion after 5 reuse tests, the XRD pattern of the reactivated M-350 did not show any obvious change. Lattice oxygen mobility and (Mn³⁺ + Mn⁴⁺)/Mn²⁺ ratio were found to play the important roles in the catalytic activity of aerobic reactions.

关键词: Oxalate route, Controllable synthesis, Manganese oxide, Imine synthesis, Heterogeneous catalysis, Aerobic oxidation

Abstract: A novel template-free oxalate route was applied to synthesize different mesoporous manganese oxides (amorphous manganese oxide (AMO), Mn₅O₈, Mn₃O₄, MnO₂) in the narrow temperature range from 350℃ to 400℃ by controlling the calcination conditions, which were employed as the efficient catalysts for the oxidative coupling of alcohols with amines to imines. The chemical and structural properties of the manganese oxides were characterized by the methods of thermogravimetry analysis and heat flow (TG-DSC), X-ray diffraction (XRD), nitrogen sorption, scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), H₂ temperature-programmed reduction (H₂-TPR), and inductively coupled plasma optical emission spectrometry (ICP-OES) techniques. The structures of different manganese oxides were confirmed by characterization. The M-350 (AMO) presented the maximum surface area, amorphous nature, the lowest reduction temperature, the higher (Mn³⁺ + Mn⁴⁺)/Mn²⁺ ratio, and the higher adsorbed oxygen species compared to other samples. Among the catalysts, M-350 showed the best catalytic performance using air as an oxidant, and the conversion of benzyl alcohol (BA) and the selectivity of N-benzylideneaniline (NBA) reached as high as 100% and 97.1% respectively at the lower reaction temperature (80℃) for 1 h. M-350 had also the highest TOF value (0.0100 mmol·mg^-1·h^-1) compared to the other manganese oxide catalysts. The catalyst was reusable and gave 95.8% conversion after 5 reuse tests, the XRD pattern of the reactivated M-350 did not show any obvious change. Lattice oxygen mobility and (Mn³⁺ + Mn⁴⁺)/Mn²⁺ ratio were found to play the important roles in the catalytic activity of aerobic reactions.

Key words: Oxalate route, Controllable synthesis, Manganese oxide, Imine synthesis, Heterogeneous catalysis, Aerobic oxidation

Fushan Chen, Songlin Zhao, Tao Yang, Taotao Jiang, Jun Ni, Houfeng Xiong, Qunfeng Zhang, Xiaonian Li. Controllable synthesis of novel nanoporous manganese oxide catalysts for the direct synthesis of imines from alcohols and amines[J]. 中国化学工程学报, 2019, 27(10): 2438-2446.

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Controllable synthesis of novel nanoporous manganese oxide catalysts for the direct synthesis of imines from alcohols and amines

Controllable synthesis of novel nanoporous manganese oxide catalysts for the direct synthesis of imines from alcohols and amines

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