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

Chinese Journal of Chemical Engineering ›› 2019, Vol. 27 ›› Issue (10): 2438-2446.DOI: 10.1016/j.cjche.2019.01.038

• Catalysis, kinetics and reaction engineering • Previous Articles Next Articles

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:2020-01-17 Published:2019-10-28
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).

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

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).

Abstract

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

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

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]. Chinese Journal of Chemical Engineering, 2019, 27(10): 2438-2446.

References

[1] B. Chen, L. Wang, S. Gao, Recent advances in aerobic oxidation of alcohols and amines to imines, ACS Catal. 5(2015) 5851-5876.
[2] S. Kobayashi, Y. Mori, J.S. Fossey, M.M. Salter, Catalytic enantioselective formation of C-C bonds by addition to imines and Hydrazones:A ten-year update, Chem. Rev. 111(2011) 2626-2704.
[3] R.D. Patil, S. Adimurthy, Catalytic methods for imine synthesis, Asian J. Org. Chem. 2(2013) 726-744.
[4] S. Kobayashi, H. Ishitani, Catalytic enantioselective addition to imines, Chem. Rev. 99(1999) 1069-1094.
[5] F.H. Westheimer, K. Taguchi, Catalysis by molecular sieves in the preparation of ketimines and enamines, J. Org. Chem. 36(1971) 1570-1572.
[6] H. Naeimi, F. Salimi, K. Rabiei, Mild and convenient one pot synthesis of Schiff bases in the presence of P₂O₅/Al₂O₃ as new catalyst under solvent-free conditions, J. Mol. Catal. A Chem. 260(2006) 100-104.
[7] S. Biswas, B. Dutta, K. Mullick, C.H. Kuo, A.S. Poyraz, S.L. Suib, Aerobic oxidation of amines to imines by cesium-promoted mesoporous manganese oxide, ACS Catal. 5(2015) 4394-4403.
[8] S. Sithambaram, R. Kumar, Y.C. Son, S.L. Suib, Tandem catalysis:Direct catalytic synthesis of imines from alcohols using manganese octahedral molecular sieves, J. Catal. 253(2008) 269-277.
[9] X. Huang, L. Liu, H. Gao, W. Dong, M. Yang, G. Wang, Hierarchically nanostructured MnCo₂O₄ as active catalysts for the synthesis of N-benzylideneaniline from benzyl alcohol and aniline, Green Chem. 19(2017) 769-777.
[10] B. Chen, J. Li, W. Dai, L. Wang, S. Gao, Direct imine formation by oxidative coupling of alcohols and amines using supported manganese oxides under an air atmosphere, Green Chem. 16(2014) 3328-3334.
[11] M. Tamura, K. Tomishige, Redox properties of CeO₂ at low temperature:The direct synthesis of imines from alcohol and amine, Angew. Chem. Int. Edit. 54(2015) 864-867.
[12] S. Furukawa, A. Suga, T. Komatsu, Highly efficient aerobic oxidation of various amines using Pd₃Pb intermetallic compounds as catalysts, Chem. Commun. 50(2014) 3277-3280.
[13] X.H. Lu, Y.W. Sun, X.L. Wei, C. Peng, D. Zhou, Q.H. Xia, Solid base catalyzed highly efficient N-alkylation of amines with alcohols in a solvent-free system, Catal. Commun. 55(2014) 78-82.
[14] Y.W. Sun, X.H. Lu, X.L. Wei, D. Zhou, Q.H. Xia, Solvent-free synthesis of imines via Nalkylation of aromatic amines with alcohols over Co²⁺-exchanged zeolites, Catal. Commun. 43(2014) 213-217.
[15] P. Liu, C. Li, E.J.M. Hensen, Efficient tandem synthesis of methyl esters and imines by using versatile Hydrotalcite-supported gold nanoparticles, Chem. Eur. J. 18(2012) 12122-12129.
[16] L. Zhang, W. Wang, A. Wang, Y. Cui, X. Yang, Y. Huang, X. Liu, W. Liu, J.Y. Son, H. Oji, T. Zhang, Aerobic oxidative coupling of alcohols and amines over Au-Pd/resin in water:Au/Pd molar ratios switch the reaction pathways to amides or imines, Green Chem. 15(2013) 2680-2684.
[17] W. He, L. Wang, C. Sun, K. Wu, S. He, J. Chen, P. Wu, Z. Yu, Pt-Sn/γ-Al₂O₃-catalyzed highly efficient direct synthesis of secondary and tertiary amines and imines, Chem. Eur. J. 17(2011) 13308-13317.
[18] K.J. Won, H. Jinling, Y. Kazuya, M. Noritaka, Heterogeneously catalyzed one-pot synthesis of aldimines from primary alcohols and amines by supported ruthenium hydroxides, Chem. Lett. 38(2009) 920-921.
[19] Z.R. Tian, W. Tong, J.Y. Wang, N.G. Duan, V.V. Krishnan, S.L. Suib, Manganese oxide mesoporous structures:Mixed-valent semiconducting catalysts, Science 276(1997) 926-930.
[20] B. Dutta, S. Biswas, V. Sharma, N.O. Savage, S.P. Alpay, S.L. Suib, Mesoporous manganese oxide catalyzed aerobic oxidative coupling of anilines to aromatic azo compounds, Angew. Chem. Int. Edit. 55(2016) 2171-2175.
[21] T. Oishi, K. Yamaguchi, N. Mizuno, Conceptual design of heterogeneous oxidation catalyst:Copper hydroxide on manganese oxide-based octahedral molecular sieve for aerobic oxidative alkyne homocoupling, ACS Catal. 1(2011) 1351-1354.
[22] A.S. Poyraz, C.H. Kuo, S. Biswas, C.K. King'ondu, S.L. Suib, A general approach to crystalline and monomodal pore size mesoporous materials, Nat. Commun. 4(2013) 2952.
[23] S. Biswas, K. Mullick, S.Y. Chen, A. Gudz, D.M. Carr, C. Mendoza, A.M. Angeles-Boza, S.L. Suib, Facile access to versatile functional groups from alcohol by single multifunctional reusable catalyst, Appl. Catal. B Environ. 203(2017) 607-614.
[24] C. Yu, L. Zhang, J. Shi, J. Zhao, J. Gao, D. Yan, A simple template-free strategy to synthesize nanoporous manganese and nickel oxides with narrow pore size distribution, and their electrochemical properties, Adv. Funct. Mater. 18(2008) 1544-1554.
[25] W. Tang, X. Wu, D. Li, Z. Wang, G. Liu, H. Liu, Y. Chen, Oxalate route for promoting activity of manganese oxide catalysts in total VOCs' oxidation:Effect of calcination temperature and preparation method, J. Mater. Chem. A 2(2014) 2544-2554.
[26] X. Ma, N. Campbell, L. Madec, M.A. Rankin, L.M. Croll, J.R. Dahn, Novel nanoporous MnO_x(_x=～1.75) sorbent for the removal of SO₂ and NH₃ made from MnC₂O₄·2H₂O, J. Colloid Interface Sci. 465(2016) 323-332.
[27] K. Frey, V. Iablokov, G. Sáfrán, J. Osán, I. Sajó, R. Szukiewicz, S. Chenakin, N. Kruse, Nanostructured MnO x as highly active catalyst for CO oxidation, J. Catal. 287(2012) 30-36.
[28] F. Chen, S. Zhao, T. Yang, T. Jiang, J. Ni, Q. Zhang, X. Li, Highly efficient oxidative dehydrogenation aromatization of 1,2,3,4-Tetrahydroquinoline by Cu2-MnO_x catalyst, Acta Phys. Chim. Sin. 35(2019) 775-786.
[29] S. Fritsch, J. Sarrias, A. Rousset, G.U. Kulkarni, Low-temperature oxidation of Mn₃O₄ hausmannite, Mater. Res. Bull. 33(1998) 1185-1194.
[30] A.N. Puzan, V.N. Baumer, D.V. Lisovytskiy, P.V. Mateychenko, Structure disordering and thermal decomposition of manganese oxalate dihydrate, MnC₂O₄·2H₂O, J. Solid State Chem. 260(2018) 87-94.
[31] B. Donkova, D. Mehandjiev, Mechanism of decomposition of manganese(II) oxalate dihydrate and manganese(II) oxalate trihydrate, Thermochim. Acta 421(2004) 141-149.
[32] B. Donkova, G. Avdeev, Synthesis and decomposition mechanism of γ-MnC₂O₄·2H₂O rods under non-isothermal and isothermal conditions, J. Therm. Anal. Calorim. 121(2015) 567-577.
[33] K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquerol, T. Siemieniewska, Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity, Pure Appl. Chem. 57(1985) 603-619.
[34] L.V. Stebounova, N.I. Gonzalez-Pech, T.M. Peters, V.H. Grassian, Physicochemical properties of air discharge-generated manganese oxide nanoparticles:comparison to welding fumes, Environn Sci-Nano 5(2018) 696-707.
[35] G. Liu, L. Sun, J. Liu, F. Wang, C.J. Guild, Aerobic oxidation of primary amines into corresponding nitriles over MnxCe_1-xO_s catalysts prepared by co-impregnation method, Mol. Catal. 440(2017) 148-157.
[36] F. Kapteijn, L. Singoredjo, A. Andreini, J.A. Moulijn, Activity and selectivity of pure manganese oxides in the selective catalytic reduction of nitric oxide with ammonia, Appl. Catal. B Environ. 3(1994) 173-189.
[37] S. Biswas, A.S. Poyraz, Y. Meng, C.H. Kuo, C. Guild, H. Tripp, S.L. Suib, Ion induced promotion of activity enhancement of mesoporous manganese oxides for aerobic oxidation reactions, Appl. Catal., B 165(2015) 731-741.
[38] K. Qi, J. Xie, D. Fang, X. Liu, P. Gong, F. Li, D. Han, F. He, Mn₅O₈ nanoflowers prepared via a solvothermal route as efficient denitration catalysts, Mater. Chem. Phys. 209(2018) 10-15.
[39] D. Biswanath, B. Sourav, S. Vinit, S.N. Ortins, A.S. Pamir, S.S. L, Mesoporous manganese oxide catalyzed aerobic oxidative coupling of anilines to aromatic azo compounds, Angew Chem. Int. Edit. 128(2016) 2211-2215.
[40] A.S. Poyraz, W. Song, D. Kriz, C.-H. Kuo, M.S. Seraji, S.L. Suib, Crystalline mesoporous K_2-xMn₈O₁₆ and ε-MnO₂ by mild transformations of amorphous mesoporous manganese oxides and their enhanced redox properties, ACS Appl. Mater. Interfaces 6(2014) 10986-10991.
[41] V. Iablokov, K. Frey, O. Geszti, N. Kruse, High catalytic activity in CO oxidation over MnO x nanocrystals, Catal. Lett. 134(2010) 210-216.
[42] X. Zhang, H. Li, Y. Yang, T. Zhang, X. Wen, N. Liu, D. Wang, Facile synthesis of new efficient Cu/MnO₂ catalysts from used battery for CO oxidation, J. Environ. Chem. Eng. 5(2017) 5179-5186.
[43] X. Nature Cell, Z. BiologyWu, H. Fang, Y. Pan, D. Zheng, J. Jiang, X. Li Ni, Active oxygen species on Mg-La mixed oxides:the effect of Mg and La oxide interactions, Catal. Sci. Technol. 7(2017) 797-801.
[44] C. Doornkamp, V. Ponec, The universal character of the Mars and Van Krevelen mechanism, J. Mol. Catal. A Chem. 162(2000) 19-32.
[45] V.D. Makwana, Y.-C. Son, A.R. Howell, S.L. Suib, The role of lattice oxygen in selective benzyl alcohol oxidation using OMS-2 catalyst:A kinetic and isotope-labeling study, J. Catal. 210(2002) 46-52.
[46] S. Mandal, S. Maity, S. Saha, B. Banerjee, MnOx supported on a TiO₂@SBA-15 nanoreactor used as an efficient catalyst for one-pot synthesis of imine by oxidative coupling of benzyl alcohol and aniline under atmospheric air, RSC Adv. 6(2016) 73906-73914.

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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