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Nanosized Pd assembled on superparamagnetic core-shell microspheres：Synthesis, characterization and recyclable catalytic properties for the Heck reaction

Hao Yang ,  Da Shi ,  Sheng-Fu Ji ,  Dan-Ni Zhang ,  Xue-Fei Liu

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Citation:  Hao Yang, Da Shi, Sheng-Fu Ji, Dan-Ni Zhang, Xue-Fei Liu. Nanosized Pd assembled on superparamagnetic core-shell microspheres：Synthesis, characterization and recyclable catalytic properties for the Heck reaction[J]. Chinese Chemical Letters, 2014, 25(9): 1265-1270. doi: 10.1016/j.cclet.2014.05.003 shu

Nanosized Pd assembled on superparamagnetic core-shell microspheres：Synthesis, characterization and recyclable catalytic properties for the Heck reaction

    • 通讯作者: Sheng-Fu Ji,
  • 基金项目:

    Financial support from the National Natural Science Foundation of China (No. 21173018) is gratefully acknowledged. (No. 21173018)

摘要: A series of magnetically recyclable Pd/Fe3O4@γ-Al2O3 catalysts were synthesized using the superparamagnetic Fe3O4@γ-Al2O3 core-shell microspheres as the supporter and nano-Pd particles assembled on γ-Al2O3 shell as the active catalytic component. The structure of the catalysts was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption-desorption and vibrating sample magnetometer (VSM). The catalytic activity and the recyclability properties of the catalysts for the Heck coupling reaction with aryl bromides and the olefins were investigated. The results show that the microspheres of the magnetic Pd/Fe3O4@γ-Al2O3 catalysts were about 400 nm and the nano-Pd particles assembled on γ-Al2O3 shell were about 3-4 nm in size. The saturation magnetization (MS) of the magnetic catalysts was sufficiently high to allow magnetic separations. In the Heck coupling reactions, the magnetic Pd/Fe3O4@γ-Al2O3 catalysts exhibited good catalytic activity and recyclability. With Pd/Fe3O4@γ-Al2O3 (0.021 mol%) catalyst, the bromobenzene conversion and product yield reached about 96.8% and 91.2%, respectively, at 120℃ and in 14 h. After being recycled for six times, the conversion of bromobenzene and the recovery of the catalyst were about 80% and 90%, respectively. The nano-Pd particles were kept well dispersed in the used Pd/Fe3O4@γ-Al2O3 catalysts.

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    1. [1] T. Mizoroki, K. Mori, A. Ozaki, Arylation of olefin with aryl iodide catalyzed by palladium, Bull. Chem. Soc. Jpn. 44 (1971) 581.[1] T. Mizoroki, K. Mori, A. Ozaki, Arylation of olefin with aryl iodide catalyzed by palladium, Bull. Chem. Soc. Jpn. 44 (1971) 581.

    2. [2] R.F. Heck, J.P. Nolley, Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides, J. Org. Chem. 37 (1972) 2320-2322.[2] R.F. Heck, J.P. Nolley, Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides, J. Org. Chem. 37 (1972) 2320-2322.

    3. [3] R.A. Sheldon, H. van Bekkum, Fine Chemicals Through Heterogeneous Catalysis, Wiley-VCH, Weinheim, 2001.[3] R.A. Sheldon, H. van Bekkum, Fine Chemicals Through Heterogeneous Catalysis, Wiley-VCH, Weinheim, 2001.

    4. [4] L.X. Yin, J. Liebscher, Carbon-carbon coupling reactions catalyzed by heterogeneous palladium catalysts, Chem. Rev. 107 (2007) 133-173.[4] L.X. Yin, J. Liebscher, Carbon-carbon coupling reactions catalyzed by heterogeneous palladium catalysts, Chem. Rev. 107 (2007) 133-173.

    5. [5] Z.H. Li, J. Chen, W.P. Su, M.C. Hong, A titania-supported highly dispersed palladium nano-catalyst generated via in situ reduction for efficient Heck coupling reaction, J. Mol. Catal. A: Chem. 328 (2010) 93-98.[5] Z.H. Li, J. Chen, W.P. Su, M.C. Hong, A titania-supported highly dispersed palladium nano-catalyst generated via in situ reduction for efficient Heck coupling reaction, J. Mol. Catal. A: Chem. 328 (2010) 93-98.

    6. [6] P.Y. Wang, X.P. Zheng, Pd/SBA-15 nanocomposite: synthesis, structure and catalytic properties in Heck reactions, Powder Technol. 210 (2011) 115-121.[6] P.Y. Wang, X.P. Zheng, Pd/SBA-15 nanocomposite: synthesis, structure and catalytic properties in Heck reactions, Powder Technol. 210 (2011) 115-121.

    7. [7] X.J. Feng, M. Yan, X. Zhang, M. Bao, Preparation and application of SBA-15-supported palladium catalyst for Heck reaction in supercritical carbon dioxide, Chin. Chem. Lett. 22 (2011) 643-646.[7] X.J. Feng, M. Yan, X. Zhang, M. Bao, Preparation and application of SBA-15-supported palladium catalyst for Heck reaction in supercritical carbon dioxide, Chin. Chem. Lett. 22 (2011) 643-646.

    8. [8] M. Bakherad, S. Jajarmi, A dithizone-functionalized polystyrene resin-supported Pd(II) complex as an effective catalyst for Suzuki, Heck, and copper-free Sonogashira reactions under aerobic conditions in water, J. Mol. Catal. A: Chem. 370 (2013) 152-159.[8] M. Bakherad, S. Jajarmi, A dithizone-functionalized polystyrene resin-supported Pd(II) complex as an effective catalyst for Suzuki, Heck, and copper-free Sonogashira reactions under aerobic conditions in water, J. Mol. Catal. A: Chem. 370 (2013) 152-159.

    9. [9] A. Molnar, A. Papp, Efficient heterogeneous palladium-montmorillonite catalysts for heck coupling of aryl bromides and chlorides, Syn. Lett. 18 (2006) 3130-3134.[9] A. Molnar, A. Papp, Efficient heterogeneous palladium-montmorillonite catalysts for heck coupling of aryl bromides and chlorides, Syn. Lett. 18 (2006) 3130-3134.

    10. [10] J.H. Ji, S.F. Ji, W. Yang, C.Y. Li, Preparation and application of magnetic Fe3O4 nanocrystalline, Prog. .Chem. 22 (2010) 1566-1574.[10] J.H. Ji, S.F. Ji, W. Yang, C.Y. Li, Preparation and application of magnetic Fe3O4 nanocrystalline, Prog. .Chem. 22 (2010) 1566-1574.

    11. [11] B. Baruwati, D. Guin, S.V. Manorama, Pd on surface-modified NiFe2O4 nanoparticles: a magnetically recoverable catalyst for Suzuki and Heck reactions, Org. Lett. 9 (26) (2007) 5377-5380.[11] B. Baruwati, D. Guin, S.V. Manorama, Pd on surface-modified NiFe2O4 nanoparticles: a magnetically recoverable catalyst for Suzuki and Heck reactions, Org. Lett. 9 (26) (2007) 5377-5380.

    12. [12] J. Park, J. Joo, S.G. Kwon, Y. Jang, T. Hyeon, Synthesis of monodisperse spherical nanocrystals, Angew. Chem. Int. Ed. 46 (2007) 4630-4660.[12] J. Park, J. Joo, S.G. Kwon, Y. Jang, T. Hyeon, Synthesis of monodisperse spherical nanocrystals, Angew. Chem. Int. Ed. 46 (2007) 4630-4660.

    13. [13] H.F. Liu, S.F. Ji, H. Yang, H. Zhang, M. Tang, Ultrasonic-assisted ultra-rapid synthesis of monodisperse meso-SiO2@Fe3O4 microspheres with enhanced mesoporous structure, Ultrason. Sonochem. 21 (2014) 505-512.[13] H.F. Liu, S.F. Ji, H. Yang, H. Zhang, M. Tang, Ultrasonic-assisted ultra-rapid synthesis of monodisperse meso-SiO2@Fe3O4 microspheres with enhanced mesoporous structure, Ultrason. Sonochem. 21 (2014) 505-512.

    14. [14] H. Zhang, D.L. Liu, L.L. Zeng, M. Li, β-Cyclodextrin assisted one-pot synthesis of mesoporous magnetic Fe3O4@C and their excellent performance for the removal of Cr (VI) from aqueous solutions, Chin. Chem. Lett. 24 (2013) 341-343.[14] H. Zhang, D.L. Liu, L.L. Zeng, M. Li, β-Cyclodextrin assisted one-pot synthesis of mesoporous magnetic Fe3O4@C and their excellent performance for the removal of Cr (VI) from aqueous solutions, Chin. Chem. Lett. 24 (2013) 341-343.

    15. [15] Y. Li, T.H. Leng, H.Q. Lin, et al., Preparation of Fe3O4@ZrO2 core-shell microspheres as affinity probes for selective enrichment and direct determination of phosphopeptides using matrix-assisted laser desorption ionization mass spectrometry, J. Proteome Res. 6 (2007) 4498-4510.[15] Y. Li, T.H. Leng, H.Q. Lin, et al., Preparation of Fe3O4@ZrO2 core-shell microspheres as affinity probes for selective enrichment and direct determination of phosphopeptides using matrix-assisted laser desorption ionization mass spectrometry, J. Proteome Res. 6 (2007) 4498-4510.

    16. [16] J. Jin, F. Yang, F.W. Zhang, et al., 2,2-(Phenylazanediyl) diacetic acid modified Fe3O4@PEI for selective removal of cadmium ions from blood, Nanoscale 4 (2012) 733-737.[16] J. Jin, F. Yang, F.W. Zhang, et al., 2,2-(Phenylazanediyl) diacetic acid modified Fe3O4@PEI for selective removal of cadmium ions from blood, Nanoscale 4 (2012) 733-737.

    17. [17] X.X. Yang, E. Larry, L.E. Erickson, K.L. Hohn, Sol-gel Cu-Al2O3 adsorbents for selective adsorption of thiophene out of hydrocarbon, Ind. Eng. Chem. Res. 45 (2006) 6169-6174.[17] X.X. Yang, E. Larry, L.E. Erickson, K.L. Hohn, Sol-gel Cu-Al2O3 adsorbents for selective adsorption of thiophene out of hydrocarbon, Ind. Eng. Chem. Res. 45 (2006) 6169-6174.

    18. [18] S.A. Sadaphal, A.H. Kategaonkar, V.B. Labade, M.S. Shingare, Synthesis of bis (indolyl) methanes using aluminium oxide (acidic) in dry media, Chin. Chem. Lett. 21 (2010) 39-42.[18] S.A. Sadaphal, A.H. Kategaonkar, V.B. Labade, M.S. Shingare, Synthesis of bis (indolyl) methanes using aluminium oxide (acidic) in dry media, Chin. Chem. Lett. 21 (2010) 39-42.

    19. [19] H. Tajizadegan, M. Rashidzadeh, M. Jafari, R.E. Kahrizsangi, Novel ZnO-Al2O3 composite particles as sorbent for low temperature H2S removal, Chin. Chem. Lett. 24 (2013) 167-169.[19] H. Tajizadegan, M. Rashidzadeh, M. Jafari, R.E. Kahrizsangi, Novel ZnO-Al2O3 composite particles as sorbent for low temperature H2S removal, Chin. Chem. Lett. 24 (2013) 167-169.

    20. [20] J. Huang, Y. Wang, J.M. Zheng, W.L. Dai, K.N. Fan, Influence of support surface basicity and gold particle size on catalytic activity of Au/γ-AlOOH and Au/γ-Al2O3 catalyst in aerobic oxidation α, ω-diols to lactones, Appl. Catal. B: Environ. 103 (2011) 343-350.[20] J. Huang, Y. Wang, J.M. Zheng, W.L. Dai, K.N. Fan, Influence of support surface basicity and gold particle size on catalytic activity of Au/γ-AlOOH and Au/γ-Al2O3 catalyst in aerobic oxidation α, ω-diols to lactones, Appl. Catal. B: Environ. 103 (2011) 343-350.

    21. [21] M.I. Cobo, J.A. Conesa, C.M. Correa, The effect of NaOH on the liquid-phase hydrodechlorination of dioxins over Pd/γ-Al2O3, J. Phys. Chem. A 112 (2008) 8715-8722.[21] M.I. Cobo, J.A. Conesa, C.M. Correa, The effect of NaOH on the liquid-phase hydrodechlorination of dioxins over Pd/γ-Al2O3, J. Phys. Chem. A 112 (2008) 8715-8722.

    22. [22] B.B. Chen, X.B. Zhu, M. Croker, Y. Wang, C. Shi, Complete oxidation of formaldehyde at ambient temperature over γ-Al2O3 supported Au catalyst, Catal. Commun. 42 (2013) 93-97.[22] B.B. Chen, X.B. Zhu, M. Croker, Y. Wang, C. Shi, Complete oxidation of formaldehyde at ambient temperature over γ-Al2O3 supported Au catalyst, Catal. Commun. 42 (2013) 93-97.

    23. [23] X. Li, C.H. Xu, C.Q. Liu, Y. Chen, J.Y. Liu, Synthesis of pyrazinyl compounds from glycerol and 1,2-propanediamine over Cu-TiO2 catalysts supported on γ-Al2O3, Chin. Chem. Lett. 24 (2013) 751-754.[23] X. Li, C.H. Xu, C.Q. Liu, Y. Chen, J.Y. Liu, Synthesis of pyrazinyl compounds from glycerol and 1,2-propanediamine over Cu-TiO2 catalysts supported on γ-Al2O3, Chin. Chem. Lett. 24 (2013) 751-754.

    24. [24] H.F. Liu, S.F. Ji, Y.Y. Zheng, M. Li, H. Yang, Modified solvothermal synthesis of magnetic microspheres with multifunctional surfactant cetyltrimethyl ammonium bromide and directly coated mesoporous shell, Powder Technol. 246 (2013) 520-529.[24] H.F. Liu, S.F. Ji, Y.Y. Zheng, M. Li, H. Yang, Modified solvothermal synthesis of magnetic microspheres with multifunctional surfactant cetyltrimethyl ammonium bromide and directly coated mesoporous shell, Powder Technol. 246 (2013) 520-529.

    25. [25] Y.Y. Zheng, S.F. Ji, H.F. Liu, M. Li, H. Yang, Synthesis of mesoporous γ-AlOOH@-Fe3O4 magnetic nanomicrospheres, Particuology 10 (2012) 751-758.[25] Y.Y. Zheng, S.F. Ji, H.F. Liu, M. Li, H. Yang, Synthesis of mesoporous γ-AlOOH@-Fe3O4 magnetic nanomicrospheres, Particuology 10 (2012) 751-758.

    26. [26] W. Li, B.L. Zhang, X.J. Li, H.P. Zhang, Q.Y. Zhang, Preparation and characterization of novel immobilized Fe3O4@SiO2@mSiO2-Pd(0) catalyst with large pore-size mesoporous for Suzuki coupling reaction, Appl. Catal. A: Gen. 459 (2013) 65-72.[26] W. Li, B.L. Zhang, X.J. Li, H.P. Zhang, Q.Y. Zhang, Preparation and characterization of novel immobilized Fe3O4@SiO2@mSiO2-Pd(0) catalyst with large pore-size mesoporous for Suzuki coupling reaction, Appl. Catal. A: Gen. 459 (2013) 65-72.

    27. [27] G.B. Donna, Reaction progress kinetic analysis: a powerful methodology for mechanistic studies of complex catalytic reactions, Angew. Chem. Int. Ed. 44 (2005) 4302-4320.[27] G.B. Donna, Reaction progress kinetic analysis: a powerful methodology for mechanistic studies of complex catalytic reactions, Angew. Chem. Int. Ed. 44 (2005) 4302-4320.

    28. [28] J. Zhu, J.H. Zhou, T.J. Zhao, et al., Carbon nanofiber-supported palladium nanoparticles as potential recyclable catalysts for the Heck reaction, Appl. Catal. A: Gen. 353 (2009) 243-250.[28] J. Zhu, J.H. Zhou, T.J. Zhao, et al., Carbon nanofiber-supported palladium nanoparticles as potential recyclable catalysts for the Heck reaction, Appl. Catal. A: Gen. 353 (2009) 243-250.

    29. [29] C.P. Mehnert, D.W. Weaver, J.Y. Yin, Heterogeneous Heck catalysis with palladium-grafted molecular sieves, J. Am. Chem. Soc. 120 (1998) 12289-12296.[29] C.P. Mehnert, D.W. Weaver, J.Y. Yin, Heterogeneous Heck catalysis with palladium-grafted molecular sieves, J. Am. Chem. Soc. 120 (1998) 12289-12296.

    30. [30] F.W. Zhang, J. Jin, X. Zhong, et al., Pd immobilized on amine functionalized magnetite nanoparticles: a novel and highly active catalyst for hydrogenation and Heck reactions, Green Chem. 13 (2011) 1238-1243.[30] F.W. Zhang, J. Jin, X. Zhong, et al., Pd immobilized on amine functionalized magnetite nanoparticles: a novel and highly active catalyst for hydrogenation and Heck reactions, Green Chem. 13 (2011) 1238-1243.

    31. [31] J.A. Bennett, I.P. Mikheenko, K. Deplanche, et al., Nanoparticles of palladium supported on bacterial biomass: new re-usable heterogeneous catalyst with comparable activity to homogeneous colloidal Pd in the Heck reaction, Appl. Catal. A: Environ. 140 (2013) 700-707.[31] J.A. Bennett, I.P. Mikheenko, K. Deplanche, et al., Nanoparticles of palladium supported on bacterial biomass: new re-usable heterogeneous catalyst with comparable activity to homogeneous colloidal Pd in the Heck reaction, Appl. Catal. A: Environ. 140 (2013) 700-707.

    32. [32] A. Balanta, C. Godard, C. Claver, Cross coupling reactions in organic synthesis themed issue, Chem. Soc. Rev. 40 (2011) 4973-4985.[32] A. Balanta, C. Godard, C. Claver, Cross coupling reactions in organic synthesis themed issue, Chem. Soc. Rev. 40 (2011) 4973-4985.

    33. [33] M.Y. Zhu, G.W. Diao, Magnetically recyclable Pd nanoparticles immobilized on magnetic Fe3O4@C nanocomposites: preparation, characterization, and their catalytic activity toward Suzuki and Heck coupling reactions, J. Phys. Chem. 115 (2011) 24743-24749.[33] M.Y. Zhu, G.W. Diao, Magnetically recyclable Pd nanoparticles immobilized on magnetic Fe3O4@C nanocomposites: preparation, characterization, and their catalytic activity toward Suzuki and Heck coupling reactions, J. Phys. Chem. 115 (2011) 24743-24749.

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  • 收稿日期:  2014-01-31
  • 网络出版日期:  2014-04-29
通讯作者: 陈斌, bchen63@163.com
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