负载型铁基催化剂的制备、表征及其催化合成邻溴苯胺的工艺研究进展
Research Process on Preparation, Characterization and Catalytic Synthesis of ortho-Bromoaniline Using Supported Iron-Based Catalysts
摘要: 文章探讨了负载型铁基催化剂在催化合成邻溴苯胺方面的应用。邻溴苯胺是一种重要的有机中间体,广泛应用于农药、染料及医药等领域。文章首先介绍了邻溴苯胺的合成方法,包括铁粉加酸还原法、催化加氢法、催化转移氢化法以及其他还原方法。其中,催化加氢法和催化转移氢化法因其在温和条件下操作且环境友好而受到关注。随后,文章重点讨论了负载型铁基催化剂的制备与表征,包括催化剂载体(如碳材料和杂原子掺杂型材料)的选择、催化剂的活性组分以及催化剂的结构优化。最后,总结了负载型铁基催化剂在催化还原邻溴硝基苯为邻溴苯胺的过程中表现出良好的催化活性和选择性。同时,对负载型铁基催化剂在催化还原硝基化合物领域的应用前景进行展望。
Abstract: The application of supported iron-based catalysts in the catalytic synthesis of o-bromoaniline was explored in this review. o-Bromoaniline is an important organic intermediate widely used in the fields of pesticides, dyes, and pharmaceuticals. The synthesis methods of o-bromoaniline, including the iron powder-acid reduction method, catalytic hydrogenation, catalytic transfer hydrogenation, and other reduction methods were firstly introduced in this review. Among these, catalytic hydrogenation and catalytic transfer hydrogenation have garnered attention for their operation under mild conditions and environmental friendliness. Subsequently, the article focuses on the preparation and characterization of supported iron-based catalysts, including the selection of catalyst supports (such as carbon materials and heteroatom-doped materials), the active components of the catalysts, and the structural optimization of the catalysts. Finally, the excellent catalytic activity and selectivity exhibited by supported iron-based catalysts in the catalytic reduction of nitrobenzene to o-bromoaniline was summarized in this review. The prospects of supported iron-based catalysts in the field of catalytic reduction of nitro compounds were also looked ahead.
文章引用:伏建康, 米春冬, 储卫玲, 杨茂盏, 张千峰. 负载型铁基催化剂的制备、表征及其催化合成邻溴苯胺的工艺研究进展[J]. 化学工程与技术, 2025, 15(1): 1-11. https://doi.org/10.12677/hjcet.2025.151001

参考文献

[1] Tiz, D.B. and Podlipnik, Č. (2023) A Review of FDA-Approved Antiparasitic Drugs in USA for Sheep and Goats: Their Synthesis and Pharmaceutical Use. Trends in Pharmaceutical Sciences, 9, 221-236.
[2] Mahudeswaran, A., Vivekanandan, J. and Vijayanand, P.S. (2021) A Study on Silver Nanoparticles Embedded DBSA Doped Nanostructured Poly(Aniline-Co-2-Bromoaniline). Materials Today: Proceedings, 47, 2154-2158. [Google Scholar] [CrossRef
[3] Obi, J.C., Emmanuel, I.V., Okoro, L.N., et al. (2022) Synthesis, Spectroscopic Studies and Fastness Properties of Monoazo Dyes Derived from Substituted Arylamines. Science World Journal, 17, 143-147.
[4] Yamamoto, Y., Mita, S., Sato, Y., Yano, K. and Ogawa, A. (2023) Practical Synthesis of 1, 3-Benzoazaphosphole Analogues. Frontiers in Chemistry, 11, Article 1174895. [Google Scholar] [CrossRef] [PubMed]
[5] Serna, P. and Corma, A. (2015) Transforming Nano Metal Nonselective Particulates into Chemoselective Catalysts for Hydrogenation of Substituted Nitrobenzenes. ACS Catalysis, 5, 7114-7121. [Google Scholar] [CrossRef
[6] Pietrowski, M. (2012) Recent Developments in Heterogeneous Selective Hydrogenation of Halogenated Nitroaromatic Compounds to Halogenated Anilines. Current Organic Synthesis, 9, 470-487. [Google Scholar] [CrossRef
[7] Bonku, E.M., Qin, H., Odilov, A., Abduahadi, S., Guma, S.D., Yang, F., et al. (2024) Improved and Ligand-Free Copper-Catalyzed Cyclization for an Efficient Synthesis of Benzimidazoles from o-Bromoarylamine and Nitriles. RSC Advances, 14, 6906-6916. [Google Scholar] [CrossRef] [PubMed]
[8] 杜春晖. 硝基类化合物的绿色还原工艺开发[D]: [硕士学位论文]. 青岛: 青岛科技大学, 2023.
[9] 樊金红, 徐文英, 高廷耀. 零价铁预处理硝基苯废水机理的研究[J]. 工业用水与废水, 2004, 35(6): 53-56.
[10] Klausen, J., Ranke, J. and Schwarzenbach, R.P. (2001) Influence of Solution Composition and Column Aging on the Reduction of Nitroaromatic Compounds by Zero-Valent Iron. Chemosphere, 44, 511-517. [Google Scholar] [CrossRef] [PubMed]
[11] Waldvogel, S.R. (2010) Comprehensive Organic Name Reactions and Reagents. Synthesis, 2010, 892-892. [Google Scholar] [CrossRef
[12] 史成玲, 刘秀杰, 孟杰. 邻碘和邻溴苯胺的合成[J]. 天津理工大学学报, 2010, 26(6): 60-62.
[13] Li, J., Yan, Z., Bao, L., Sun, C. and Pang, S. (2021) Controllable Coordination of a Phosphotungstic Acid-Modified Carbon Matrix for Anchoring PT Species with Different Sizes: From Single Atoms and Subnanoclusters to Nanoparticles. Catalysis Science & Technology, 11, 1791-1800. [Google Scholar] [CrossRef
[14] Kantam, M.L., Chakravarti, R., Pal, U., Sreedhar, B. and Bhargava, S. (2008) Nanocrystalline Magnesium Oxide‐stabilized Palladium(0): An Efficient and Reusable Catalyst for Selective Reduction of Nitro Compounds. Advanced Synthesis & Catalysis, 350, 822-827. [Google Scholar] [CrossRef
[15] Serna, P., Boronat, M. and Corma, A. (2011) Tuning the Behavior of Au and Pt Catalysts for the Chemoselective Hydrogenation of Nitroaromatic Compounds. Topics in Catalysis, 54, 439-446. [Google Scholar] [CrossRef
[16] Sorribes, I., Liu, L. and Corma, A. (2017) Nanolayered Co-Mo-S Catalysts for the Chemoselective Hydrogenation of Nitroarenes. ACS Catalysis, 7, 2698-2708. [Google Scholar] [CrossRef
[17] Vilé, G., Almora-Barrios, N., López, N. and Pérez-Ramírez, J. (2015) Structure and Reactivity of Supported Hybrid Platinum Nanoparticles for the Flow Hydrogenation of Functionalized Nitroaromatics. ACS Catalysis, 5, 3767-3778. [Google Scholar] [CrossRef
[18] Zhang, S., Chang, C., Huang, Z., Li, J., Wu, Z., Ma, Y., et al. (2016) High Catalytic Activity and Chemoselectivity of Sub-Nanometric Pd Clusters on Porous Nanorods of CeO2 for Hydrogenation of Nitroarenes. Journal of the American Chemical Society, 138, 2629-2637. [Google Scholar] [CrossRef] [PubMed]
[19] Leng, F., Gerber, I.C., Lecante, P., Moldovan, S., Girleanu, M., Axet, M.R., et al. (2016) Controlled and Chemoselective Hydrogenation of Nitrobenzene over Ru@C60 Catalysts. ACS Catalysis, 6, 6018-6024. [Google Scholar] [CrossRef
[20] Tomkins, P., Gebauer-Henke, E., Leitner, W. and Müller, T.E. (2014) Concurrent Hydrogenation of Aromatic and Nitro Groups over Carbon-Supported Ruthenium Catalysts. ACS Catalysis, 5, 203-209. [Google Scholar] [CrossRef
[21] Margalef, J., Pàmies, O. and Diéguez, M. (2020) Iridium-Catalyzed Asymmetric Hydrogenation. In: Oro, L.A. and Claver, C., Eds., Iridium Catalysts for Organic Reactions, Springer, 153-205. [Google Scholar] [CrossRef
[22] Sun, Y., Darling, A.J., Li, Y., Fujisawa, K., Holder, C.F., Liu, H., et al. (2019) Defect-Mediated Selective Hydrogenation of Nitroarenes on Nanostructured WS2. Chemical Science, 10, 10310-10317. [Google Scholar] [CrossRef] [PubMed]
[23] Sharma, R.K., Yadav, S., Dutta, S., Kale, H.B., Warkad, I.R., Zbořil, R., et al. (2021) Silver Nanomaterials: Synthesis and (Electro/Photo) Catalytic Applications. Chemical Society Reviews, 50, 11293-11380. [Google Scholar] [CrossRef] [PubMed]
[24] Shi, J., Wang, Y., Du, W. and Hou, Z. (2016) Synthesis of Graphene Encapsulated Fe3C in Carbon Nanotubes from Biomass and Its Catalysis Application. Carbon, 99, 330-337. [Google Scholar] [CrossRef
[25] Westerhaus, F.A., Jagadeesh, R.V., Wienhöfer, G., Pohl, M., Radnik, J., Surkus, A., et al. (2013) Heterogenized Cobalt Oxide Catalysts for Nitroarene Reduction by Pyrolysis of Molecularly Defined Complexes. Nature Chemistry, 5, 537-543. [Google Scholar] [CrossRef] [PubMed]
[26] Xiao, M., Zhu, J., Feng, L., Liu, C. and Xing, W. (2015) Meso/Macroporous Nitrogen‐Doped Carbon Architectures with Iron Carbide Encapsulated in Graphitic Layers as an Efficient and Robust Catalyst for the Oxygen Reduction Reaction in Both Acidic and Alkaline Solutions. Advanced Materials, 27, 2521-2527. [Google Scholar] [CrossRef] [PubMed]
[27] Dai, Y., Li, X., Wang, L. and Xu, X. (2021) Highly Efficient Hydrogenation Reduction of Aromatic Nitro Compounds Using MOF Derivative Co-N/C Catalyst. New Journal of Chemistry, 45, 22908-22914. [Google Scholar] [CrossRef
[28] Das, V.K., Mazhar, S., Gregor, L., Stein, B.D., Morgan, D.G., Maciulis, N.A., et al. (2018) Graphene Derivative in Magnetically Recoverable Catalyst Determines Catalytic Properties in Transfer Hydrogenation of Nitroarenes to Anilines with 2-Propanol. ACS Applied Materials & Interfaces, 10, 21356-21364. [Google Scholar] [CrossRef] [PubMed]
[29] Fountoulaki, S., Daikopoulou, V., Gkizis, P.L., Tamiolakis, I., Armatas, G.S. and Lykakis, I.N. (2014) Mechanistic Studies of the Reduction of Nitroarenes by NaBH4 or Hydrosilanes Catalyzed by Supported Gold Nanoparticles. ACS Catalysis, 4, 3504-3511. [Google Scholar] [CrossRef
[30] Wang, D., Deraedt, C., Ruiz, J. and Astruc, D. (2015) Sodium Hydroxide-Catalyzed Transfer Hydrogenation of Carbonyl Compounds and Nitroarenes Using Ethanol or Isopropanol as Both Solvent and Hydrogen Donor. Journal of Molecular Catalysis A: Chemical, 400, 14-21. [Google Scholar] [CrossRef
[31] Formenti, D., Ferretti, F., Topf, C., Surkus, A., Pohl, M., Radnik, J., et al. (2017) Co-Based Heterogeneous Catalysts from Well-Defined α-Diimine Complexes: Discussing the Role of Nitrogen. Journal of Catalysis, 351, 79-89. [Google Scholar] [CrossRef
[32] Ai, Y., Liu, L., Zhang, C., Qi, L., He, M., Liang, Z., et al. (2018) Amorphous Flowerlike Goethite Feooh Hierarchical Supraparticles: Superior Capability for Catalytic Hydrogenation of Nitroaromatics in Water. ACS Applied Materials & Interfaces, 10, 32180-32191. [Google Scholar] [CrossRef] [PubMed]
[33] Chaubal, N.S. and Sawant, M.R. (2007) Nitro Compounds Reduction via Hydride Transfer Using Mesoporous Mixed Oxide Catalyst. Journal of Molecular Catalysis A: Chemical, 261, 232-241. [Google Scholar] [CrossRef
[34] Aditya, T., Pal, A. and Pal, T. (2015) Nitroarene Reduction: A Trusted Model Reaction to Test Nanoparticle Catalysts. Chemical Communications, 51, 9410-9431. [Google Scholar] [CrossRef] [PubMed]
[35] Hu, L., Zhang, R., Wei, L., Zhang, F. and Chen, Q. (2015) Synthesis of FeCo Nanocrystals Encapsulated in Nitrogen-Doped Graphene Layers for Use as Highly Efficient Catalysts for Reduction Reactions. Nanoscale, 7, 450-454. [Google Scholar] [CrossRef] [PubMed]
[36] Cheong, W., Yang, W., Zhang, J., Li, Y., Zhao, D., Liu, S., et al. (2019) Isolated Iron Single-Atomic Site-Catalyzed Chemoselective Transfer Hydrogenation of Nitroarenes to Arylamines. ACS Applied Materials & Interfaces, 11, 33819-33824. [Google Scholar] [CrossRef] [PubMed]
[37] Hine, J., Hahn, S., Miles, D.E. and Ahn, K. (1985) The Synthesis and Ionization Constants of Some Derivatives of 1-biphenylenol. The Journal of Organic Chemistry, 50, 5092-5096. [Google Scholar] [CrossRef
[38] Jang, Y., Kim, S., Jun, S.W., Kim, B.H., Hwang, S., Song, I.K., et al. (2011) Simple One-Pot Synthesis of Rh-Fe3O4 Heterodimer Nanocrystals and Their Applications to a Magnetically Recyclable Catalyst for Efficient and Selective Reduction of Nitroarenes and Alkenes. Chemical Communications, 47, 3601-3603. [Google Scholar] [CrossRef] [PubMed]
[39] Lauwiner, M., Rys, P. and Wissmann, J. (1998) Reduction of Aromatic Nitro Compounds with Hydrazine Hydrate in the Presence of an Iron Oxide Hydroxide Catalyst. I. The Reduction of Monosubstituted Nitrobenzenes with Hydrazine Hydrate in the Presence of Ferrihydrite. Applied Catalysis A: General, 172, 141-148. [Google Scholar] [CrossRef
[40] Benz, M., van der Kraan, A.M. and Prins, R. (1998) Reduction of Aromatic Nitrocompounds with Hydrazine Hydrate in the Presence of an Iron Oxide Hydroxide Catalyst: II. Activity, X-Ray Diffraction and Mössbauer Study of the Iron Oxide Hydroxide Catalyst. Applied Catalysis A: General, 172, 149-157. [Google Scholar] [CrossRef
[41] Lauwiner, M., Roth, R. and Rys, P. (1999) Reduction of Aromatic Nitro Compounds with Hydrazine Hydrate in the Presence of an Iron Oxide/Hydroxide Catalyst. III. The Selective Reduction of Nitro Groups in Aromatic Azo Compounds. Applied Catalysis A: General, 177, 9-14. [Google Scholar] [CrossRef
[42] Benz, M. and Prins, R. (1999) Kinetics of the Reduction of Aromatic Nitro Compounds with Hydrazine Hydrate in the Presence of an Iron Oxide Hydroxide Catalyst. Applied Catalysis A: General, 183, 325-333. [Google Scholar] [CrossRef
[43] Cui, X., Zhou, X. and Dong, Z. (2018) Ultrathin γ-Fe2O3 Nanosheets as a Highly Efficient Catalyst for the Chemoselective Hydrogenation of Nitroaromatic Compounds. Catalysis Communications, 107, 57-61. [Google Scholar] [CrossRef
[44] Yun, R., Hong, L., Ma, W., Jia, W., Liu, S. and Zheng, B. (2018) Fe/ Fe2O3@n‐Dopped Porous Carbon: A High‐Performance Catalyst for Selective Hydrogenation of Nitro Compounds. ChemCatChem, 11, 724-728. [Google Scholar] [CrossRef
[45] Wain, A.J. and Compton, R.G. (2006) Hydrodynamic Cryoelectrochemical ESR: The Reduction of Ortho-Bromonitrobenzene in Acetonitrile. Journal of Electroanalytical Chemistry, 587, 203-212. [Google Scholar] [CrossRef
[46] Neukermans, S., Vorobjov, F., Kenis, T., De Wolf, R., Hereijgers, J. and Breugelmans, T. (2020) Electrochemical Reduction of Halogenated Aromatic Compounds at Metal Cathodes in Acetonitrile. Electrochimica Acta, 332, Article ID: 135484. [Google Scholar] [CrossRef
[47] Srivastava, S.K., Yamada, R., Ogino, C. and Kondo, A. (2013) Biogenic Synthesis and Characterization of Gold Nanoparticles by Escherichia coli K12 and Its Heterogeneous Catalysis in Degradation of 4-Nitrophenol. Nanoscale Research Letters, 8, Article No. 70. [Google Scholar] [CrossRef] [PubMed]
[48] Prabhu Charan, K.T., Pothanagandhi, N., Vijayakrishna, K., Sivaramakrishna, A., Mecerreyes, D. and Sreedhar, B. (2014) Poly(Ionic Liquids) as “Smart” Stabilizers for Metal Nanoparticles. European Polymer Journal, 60, 114-122. [Google Scholar] [CrossRef
[49] Layek, K., Kantam, M.L., Shirai, M., Nishio-Hamane, D., Sasaki, T. and Maheswaran, H. (2012) Gold Nanoparticles Stabilized on Nanocrystalline Magnesium Oxide as an Active Catalyst for Reduction of Nitroarenes in Aqueous Medium at Room Temperature. Green Chemistry, 14, 3164-3174. [Google Scholar] [CrossRef
[50] Luo, P., Xu, K., Zhang, R., Huang, L., Wang, J., Xing, W., et al. (2012) Highly Efficient and Selective Reduction of Nitroarenes with Hydrazine over Supported Rhodium Nanoparticles. Catalysis Science & Technology, 2, 301-304. [Google Scholar] [CrossRef
[51] Tian, H., Zhou, J., Li, Y., Wang, Y., Liu, L., Ai, Y., et al. (2019) Rh Catalyzed Selective Hydrogenation of Nitroarenes under Mild Conditions: Understanding the Functional Groups Attached to the Nanoparticles. ChemCatChem, 11, 5543-5552. [Google Scholar] [CrossRef
[52] 云瑞瑞, 马婉娇. 铁基催化剂Fe2P/C的设计合成及其温和条件下对硝基化合物的选择性催化加氢性能研究[J]. 聊城大学学报(自然科学版), 2019, 32(3): 61-67.
[53] Sun, X., Olivos-Suarez, A.I., Osadchii, D., Romero, M.J.V., Kapteijn, F. and Gascon, J. (2018) Single Cobalt Sites in Mesoporous N-Doped Carbon Matrix for Selective Catalytic Hydrogenation of Nitroarenes. Journal of Catalysis, 357, 20-28. [Google Scholar] [CrossRef
[54] Xu, X., Li, Y., Gong, Y., Zhang, P., Li, H. and Wang, Y. (2012) Synthesis of Palladium Nanoparticles Supported on Mesoporous N-Doped Carbon and Their Catalytic Ability for Biofuel Upgrade. Journal of the American Chemical Society, 134, 16987-16990. [Google Scholar] [CrossRef] [PubMed]
[55] Tian, M., Cui, X., Liang, K., Ma, J. and Dong, Z. (2016) Efficient and Chemoselective Hydrogenation of Nitroarenes by γ-Fe2O3 Modified Hollow Mesoporous Carbon Microspheres. Inorganic Chemistry Frontiers, 3, 1332-1340. [Google Scholar] [CrossRef
[56] 曹鹏伟. 氮掺杂碳负载铁、钴催化剂的制备及其催化硝基还原反应[D]: [硕士学位论文]. 天津: 河北工业大学, 2021.
[57] Sassykova, L.R., Aubakirov, Y.A., Sendilvelan, S., Tashmukhambetova, Z.K., Zhakirova, N.K., Faizullaeva, M.F., et al. (2019) Studying the Mechanisms of Nitro Compounds Reduction (A-Review). Oriental Journal of Chemistry, 35, 22-38. [Google Scholar] [CrossRef
[58] Karwa, S.L. and Rajadhyaksha, R.A. (1988) Selective Catalytic Hydrogenation of Nitrobenzene to Hydrazobenzene. Industrial & Engineering Chemistry Research, 27, 21-24. [Google Scholar] [CrossRef
[59] Ma, X., Zhou, Y., Liu, H., Li, Y. and Jiang, H. (2016) A MOF-Derived Co-CoO@n-Doped Porous Carbon for Efficient Tandem Catalysis: Dehydrogenation of Ammonia Borane and Hydrogenation of Nitro Compounds. Chemical Communications, 52, 7719-7722. [Google Scholar] [CrossRef] [PubMed]
[60] 盛瑶. 芳硝基化合物还原制芳胺催化剂的研究[D]: [博士学位论文]. 上海: 上海大学, 2021.
[61] Liao, C., Liu, B., Chi, Q. and Zhang, Z. (2018) Nitrogen-Doped Carbon Materials for the Metal-Free Reduction of Nitro Compounds. ACS Applied Materials & Interfaces, 10, 44421-44429. [Google Scholar] [CrossRef] [PubMed]
[62] 吕静. 铁、氮掺杂碳材料催化剂及其还原芳香族硝基化合物催化性能研究[D]: [硕士学位论文]. 兰州: 兰州大学, 2019.