Bimetallic Pd-Cu/Al₂O₃ Catalyst for the Green Catalytic Synthesis of 2,2′-bipyridine from Pyridine

Abstract

Bimetallic Pd-Cu/Al₂O₃ was prepared by wetness impregnation method and its catalytic activity on coupling reaction of pyridine to 2,2′-bipyridine was assessed in view of the effects of different molar ratios of Pd:Cu. It is found that Pd-Cu/Al₂O₃ has the small particle size and good dispersion through the characterization. Compared with Pd/Al₂O₃, Pd-Cu (1:2)/Al₂O₃ is the preferable catalyst under the optimum conditions of 1 MPa N₂ pressure, 310 °C and 16 h. The conversion of pyridine is 35.4%, and the selectivity for 2,2′-Bipyridine is up to 99%, which is much higher activity than Pd/Al₂O₃. The directly coupled synthesis meets the requirements of the atomic economy better. The addition of Cu also reduces the dosage of Pd and lowers the cost. It is worth noting that the recycled Pd-Cu/Al₂O₃ catalyst still shows high activity and stability after three times.

Keywords

Pd-Cu/Al₂O₃ / X-ray diffraction / atomic economy / 2,2′-bipyridine / catalytic activity

References

[1] Shang Y, Xu X, Gao B, et al. Single-atom Catalysis in Advanced Oxidation Processes for Environmental Remediation[J]. Chemical Society Reviews, 2021, 50(8): 5 281-5 322.

[2] Dutta S, Yu IKM, Tsang DCW, et al. Green Synthesis of Gamma-valerolactone (GVL) Through Hydrogenation of Biomass-derived Levulinic Acid using Non-noble Metal Catalysts: A Critical Review[J]. Chemical Engineering Journal, 2019, 372: 992-1006.

[3] Singh J, Dutta T, Kim K-H, et al. “Green’ Synthesis of Metals and Their Oxide Nanoparticles: Applications for Environmental Remediation[J]. Journal of Nanobiotechnology, 2018, 16: 84.

[4] Ai JJ, Li J, Ji SJ, et al. One-pot Two-step Reaction of Selenosulfonate with Isocyanides and Allyl Alcohol under Aqueous Conditions: Atom-economic Synthesis of Selenocarbamates and Allyl Sulfones[J]. Chinese Chemical Letters, 2021, 32(2): 721-724.

[5] Yu H, Shang F, Chu Q, et al. Cleaner and Atomic Economy Production of Hydroxylamine Hydrochloride under Solvent-free Conditions Through Process Intensification[J]. Journal of Cleaner Production, 2020, 269: 122 187.

[6] Lu Z, Li T, Mudshinge SR, et al. Optimization of Catalysts and Conditions in Gold(I) Catalysis-Counterion and Additive Effects[J]. Chemical Reviews, 2021, 121(14): 8 452-8 477.

[7] Ali W, Prakash G, Maiti D. Recent Development in Transition Metal-catalysed C-H Olefination[J]. Chemical Science, 2021, 12(8): 2 735-2 759.

[8] Friscic T, Mottillo C, Titi HM. Mechanochemistry for Synthesis[J]. Angewandte Chemie-International Edition, 2020, 59(3): 1 018-1 029.

[9] Jorge de Souza TA, Rosa Souza LR, Franchi LP. Silver Nanoparticles: An Integrated View of Green Synthesis Methods, Transformation in the Environment, and Toxicity[J]. Ecotoxicology and Environmental Safety, 2019, 171: 691-700.

[10] Khandehyal S, Tailor YK, Kumar M. Deep Eutectic Solvents (DESs) as Eco-friendly and Sustainable Solvent/Catalyst Systems in Organic Transformations[J]. Journal of Molecular Liquids, 2016, 215: 345-386.

[11] Burriss A, Edmunds AJF, Emery D, et al. The Importance of Trifluoromethyl Pyridines in Crop Protection[J]. Pest Management Science, 2018, 74(6): 1 228-1 238.

[12] Blumenberg A, Benabbas R, deSouza IS, et al. Utility of 2-Pyridine Aldoxime Methyl Chloride (2-PAM) for Acute Organophosphate Poisoning: A Systematic Review and Meta-Analysis[J]. Journal of Medical Toxicology: Official Journal of the American College of Medical Toxicology, 2018, 14(1): 91-98.

[13] Okamoto S. Synthesis of 2,2′-bipyridines by Transition Metal-catalyzed Alkyne/nitrile 2+2+2 Cycloaddition Reactions[J]. Heterocycles, 2012, 85(7): 1 579-1 602.

[14] Newkome GR, Patri AK, Holder E, et al. Synthesis of 2,2′-bipyridines: Versatile Building Blocks for Sexy Architectures and Functional Nanomaterials[J]. European Journal of Organic Chemistry, 2004,(2): 235–254

[15] Hapke M, Brandt L, Luetzen A. Versatile tools in the Construction of Substituted 2,2′-bipyridines-cross-coupling Reactions with Tin, Zinc and Boron Compounds[J]. Chemical Society Reviews, 2008, 37(12): 2 782-2 797.

[16] Varela JA, Saa C. Construction of Pyridine Rings by Metal-mediated 2+2+2 Cycloaddition[J]. Chemical Reviews, 2003, 103(9): 3 787-3 801.

[17] Szakonyi Z, Fulop F, Tourwe D, et al. Synthesis of 1,2,7,7a-tetrahydro-1aH-cyclopropa b Quinoline-1a-carboxylic Acid Derivatives, Doubly Constrained ACC Derivatives, by a Remarkable Cyclopropanation Process[J]. Journal of Organic Chemistry, 2002, 67(7): 2 192-2 196.

[18] Dhital RN, Kamonsatikul C, Somsook E, et al. Bimetallic Gold-palladium Alloy Nanoclusters: An Effective Catalyst for Ullmann Coupling of Chloropyridines under Ambient Conditions[J]. Catalysis Science & Technology, 2013, 3(11): 3 030-3 035.

[19] Kabir MS, Lorenz M, Namjoshi OA, et al. First Application of an Efficient and Versatile Ligand for Copper-Catalyzed Cross-Coupling Reactions of Vinyl Halides with N-Heterocycles and Phenols[J]. Organic Letters, 2010, 12(3): 464-467.

[20] Hussain N, Hussain A. Advances in Pd-catalyzed C-C bond Formation in Carbohydrates and Their Applications in the Synthesis of Natural Products and Medicinally Relevant Molecules[J]. Rsc Advances, 2021, 11(54): 34 369-34 391.

[21] Wang X, Liang X, Geng P, et al. Recent Advances in Selective Hydrogenation of Cinnamaldehyde over Supported Metal-based Catalysts[J]. Acs Catalysis, 2020, 10(4): 2 395-2 412.

[22] Tu P, Jiang J, Xiao H, et al. Green Synthesis of Aryl Thioethers through Cu-catalysed C-S Coupling of Thiols and Aryl Boronic Acids in Water[J]. Journal of Wuhan University of Technology-Materials Science Edition, 2019, 34(4): 987-993.

[23] Li Y, Hu Y, Wu XF. Non-noble Metal-catalysed Carbonylative Trans-Formations[J]. Chemical Society Reviews, 2018, 47(1): 172-194.

[24] Tan H, Zhou Y, Yan Y, et al. Preparation of Cerium Doped Cu/MIL-53(Al) Catalyst and Its Catalytic Activity in CO Oxidation Reaction[J]. Journal of Wuhan University of Technology-Materials Science Edition, 2017, 32(1): 23-28.

[25] Gao WL, Guan NJ, Chen JX, et al. Titania Supported Pd-Cu Bimetallic Catalyst for the Reduction of Nitrate in Drinking Water[J]. Applied Catalysis B-Environmental, 2003, 46(2): 341-351.

[26] Sreethawong T, Yoshikawa S. Comparative Investigation on Photocatalytic Hydrogen Evolution Over Cu-, Pd-, and Au-loaded Mesoporous TiO₂ Photocatalysts[J]. Catalysis Communications, 2005, 6(10): 661-668.

[27] Batista J, Pintar A, Mandrino D, et al. XPS and TPR Examinations of Gamma-alumina-supported Pd-Cu Catalysts[J]. Applied Catalysis a-General, 2001, 206(1): 113-124.

[28] Wang M, Ma ZZ, Li RX, et al. Novel Flower-like PdAu(Cu) Anchoring on a 3D rGO-CNT Sandwich-stacked Framework for Highly Efficient Methanol and Ethanol Electro-oxidation[J]. Electrochimica Acta, 2017, 227: 330-344.

[29] Jung J, Bae S, Lee W. Nitrate Reduction by Maghemite Supported Cu-Pd Bimetallic Catalyst[J]. Applied Catalysis B-Environmental, 2012, 127: 148-158.

[30] Mandal K, Bhattacharjee D, Roy PS, et al. Room Temperature Synthesis of Pd-Cu Nanoalloy Catalyst with Enhanced Electrocatalytic Activity for the Methanol Oxidation Reaction[J]. Applied Catalysis a-General, 2015, 492: 100-106.