Journal of Sciences, Islamic Republic of Iran

From The Rational Design of Cobalt-zinc Bimetallic MOF to Catalytic Behavior in Knoevenagel Condensation Reaction

Document Type : Original Paper

Authors

1 1 School of Chemistry, College of Science, University of Tehran, Tehran, Islamic Republic of Iran

2 2 Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Islamic Republic of Iran

3 3 School of Chemistry, College of Science, University of Tehran, Tehran, Islamic Republic of Iran

Abstract

In this study, a bimetallic Co-Zn metal-organic framework (Co-Zn-MOF) was synthesized through solvothermal conditions by using Co2+ and Zn2+ salts, DABCO and H2BDC as the rigid ligands (DABCO= 1,4-diazabicyclo (2.2.2) octane, H2BDC=Benzene-1,4-dicarboxylic acid). This bimetallic MOF was used as a catalyst for the Knoevenagel condensation reaction and exhibited enhanced catalytic activity compared to its parents' single metal MOFs derived from DABCO and H2BDC precursors (Co-MOF and Zn-MOF) at mild reaction conditions, which could be attributed to the synergistic effect between the metal ions.

Keywords

Main Subjects

  1. Almáši M, Zeleňák V, Opanasenko M, Císařová I. Ce (III) and Lu (III) metal-organic frameworks with Lewis acid metal sites: Preparation, sorption properties and catalytic activity in Knoevenagel condensation. Catalysis today. 2015 Apr 1;243:184-94.
  2. Zhao S. A novel 3D MOF with rich Lewis basic sites as a base catalysis toward knoevenagel condensation reaction. Journal of Molecular Structure. 2018 Sep 5;1167:11-5.
  3. Yao C, Zhou S, Kang X, Zhao Y, Yan R, Zhang Y, Wen L. A cationic zinc–organic framework with Lewis acidic and basic bifunctional sites as an efficient solvent-free catalyst: CO2 fixation and Knoevenagel condensation reaction. Inorganic Chemistry. 2018 Aug 23;57(17):11157-64.
  4. Wang R, Sheng K, Huang XQ, Azam M, Tung CH, Sun D. A robust Ag/Ti nanocluster as an efficient heterogeneous Lewis Acid-Base catalyst for C–C bond formation. Journal of Catalysis. 2023 Aug 1;424:189-96.
  5. Goetjen TA, Liu J, Wu Y, Sui J, Zhang X, Hupp JT, Farha OK. Metal-organic framework (MOF) materials as polymerization catalysts: a review and recent advances. Chemical Communications. 2020;56(72):10409-18.
  6. Liu M, Wu J, Hou H. Metal-Organic Framework (MOF)‐based materials as heterogeneous catalysts for C–H bond activation. Chemistry–A European Journal. 2019 Feb 26;25(12):2935-48.
  7. Wu CD, Zhao M. Incorporation of molecular catalysts in metal-organic frameworks for highly efficient heterogeneous catalysis. Advanced Materials. 2017 Apr;29(14):1605446.
  8. Zamani S, Abbasi A, Masteri-Farahani M, Rayati S. One-pot, facile synthesis and fast separation of a UiO-66 composite by a metalloporphyrin using nanomagnetic materials for oxidation of olefins and allylic alcohols. New Journal of Chemistry. 2022;46(2):654-62.
  9. Bavykina A, Kolobov N, Khan IS, Bau JA, Ramirez A, Gascon J. Metal-organic frameworks in heterogeneous catalysis: recent progress, new trends, and future perspectives. Chemical reviews. 2020 Mar 30;120(16):8468-535.
  10. Abbasi A, Soleimani M, Najafi M, Geranmayeh S. Synthesis of nanostructured NiO/Co3O4 through thermal decomposition of a bimetallic (Ni/Co) metal-organic framework as catalyst for cyclooctene epoxidation. Journal of Molecular Structure. 2017 Apr 5;1133:458-63.
  11. Konnerth H, Matsagar BM, Chen SS, Prechtl MH, Shieh FK, Wu KC. Metal-organic framework (MOF)-derived catalysts for fine chemical production. Coordination Chemistry Reviews. 2020 Aug 1;416:213319.
  12. Naskar K, Maity S, Maity HS, Sinha C. A reusable efficient green catalyst of 2D Cu-MOF for the click and knoevenagel reaction. Molecules. 2021 Aug 31;26(17):5296.
  13. Tom L, Kurup MR. A 2D-layered Cd (II) MOF as an efficient heterogeneous catalyst for the Knoevenagel reaction. Journal of Solid-State Chemistry. 2021 Feb 1;294:121846.
  14. Xiong P, Xie TT, Zhou M, Li SM, Wang XJ, Ni QL, Gui LC. A stable 3D Sr-MOF as an efficient heterogeneous catalyst for the cycloadditions of CO2 and knoevenagel condensation reactions. Journal of Molecular Structure. 2024 May 5;1303:137466.
  15. Chen L, Wang HF, Li C, Xu Q. Bimetallic metal-organic frameworks and their derivatives. Chemical Science. 2020;11(21):5369-403.
  16. Li W, Fang W, Wu C, Dinh KN, Ren H, Zhao L, Liu C, Yan Q. Bimetal–MOF nanosheets as efficient bifunctional electrocatalysts for oxygen evolution and nitrogen reduction reaction. Journal of Materials Chemistry A. 2020;8(7):3658-66.
  17. Hu Y, Zhang J, Huo H, Wang Z, Xu X, Yang Y, Lin K, Fan R. One-pot synthesis of bimetallic metal-organic frameworks (MOFs) as acid-base bifunctional catalysts for tandem reaction. Catalysis Science & Technology. 2020;10(2):315-22.
  18. Yang Q, Zhang HY, Wang L, Zhang Y, Zhao J. Ru/UiO-66 catalyst for the reduction of nitroarenes and tandem reaction of alcohol oxidation/Knoevenagel condensation. ACS omega. 2018 Apr 13;3(4):4199-212.
  19. Zanon A, Chaemchuen S, Verpoort F. Zn@ ZIF-67 as catalysts for the Knoevenagel condensation of aldehyde derivatives with malononitrile. Catalysis Letters. 2017 Sep;147:2410-20.
  20. Kim Y, Haldar R, Kim H, Koo J, Kim K. The guest-dependent thermal response of the flexible MOF Zn2(BDC)2 (DABCO). Dalton Transactions. 2016;45(10):4187-92.
  21. Wang H, Getzschmann J, Senkovska I, Kaskel S. Structural transformation and high-pressure methane adsorption of Co2 (1, 4-bdc) 2dabco. Microporous and Mesoporous Materials. 2008 Dec 1;116(1-3):653-7.
  22. Wang Y, Kretschmer K, Zhang J, Mondal AK, Guo X, Wang G. Organic sodium terephthalate@ graphene hybrid anode materials for sodium-ion batteries. RSC Advances. 2016;6(62):57098-102.
  23. Rahvar Y, Motakef-Kazemi N, Hosseini Doust R. Synthesis of Zn2(BDC)2(DABCO) MOF by solution and solvothermal methods and evaluation of its anti-bacterial. Nanomedicine Research Journal. 2021 Nov 1;6(4):360-8.

 
  1. Zhang F, Hao L, Zhang L, Zhang X. Solid-state thermolysis preparation of Co3O4 nano/micro superstructures from metal-organic framework for supercapacitors. International Journal of Electrochemical Science. 2011 Jul 1;6(7):2943-54.
  2. Chinthamreddy A, Karreddula R, Pitchika GK, SurendraBabu MS. Synthesis, characterization of [Co (BDC)(Phen) H2O] and [Co (BDC)(DABCO)] MOFs, π. π interactions, Hirshfeld surface analysis and biological activity. Journal of Inorganic and Organometallic Polymers and Materials. 2021 Mar;31(3):1381-94.
  3. Aamer I, Iqbal N, Noor T, Asghar A. Synthesis, characterization and CO2 adsorption studies of DABCO based pillared Zn-BDC and Co-BDC metal-organic frameworks. Materials Research Express. 2021 Jul 27;8(7):075506.
  4. Filpi A, Boccia M, Pucci A, Ciardelli F. Modulation of the electrochemical properties of SBS-based anionic membranes by the amine molecular structure. e-Polymers. 2013 Aug;2013(1):1-4.
  5. Shirini F, Langarudi MS, Daneshvar N. Preparation of a new DABCO-based ionic liquid [H2-DABCO] [H2PO4] 2} and its application in the synthesis of tetrahydrobenzo [b] pyran and pyrano [2, 3-d] pyrimidinone derivatives. Journal of Molecular Liquids. 2017 May 1;234:268-78.
  6. Johari S, Johan MR, Khaligh NG. An overview of metal-free sustainable nitrogen-based catalytic Knoevenagel condensation reaction. Organic & Biomolecular Chemistry. 2022;20(11):2164-86.
  7. Dogan A, Eylem CC, Akduman NE. Application of green methodology to pharmaceutical analysis using eco-friendly ethanol-water mobile phases. Microchemical Journal. 2020 Sep 1;157:104895.
  8. Rafiee Z. Fabrication of efficient Zn-MOF/COF catalyst for the Knoevenagel condensation reaction. Journal of the Iranian Chemical Society. 2021 Oct;18(10):2657-64.
  9. Zare E, Rafiee Z. Cellulose stabilized Fe3O4 and carboxylate‐imidazole and Co‐based MOF growth as an exceptional catalyst for the Knoevenagel reaction. Applied Organometallic Chemistry. 2020 Apr;34(4): e5516.
  10. Tom L, Kurup MR. A 2D-layered Cd (II) MOF as an efficient heterogeneous catalyst for the Knoevenagel reaction. Journal of Solid-State Chemistry. 2021 Feb 1;294:121846.
  11. Sefidabi F, Abbasi A, Mortazavi SS, Masteri‐Farahani M. A new 2D cadmium coordination polymer based on hydroxyl‐substituted benzenedicarboxylic acid as an effective heterogeneous catalyst for Knoevenagel condensation. Applied Organometallic Chemistry. 2020 Oct;34(10):e5890.
  12. Ghasempour H, Tehrani AA, Morsali A, Wang J, Junk PC. Two pillared metal–organic frameworks comprising a long pillar ligand used as fluorescent sensors for nitrobenzene and heterogeneous catalysts for the Knoevenagel condensation reaction. Cryst Eng Comm. 2016;18(14):2463-8.
Journal of Sciences, Islamic Republic of Iran
Volume 35, Issue 1
March 2024
Pages 15-23