Sustainable Heterogeneous Catalysts for CO2 Utilization by Using Dual Ligand ZnII /CdII Metal-Organic Frameworks

Bhavesh Parmar; Parth Patel; Rukhsana I Kureshy; Noor-Ul H Khan; Eringathodi Suresh

doi:10.1002/chem.201802387

Sustainable Heterogeneous Catalysts for CO₂ Utilization by Using Dual Ligand Zn^II /Cd^II Metal-Organic Frameworks

Chemistry. 2018 Oct 22;24(59):15831-15839. doi: 10.1002/chem.201802387. Epub 2018 Sep 25.

Authors

Bhavesh Parmar^{1

2}, Parth Patel^{3

4}, Rukhsana I Kureshy^{1

3

4}, Noor-Ul H Khan^{1

3

4}, Eringathodi Suresh^{1

2}

Affiliations

¹ Academy of Scientific and Innovative Research (AcSIR), CSIR-Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-, 364 002, Gujarat, India.
² Analytical and Environmental Science Division and Centralized Instrument Facility, CSIR-Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-, 364 002, India.
³ Inorganic Material and Catalytic Division, CSIR-Central Salt and Marine Chemicals Research Institute, G. B. Marg, Bhavnagar-, 364 002, Gujarat, India.
⁴ Charotar University of Science & Technology, Changa-, 388 421, Anand, Gujarat, India.

PMID: 30044524
DOI: 10.1002/chem.201802387

Abstract

Two-dimensional Zn^II /Cd^II -based dual ligand metal-organic frameworks (MOFs) {[M(CHDC)(L)]⋅H₂ O}_n involving 4-pyridyl carboxaldehyde isonicotinoylhydrazone (L) in combination with flexible 1,4-cyclohexanedicarboxylic acid (H₂ CHDC) as linkers have been synthesized by adaptable synthetic protocols including a green mechanochemical (grinding) method. Characterization, chemical/thermal stability, phase purity, and solid-state luminescent properties of both MOFs have been established by various analytical methods. Structural analysis revealed dimeric metal clusters composed of [M₂ (CHDC)₂ ]_n loops doubly pillared with L, generating a 2D framework. Both MOFs can be used as highly active solvent-free binary catalysts for CO₂ cycloaddition with epoxides in the presence of the co-catalyst tetrabutylammonium bromide (TBAB) with good catalytic conversion in up to six catalytic cycles without significant loss of activity. The present investigation demonstrates the application of MOFs as efficient heterogeneous catalysts for CO₂ utilization under moderate reaction conditions. Based on the single-crystal X-ray data, a probable mechanism for the cycloaddition reaction has also been proposed.

Keywords: carbon dioxide; cycloaddition; grinding; heterogeneous catalysis; metal-organic frameworks.