Metal-Organic Frameworks of Cu(II) Constructed from Functionalized Ligands for High Capacity H2 and CO2 Gas Adsorption and Catalytic Studies

Mayank Gupta; Nabanita Chatterjee; Dinesh De; Ranajit Saha; Pratim Kumar Chattaraj; Clive L Oliver; Parimal K Bharadwaj

doi:10.1021/acs.inorgchem.9b03012

Metal-Organic Frameworks of Cu(II) Constructed from Functionalized Ligands for High Capacity H₂ and CO₂ Gas Adsorption and Catalytic Studies

Inorg Chem. 2020 Feb 3;59(3):1810-1822. doi: 10.1021/acs.inorgchem.9b03012. Epub 2020 Jan 22.

Authors

Mayank Gupta¹, Nabanita Chatterjee², Dinesh De³, Ranajit Saha⁴, Pratim Kumar Chattaraj^{4

5}, Clive L Oliver², Parimal K Bharadwaj^{1

5}

Affiliations

¹ Department of Chemistry , Indian Institute of Technology Kanpur , Kanpur 208016 , India.
² Centre for Supramolecular Chemistry Research (CSCR), Department of Chemistry , University of Cape Town , Cape Town , South Africa.
³ Department of Basic Science, Vishwavidyalaya Engineering College, Lakhanpur , Sarguja University , Lakhanpur , Chhattisgarh - 497116 , India.
⁴ Department of Chemistry and Center for Theoretical Studies , Indian Institute of Technology Kharagpur , Kharagpur 721302 , India.
⁵ Department of Chemistry , Indian Institute of Technology Bombay , Mumbai 400076 , India.

PMID: 31965795
DOI: 10.1021/acs.inorgchem.9b03012

Abstract

Two Cu(II)-based metal-organic frameworks (MOFs) having paddle-wheel secondary building units (SBUs), namely, 1_Me and 1_ipr, were synthesized solvothermally using two new bent di-isophthalate ligands incorporating different substituents. The MOFs showed high porosity (BET surface area, 2191 m²/g for 1_Me and 1402 m²/g for 1_ipr). For 1_Me, very high CO₂ adsorption (98.5 wt % at 195 K, 42.9 wt % at 273 K, 23.3 wt % at 298 K) at 1 bar was found, while for 1_ipr, it was significantly less (14.3 wt % at 298 K and 1 bar, 54.4 wt % at 298 K at 50 bar). 1_Me exhibited H₂ uptake of 3.2 wt % at 77 K and 1 bar of pressure, which compares well with other benchmark MOFs. For 1_ipr, the H₂ uptake was found to be 2.54 wt % under similar experimental conditions. The significant adsorption of H₂ and CO₂ for 1_Me could be due to the presence of micropores as well as unsaturated metal sites in these MOFs besides the presence of substituents that interact with the gas molecules. The experimental adsorption behavior of the MOFs could be justified by theoretical calculations. Additionally, catalytic conversions of CO₂ and CS₂ into useful chemicals like cyclic carbonates, cyclic trithiocarbonates, and cyclic dithiocarbonates could be achieved.