Copper-Based Bio-MOF/GO with Lewis Basic Sites for CO2 Fixation into Cyclic Carbonates and C-C Bond-Forming Reactions.

Abstract

Several measures, including crude oil recovery improvement and carbon dioxide (CO2) conversion into valuable chemicals, have been considered to decrease the greenhouse effect and ensure a sustainable low-carbon future. The Knoevenagel condensation and CO2 fixation have been introduced as two principal solutions to these challenges. In the present study for the first time, bio-metal-organic frameworks (MOF)(Cu)/graphene oxide (GO) nanocomposites have been used as catalytic agents for these two reactions. In view of the attendance of amine groups, biological MOFs with NH2 functional groups as Lewis base sites protruding on the channels' internal surface were used. The bio-MOF(Cu)/20%GO performs efficaciously in CO2 fixation, leading to more than 99.9% conversion with TON = 525 via a solvent-free reaction under a 1 bar CO2 atmosphere. It has been shown that these frameworks are highly catalytic due to the Lewis basic sites, i.e., NH2, pyrimidine, and C═O groups. Besides, the Lewis base active sites exert synergistic effects and render bio-MOF(Cu)/10%GO nanostructures as highly efficient catalysts, significantly accelerating Knoevenagel condensation reactions of aldehydes and malononitrile as substrates, thanks to the high TOF (1327 h-1) and acceptable reusability. Bio-MOFs can be stabilized in reactions using GO with oxygen-containing functional groups that contribute as efficient substitutes, leading to an expeditious reaction speed and facilitating substrate absorption.