Light assisted nickel(II) grafted-g-carbon nitride molecular hybrid promoted hydrocarboxylation of olefins with CO2 at atmospheric pressure condition. (January 2022)

• Record Type: Journal Article
• Authors: Saini, Sandhya; Abraham, B. Moses; Jain, Suman L.
• Is Part Of: Journal of CO₂ utilization. Volume 55(2022)
• Publication Date: 2022-01
• Subjects: Nickel -- Hydrocarboxylation -- Carbon dioxide -- Olefin -- Acid -- Hybrid; Carbon dioxide -- Periodicals; Carbon dioxide -- Environmental aspects -- Periodicals; Carbon dioxide mitigation -- Periodicals; Carbon dioxide; Carbon dioxide -- Environmental aspects; Carbon dioxide mitigation; Periodicals; 628.53205
• DOI: 10.1016/j.jcou.2021.101812
• Languages: English
• ISSNs: 2212-9820

Abstract

Highlights: Photoredox catalyzed hydrocarboxylation using CO2 under atmospheric pressure and room temperature. Highly regioselective hydrocarboxylation of unsaturated hydrocarbons with CO2 . Molecular hybrid consisting of nickel(II)phthalocyanine grafted on graphitic carbon nitride as low cost photocatalyst. Highly stable, heterogeneous and reusable photocatalyst. Higher CO2 adsorption on the photocatalyst via binding with nickel(II) in hybrid afforded higher conversion. Abstract: An efficient photocatalytic method was developed for the hydrocarboxylation of olefins to corresponding acids using carbon dioxide assisted by a molecular hybrid photocatalyst consisting of nickel phthalocyanine complex grafted to graphitic carbon nitride support (NiPc/g-C3 N4 ) under ambient temperature and pressure conditions. The reaction is found to be regioselective in nature as aromatic olefins i.e. styrenes and its derivatives afforded α-carboxylated products; whereas aliphatic olefins yielded terminal acids selectively in moderate-to-good yields. The DFT calculations suggested the higher efficiency of the hybrid photocatalyst as compared to its individual components. Based on the electrochemical measurements and adsorption behaviour of the CO2 on the catalyst and corresponding bond distances calculated by DFT, a possible mechanism is proposed. Furthermore, triethylamine was used as a sacrificial donor that provided the required electrons to complete the redox cycle of the reaction.