Synthesis of metal-phenanthroline-modified hypercrosslinked polymer for enhanced CO₂ capture and conversion via chemical and photocatalytic methods under ambient conditions

Abstract

Catalytic conversion of CO₂ into valuable chemicals is a promising approach to mitigate the greenhouse effect and alleviate energy shortages. Hypercrosslinked polymers (HCPs) offer a scalable and stable platform for this conversion, but they often suffer from low CO₂ adsorption and activation capabilities, necessitating high temperatures and pressures for effectiveness. To overcome these limitations, nitrogen-based CO₂-philic active sites have been integrated into the structure of HCPs, enhancing CO₂ attraction and leading to superior adsorption performance. The incorporation of cobalt ions further bolsters CO₂ affinity, with HCP-PNTL-Co-B achieving the highest observed adsorption heat of 33.0 kJ·mol^-1 alongside a substantial 2.0 mmol·g^-1 CO₂ uptake. These modified HCPs exhibit higher yields and reaction rates in cycloaddition reactions with cocatalyst tetrabutylammonium bromide at room temperature and atmospheric pressure, while HCP-1,10-phenanthroline (PNTL)-Co-B demonstrates a higher CO production rate (2,173 μmol·g^-1·h^-1) and selectivity (84%) in photocatalytic reduction reaction. This research has successfully achieved outstanding carbon dioxide capture and conversion performance at room temperature and atmospheric pressure by introducing CO₂-philic active sites and cobalt ions into HCPs via facile one-step polymerization. This study provides a new method to design highly efficient organic catalysts for CO₂ conversion.

Keywords

Hypercrosslinked polymers / N heteroatoms / CO₂ cycloaddition / CO₂ photoreduction

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