Ionic Liquid-Modified Porous Organometallic Polymers as Efficient and Selective Photocatalysts for...

In the photoreduction of CO₂ to CO, the competitive H₂ evolution is always inevitable due to the approximate reduction potentials of H⁺/H₂ and CO₂/CO, which results in poor selectivity for CO production. Herein, imidazolium-type ionic liquid- (IL-) modified rhenium bipyridine-based porous organometallic polymers (Re-POMP-IL) were designed as efficient and selective photocatalysts for visible-light CO₂ photoreduction to CO based on the affinity of IL with CO₂. Photoreduction studies demonstrated that CO₂ photoreduction promoted by Re-POMP-IL functioning as the catalyst exhibits excellent CO selectivity up to 95.5% and generate 40.1 mmol CO/g of Re-POMP-IL1.0 (obtained by providing equivalent [(5,5'-divinyl-2,2'-bipyridine)Re(CO)₃Cl] and 3-ethyl-1-vinyl-1H-imidazol-3-ium bromide) at 12 h, outperforming that attained with the corresponding Re-POMP analogue without IL, which highlights the crucial role of IL. Notably, CO₂ adsorption, light harvesting, and transfer of photogenerated charges as key steps for CO₂RR were studied by employing POMPs modified with different amounts of IL as photocatalysts, among which the CO₂ affinity as an important factor for POMPs catalyzed CO₂ reduction is revealed. Overall, this work provides a practical pathway to improve the CO₂ photoreduction efficiency and CO selectivity by employing IL as a regulator.