Photocatalytic Aqueous CO₂ Reduction to CO and CH₄ Sensitized by Ullazine Supramolecular Polymers

There has been rapid progress on the chemistry of supramolecular scaffolds that harness sunlight for aqueous photocatalytic production of hydrogen. However, great efforts are still needed to develop similar photosynthetic systems for the great challenge of CO₂ reduction especially if they avoid the use of nonabundant metals. This work investigates the synthesis of supramolecular polymers capable of sensitizing catalysts that require more negative potentials than proton reduction. The monomers are chromophore amphiphiles based on a diareno-fused ullazine core that undergo supramolecular polymerization in water to create entangled nanoscale fibers. Under 450 nm visible light these fibers sensitize a dinuclear cobalt catalyst for CO₂ photoreduction to generate carbon monoxide and methane using a sacrificial electron donor. The supramolecular photocatalytic system can generate amounts of CH₄ comparable to those obtained with a precious metal-based [Ru(phen)₃](PF₆)₂ sensitizer and, in contrast to Ru-based catalysts, retains photocatalytic activity in all aqueous media over 6 days. The present study demonstrates the potential of tailored supramolecular polymers as renewable energy and sustainability materials.