A Phenazine‐Based Two‐Dimensional Covalent Organic Framework for Photochemical CO₂ Reduction with Increased Selectivity for Two‐Carbon Products

The reduction of carbon dioxide (CO₂) into valuable products will contribute to sustainable carbon use. Here we report the photocatalytic reduction of CO₂ to carbon monoxide, formate, and oxalate ions using a redox-active phenazine-based 2D covalent organic framework (Phen-COF) and its phenazine monomer. Under similar irradiation conditions, Phen-COF produced 2.9 times more CO, 11 times more formate, and 13 times more oxalate compared to equimolar amounts of the monomeric phenazine, demonstrating that the COF architecture enhances catalytic performance (TOF_COF: 10^-7 s^-1 CO, 10^-8 s^-1 formate, and 10^-11 s^-1 oxalate). Structural analysis, including X-ray diffraction and N₂ porosimetry, confirmed the COF's long-range order and porosity. Mechanistic studies suggest a sequential formate-to-oxalate pathway, with CO and formate acting as intermediates. These results demonstrate the potential of the COF architecture to improve the performance of metal-free, redox-active aromatic systems such as phenazines to facilitate efficient and selective CO₂ conversion under mild conditions.