Integrating Single Atoms with Different Microenvironments into One Porous Organic Polymer for Efficient...

The precise identification of single-atom catalysts (SACs) activity and boosting their efficiency toward CO₂ conversion is imperative yet quite challenging. Herein, for the first time a series of porous organic polymers is designed and prepared simultaneously, containing well-defined M-N₄ and M-N₂ O₂ single-atom sites. Such a strategy not only offers multiactive sites to promote the catalytic efficiency but also provides a more direct chance to identify the metal center activity. The CO₂ photoreduction results indicate that the introduction of salphen unit with Ni-N₂ O₂ catalytic centers into pristine phthalocyanine-based Ni-N₄ framework achieves remarkable CO generation ability (7.77 mmol g^-1 ) with a high selectivity of 96% over H₂ . In combination with control experiments, as well as theoretical studies, the Ni-N₂ O₂ moiety is evidenced as a more active site for CO₂ RR compared with the traditional Ni-N₄ moiety, which can be ascribed to the M-N₂ O₂ active sites effectively reducing the energy barrier, facilitating the adsorption of reaction radicals *COOH, and improving the charge transportation. This work might shed some light on designing more efficient SACs toward CO₂ reduction through modification of their coordination environments.