Ferrocene-Functionalized Crystalline Biomimetic Catalysts for Efficient CO 2 Photoreduction.

Photoreducing carbon dioxide (CO 2 ) into highly valued chemicals or energy products has been recognized as one of the most promising proposals to degrade atmospheric CO 2 concentration and achieve carbon neutrality. Adenine with a photosensitive amino group and aromatic nitrogen atom can strongly interact with CO 2 and has been authenticated for its catalytic activity for the CO 2 photoreduction reaction (CO 2 RR). Herein, two adenine-constructed crystalline biomimetic photocatalysts (Co 2 -AW and Co 2 -AF) were designed and synthesized to achieve CO 2 RR. Between them, Co 2 -AF displayed higher photocatalytic activity (225.8 μmol g -1 h -1 ) for CO 2 -to-HCOOH conversion than that of Co 2 -AW. It was found that the superior charge transfer capacity of the functional ferrocene group in Co 2 -AF is the primary reason to facilitate the photocatalytic performance efficiently. Additionally, this work also demonstrated the great potential of the ferrocene group as an electron donor and mediator in improving the photocatalytic activity of crystalline coordination catalysts.