Novel Inorganic‐Organic Dual‐Photosensitizing Dinuclear‐Metal Self‐Assembly System for Efficient Artificial Photosynthesis without Sacrificial Electron Donors

Abstract Owing to the unique synergistic effect, dinuclear‐metal‐molecule‐catalysts (DMCs) show excellent performance in catalytic fields. However, for overall photocatalytic CO 2 reaction (CO 2 RR), it is still a challenge to construct well‐matched photosensitizer (PS) components for DMCs‐based photocatalysts. Inorganic‐quantum‐dot PS possesses capacities of multiple exciton generation and catalyzing water oxidation but is incompatible with DMCs. In contrast, organic PS can be covalently linked with DMCs but inescapable of using sacrificial electron donors. For overall photocatalytic CO 2 RR, organic–inorganic dual‐photosensitizing system might be a promising candidate. Herein, we employed covalent‐linking and electrostatic‐driven approaches to construct the self‐assembly of pyrene‐sensitized Co 2 L DMCs (Py‐Co 2 L) and perovskite (PVK) quantum dots, i.e., PVK@[Py‐Co 2 L]. Using H 2 O as an electron donor, PVK@[Py‐Co 2 L] realized 105.24 μmol ⋅ g −1 ⋅h −1 CO yield in photocatalytic CO 2 RR, much higher than PVK (15.44 μmol ⋅ g −1 ⋅h −1 ) and PVK@Co 2 L (32.30 μmol ⋅ g −1 ⋅ h −1 ), ascribing to the efficient photogenerated charge separation and transfer. The experimental results and theoretical investigations demonstrated that the pyrene linked on Co 2 L boosted the electron delivery from PVK to DMCs. Besides, this strategy could also be extended to the photocatalytic H 2 evolution coupled with alcohol oxidation. As a proof‐of‐concept, our work lightens the integration of DMCs, organic and inorganic PS components, promoting the development of photocatalysis without sacrificial electron donors.