Engineering NH2‐Cu‐NH2 Triple‐atom Sites in Defective MOFs for Selective Overall Photoreduction of CO2 into CH3COCH3.

Selective photoreduction of CO2 to multicarbon products, is an important but challenging task, due to high CO2 activation barriers and insufficient catalytic sites for C−C coupling. Herein, a defect engineering strategy for incorporating copper sites into the connected nodes of defective metal–organic framework UiO‐66‐NH2 for selective overall photo‐reduction of CO2 into acetone. The Cu2+ site in well‐modified CuN2O2 units served as a trapping site to capture electrons via efficient electron‐hole separation, forming the active Cu+ site for CO2 reduction. Two NH2 groups in CuN2O2 unit adsorb CO2 and cooperated with copper ion to functionalize as a triple atom catalytic site, each interacting with one CO2 molecule to strengthen the binding of *CO intermediate to the catalytic site. The deoxygenated *CO attached to the Cu site interacted with *CH3 fixed at one amino group to form the key intermediate CO*‐CH3, which interacted with the third reduction intermediate on another amino group to produce acetone. Our photocatalyst realizes efficient overall CO2 reduction to C3 product acetone CH3COCH3 with an evolution rate of 70.9 μmol gcat−1 h−1 and a selectivity up to 97 % without any adducts, offering a promising avenue for designing triple‐atomic sites to producing C3 product from photosynthesis with water. [ABSTRACT FROM AUTHOR]