Modulating the Reaction Configuration by Breaking the Structural Symmetry of Active Sites for Efficient Photocatalytic Reduction of Low‐concentration CO2

Abstract Photocatalytic conversion of low‐concentration CO 2 is considered as a promising way to simultaneously mitigate the environmental and energy issues. However, the weak CO 2 adsorption and tough CO 2 activation process seriously compromise the CO production, due to the chemical inertness of CO 2 molecule and the formed fragile metal‐C/O bond. Herein, we designed and fabricated oxygen vacancy contained Co 3 O 4 hollow nanoparticles on ordered macroporous N‐doped carbon framework (Vo−HCo 3 O 4 /OMNC) towards photoreduction of low‐concentration CO 2 . In situ spectra and ab initio molecular dynamics simulations reveal that the constructed oxygen vacancy is able to break the local structural symmetry of Co−O−Co sites. The formation of asymmetric active site switches the CO 2 configuration from a single‐site linear model to a multiple‐sites bending one with a highly stable configuration, enhancing the binding and structural polarization of CO 2 molecules. As a result, Vo−HCo 3 O 4 /OMNC shows unprecedent activity in the photocatalytic conversion of low‐concentration CO 2 (10 % CO 2 /Ar) under laboratory light source or even natural sunlight, affording a syngas yield of 337.8 or 95.2 mmol g −1 h −1 , respectively, with an apparent quantum yield up to 4.2 %.