Herein, covalent triazine frameworks in eclipsed AA and staggered AB stacking modes are respectively used for the in-situ growth of TiO2, and two heterostructures are obtained. Due to the highly organized stacking of the molecular layer in CTF-AA that strengthens the interlayer interaction, the light absorption and carrier migration of CTF-AA/TiO2 are both enhanced in comparison to those of its component or CTF-AB/TiO2. Correspondently, the photocatalytic CO2 reduction reaction (CO2RR) of CTF-AA/TiO2 proffers 9.19 μmol·g-1·h-1 CH4 and 2.32 μmol·g-1·h-1 CO production, about 9.2 and 4.3 times greater than that of pristine TiO2, respectively. Even though the innate photoresponse of the triazine unit endows CTF-AB/TiO2 with augmented light capturing, its photocatalytic CO2 conversion is relatively insignificant. According to the analyses of the planar-averaged electron density difference and Bader charge, the unproductive CO2 efficiency might be due to the insufficient interfacial electron transfer from TiO2 to CTF-AB. Given that the ΔG (-3.22 eV) of CHO intermediate generation is lower than that of CO desorption (-1.23 eV), the reaction tends to further generate CH4 other than yielding CO. This study could shed fresh light over the reasonable design of effective photocatalytic heterostructures.
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