Steering electron flow by constructing an integrated structure in a metal–organic framework (MOF) <i>via</i> iminopyridine units for efficient CO₂ photoreduction to C₂H₄ and C₂H₆

Selective photoreduction of CO₂ to C₂₊ products has attracted increasing interest, but it remains challenging. Herein, we reported a novel strategy to steer electron flow by constructing integrated photocatalysts to achieve selective photoreduction of CO₂ to C₂H₄ and C₂H₆. Using iminopyridine units in NH₂-MIL-125(Ti) (Ti-MOF) as a tag, both the Ru photosensitizer and CuCo active sites were assembled within the Ti-MOF to form the integrated structure. Due to the strong interaction of the Ru photosensitizer and CuCo with Ti-MOF, the integrated CuCo/Ti-MOF-Py-Ru exhibited accelerated charge separation and migration efficiency, resulting in significant electron accumulation around CuCo. Compared with the discrete counterparts, the CO₂ photoreduction products were upgraded from CO and CH₄ to C₂H₄ and C₂H₆, with a high C₂ selectivity of 86.1% over the integrated CuCo/Ti-MOF-Py-Ru, highlighting the critical role of the integrated structure in enhancing the selective CO₂ photoreduction to C₂₊ products.