Confining charge-transfer complex in a metal-organic framework for photocatalytic CO₂ reduction in water

In the quest for renewable fuel production, the selective conversion of CO₂ to CH₄ under visible light in water is a leading-edge challenge considering the involvement of kinetically sluggish multiple elementary steps. Herein, 1-pyrenebutyric acid is post-synthetically grafted in a defect-engineered Zr-based metal organic framework by replacing exchangeable formate. Then, methyl viologen is incorporated in the confined space of post-modified MOF to achieve donor-acceptor complex, which acts as an antenna to harvest visible light, and regulates electron transfer to the catalytic center (Zr-oxo cluster) to enable visible-light-driven CO₂ reduction reaction. The proximal presence of the charge transfer complex enhances charge transfer kinetics as realized from transient absorption spectroscopy, and the facile electron transfer helps to produce CH₄ from CO₂. The reported material produces 7.3 mmol g^-1 of CH₄ under light irradiation in aqueous medium using sacrificial agents. Mechanistic information gleans from electron paramagnetic resonance, in situ diffuse reflectance FT-IR and density functional theory calculation.