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

Abstract

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.