Boosting electron transfer in Lewis-acid MOF facilitates photoreduction of CO2 to ethanol

Photoreduction of CO 2 to alcohol offers a sustainable solution to the energy crisis. The unsatisfactory selectivity and activity are hindered by the poor adsorption of *CO and sluggish C-C coupling process kinetics. Herein, the dual-channel ligand-to-metal charge transfer (LMCT) pathways were constructed by coordinating an electron-donor Ferrocene (Fc) on Lewis acid L-Cu-MOF-74 to produce Fc-Cu-MOF-74, aiming to modulate the d-band center and electron density, as well as enhance the electron transfer efficiency. As catalyzed by Fc-Cu-MOF-74, the evolution rate of photoreduction of CO 2 to ethanol achieved 103.3 μmol∙g −1 ∙h −1 with a selectivity of 64.9 %, which is higher than that of Cu-MOF-74 and L-Cu-MOF-74. Photoelectrochemical studies reveal that the incorporation of the electron donor Fc on L-Cu-MOF-74 effectively accelerates the electron transfer efficiency, reduces the energy of the LMCT. In-situ FT-IR and theoretical calculations reveal that the chemisorption of *CO and subsequent C-C coupling process are accelerated on the Cu site of Fc-Cu-MOF-74, which exhibits appropriate Lewis acidity. This electron transfer strategy provides a new pathway for the construction of high-performance CO 2 reduction reaction photocatalysts.