Hierarchically Porous Metal–Organic Framework/MoS₂ Interface for Selective Photocatalytic Conversion of CO₂ with H₂O into CH₃COOH

Metal-organic frameworks (MOFs) provide a platform to design new heterogeneous catalysts for catalytic CO₂ reduction, but selective formation of C2 valuable liquid fuel products remains a challenge. Herein, we propose a strategy to synthesize composites by integrating MoS₂ nanosheets into hierarchically porous defective UiO-66 (d-UiO-66) to form Mo-O-Zr bimetallic sites on the interfaces between UiO-66 and MoS₂ . The active interfaces are favorable for the efficient transfer of photo-generated charge carriers and for promoting the activity, whereas, the synergy of the components at the interfaces achieves selectivity for C2 production. The d-UiO-66/MoS₂ composite facilitates the photo-catalytic conversion of gas phase CO₂ and H₂ O to CH₃ COOH under visible light irradiation without any other adducts. The evolution rate and selectivity of CH₃ COOH reached 39.0 μmol g⁻¹ h⁻¹ and 94 %, respectively, without any C1 products, suggesting a new approach for the design of highly efficient photocatalysts of CO₂ for C2 production. Theoretical calculations demonstrate the charge-polarized Zr-O-Mo aided the C-C coupling process with the largely reduced energy barrier.