Filling COFs with bimetallic nanoclusters for CO2-to-alcohols conversion with H2O oxidation

Solar-driven CO2 reduction with H2O oxidation into liquid fuels is highly desirable for sustainable carbon cycle to achieve carbon neutral, but represents a great challenge for artificial photosynthesis. Herein, bimetallic PdIn nanoclusters are confined in a photosensitizing covalent organic framework (N-3-COF) to facilely construct PdxIny@N-3-COF composites (x:y = 1:0, 0:1, 1:2, 1:1, 2:1). The resulting PdIn@N-3-COF exhibits excellent activity for CO2 photoreduction with H2O oxidation as the H+ and e(-) source, showing a record-high total yield of 798 mu mol g(-1) for producing CH3OH (74 %) and CH3CH2OH (26 %) among the framework materials. The synergy in both the bimetallic nanocluster and cluster@N-3-COF contributes greatly to C-C coupling and interfacial charge transfer, thus achieving excellent activity for conversion of CO2 to C-1/C-2 alcohols on the non-copper catalysts. This work highlights the amazing potential for constructing bimetallic nanocluster@photosensitizing supports to produce alcohols in artificial photosynthesis with H2O oxidation.