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

Solar-driven CO 2 reduction with H 2 O 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 Pd x In y @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 CO 2 photoreduction with H 2 O oxidation as the H + and e − source, showing a record-high total yield of 798 μmol g -1 for producing CH 3 OH (74 %) and CH 3 CH 2 OH (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 CO 2 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 H 2 O oxidation.