Light, Heat and Electricity Integrated Energy Conversion System: Photothermal‐Assisted Co‐Electrolysis of CO2 and Methanol

Abstract Strategy that can design powerful photothermal‐catalysts to achieve photothermal‐effect assisted coupling‐catalysis is much desired for the improvement of energy conversion efficiency and redox product value in CO 2 electroreduction system. Herein, a kind of bifunctional viologen‐containing covalent organic framework (Ni‐2CBpy 2+ ‐COF) has been prepared and successfully applied in photothermal‐assisted co‐electrolysis of CO 2 and methanol. Specifically, the FE CO (cathode) and FE HCOOH (anode) for Ni‐2CBpy 2+ ‐COF can reach up to ≈100 % at 1.9 V with ≈31.5 % saved overall electricity‐consumption when the anodic oxygen evolution reaction (OER) is replaced by methanol oxidation. The superior performance could be attributed to the cyclic diquats in Ni‐2CBpy 2+ ‐COF that enhance the photothermal effect (Δ T =49.1 °C) to accelerate faster charge transfer between catalyst and immediate species as well as higher selectivity towards desired products as revealed by DFT calculations and characterizations.