Photo‐thermal Cooperative Carbonylation of Ethanol with CO2 on Cu2O‐SrTiCuO3‐x

Abstract Carbonylation of ethanol with CO 2 as carbonyl source into value‐added esters is of considerable significance and interest, while remains of great challenge due to the harsh conditions for activation of inert CO 2 in that the harsh conditions result in undesired activation of α‐C−H and even cleavage of C−C bond in ethanol to deteriorate the specific activation of O−H bond. Herein, we propose a photo‐thermal cooperative strategy for carbonylation of ethanol with CO 2 , in which CO 2 is activated to reactive CO via photo‐catalysis with the assistance of *H from thermally‐catalyzed dissociation of alcoholic O−H bond. To achieve this proposal, an interfacial site and oxygen vacancy both abundant SrTiCuO 3‐x supported Cu 2 O (Cu 2 O‐SrTiCuO 3‐x ) has been designed. A production of up to 320 μmol g −1 h −1 for ethyl formate with a selectivity of 85.6 % to targeted alcoholic O−H activation has been afforded in photo‐thermal assisted gas‐solid process under 3.29 W cm −1 of UV/Vis light irradiation (144 °C) and 0.2 MPa CO 2 . In the photo‐driven activation of CO 2 and following carbonylation, CO 2 activation energy decreases to 12.6 kJ mol −1 , and the cleavage of alcoholic α‐C−H bond has been suppressed.