Photo-thermal Cooperative Carbonylation of Ethanol with CO₂ on Cu₂ O-SrTiCuO_3-x

Carbonylation of ethanol with CO₂ 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 CO₂ 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 CO₂ , in which CO₂ 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 Cu₂ O (Cu₂ 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 CO₂ . In the photo-driven activation of CO₂ and following carbonylation, CO₂ activation energy decreases to 12.6 kJ mol^-1 , and the cleavage of alcoholic α-C-H bond has been suppressed.