A TiO2 -Co(terpyridine)2 Photocatalyst for the Selective Oxidation of Cellulose to Formate Coupled to the Reduction of CO2 to Syngas.

Immobilization of a phosphonated cobalt bis(terpyridine) catalyst on TiO2 nanoparticles generates a photocatalyst that allows coupling aqueous CO2 -to-syngas (CO and H2 ) reduction to selective oxidation of biomass-derived oxygenates or cellulose to formate. An enzymatic saccharification pre-treatment process is employed that enables the use of insoluble cellulose as an electron-donating substrate under benign aqueous conditions suitable for photocatalytic CO2 conversion. The hybrid photocatalyst consists of solely earth-abundant components, and its heterogeneous nature allows for reuse and operation in aqueous solution for several days at 25 °C, reaching a cellulose-to-formate conversion yield of 17 %. Thus, the proof-of-concept for valorizing two waste streams (CO2 and biomass) simultaneously into value-added chemicals through solar-driven catalysis is demonstrated.