Simultaneous Conversion of CO2 and Cellulose to Formate Using a Floating TiO2-Enzyme Photoreforming Catalyst.

Abstract

Formate production via both CO2 reduction and cellulose oxidation in a solar-driven process is achieved by a semiartificial biohybrid photocatalyst consisting of immobilized formate dehydrogenase on titanium dioxide (TiO2|FDH) producing up to 1.16±0.04 mmolformate gTiO2-1 in 24 hours. Isotopic labelling experiments with 13C-labelled substrates support the mechanism of stoichiometric formate formation through both redox half-reactions. TiO2|FDH was further immobilized on hollow glass microspheres to perform more practical floating photoreforming allowing vertical solar light illumination with optimal light exposure of the photocatalyst to real sunlight. Enzymatic cellulose depolymerization coupled to the floating photoreforming catalyst generates 0.36±0.04 mmolformate mirr-2 after 24 h. This work thus presents simultaneous solar-driven valorization of waste streams, demonstrates the advantages of biohybrid photocatalysts in photoreforming for the first time and will provide inspiration for the development of future semi-artificial waste-to-chemical conversion strategies.