Semiartificial Photoelectrochemistry for CO2-Mediated Enantioselective Organic Synthesis.

Abstract

Photoelectrochemical (PEC) cells are under intensive development for the synthesis of solar fuels, but CO2 reduction typically only results in simple building blocks such as HCOO-. Here, we demonstrate that CO2-converting PEC cells can drive integrated enzymatic domino catalysis to produce chiral organic molecules by using CO2/HCOO- as a sustainable redox couple. First, we establish a semiartificial electrode consisting of three enzymes co-immobilized on a high surface area electrode based on carbon felt covered by a mesoporous indium tin oxide (ITO) coating. When applying a mild cathodic potential (-0.25 V vs the reversible hydrogen electrode (RHE)), CO2 is reduced to HCOO- using a W-formate dehydrogenase (FDHNvH) from Nitratidesulfovibrio vulgaris Hildenborough, which then enables the reduction of NAD+ to NADH by an NAD+-cofactor-dependent formate dehydrogenase from Candida boidinii (FDHCB). Subsequently, an alcohol dehydrogenase (ADH) uses NADH generated from CO2/HCOO- cycling to reduce acetophenone to chiral 1-phenylethanol in good enantiomeric excess (93%) and conversion yields (38%). Depending on the specific ADH (ADHS or ADHR), either (S)- or (R)-1-phenylethanol can be synthesized at pH 6 and 20 °C. To illustrate solar energy utilization, we integrate the three nanoconfined enzymes with a PEC platform based on an integrated organic semiconductor photocathode to allow for enantioselective synthesis (at +0.8 V vs RHE) based on a solar fuel device. This proof-of-principle demonstration shows that concepts and devices from artificial photosynthesis can be readily translated to precise and sustainable biocatalysis, including the production of chiral organic molecules using light.