Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Photoelectrochemical (PEC) cells are under intensive development for the synthesis of solar fuels, but CO 2 reduction typically only results in simple building blocks such as HCOO – . Here, we demonstrate that CO 2 -converting PEC cells can drive integrated enzymatic domino catalysis to produce chiral organic molecules by using CO 2 /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)), CO 2 is reduced to HCOO – using a W-formate dehydrogenase (FDH NvH ) from Nitratidesulfovibrio vulgaris Hildenborough, which then enables the reduction of NAD + to NADH by an NAD + -cofactor-dependent formate dehydrogenase from Candida boidinii (FDH CB ). Subsequently, an alcohol dehydrogenase (ADH) uses NADH generated from CO 2 /HCOO – cycling to reduce acetophenone to chiral 1-phenylethanol in good enantiomeric excess (93%) and conversion yields (38%). Depending on the specific ADH (ADH S or ADH R ), 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.
DOI: 10.1021/jacs.5c02250
Language: English
Subfield: Molecular Biology
Domain: Life Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Funders: UK Research and Innovation, Leverhulme Trust, Royal Academy of Engineering, Agency for Science, Technology and Research, Nederlandse Organisatie voor Wetenschappelijk Onderzoek, Isaac Newton Trust, Engineering and Physical Sciences Research Council, Fundação para a Ciência e a Tecnologia, Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa
Awards: G1187624108, G2387188075, EPSRC Centre for Doctoral Training in Integrated Functional Nano (i4Nano), G3309579038, G3340144160, G3932266038, G3948860332, G4135207624, G4504718640, Accessing medicines worldwide using solar light, G4634724399, G4941345466, Ciências da Vida para um Futuro Saudável e Sustentável, G6145639401, Microbiologia Molecular, Estrutural e Celular - – Instituto de Tecnologia Química e Biológica António Xavier, G6450032367, G6809281892, G7315488542, G7406465651, G7707145192, Microbiologia Molecular, Estrutural e Celular - – Instituto de Tecnologia Química e Biológica António Xavier, domino4chem: Semi-biological Domino Catalysis for Solar Chemical Synthesis
OpenAlex ID: W4409458934