Solar‐Assisted eBiorefinery: Photoelectrochemical Pairing of Oxyfunctionalization and Hydrogenation Reactions

• Published in: Angewandte Chemie International Edition Vol. 59; no. 37; pp. 15886 - 15890
• Main Authors: Choi, Da Som, Kim, Jinhyun, Hollmann, Frank, Park, Chan Beum
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 07.09.2020
• Edition: International ed. in English
• Subjects: Biocatalysis; Bismuth - chemistry; Bismuth oxides; Catalysis; Chemicals; Dielectric Spectroscopy; eBiorefinery; Electrochemical Techniques - methods; Electrons; Ethylbenzene; Flavin; Hydrogen - chemistry; Hydrogen peroxide; Hydrogenation; Hydroxylation; Molybdenum; Oxidation; Oxidation process; Oxidation-Reduction; photobiocatalysis; Photochemical Processes; photoelectrochemistry; Photosynthesis; redox biocatalysis; Reductases; Solar Energy; Solar energy conversion; Solar power; Spectrophotometry, Ultraviolet; Vanadates; Vanadates - chemistry; redox biocatalysis; photoelectrochemistry; eBiorefinery; photosynthesis; photobiocatalysis
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202006893

Inspired by natural photosynthesis, biocatalytic photoelectrochemical (PEC) platforms are gaining prominence for the conversion of solar energy into useful chemicals by combining redox biocatalysis and photoelectrocatalysis. Herein, we report a dual biocatalytic PEC platform consisting of a molybdenum (Mo)‐doped BiVO4 (Mo:BiVO4) photoanode and an inverse opal ITO (IO‐ITO) cathode that gives rise to the coupling of peroxygenase and ene‐reductase‐mediated catalysis, respectively. In the PEC cell, the photoexcited electrons generated from the Mo:BiVO4 are transferred to the IO‐ITO and regenerate reduced flavin mononucleotides to drive ene‐reductase‐catalyzed trans‐hydrogenation of ketoisophrone to (R)‐levodione. Meanwhile, the photoactivated Mo:BiVO4 evolves H2O2 in situ via a two‐electron water‐oxidation process with the aid of an applied bias, which simultaneously supplies peroxygenases to drive selective hydroxylation of ethylbenzene into enantiopure (R)‐1‐phenyl‐1‐hydroxyethane. Thus, the deliberate integration of PEC systems with redox biocatalytic reactions can simultaneously produce valuable chemicals on both electrodes using solar‐powered electrons and water. A biocatalytic photoelectrochemical platform for solar‐assisted dual biotransformations is constructed by wiring a Mo‐doped BiVO4 photocathode and a hierarchical porous ITO electrode. The deliberate integration of enzymatic redox processes into the photoelectrochemical cell simultaneously facilitates peroxygenase‐ and ene‐reductase‐mediated enantioselective synthesis of high‐value chemicals using solar‐powered electrons and water.