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Solar‐Assisted eBiorefinery: Photoelectrochemical Pairing of Oxyfunctionalization and Hydrogenation Reactions
Author(s) -
Choi Da Som,
Kim Jinhyun,
Hollmann Frank,
Park Chan Beum
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202006893
Subject(s) - chemistry , redox , catalysis , photochemistry , artificial photosynthesis , biocatalysis , flavin group , photoelectrochemistry , molybdenum , electrochemistry , combinatorial chemistry , electrode , inorganic chemistry , organic chemistry , photocatalysis , reaction mechanism , enzyme
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 BiVO 4 (Mo:BiVO 4 ) 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:BiVO 4 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:BiVO 4 evolves H 2 O 2 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.