Print Email Facebook Twitter Unbiased Photoelectrode Interfaces for Solar Coupling of Lignin Oxidation with Biocatalytic C=C Bond Hydrogenation Title Unbiased Photoelectrode Interfaces for Solar Coupling of Lignin Oxidation with Biocatalytic C=C Bond Hydrogenation Author Kim, Jinhyun (Korea Advanced Institute of Science and Technology) Um, Yunna (Korea Advanced Institute of Science and Technology) Han, Seunghyun (Ulsan National Institute of Science and Technology) Hilberath, T. (TU Delft BT/Biocatalysis) Kim, Yong Hwan (Ulsan National Institute of Science and Technology) Hollmann, F. (TU Delft BT/Biocatalysis) Park, Chan Beum (Korea Advanced Institute of Science and Technology) Date 2022 Abstract The pulp and paper manufacturers generate approximately 50 million metric tons of lignin per annum, most of which has been abandoned or incinerated because of lignin's recalcitrant nature. Here, we report bias-free photoelectrochemical (PEC) oxidation of lignin coupled with asymmetric hydrogenation of C=C bonds. The PEC platform consists of a hematite (α-Fe2O3) photoanode and a silicon photovoltaic-wired mesoporous indium tin oxide (Si/mesoITO) photocathode. We substantiate a new function of photoelectroactivated α-Fe2O3 to extract electrons from lignin. The extracted electrons are transferred to the Si/mesoITO photocathode for regenerating synthetic nicotinamide cofactor analogues (mNADHs). We demonstrate that the reduction kinetics of mNAD+s depend on their reduction peak potentials. The regenerated mNADHs activate ene-reductases from the old yellow enzyme (OYE) family, which catalyze enantioselective reduction of α,β-unsaturated hydrocarbons. This lignin-fueled biocatalytic PEC system exhibits an excellent OYE's turnover frequency and total turnover number for photobiocatalytic trans-hydrogenation through cofactor regeneration. This work presents the first example of PEC regeneration of mNADHs and opens up a sustainable route for bias-free chemical synthesis using renewable lignin waste as an electron feedstock. Subject biocatalysishematiteligninphotoelectrocatalysistrans-hydrogenation To reference this document use: http://resolver.tudelft.nl/uuid:92d673e7-5c45-4309-bf87-5c91c56b18e8 DOI https://doi.org/10.1021/acsami.1c24342 Embargo date 2022-08-23 ISSN 1944-8244 Source ACS applied materials & interfaces, 14 (9), 11465-11473 Bibliographical note Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public. Part of collection Institutional Repository Document type journal article Rights © 2022 Jinhyun Kim, Yunna Um, Seunghyun Han, T. Hilberath, Yong Hwan Kim, F. Hollmann, Chan Beum Park Files PDF acsami.1c24342taverne.pdf 4.64 MB Close viewer /islandora/object/uuid:92d673e7-5c45-4309-bf87-5c91c56b18e8/datastream/OBJ/view