Ru–protein–Co biohybrids designed for solar hydrogen production: understanding electron transfer pathways related to photocatalytic function† †Electronic supplementary information (ESI) available: Time traces of photocatalysis, additional EPR spectra and parameters, UV-visible spectroscopy data, and kinetic fits of TA traces. See DOI: 10.1039/c6sc03121h Click here for additional data file

• Published in: Chemical science (Cambridge) 2016-08, Vol.7 (12), p.7068-7078
• Main Authors: Soltau, Sarah R., Dahlberg, Peter D., Niklas, Jens, Poluektov, Oleg G., Mulfort, Karen L., Utschig, Lisa M.
• Format: Article
• Language: English
• Subjects: Chemistry
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c6sc03121h

Two ruthenium-protein-cobaloxime biohybrids produce photocatalytic hydrogen through different catalytic pathways characterized by EPR and transient optical spectroscopies. A series of Ru–protein–Co biohybrids have been prepared using the electron transfer proteins ferredoxin (Fd) and flavodoxin (Fld) as scaffolds for photocatalytic hydrogen production. The light-generated charge separation within these hybrids has been monitored by transient optical and electron paramagnetic resonance spectroscopies. Two distinct electron transfer pathways are observed. The Ru–Fd–Co biohybrid produces up to 650 turnovers of H 2 utilizing an oxidative quenching mechanism for Ru( ii )* and a sequential electron transfer pathway via the native [2Fe–2S] cluster to generate a Ru( iii )–Fd–Co( i ) charge separated state that lasts for ∼6 ms. In contrast, a direct electron transfer pathway occurs for the Ru–ApoFld–Co biohybrid, which lacks an internal electron relay, generating Ru( i )–ApoFld–Co( i ) charge separated state that persists for ∼800 μs and produces 85 turnovers of H 2 by a reductive quenching mechanism for Ru( ii )*. This work demonstrates the utility of protein architectures for linking donor and catalytic function via direct or sequential electron transfer pathways to enable stabilized charge separation which facilitates photocatalysis for solar fuel production.