Tapping Bio-Inspired Tricks : Controlling Charge Transfer, Accumulation, and Utilization in Catalytic Systems

Nature has perfected the design of the photosynthetic apparatus and enzymes to control the transfer of electrons and protons, and their eventual accumulation and utilization in catalyzing the transformation of small molecules such as water (H₂O) and carbon dioxide (CO₂). All of these processes are well orchestrated at minimum energy consumption, while maintaining high efficiency and selectivity. In this seminar, we will discuss two bio-inspired aspects : (i) an artificial system based on Photosystem II that oxidizes H2O to oxygen, producing electrons and protons,¹ and (ii) an improved catalyst design based on carbon monoxide dehydrogenase (CODH) that utilizes electrons and protons to transform CO₂.^2–6 Investigations center on our complementary expertise of synthesis, electrochemistry, and spectroscopy to gain basic understanding and to leverage the learned tricks towards optimized artificial strategies.

(1) Gotico, P. ; Herrero, C. ; Protti, S. ; Quaranta, A. ; Sheth, S. ; Fallahpour, R. ; Farran, R. ; Halime, Z. ; Sircoglou, M. ; Aukauloo, A. ; Leibl, W. Proton-Controlled Action of an Imidazole as Electron Relay in a Photoredox Triad. Photochem Photobiol Sci 2022, 21 (2), 247–259. https://doi.org/10.1007/s43630-021-00163-2.
(2) Gotico, P. ; Boitrel, B. ; Guillot, R. ; Sircoglou, M. ; Quaranta, A. ; Halime, Z. ; Leibl, W. ; Aukauloo, A. Second-Sphere Biomimetic Multipoint Hydrogen-Bonding Patterns to Boost CO2 Reduction of Iron Porphyrins. Angew. Chem. Int. Ed 2019, 58 (14), 4504–4509. https://doi.org/10.1002/anie.201814339.
(3) Gotico, P. ; Roupnel, L. ; Guillot, R. ; Sircoglou, M. ; Leibl, W. ; Halime, Z. ; Aukauloo, A. Atropisomeric Hydrogen Bonding Control for CO2 Binding and Enhancement of Electrocatalytic Reduction at Iron Porphyrins. Angew. Chem. Int. Ed 2020, 59 (50), 22451–22455. https://doi.org/10.1002/anie.202010859.
(4) Khadhraoui, A. ; Gotico, P. ; Boitrel, B. ; Leibl, W. ; Halime, Z. ; Aukauloo, A. Local Ionic Liquid Environment at a Modified Iron Porphyrin Catalyst Enhances the Electrocatalytic Performance of CO2 to CO Reduction in Water. Chem. Commun. 2018, 54 (82), 11630–11633. https://doi.org/10.1039/C8CC06475J.
(5) Khadhraoui, A. ; Gotico, P. ; Leibl, W. ; Halime, Z. ; Aukauloo, A. Through-Space Electrostatic Interactions Surpass Classical Through-Bond Electronic Effects in Enhancing CO2 Reduction Performance of Iron Porphyrins. ChemSusChem 2021, 14 (5), 1308–1315. https://doi.org/10.1002/cssc.202002718.
(6) Pugliese, E. ; Gotico, P. ; Wehrung, I. ; Boitrel, B. ; Quaranta, A. ; Ha-Thi, M.-H. ; Pino, T. ; Sircoglou, M. ; Leibl, W. ; Halime, Z. ; Aukauloo, A. Dissection of Light-Induced Charge Accumulation at a Highly Active Iron Porphyrin : Insights in the Photocatalytic CO2 Reduction. Angew. Chem. Int. Ed. 2022, 61 (14), e202117530. https://doi.org/10.1002/anie.202117530.