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Enhancing Oxygenic Photosynthesis by Cross-Linked Perylenebisimide "Quantasomes".
- Source :
-
Journal of the American Chemical Society [J Am Chem Soc] 2022 Aug 10; Vol. 144 (31), pp. 14021-14025. Date of Electronic Publication: 2022 Jul 26. - Publication Year :
- 2022
-
Abstract
- As the natural-born photoelectrolyzer for oxygen delivery, photosystem II (PSII) is hardly replicated with man-made constructs. However, building on the "quantasome" hypothesis ( Science 1964, 144, 1009-1011), PSII mimicry can be pared down to essentials by shaping a photocatalytic ensemble (from the Greek term "soma" = body) where visible-light quanta trigger water oxidation. PSII-inspired quantasomes (QS) readily self-assemble into hierarchical photosynthetic nanostacks, made of bis-cationic perylenebisimides (PBI <superscript>2+</superscript> ) as chromophores and deca-anionic tetraruthenate polyoxometalates (Ru <subscript>4</subscript> POM) as water oxidation catalysts ( Nat. Chem. 2019, 11, 146-153). A combined supramolecular and click-chemistry strategy is used herein to interlock the PBI-QS with tetraethylene glycol (TEG) cross-linkers, yielding QS-TEG <subscript>lock</subscript> with increased water solvation, controlled growth, and up to a 340% enhancement of the oxygenic photocurrent compared to the first generation QS, as probed on 3D-inverse opal indium tin oxide electrodes at 8.5 sun irradiance (λ > 450 nm, 1.28 V vs RHE applied bias, TOF <subscript>max</subscript> = 0.096 ± 0.005 s <superscript>-1</superscript> , FE <subscript>O2</subscript> > 95%). Action spectra, catalyst mass-activity, light-management, photoelectrochemical impedance spectroscopy (PEIS) together with Raman mapping of TEG-templated hydration shells point to a key role of the cross-linked PBI/Ru <subscript>4</subscript> POM nanoarrays, where the interplay of hydrophilic/hydrophobic domains is reminiscent of PSII-rich natural thylakoids.
Details
- Language :
- English
- ISSN :
- 1520-5126
- Volume :
- 144
- Issue :
- 31
- Database :
- MEDLINE
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 35881505
- Full Text :
- https://doi.org/10.1021/jacs.2c05857