Work

Combined Covalent and Supramolecular Polymerization to Reinforce Perylenebisimide Photosynthetic “Quantasomes”

Year: 2024

Type: article

Abstract: PSII‐inspired quantasomes have emerged as promising artificial photosystems evolving oxygen from water due to their integrated multi‐chromophore asset, hierarchical architecture, and efficient light‐harvesting capabilities. In this study, we adopt a combined covalent and supramolecular strategy by implementing a poly‐styrene backbone that reinforces proximity and pairing between adjacent perylenebisimide (PBI) quantasome units. The covalent fixation of the quantasome network results in a significant enhancement of the photoelectrocatalytic performance on engineered IO‐ITO photoanodes, with up to 290 % photocurrent increase (J up to 100 μA cm−2, λ >450 nm, applied bias <1.23 V vs RHE, F.E.O2 >80 %) compared to the non‐polymerized analog. Moreover, the direct PBI‐quantasome polymerization on the photoanode surface was performed by light irradiation of the radical initiator 2,2’‐Azobis(2‐methylpropionamidine), improving the photoelectrode robustness under high solar irradiance (>8 suns) and limiting the photocurrent loss (<20 %) at 1.52 V vs RHE compared to the non‐polymerized system.

Source: Chemistry - A European Journal

DOI: 10.1002/chem.202303784