Limiting Molecular Twisting: Upgrading a Donor–Acceptor Dye to Drive H2 Evolution

Limiting Molecular Twisting: Upgrading a Donor–Acceptor Dye to Drive H2 Evolution

Abstract The donor–acceptor (D–A) dye 4‐(bis‐4‐(5‐(2,2‐dicyano‐vinyl)‐thiophene‐2‐yl)‐phenyl‐amino)‐benzoic acid (P1) has been frequently used to functionalize NiO photocathodes and induce photoelectrochemical reduction of protons when coupled to a suitable catalyst. Photoinduced twisting of the P1...

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Bibliographic Details
Main Authors: Kaijian Zhu, Ainoa Paradelo Rodríguez, Maria B. Brands, Titus deHaas, Francesco Buda, Joost N.H. Reek, Guido Mul, Annemarie Huijser
Format: Article
Language:English
Published: Wiley 2024-10-01
Series:Advanced Science
Subjects:
donor–acceptor dye
dye‐sensitized photocathode
H2 evolution
molecular twisting
TICT
Online Access:https://doi.org/10.1002/advs.202403454
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Summary:Abstract The donor–acceptor (D–A) dye 4‐(bis‐4‐(5‐(2,2‐dicyano‐vinyl)‐thiophene‐2‐yl)‐phenyl‐amino)‐benzoic acid (P1) has been frequently used to functionalize NiO photocathodes and induce photoelectrochemical reduction of protons when coupled to a suitable catalyst. Photoinduced twisting of the P1 dye is steered on NiO by co‐adsorption of tetradecanoic acid (C14, myristic acid (MA)). Density Functional Theory and time‐resolved photoluminescence studies confirm that twisting lowers the energy levels of the photoexcited D–A dye. The apolar environment provided by the MA suppresses photoinduced D–A twisting, retards charge recombination following photoinduced charge separation between P1 and NiO, and provides a larger electrochemical potential increasing the photocurrent. Very interestingly, co‐adsorption of MA induces H2 evolution upon photoexcitation without the presence of an H2 evolution catalyst. Based on prior art, the formation of H2 is assigned to the dissolution of Ni2+, followed by reduction and re‐deposition of Ni nanoparticles acting as the catalytically active site. It propose that only excited P1 with suppressed twisting provides the sufficient electrochemical potential to induce deposition of Ni nanoparticles. The work illustrates the importance of understanding the effects of photoinduced intramolecular twisting and highlights the promise of designing twisting‐limited D–A dyes to create efficient solar fuel devices.
ISSN:2198-3844

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