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Pushing the limits in photosensitizer-catalyst interaction via a short cyanide bridge for water oxidation

By Ghobadi, Turkan Gamze Ulusoy; Ghobadi, Amir; Demirtas, Merve; Phul, Ruby; Yildiz, Elif Akhuseyin; Yaglioglu, Halime Gul; Durgun, Engin; Ozbay, Ekmel; Karadas, Ferdi
Published in Cell Reports Physical Science 2021

Abstract

Summary The realization of high-performance, precious-metal-free, stable, and robust photoanodes for water oxidation is one of the bottlenecks for dye-sensitized water splitting. Herein, we integrate an organic photosensitizer, which absorbs visible light above 500 nm, with a Prussian blue (PB) network to sensitize a visible-light-absorbing semiconductor, WO3. Through comprehensive steady-state and ultrafast transient absorption studies, we show that the coupling of a photosensitizer to a catalyst through a short cyanide bridging group in a PB structure generates appropriate energy levels for an efficient charge transfer from the photosensitizer to the visible-light-absorbing semiconductor. The photoanode retains its structural integrity and high photoelectrochemical activity for at least 2 h of solar irradiation under mildly acidic conditions (pH 3), which reaches around 1.30 mA/cm2 at 1.23 VRHE. This work provides a simple recipe with a toolbox that can be extended to a variety of organic photosensitizers and semiconductors.

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