Building an iron chromophore incorporating prussian blue analogue for photoelectrochemical water oxidation
Ghobadi Ulusoy, Gamze and Ghobadi, Amir and Demirtas, Merve and Buyuktemiz, Muhammed and Ozvural, Kubra and Akhuseyin, Elif and Erdem, Emre and Yaglioglu, Gül and Durgun, Engin and Ozbay, Ekmel and Karadas, Ferdi (2021) Building an iron chromophore incorporating prussian blue analogue for photoelectrochemical water oxidation. Chemistry - A European Journal (SI), 27 (35). pp. 8966-8976. ISSN 0947-6539 (Print) 1521-3765 (Online)
Official URL: http://dx.doi.org/10.1002/chem.202100654
The replacement of traditional ruthenium-based photosensitizers with low-cost and abundant iron analogs is a key step for the advancement of scalable and sustainable dye-sensitized water splitting cells. In this proof-of-concept study, a pyridinium ligand coordinated pentacyanoferrate(II) chromophore is used to construct a cyanide-based CoFe extended bulk framework, in which the iron photosensitizer units are connected to cobalt water oxidation catalytic sites through cyanide linkers. The iron-sensitized photoanode exhibits exceptional stability for at least 5 h at pH 7 and features its photosensitizing ability with an incident photon-to-current conversion capacity up to 500 nm with nanosecond scale excited state lifetime. Ultrafast transient absorption and computational studies reveal that iron and cobalt sites mutually support each other for charge separation via short bridging cyanide groups and for injection to the semiconductor in our proof-of-concept photoelectrochemical device. The reorganization of the excited states due to the mixing of electronic states of metal-based orbitals subsequently tailor the electron transfer cascade during the photoelectrochemical process. This breakthrough in chromophore-catalyst assemblies will spark interest in dye-sensitization with robust bulk systems for photoconversion applications.
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