Building an Iron Chromophore Incorporating Prussian Blue Analogue for Photoelectrochemical Water Oxidation.

Invited for the cover of this issue is the Ferdi Karadas and Ekmel Ozbay groups at Bilkent University and co-workers. The image presents an utopic city in Iron Age, which is powered by an iron photosensitizer that bridges semiconductor buildings (TiO2 nanowires) and the catalyst (cobalt site). Read the full text of the article at 10.1002/chem.202100654.

Building an Iron Chromophore Incorporating Prussian Blue Analogue for Photoelectrochemical Water Oxidation.

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.

Strong Light-Matter Interactions in Au Plasmonic Nanoantennas Coupled with Prussian Blue Catalyst on BiVO4 for Photoelectrochemical Water Splitting.

Invited for this month's cover is the group of Ferdi Karadas and Ekmel Ozbay at Bilkent University. The image proposes a hybrid architecture, in which the semiconductor photoactive host is coupled to a plasmonic particle and a catalyst, to significantly substantiate the photoactivity of the cell. The Full Paper itself is available at 10.1002/cssc.202000294.

Strong Light-Matter Interactions in Au Plasmonic Nanoantennas Coupled with Prussian Blue Catalyst on BiVO4 for Photoelectrochemical Water Splitting.

A facial and large-scale compatible fabrication route is established, affording a high-performance heterogeneous plasmonic-based photoelectrode for water oxidation that incorporates a CoFe-Prussian blue analog (PBA) structure as the water oxidation catalytic center. For this purpose, an angled deposition of gold (Au) was used to selectively coat the tips of the bismuth vanadate (BiVO4 ) nanostructures, yielding Au-capped BiVO4 (Au-BiVO4 ). The formation of multiple size/dimension Au capping islands provides strong light-matter interactions at nanoscale dimensions. These plasmonic particles not only enhance light absorption in the bulk BiVO4 (through the excitation of Fabry-Perot (FP) modes) but also contribute to photocurrent generation through the injection of sub-band-gap hot electrons. To substantiate the activity of the photoanodes, the interfacial electron dynamics are significantly improved by using a PBA water oxidation catalyst (WOC) resulting in an Au-BiVO4 /PBA assembly. At 1.23 V (vs. RHE), the photocurrent value for a bare BiVO4 photoanode was obtained as 190 µA cm-2 , whereas it was boosted to 295 µA cm-2 and 1800 µA cm-2 for Au-BiVO4 and Au-BiVO4 /PBA, respectively. Our results suggest that this simple and facial synthetic approach paves the way for plasmonic-based solar water splitting, in which a variety of common metals and semiconductors can be employed in conjunction with catalyst designs.