Dibranched donor-(π-acceptor)2 dyes, where phenothiazine is the donor core, cyanoacrylic acid is the acceptor/anchoring group, and π is represented by mono- and poly-cyclic simple and fused thiophene derivatives, were tested as photosensitizers in the photocatalytic production of H2 , in combination with a Pt/TiO2 catalyst. The optical and electrochemical properties of the dyes were investigated, showing that careful design of the thiophene-based π spacer afforded enhanced optical properties. In the H2 production over 20 h, the new thiophene-based sensitizers revealed improved stability after longer irradiation times and enhanced performances, in terms of H2 production rates and light-to-fuel efficiencies, after an initial activation period, which were for the first time associated with enhanced stability under photocatalytic production of H2 and the absence of critical dye degradation.

A thiophene-based donor-acceptor phenothiazine dye has been functionalized with a peripheral glucose unit (PTZ-GLU) to bust its affinity to water and enhance dye-sensitized photogeneration of hydrogen. Compared to the corresponding alkyl derivative (PTZ-ALK), as well as the common hydrophilic triethylene glycol substitution (PTZ-TEG), the sugar derivative shows a lower contact angle; PTZ-GLU performed twice more efficient than PTZ-TEG in the photogeneration of hydrogen in terms of evolved gas and turnover number.

Photocatalytic reactions could enhance the share of chemicals produced through renewable sources. The efficiency of photocatalysts drastically depends on light absorption, on the surface energy of the crystals, and on the properties of the nanobuilding blocks assembled in devices. Here, we show that photoelectrochemical water oxidation on brookite TiO2 nanorods is greatly enhanced by engineering the location of Au nanoparticles deposition. Brookite photoanodes show a very low onset potential for water oxidation to H2O2 of −0.2 VRHE due to energetics of exposed crystal facets. By combining electrochemical measurements and ultrafast optical spectroscopy, we link the water oxidation activity with electron–hole recombination phenomena. The preferential Au decoration at the electrode/water interface produces highly enhanced photocurrent, while when Au is distributed along the whole film thickness, the activity is depressed with respect to pure brookite. In the latter case, Au nanoparticles act as recombination centers with plasmonic carriers recombining on the same time scale of their generation (fs). Conversely, Au surface decoration enables a hot electrons lifetime 4 orders of magnitude longer (ns) due to efficient hopping on brookite lateral facets, thus providing an efficient path for plasmon-enhanced solar water oxidation

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