Polymer Networks Assembled by Ruthenium Catalysts for Enhanced Water Splitting Performance in Calixarene Dye-Sensitized Photoelectrochemical Cells.

Metal-free photosensitizers for the construction of low-cost and eco-friendly dye-sensitized photoelectrochemical cells (DSPECs) have recently been greatly improved, but the optimization of water oxidation catalysts (WOCs) used in DSPECs based on metal-free dyes has received little attention. Herein, a series of polymer networks (RuTPA, RuCz, RuPr and RuTz) assembled by ruthenium WOCs (RuCHO) with various organic donors are constructed and combined with calixarene dyes to prepare DSPEC devices. The FTO|TiO₂|C4BTP+RuTPA photoanode shows the best performance with 85 % Faraday efficiency for oxygen production and 477 μA cm^-2 photocurrent density after 200 s chopping irradiation at 0 V vs. Ag/AgCl, one of the highest records among other reported dye-sensitized photoanodes. Compared to monomeric RuCHO, Ru-based polymers with lower Ru content have higher activity and stability due to their rapid electron transfer and anti-aggregation ability. Meanwhile, RuTPA loaded electrodes show better performance due to the lower overpotential of the water oxidation reaction caused by the higher electron donating ability of its donor. This pioneering work incorporates Ru polymer networks as WOCs into the calixarene-sensitized DSPEC system, which has significant potential as a highly efficient and stable photoelectrochemical water splitting device.