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A hybrid photoanode based on a molecular water oxidation precatalyst was prepared from TiO 2 -protected n- or p + -Si coated with multiwalled carbon nanotubes (CNT) and the ruthenium-based water oxidation precatalyst [Ru IV (tda)(py-pyr) 2 (O)], 1(O) (tda 2- is [2,2':6',2″-terpyridine]-6,6″-dicarboxylato and py-pir is 4-(pyren-1-yl)-N-(pyridin-4-ylmethyl)butanamide). The Ru complex was immobilized by π-π stacking onto CNTs that had been deposited by drop casting onto Si electrodes coated with 60 nm of amorphous TiO 2 and 20 nm of a layer of sputtered C. At pH = 7 with 3 Sun illumination, the n-Si/TiO 2 /C/CNT/[1+1(O)] electrodes exhibited current densities of 1 mA cm -2 at 1.07 V vs NHE. The current density was maintained for &gt;200 min at a constant potential while intermittently collecting voltammograms that indicated that over half of the Ru was still in molecular form after O 2 evolution.

Photoelectrochemical Behavior of a Molecular Ru-Based Water-Oxidation Catalyst Bound to TiO2-Protected Si Photoanodes

Photoelectrochemical Behavior of a Molecular Ru-Based Water-Oxidation Catalyst Bound to TiO₂-Protected Si Photoanodes