Silatrane Functional Rubds‐Based Catalyst for Stabilized Heterogenized Water Oxidation

Dye‐sensitized photoelectrochemical cells (DSPECs) for water splitting into hydrogen and oxygen represent a promising approach to storing solar energy in chemical bonds. The surface‐immobilized catalyst plays a crucial role in DSPEC performance. However, the water oxidation process requires substantial energy to break OH bonds, resulting in sluggish reaction kinetics. Consequently, depositing highly efficient and durable molecular water oxidation catalysts onto metal oxide surfaces presents a significant research challenge. Here, this study introduces a ruthenium‐based pyridine water oxidation complex featuring a bds 2− ligand (bds 2− = 2,2′‐bipyridine‐6,6′‐disulfonate) and a silatrane anchoring group for stable attachment to metal oxide semiconductors, forming a robust single‐site heterogeneous catalyst. In pH 7 aqueous solution, the resulting Ru‐bds (F‐doped tin oxide/nanoATO/2C‐bds). catalyst achieves a stable current density of 0.89 mA cm −2 and a turnover frequency of 5.1 s −1 over a 2 h test under an applied bias of 1.6 V versus normal hydrogen electrode. A variety of Ru‐oxo intermediates generated during water oxidation are analyzed using in situ ultraviolet‐visible, Raman, and infrared spectroscopies. These techniques provide data that support the proposed mechanism of heterogeneous water oxidation over Ru‐bds catalysts. This work presents a streamlined strategy for designing stable, single‐site heterogeneous catalysts for efficient solar‐driven water oxidation.