Photocatalytic Water Splitting on Ni-Intercalated Ruddlesden−Popper Tantalate H₂La_2/3Ta₂O₇

A series of Ruddlesden−Popper-type hydrous layered perovskites, ATa 2 O 7 (A‘ = H or K, A = La 2/3 or Sr), were presented as novel catalysts for photocatalytic water splitting into H 2 and O 2 under UV irradiation. These hydrous perovskites showed higher activity than anhydrous perovskites (KTaO 3, La 1/3 TaO 3 ) for overall splitting of water. Results of photoluminescence spectroscopy and H 2 evolution from aqueous n -butylamine solution support the hypothesis that the high activity of the hydrous perovskites results from their hydrated layered structure, where the photogenerated electrons and holes can be effectively transferred to the intercalated substrates (H 2 O and n -butylamine). Addition of Ni cocatalyst to H 2 La 2/3 Ta 2 O 7 via an ion-exchange reaction increased the activity, while Ni addition did not improve the activity of H 2 SrTa 2 O 7 . Ni K-edge EXAFS/XANES, UV−vis spectroscopy, and TEM results for Ni-loaded catalysts indicate that Ni 2+ ions and small NiO clusters are intercalated into the layers of H 2 La 2/3 Ta 2 O 7, while relatively large NiO particles at the external surface of the perovskite are the main Ni species in H 2 SrTa 2 O 7 . Thus, the highly dispersed Ni(II) species at the interlayer space are shown to act as effective sites for H 2 evolution in the photocatalytic water splitting.