Efficient Chemical and Visible-Light-Driven Water Oxidation using Nickel Complexes and Salts as Precatalysts

Chemical and visible-light-driven water oxidation catalyzed by a number of Ni complexes and salts have been investigated at pH 7-9 in borate buffer. For chemical oxidation, [Ru(bpy)(3)](3+) (bpy=2,2'-bipyridine) was used as the oxidant, with turnover numbers (TONs) >65 and a maximum turnover frequency (TOFmax) >0.9 s(-1). Notably, simple Ni salts such as Ni(NO3)(2) are more active than Ni complexes that bear multidentate N-donor ligands. The Ni complexes and salts are also active catalysts for visible-light-driven water oxidation that uses [Ru(bpy)(3)](2+) as the photosensitizer and S2O82- as the sacrificial oxidant; a TON>1200 was obtained at pH 8.5 by using Ni(NO3)(2) as the catalyst. Dynamic light scattering measurements revealed the formation of nanoparticles in chemical and visible-light-driven water oxidation by the Ni catalysts. These nanoparticles aggregated during water oxidation to form submicron particles that were isolated and shown to be partially reduced beta-NiOOH by various techniques, which include SEM, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, XRD, and IR spectroscopy. These results suggest that the Ni complexes and salts act as precatalysts that decompose under oxidative conditions to form an active nickel oxide catalyst. The nature of this active oxide catalyst is discussed.