Highly Active Visible Light-Promoted Ir/ g -C 3 N 4 Photocatalysts for the Water Oxidation Reaction Prepared from a Halogen-Free Iridium Precursor.

A combination of the exceptional stability of fac -[Ir(H 2 O) 3 (NO 2 ) 3 ] together with thermolability of nitro and aqua ligands and high solubility in various solvents makes it promising as a brand-new chlorine-free precursor of iridium for the preparation of heterogeneous catalysts. In the current work, a new technique of fac -[Ir(H 2 O) 3 (NO 2 ) 3 ] preparation based on hydrothermal treatment of (NH 4 ) 3 [Ir(NO 2 ) 6 ] was developed. For this purpose, the influence of reaction parameters such as the reaction time, temperature, and pH of the solution on the process of hexanitroiridate salt hydrolysis was investigated. The synthesized fac -[Ir(H 2 O) 3 (NO 2 ) 3 ] solution in this optimized way was used for the preparation of the series of Ir/g-C 3 N 4 catalysts, which were evaluated in the water oxidation reaction with NaIO 4 utilized as a sacrificial reagent. A 20-fold enhancement of the oxygen evolution reaction (OER) activity was found to take place under visible light (λ = 411 nm) illumination of the systems. The highest rate of the photoinduced OER per iridium center was achieved by the Ir 0.005 /g-C 3 N 4 (air, 400°C) catalyst with an exceptional turnover frequency value of 967 min -1 approaching the activity of known homogeneous iridium OER catalysts. The leaching experiments have shown that aquated Ir species are generated in a solution after prolonged functioning of the catalysts. Despite this, in the closed system the photodriven OER activity persists at a steady-state level evidencing an equilibrium achieved between dissolved and anchored Ir species forming catalytic tandem with the g-C 3 N 4 .