Hybrid tantalum oxide nanoparticles from the hydrolysis of imidazolium tantalate ionic liquids: efficient catalysts for hydrogen generation from ethanol/water solutions

The reaction of equimolar amounts of 1-n-butyl-3-methylimidazolium chloride (BMI.Cl) or 1-n-decyl-3-methylimidazolium chloride (DMI.Cl) with TaCl5 affords imidazolium tantalate ionic liquids (ILs) BMI.TaCl6 1 and DMI.TaCl6 2. The hydrolysis of ILs 1 and 2 yields hybrid-like tantalum oxide nanoparticles (NPs) with size distribution dependent on the nature of the IL used (3.8-22 nm from IL 1 and 1.5-6 nm from 2). A significant aggregation/agglomeration of the particles was observed after the removal of the IL content of the hybrid material by calcination, forming predominantly large particles (mainly bulk tantalum oxides). These new hybrid-like Ta2O5/IL NPs are highly active photocatalyst nanomaterials for hydrogen production by reforming of ethanol at ambient temperature. Hydrogen evolution rates up to 7.2 mmol H-2 g(-1) h(-1) and high apparent quantum yields up to 17% were measured. The hybrid-like Ta2O5/IL NPs sputtered-decorated with ultra-small Pt NPs (1.0 +/- 0.3 nm) as co-catalysts reached activities leading to even higher hydrogen production (9.2 H-2 mmol g(-1) h(-1); apparent quantum yield of 22%). The calcined materials (with or without Pt NPs) showed much lower photocatalytic activity under the same reaction conditions (up to 2.8 mmol g(-1) of H-2). The remarkable activity of the hybrid-like Ta2O5/IL NPs may be related to the presence of the remaining IL that provides hydrophilic regions, facilitating the approach of polar molecules (water and alcohol) to the semiconductor active photocatalytic sites.