Spontaneous nitride formation in the reaction of mesoporous titanium oxide with bis(toluene) titanium in a nitrogen atmosphere

摘要

Recently we showed that mesoporous niobium oxide reduced with bis(toluene) niobium reacts at room temperature with dinitrogen, leaving a thin coat of sp~3 hybridized nitride on the low valent niobium oxide surface. In this report we show that mesoporous titanium oxide reduced with bis(toluene) titanium in the presence of dinitrogen leads to formation of a new mesoporous titanium oxide with surface nitride. All materials in this study were characterized by X-ray photoelectron spectroscopy, X-ray powder diffraction, nitrogen adsorption, elemental analyses, and superconducting quantum interference detector magnetometry. ~(15)N-MAS NMR labeling experiments confirmed that ambient dinitrogen was the source of the surface nitride species. Direct cleavage of dinitrogen is extremely rare and has never been reported on the surface of a porous oxide. These results demonstrate that this system may be useful in designing catalysts for nitrogen activation and incorporation of nitrogen in small molecules.