Synthesis, plasmonic properties, and CWA simulant decontamination activity of first row early transition metal nitride powders and nanomaterials

The complexes MCl 3 (THF) 3 (M = Ti, V, Cr) were used as precursors to form early transition metal nitrides, and solid solutions of these isomorphous complexes M x M’ 1−x Cl 3 (THF) 3 were prepared by co-crystallization. Heating the precursor under NH 3 flow from 800 to 950 °C produced powders of the nitride MN, and solid solutions of these precursors produced alloys of the nitrides. Nanomaterials were synthesized by two methods: (1) reaction of a MCl 3 (THF) 3 solution with 3 eq of KNH 2 in THF in the presence (or absence) of oleylamine, followed by nitridation under NH 3 flow at 650–950 °C and (2) loading a porous catalyst support such as pelletized Al 2 O 3 with the MCl 3 (THF) 3 complex, followed by similar heat treatment. The materials were characterized by powder X-ray diffraction, elemental analysis, SEM, and optical spectroscopy. Diffuse reflectance and UV–Vis-NIR spectroscopy showed the local surface plasmonic resonances (LSPRs). Although diffuse reflectance and UV–Vis-NIR spectroscopy showed LSPRs whose position was sensitive to surface functionalization and conditions of preparation, preliminary results show TiN nanoparticles have some activity in the degradation of the Chemical Warfare Agent (CWA) simulant DEMETON-S, but light plays no role in the mechanism.