Synthesis, plasmonic properties, and CWA simulant decontamination activity of first row early transition metal nitride p
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Synthesis, plasmonic properties, and CWA simulant decontamination activity of first row early transition metal nitride powders and nanomaterials Andrew P. Purdy1 · Olga A. Baturina1 · Blake S. Simpkins1 · Spencer Giles1 · Todd Brintlinger2 · James Wynne1 Received: 3 February 2020 / Accepted: 30 March 2020 / Published online: 11 April 2020 © This is a U.S. Government work and not under copyright protection in the U.S.; foreign copyright protection may apply 2020
Abstract The complexes MCl3(THF)3 (M = Ti, V, Cr) were used as precursors to form early transition metal nitrides, and solid solutions of these isomorphous complexes MxM’1−xCl3(THF)3 were prepared by co-crystallization. Heating the precursor under NH3 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 MCl3(THF)3 solution with 3 eq of KNH2 in THF in the presence (or absence) of oleylamine, followed by nitridation under NH3 flow at 650–950 °C and (2) loading a porous catalyst support such as pelletized Al2O3 with the MCl3(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. Keywords Titanium nitride · Plasmon · Solid solutions,∙nanomaterials,∙demeton-S · Refractory plasmonics
1 Introduction Some early transition metal nitrides, particularly TiN and ZrN, have optical properties similar to noble metals (e.g., Au, Ag), making them potential drop-in replacements for these expensive and, in some cases, chemically unstable materials. In fact, TiN has been shown to exhibit plasmonic resonances similar to those of Au but at a far reduced cost and with much greater thermal stability [1–7]. Additionally, there is already a fair body of literature that already
describes the use of hot charge carriers, generated via plasmon decay [8], to perform a number of reactions [9], including water oxidation [10, 11], water reduction [12–14], oxidation of amines to aldehydes [15], CO2 reduction [16], and NH3 decomposition [17]. Typically, these demonstrations have utilized Au plasmonic nanoparticles on a semiconducting support, [18] often TiO2 [19]. These metal–semiconductor heterosystems may serve to enhance charge separation as well as promote the reaction of interest if a catalytic semiconductor is used. In the
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s42452-020-2648-9) contains supplementary material, which is available
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