Synthesis and Structural Characterization of an Amorphous and Photoluminescent Mixed Eu/Zr Coordination Compound, a Potential Marker for Gunshot Residues

Abstract

Hydrogels based on mixed zirconium/europium ions and benzene tricarboxylic acid were synthesized by hydrothermal reaction. A solid glass-like material is formed upon drying, showing strong reddish luminescence. The system was characterized by solid-state nuclear magnetic resonance, thermal analyses, and infrared spectroscopy. The results reveal the amorphous character of the structure and the presence of at least four types of binding modes between the metal oxide clusters and benzene tricarboxylic acid. On the other hand, thermogravimetric analysis (TGA) showed high thermal stability, with the material decomposing at temperatures higher than 500 °C. The combination of intense Eu3+ luminescence with large thermal stability makes this material a strong candidate for application as a luminescent red marker for gunshot residue (GSR). As proof of concept, we show the feasibility of this application by performing shooting tests using our compound as a GSR marker. After the shots, the residual luminescent particles could be visualized in the triggered cartridge, inner the muzzle of the firearm, and a lower amount on the hands of the shooter, using a UV lamp (λ = 254 nm). Remarkably, our results also show that the Eu3+ emission for the GSR is very similar to that observed for the original solid material. These characteristics are of huge importance since they provide a chance to use smaller amounts of the marker in the ammunition, lowering the costs of potential industrial manufacturing processes.

Keywords

• mixed-metal coordination compound
• photoluminescence
• solid state NMR
• gun-shot-residue marker