Amorphous Copper‐Based Nanoparticles with Clusterization‐Triggered Phosphorescence for Ultrasensing 2,4,6‐Trinitrotoluene

Amorphous metal-based nanostructures have attracted great attention recently due to their facilitative electron transfer and abundant reactive sites, whereas it remains enigmatic as to whether amorphous copper-based nanoparticles (CuNPs) can be achieved. Here, for synthesizing amorphous CuNPs, glutathione is adopted as a ligand to inhibit the nucleation and crystallization process via its electrostatic repulsion. By subtly tailoring the solvent polarity, not only can amorphous glutathione-functionalized CuNPs (GSH-CuNPs) with phosphorescent performance be achieved after transferring the non-conjugation of GSH ligand to through-space conjugation, namely clusterization-triggered emission, but also the phosphorescence-off of GSH-CuNPs toward 2,4,6-trinitrotoluene (TNT) can be realized by the photoinduced electron-transfer process through the hydrogen bond channel, which is established between carboxyl and amino groups of GSH-CuNPs with the nitryl group of TNT. Benefitting from the intrinsic superiorities of the amorphous CuNPs, desired phosphorescence and detection performances of GSH-CuNPs toward airborne TNT microparticulates are undoubtedly realized, including high quantum yield (13.22%), excellent specificity in 33 potential interferents, instantaneous response, and ultralow detection limit (1.56 pg). The present GSH-CuNPs are expected to stretch amorphous metal-based nanostructures and deepen the insights into amorphous materials for optical detection.