Utilizing the amidation reaction to address the “cooperative effect” of carboxylic acid/amine on the size, shape, and multicolor output of fluoride upconversion nanoparticles

Abstract

Here we elucidate the “cooperative effect” of carboxylic acid/amine on the size, shape, and multicolor output of fluoride upconversion nanoparticles (UCNPs) utilizing the amidation reaction. During the synthesis of NaYF₄ UCNPs using oleic acid (OA) and octadecylamine (OM) as ligands, the evolution of the reaction solution was monitored by FT-IR and proton nuclear magnetic resonance (¹H-NMR) spectroscopy. It is shown that N-octadecyloleamide (OOA) was formed and tightly bonded to the surface of the fluoride UCNPs. FT-IR and ¹H-NMR analyses point towards a two-step OOA formation mechanism where OA initially reacted with OM to form an acid–base complex (C₁₇H₃₃CO₂^− +NH₃C₁₈H₃₇) in reaction mixture, which further transformed into OOA before the nucleation of fluoride UCNPs at elevated temperature. Importantly, we find that the interaction of OOA with the surfaces of the fluoride UCNPs was stronger than that of OM, and that OOA could strongly quench the green-emitting levels of excited Er³⁺ ions. A series of control experiments and analyses demonstrate that OOA was not only responsible for the control of the size and shape of NaYF₄: 20% Yb, 2% Er UCNPs, but also for the multicolor tuning of them. Those observations reveal that the “cooperative effect” between carboxylic acid and amine results from the amidation reaction and its product. This paper provides us with some new deep insights into the “cooperative effect” of carboxylic acid and amine during the synthesis of inorganic nanoparticles under thermolysis. Furthermore, other lanthanide-ion doped fluoride UCNPs with controlled size, shape and multicolor output can also be obtained in the same way.