Micron-sized hexagonal single-crystalline rods of metal nitride clusterfullerene: preparation, characterization, and photoelectrochemical application

Abstract

Micron-sized hexagonal single-crystalline Sc(3)N@C(80) rods have been successfully prepared for the first time by a liquid-liquid interfacial precipitation (LLIP) method with the first utilization of p-xylene as the solvent dissolving Sc(3)N@C(80). The effect of the concentration of the Sc(3)N@C(80) solution on the size and length of the Sc(3)N@C(80) rods has been studied, indicating that the length of Sc(3)N@C(80) rods can be readily controlled by varying the concentration of the Sc(3)N@C(80) solution. The crystal structure of the Sc(3)N@C(80) rods has been investigated by XRD and the electron diffraction patterns, pointing to a hexagonal system. The growth kinetics of the Sc(3)N@C(80) rods has been studied by monitoring the morphology evolution of the Sc(3)N@C(80) crystals, and a plausible mechanism is proposed, featuring an intermediate hexagonal star-shaped prism structure with grooves. Raman spectroscopic characterization confirmed that the Sc(3)N@C(80) rods are composed of monomeric pristine Sc(3)N@C(80) molecules and no polymerization has occurred in the crystal lattice, and a significant Raman enhancement in the low-energy region is observed. According to the UV-vis-NIR absorption spectroscopic study of the Sc(3)N@C(80) rods, where much broader and stronger absorptions in the visible and near-infrared regions than that of the Sc(3)N@C(80) solution were revealed, we conclude that the electronic structure of the Sc(3)N@C(80) molecule is largely perturbed upon formation of micron-sized single-crystalline rods because of the strong intermolecular π-π interactions. Finally photoelectrochemical application of the Sc(3)N@C(80) rods was studied based on a Sc(3)N@C(80) rods-modified ITO electrode prepared by electrophoretic deposition and revealed a higher photocurrent response than that obtained in the Sc(3)N@C(80) films drop-coated onto an ITO electrode.