Closed pi-electron Network in Large Polyhedral Multi-shell Carbon Nanoparticles

TL;DR

This study reveals that astralen carbon nanoparticles have a polyhedral multi-shell structure with delocalized charge carriers, exhibiting Pauli paramagnetism and metallic-like relaxation behavior, as characterized by advanced microscopy and magnetic resonance techniques.

Contribution

It provides detailed structural and magnetic characterization of astralen nanoparticles, highlighting their delocalized charge carriers and unique magnetic properties compared to typical carbon nanostructures.

Findings

Polyhedral multi-shell structure with flat graphitic faces.

Presence of delocalized charge carriers causing Pauli paramagnetism.

Magnetic resonance relaxation times suggest metallic-like behavior.

Abstract

High Resolution Transmission Electron Microscopy (HRTEM), X-ray Diffraction (XRD) and Raman spectroscopy reveal a polyhedral multi-shell fullerene-like structure of astralen carbon nanoparticles. The polyhedra consist of large flat graphitic faces connected by defective edge regions with presumably pentagon-like structure. The faces comprise a stacking of 20-50 planar graphene sheets with inter-sheet distance of ~ 0.340 nm. Average sizes of the particles and their flat faces are ~ 40 nm and ~ 15 nm, respectively. The astralen particles are suggested to have defect-free sp^2 flat faces and all defects condense at their polyhedral edges. Electron Paramagnetic Resonance (EPR) spectra of polycrystalline astralen samples reveal two components: a very broad signal with DHpp > 1 T and an asymmetric narrow one centered close to g = 2.00. The latter consists of two overlapping Lorentzian lines. All spectral components are independent of ambient pressure. The intensities of all EPR signals show no changes on decreasing temperature from T = 300 K down to 4 K demonstrating the Pauli paramagnetism. Electron spin-lattice relaxation times T1e remain very short within the same temperature range. Temperature dependent 13C Nuclear Magneti? Resonance (NMR) measurements yield nuclear spin-lattice relaxation times T1n ~ T^-0.612. The exponent in the T1n(T)-dependence for astralen falls between the metallic behavior, T1n ~ T^-1 (Korringa relation), and the semiconductor behavior, T1n ~T^-0.5. All unusual magnetic resonance features of astralen are attributed to delocalized charge carriers which amount considerably exceeds that of spins localized in defects on multi-shell polyhedra edges.