Magnetism of Nanographene-Based Microporous Carbon and Its Applications: Interplay of Edge Geometry and Chemistry Details in the Edge State

Nanographenes have important edge geometry dependence in their electronic structures. In armchair edges, electron wave interference works to contribute to energetic stability. Meanwhile, zigzag edges possess an edge-localized and spin-polarized nonbonding edge state, which causes electronic, magnetic, and chemical activities. In addition to the geometry dependence, the electronic structures are seriously affected by edge chemistry details. The edge chemistry dependence together with edge geometries on the electronic structures are discussed with samples of randomly networked nanographenes (microporous activated carbon fibers) in pristine state and under high-temperature annealing. In the pristine sample with the edges oxidized in ambient atmospheric conditions, the edge state, which is otherwise unstable, can be stabilized because of the charge transfer from nanographene to terminating oxygen. Nanographene, whose edges consist of a combination of magnetic zigzag edges and nonmagnetic armchair edges, is found to be ferrimagnetic with a nonzero net magnetic moment created under the interplay between a strong intrazigzag-edge ferromagnetic interaction and intermediate-strength interzigzag-edge antiferromagnetic-ferromagnetic interaction. At heat-treatment temperatures just below the fusion start (approximately 1500 K), the edge-terminating structure is changed from oxygen-containing groups to hydrogen in the nanographene network. Additionally, hydrogen-terminated zigzag edges, which are present as the majority and chemically unstable, play a triggering role in fusion above 1500 K. The fusion start brings about an insulator-to-metal transition at TI-M similar to 1500 K. Local fusions taking place percolatively between nanographenes work to expand the p-bond network, eventually resulting in the development of antiferromagnetic short-range order toward spin glass in the magnetic moments of nanographenes. For applications, the edge-state spins in nanographene-based microporous carbon can be a good tool as a molecule sensor in detecting molecules having different chemical properties and sizes. The on-off magnetic switching phenomena upon the adsorption of H2O and other OH-containing molecules offers a molecule sensor. A He sensor, in which the edge-state spins is employed as a probe, is also proposed on the basis of a huge condensation of He into ultramicropores.