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Hollow graphitic carbon nanoparticles (HGCNs) obtained by catalytic graphitization of acetylene carbon black (ACB) were investigated using ultra-soft X-ray emission spectroscopy. The electronic structures of the ACB HGCNs were compared with those of HGCNs obtained from iron carbide-filled carbon nanocapsules (Fe3C@CNCs) and Q-graphenes. The occupation of the π sub-band decreased in the following sequence: Fe3C@CNC HGCNs > ACB HGCNs > Q-graphenes. This sequence can be explained by changes in the occupations of the C2p states due to the formation of bonds between carbon and residual metal atoms within the HGCNs. It was also found that the contribution of the overlapping ofppπ+ppσ-states in the ACB HGCN walls toward the spectra of the HGNCs was greater in comparison with the reference Q-graphenes. It was established that ACB was not fully transformed into the HGCNs. Scanning and transmission electron microscopy methods were used to study the spatial structures and morphologies of the fabricated HGCNs. [ABSTRACT FROM PUBLISHER]