Synthesis and Structural Features of Nanocomposites Based on Heterocyclic Polyazines and Carbon Nanomaterials

ABSTRACT

This work presents the synthesis and comprehensive structural analysis of novel polymer‐carbon nanocomposites based on heterocyclic polyazines—polyphenothiazine (PPTA) and polyphenoxazine (PPOA)—with various carbon nanomaterials (CNMs), including single‐walled carbon nanotubes (SWCNTs), multi‐walled carbon nanotubes (MWCNTs), and reduced graphene oxide (RGO). Two distinct synthetic strategies were employed: in situ interfacial oxidative polymerization of monomers in the presence of CNMs and post‐polymerization modification via solvent removal from polymer/CNM suspensions. FTIR and Raman analyses provided direct evidence of non‐covalent π‐π interactions at the polymer‐CNM interface. FTIR analysis confirms the structural integrity of the polyazine components within the nanocomposites. XPS studies unveiled distinct post‐modification pathways: PPTA undergoes cationic doping, while PPOA forms a partially quinoid structure. These interfacial and electronic structure modifications are directly linked to a tunable enhancement in electrical conductivity, with percolated CNM networks enabling a transition from frequency‐dependent hopping transport to quasi‐metallic conduction. The demonstrated ability to tailor interfacial electronic coupling and charge transport properties observed in these hybrid systems highlights their significant potential for advanced electrochemical applications, including energy storage devices and (bio)sensors.