Experimental and DFT Study of Structural And Electronic Properties of Polyfuran@nanoCuO Hybrid Polymer

Abstract

 Polyfuran (PFu) and polyfuran combined with copper oxide nanoparticles (NPs)  25 nm to form  (PFu@CuO) were synthesized using oxidation polymerization in the presence of FeCl3   and core-shell polymerization methods. The effective synthesis of PFu@CuO and the dynamics of interaction between PFu and CuO NPs were corroborated through a diverse range of characterization techniques, including field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) analysis, which elucidated the crystalline transformation of PFu in association with CuO(NPs). The vibrational modes were meticulously examined via infrared spectroscopy. UV-VIS absorption spectra were acquired, and the energy band gap was computed, demonstrating a reduction from 2.51 eV for unmodified PFu to 1.49 eV for PFu@CuO, as elucidated through the Tauc plot. The thermal characteristics were evaluated through thermogravimetric analysis (TGA). A theoretical investigation was executed to ascertain the adhesion energy of the polymer on the nano-metal oxide surface, employing the Material Studio software. Computational analyses, with a particular emphasis on PFu@CuO(NPs), systematically juxtaposed the properties of polyfuran with those of polyfuran adsorbed onto the nano-metal oxide surface. Molecular modeling, employing the COMPASS force field, clarified the intricate interactions between polymers and metal oxides, indicating an enhanced adhesion between polymer oligomers and metal oxides, which is crucial for the progression of polymer composite design. Additionally, computational evaluations of the molecular framework of polyfuran provided significant insights into its geometric, spectroscopic, and electronic properties, with density functional theory (DFT) calculations performed using the B3LYP/6-311G++ (d, p) basis set revealing a relationship between the oligomer count and the energy gap. Furthermore, molecular dynamics simulations were conducted to ascertain the glass transition temperature and to compare it with the experimentally determined glass transition temperature, as well as to evaluate the degree of compatibility between practical and theoretical aspects, thereby demonstrating the substantial capacity of molecular dynamics simulation methodologies in exploring the morphology of polymers and improving their functional characteristics. This comprehensive study advances our understanding of polymer-metal oxide interactions and informs the design of tailored polymer composites with enhanced functionality.