Enhancing the electrochemical properties of the p-type conductive polymer on the surface of the new synthesized 2-(pyridin-3-ylmethylene) hydrazine-1-carbothioamide-modified electrode: computational and electrochemical study

摘要

Herein, 2-(pyridin-3-ylmethylene)hydrazine-1-carbothioamide(3PHCT)was first fabricated through a chemical method, and subsequently, polyorthoaminophenol (POAP)/3PHCT films were prepared using electropolymerization of POAP, carried out in the presence of the as-prepared 3PHCT to serve as the active electrode for electrochemical application. Geometry optimization and calculations of structural and electronic/vibrational properties of the 3PHCT system are studied (based on the quantum atom-in-molecule theory, QTAIM). In addition, the local intra-molecular electron density, and its Laplacian, and, thus, intra-molecular virial forces, of this molecule system are calculated. These results show that the oxygen and sulfur atoms play domain role in intra-molecular charge and energy transfer in this molecular system. In addition, based on the QTAIM, it is predicted that a single electrochemical molecular system can be grouped into p-type-like and n-type-like sections, and would be good candidate to reduce intra-molecular repulsion of the bipolaron during electrochemical polymerization of POAP. Galvanostatic charge-discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy, were conducted to characterize the prepared composite films and investigate the performance of the system, respectively. In this study, novel POAP/3PHCT are presented for electrochemical redox capacitors possessing the merits of high active surface area, stability in an aqueous electrolyte and ease of synthesis.