Copolymers of bipyridinium and metal (Zn & Ni) porphyrin derivatives; theoretical insights and electrochemical activity towards CO2

RSC Adv. 2021 Jun 2;11(32):19844-19855. doi: 10.1039/d1ra01945g. eCollection 2021 May 27.

Abstract

This study reports the electropolymerization of novel keto functionalized octaethyl metal porphyrins (Zn2+ and Ni2+) in the presence of 4,4'-bipyridine (4,4'-bpy) as a bridging nucleophile. The polymer films were characterized by electrochemical, spectroscopic (UV-Vis, XPS, FT-IR and Raman spectroscopy) and imaging (AFM and SEM) techniques. The absorption and electronic spectra confirm the presence of both porphyrin and 4,4'-bipyridine units in the film. The surface morphology reveals homogeneous film deposition with average roughness values of approx. 8 nm. The theoretical studies performed offered insights into the interplay of different metal centres (Zn2+ and Ni2+) and the keto functionality of the porphyrin unit in the formation of copolymer films. The electrochemical interaction of polymer films with CO2 suggests a reversible trap and release of CO2 with low energy barriers for both the polymers.