Porphyrin based electroactive copolymers, from electropolymerization to energy and environmental applications
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Verkkojulkaisu
DOI
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A material that exhibits both electrochromic properties and energy storage capabilities can directly address the UN’s 2030 Agenda for Sustainable Development, given the global demand for cost-effective, environmentally friendly, and energy-efficient solutions.
This thesis describes an efficient electrocopolymerization approach for developing porphyrin-based copolymer thin film electrochromic supercapacitors. Three meso aminophenyl porphyrins (MTAPP; M = Zn2+, Ni2+, H2) are separately combined with 3,4-ethylenedioxythiophene (EDOT) via oxidative electrocopolymerization, yielding three copolymers: poly(NiTAPP-EDOT), poly(ZnTAPP-EDOT), and poly(H2TAPP EDOT). The MTAPP-EDOT copolymer thin films exhibit rapid electrochromic switching (< 2 s), significant optical contrast across the visible and beginning of the near-infrared regions, high coloration efficiency, and excellent open-circuit optical memory. The identity of the central metal ion strongly influences the electrochromic behavior and enables tuning of multicolor electrochromic responses. Poly(NiTAPP EDOT) displays three distinct reversible color states, whereas poly(ZnTAPP-EDOT) and poly(H2TAPP-EDOT) exhibit two distinct reversible color states. The three copolymer thin films were tested for electrochromic supercapacitor applications in 4 m ZnCl2 aqueous electrolyte. To our knowledge, this is the first study of MTAPP EDOT copolymer thin films in an aqueous electrolyte. Poly(NiTAPP-EDOT) exhibits electric-double-layer-capacitive-dominated characteristics, delivering a specific capacitance of 8.7 mF cm-2 and over 90% capacitance retention after 5000 galvanostatic charge-discharge cycles, while maintaining 100% Coulombic efficiency. Notably, poly(ZnTAPP-EDOT) and poly(H2TAPP-EDOT) exhibit EDLC behavior, retaining 85% and 98% capacitance after 10,000 and 2,000 galvanostatic charge discharge cycles, respectively.
Additionally, keto-functionalized octaethylporphyrins (MOEPK; M = Zn2+, Ni2+) are electropolymerized using 4,4′-bipyridine as a bifunctional bridging nucleophile, enabling direct polymerization without pre-functionalized monomers. These findings provide new insights into structure-property relationships in porphyrin electropolymers and support their use in sustainable multifunctional electrochemical devices operating in water-based electrolyte systems.
Sarja
Turun yliopiston julkaisuja - Annales Universitatis Turkuensis, Ser. AI: Astronomica, Chemica, Physica, Mathematica|764
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