Systematic Design and Synthesis of Conjugated Microporous Polymers Containing Pyrene and Azobenzene Building Materials for High-Performance Energy Storage

Abstract

Conjugated microporous polymers (CMPs), known for their high specific capacities, exceptional cycling stability, and outstanding rate performance, are being actively studied as advanced electrode materials for energy storage applications. The utilization of redox-active units in CMP materials in energy storage exhibits substantial promise. Nevertheless, the influence of the positioning of the redox-active region on the electrochemical behavior and battery performance remains a topic of uncertainty. Herein, we successfully created two CMPs using the Sonogashira− Hagihara coupling method, specifically by including redox-active azobenzene (Azo) moieties in the meta (m) and para (p) locations. These CMPs are named Py-mAzo-CMP and Py-pAzo-CMP. To produce them, we used precursor compounds (E)-1,2-bis(3bromophenyl)diazene (mAzo-Br 2 ) and (E)-1,2-bis(4-bromophenyl)diazene (pAzo-Br 2 ), combined with tetraethynylpyrene (Py-T). Our primary focus was to investigate the impact of substituting the Azo unit at different positions. To assess the orientation of molecules and the pores of these Py-Azo-CMPs, we conducted a thorough analysis, including BET isotherm measurements and various spectroscopic and microscopic techniques. Our findings from TGA analysis indicated that these Py-Azo-CMPs exhibit a moderate thermal stability. One remarkable discovery was the excellent electrochemical performance of Py-pAzo-CMP, which displayed a capacitance of 142 F g −1 (determined at 1 A g −1 ), showcasing its exceptional capacitive properties. Despite operating at a substantial current density of 10 A g −1 , both Py-mAzo and Py-pAzo-CMPs exhibited remarkable long-term stability, retaining over 92% of their capacity even after 5000 cycles. These results underscore the potential of Py-pAzo-CMP as a dependable and enduring choice for energy storage applications. Our findings highlight the significant promise of these Py-Azo-CMP materials and underscore their suitability for useful applications, including electrical energy storage (EES).

Hybrid Porous Polymers Combination of Octavinylsilsesquioxane/Pyrene with Benzothiadiazole Units for Robust Energy Storage and Efficient Photocatalytic Hydrogen Production from Water

“…Sigma–Aldrich supplied benzophenone (BZE, 99%), zinc powder (Zn, 99.99%), titanium chloride (TiCl 4 , 99.9%), glacial acetic acid (AcOH, 99%), 2,1,3-benzothiadiazole (BT, 98%), pyrene (Py, 98%), Br 2 solution, and potassium carbonate (K 2 CO 3 , 99%). The Py-Br 4 , TPE, and TPE-Br 4 were synthesized using previously outlined methods, with detailed preparation and spectroscopic analyses available in the Supporting Information. − …”

Tetrabenzonaphthalene and Redox-Active Anthraquinone-Linked Conjugated Microporous Polymers as Organic Electrodes for Enhanced Energy Storage Efficiency

“…The growing concerns over pollution, climate change, and the depletion of fossil fuels are intensifying global energy and environmental issues. − These challenges have spurred significant efforts to develop advanced alternative energy storage systems to satisfy future energy demands. − Consequently, there is an increasing focus on technologies for wastewater, water, and wind energy management as well as for storing materials and converting renewable energy sources. However, several challenges impede the adoption of energy storage systems, including low energy density, inadequate safety protocols, and a limited lifespan.…”

Construction of fully π-conjugated, diyne-linked conjugated microporous polymers based on tetraphenylethene and dibenzo[g,p]chrysene units for energy storage

“…CMPs exhibit a threedimensional network structure composed of interconnected pores at the molecular level. [37][38][39][40][41][42][43][44] Within this category, π-conjugated microporous polymers stand out for their extensive π-conjugated system and intrinsic nanopores. [45][46][47][48][49][50][51][52] These materials boast high surface areas, rendering them well-suited for gas adsorption.…”