Polymeric Network Hierarchically Organized on Carbon Nano-onions: Block Polymerization as a Tool for the Controlled Formation of Specific Pore Diameters

Gabriela Siemiaszko*, Agnieszka Hryniewicka, Joanna Breczko, Olivia Fernandez Delgado, Karolina H. Markiewicz, Luis Echegoyen, and Marta E. Plonska-Brzezinska*

ACS Appl. Polym. Mater. 2022, 4, 4, 2442–2458

Publication Date: March 17, 2022

https://doi.org/10.1021/acsapm.1c01788

Abstract

The organization of specific pores in carbonaceous three-dimensional networks is crucial for efficient electrocatalytic processes and electrochemical performance. Therefore, the synthesis of porous materials with ordered and well-defined pores is required in this field. The incorporation of carbon nanostructures into polymers can create material structures that are more ordered in comparison to those of the pristine polymers. In this study we applied polymer-templated methods of carbon material preparation, in which outer blocks of the star copolymers form the carbon skeleton, while the core part is pore-forming. Well-defined 6-star-(poly(methyl acrylate)-b-poly(4-acetoxystyrene)) dendrimers were synthesized by reversible addition–fragmentation chain-transfer polymerization. They were then transformed into poly(4-vinylphenol) derivatives (namely 6-star-(poly(methyl acrylate)-b-poly(4-vinylphenol)), subjected to polycondensation with formaldehyde, and pyrolyzed at 800 °C. Cross-linking of phenolic groups provides a polymer network that does not depolymerize by pyrolysis, unlike poly(methyl acrylate) chains. The selected star polymers were attached to carbon nano-onions (CNOs) to improve the organization of the polymer chains. Herein, the physicochemical properties of CNO-polymer hybrids, including the textural and the electrochemical properties, were compared with those of the pristine pyrolyzed polymers obtained under analogous experimental conditions. For these purposes, we used several experimental and theoretical methods, such as infrared, Raman, and X-ray photoelectron spectroscopy, nitrogen adsorption/desorption measurements, scanning and transmission electron microscopy, and electrochemical studies, including cyclic voltammetry. All of the porous materials were evaluated for use as supercapacitors.

KEYWORDS: carbon nano-onion, carbon nanostructure, porous material, RAFT polymerization, supercapacitor

• SUBJECTS:

  • Condensation,

  • Materials,

  • Oscillation,

  • Polymers,

  • Star polymers

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• Scheme 1. Representation of the Stepwise Synthesis of (A) PVPh-Derived Polymers and Carbon Materials from CTA, (B) CNO Modified with PVPh-Derived Polymers and Carbon Materials, and (C) CNO-Derived Chain Transfer Agent, Polymerization, and Carbon Material