ORALS

SESSION: NanomaterialsTuePM1-R3	Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands)
Tue. 28 Nov. 2023 / Room: Dreams 3
Session Chairs: Marta Plonska Brzezinska; Yuhuang Wang; Session Monitor: TBA

14:05: [NanomaterialsTuePM105] OS
CARBON NANOONIONS AS A PLATFORM FOR DESIGNING MATERIALS WITH THE HIERARCHICAL POROSITY
Marta Plonska Brzezinska¹ ; Agnieszka Hryniewicka² ; Joanna Breczko² ; Gabriela Siemiaszko² ; Krzysztof Brzezinski³ ; Anna Ilnicka⁴ ; Artur Terzyk⁴ ; Luis Echegoyen⁵ ; ¹Medical U. of Bialystok, Białystok, Poland; ²Medical University of Bialystok, Bialystok, Poland; ³Institute of Bioorganic Chemistry, Polish Academy of Sciences, Poznan, Poland; ⁴Nicolaus Copernicus University in Torun, Torun, Poland; ⁵University of Texas El-Paso, El Paso, United States;
Paper Id: 120 [Abstract]

The goal of our studies is to apply carbon nanostructures, referred to as multi-layered fullerenes or carbon nanoonions (CNOs), for the controlled organization of resins [1], polymeric chains [2],[3] or triazines [4],[5], which, as a consequence, are a significant force for the ordered organization of pores within the synthesized materials. The critical role of using CNOs to design nanocomposites is in achieving high-quality modification of the 3D architecture and organization of the porous structure in such a way that the obtained materials possess an orderly distribution of pores and a homogenous pore size distribution (micro, meso and macro). The presence of micropores in porous materials results from the surface properties of the carbon nanoparticles. Bigger pores, such as meso and macropores, arise mainly from crosslinking of the oligomeric/polymeric chains or triazines. Incorporating functionalized CNOs leads to organized polymerization or formation of triazine skeleton in a three-dimensional manner. Therefore, the suitable choice of substrate structure enables further control of the meso and macroporosity of the porous nanocomposites. These parameters can be consciously controlled by selecting appropriate components and their percentage composition in the final mixture. A synergistic effect of both components may be observed, creating a material with new and unusual porosity superior to using one type of pore. The best electrochemical performances were obtained when using the nitrile-functionalized pyrrolo[3,2-b]pyrrole unit to form triazine rings. The synthesis relies on forming a triazine ring as a covalent bond between organic building blocks to achieve covalent triazine-based frameworks (CTFs) with specific diameters forming a porous framework. CTFs constitute an emerging class of high-performance materials due to their porosity and the possibility of structural control at the molecular or atomic level. However, using CTFs as electrodes in supercapacitors is hampered by their low electrical conductivity and a strong stacking effect between adjacent CTF sheets. Therefore, we covalently immobilized triazine-based structures on CNOs to organize pores three-dimensionally. Combining CNOs with the triazine framework produced a material with unique physicochemical properties, exhibiting the highest specific capacitance value of 638 F/g in aqueous acidic solutions. It should be emphasized that the specific capacitance value for hybrids was 1.5-2 times higher than that for the CTF reference. We examined the factors responsible for such a significant increase in electrochemical efficiency. This phenomenon is attributed to many factors. The material exhibits a large surface area, a high micropore content, a high graphitic N, and N-sites with basicity and semi-crystalline character. Thanks to the high structural organization and reproducibility and remarkably high specific capacitance, these systems are promising materials for use in electrochemistry. For the first time, hybrid systems containing triazine-based frameworks and CNOs were used as electrodes for supercapacitors. The studies were performed under the financial support of the National Science Centre, Poland, grants #2017/25/B/ST5/01414 and #2019/35/B/ST5/00572 to M.E.P-B.

References:
[1] G. Siemiaszko, J. Breczko, A. Hryniewicka, A. Ilnicka, K. H. Markiewicz, A. P. Terzyk, M. E. Plonska-Brzezinska, Sci Rep 2023, 13, 6606. [2] G. Siemiaszko, A. Hryniewicka, J. Breczko, O. F. Delgado, K. H. Markiewicz, L. Echegoyen, M. E. Plonska-Brzezinska, ACS Appl. Polym. Mater. 2022, 4, 2442–2458. [3] G. Siemiaszko, A. Hryniewicka, J. Breczko, K. Brzezinski, M. E. Plonska-Brzezinska, Chem. Commun. 2022, 58, 6829–6832. [4] A. Hryniewicka, J. Breczko, G. Siemiaszko, A. Papathanassiou, K. Góra-Marek, K. Tarach, K. Brzezinski, A. Ilnicka, A. Terzyk, K. Markiewicz, L. Echegoyen, M. Plonska-Brzezinska, Pyrrolo[3,2-b]Pyrrole-Based Covalent Triazine Framework: Three-Dimensional Organization of Pores Using Nanostructural Spherical Carbon, Chemistry, 2022. [5] A. Hryniewicka, J. Breczko, G. Siemiaszko, K. Brzezinski, A. Ilnicka, A. Terzyk, M. Plonska-Brzezinska, Hierarchical Porosity of Hybrid Carbon Nanomaterials Based on a Covalent Triazine Framework for High-Performance Capacitive Energy Storage, Chemistry, 2022.