ORALS

SESSION: NanomaterialsTueAM-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: Dirk Michael Guldi; Fred Wudl; Session Monitor: TBA

11:35: [NanomaterialsTueAM01] OS Plenary
A LIFE DEDICATED TO CHEMISTRY AND NANOMATERIALS FOR ENERGY
Luis Echegoyen¹ ; ¹University of Texas El-Paso, El Paso, United States;
Paper Id: 463 [Abstract]

Following a brief introduction about the background and some personal details, a scientific history of the research work during the years will be presented along the method used to approach new and emergent areas. A scientific timeline will be presented starting from early academic career to the most recent activity and covering many research fields  from supramolecular chemistry to fullerene electrochemistry and endohedral fullerene structures. Life learned lessons  will also be described.

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.

SESSION: NanomaterialsThuAM-R3	Echegoyen International Symposium (8th Intl. Symp. on Synthesis & Properties of Nanomaterials for Future Energy Demands)
Thu. 30 Nov. 2023 / Room: Dreams 3
Session Chairs: Miguel A. Alario Franco; Mark Hersam; Session Monitor: TBA

12:50: [NanomaterialsThuAM04] OL
MULTIPURPOSE SUPRAMOLECULAR NANOCAPSULES: FROM PURIFICATION OF URANIUM-BASED EMFS TO MASKS FOR FULLERENE REGIOFUNCTIONALIZATION
Xavi Ribas¹ ; Josep Maria Poblet² ; Luis Echegoyen³ ; Carles Fuertes-Espinosa¹ ; ¹University of Girona, Girona, Spain; ²Universitat Rovira i Virgili, Tarragona, Spain; ³University of Texas El-Paso, El Paso, United States;
Paper Id: 423 [Abstract]

The design of supramolecular capsules with large cavities is attractive because they feature potential advantages as platforms to selectively bind large guests, such as fullerenes and Endohedral Metallofullerenes (EMFs).1 Generally, the practical applications of EMFs are hampered by their limited availability. Furthermore, their chromatographic purification (HLPC) is very challenging  and in some cases it is not successful. Our group reported a porphyrin-based supramolecular tetragonal prismatic nanocapsule (1),2 which features an internal cavity with size complementary and electrostatic relationship specific for a brand new family of Uranium-based EMFs.3 Nanocapsule 1 is able to sequentially and specifically recognize U2@Ih-C80 and Sc2UC@Ih-C80 among all those compounds present in the crude, simply by soaking crystals in a solution of the reaction crude. The stepwise and selective encapsulation of U-based EMFs allowed their separation and further purification by solvent-washing, obtaining highly pure fractions of the desired compounds in one step. Follow-up studies with U-based C78 soots indicate that not only the internal clusterelectronics but also the shape of the carbon cages strongly influences the selectivity of the nanocapsule.Taking advantage of the tight binding of fullerenes in our porphyrin-based supramolecular tetragonal prismatic nanocapsules, these are used as supramolecular shadow masks to tame the over-reactivity of Bingel-Hirsch-type cyclopropanation reactions and, more importantly, to have full control on the equatorial regioselectivity and on the number of additions.4 Thus, exclusively equatorial bis-, tris- and tetrakis-C60 adducts using ethyl-bromomalonate are stepwise obtained and fully characterized (NMR, UV-vis and XRD). Furthermore, the regioselectivity control is finely tuned using a three-shell Matryoshka-like assembly towards the synthesis of a single trans-3 bis-Bingel-C60 for the first time.5 These results, fully attributed to the confinement control imposed by the capsule’s cavity, represent a novel and unique strategy to infer regio-control to the synthesis of fullerene multi-adducts. We envision that the described protocol will produce a plethora of derivatives for applications such as solar cells.

 

References:
[1] C. Fuertes-Espinosa, M. Pujals and X. Ribas, Chem, 2020, 6, 3219-3262.
[2] C. García-Simón, M. Garcia-Borràs, L. Gómez, T. Parella, S. Osuna, J. Juanhuix, I. Imaz, D. Maspoch, M. Costas and X. Ribas, Nat. Commun., 2014, 5, 5557
[3] C. Fuertes-Espinosa, A. Gómez-Torres, R. Morales-Martínez, A. Rodríguez-Fortea, C. García-Simón, F. Gándara, I. Imaz, J. Juanhuix, D. Maspoch, J. M. Poblet, L. Echegoyen and X. Ribas, Angew. Chem. Int. Ed., 2018, 57, 11294-11299
[4] C. Fuertes-Espinosa, C. García-Simón, M. Pujals, M. Garcia-Borràs, L. Gómez, T. Parella, J. Juanhuix, I. Imaz, D. Maspoch, M. Costas and X. Ribas, Chem, 2020, 6, 169-186
[5] E. Ubasart, O. Borodin, C. Fuertes-Espinosa, Y. Xu, C. García-Simón, L. Gómez, J. Juanhuix, F. Gándara, I. Imaz, D. Maspoch, M. von Delius and X. Ribas, Nat. Chem., 2021, 13, 420-427