RSS-Feed abonnieren
DOI: 10.1055/a-2187-9368
Microwave-Assisted Functionalization of Single-Walled Carbon Nanotubes as a Platform for a Supported Iridium Catalyst
We gratefully acknowledge financial support from the Spanish Ministerio de Ciencia, Innovación y Universidades (project RED2018-102387-T) the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigación (AEI) (MCIN/AEI/10.13039/501100011033) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects CTQ2017-82935-P, PID2019-107268GB-I00 and PID2021-123079OB-I00), the Generalitat Valenciana (IDIFEDER/2021/013, GVA-COVID19/2021/079 and CIDEGENT/2020/058), Medalchemy S. L. (Medalchemy-18T) and the University of Alicante (VIGROB-068, UAUSTI21-05). LVR-F thanks Generalitat Valenciana for Grisolía´s fellowship (GRISOLIAP/2020/111).
Abstract
Single-walled carbon nanotubes (SWCNTs) were functionalized by treatment with imino esters through 1,3-dipolar cycloaddition activated by thermal 1,2-prototropy. The reaction was optimized and analyzed by using various heating methods. The functionalization afforded pyrrolidino-functionalized nanotubes that were characterized by using several techniques. The ester group was then transformed into the corresponding SWCNT–iridium carboxylate and, as a proof of concept, the product was tested as a catalyst in the hydrogen-transfer reaction of acetophenone to yield 1-phenylethanol.
Key words
carbon nanotubes - dipolar cycloaddition - azomethine ylides - microwaves - iridium catalysis - heterogeneous catalysisSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2187-9368.
- Supporting Information
Publikationsverlauf
Eingereicht: 30. August 2023
Angenommen nach Revision: 09. Oktober 2023
Accepted Manuscript online:
09. Oktober 2023
Artikel online veröffentlicht:
20. November 2023
© 2023. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References and Notes
- 1 Iijima S. Nature 1991; 354: 56
- 2 Maheswaran R, Shanmugavel BP. J. Electron. Mater. 2022; 51: 2786
- 3 Rathinavel S, Priyadharshini K, Panda D. Mater. Sci. Eng., B 2021; 268: 115095
- 4 Anzar N, Hasan R, Tyagi M, Yadav N, Narang J. Sens. Int. 2020; 1: 100003
- 5 Ménard-Moyon C, Kostarelos K, Prato M, Bianco A. Chem. Biol. 2010; 17: 107
- 6 Mitchell VD, Wong WW. H. In Synthetic Methods for Conjugated Polymers and Carbon Materials, Chap. 5. Leclerc M, Morin JF. Wiley-VCH; Weinheim: 2017: 159
- 7a Georgakilas V, Kordatos K, Prato M, Guldi DM, Holzinger M, Hirsch A. J. Am. Chem. Soc. 2002; 124: 760
- 7b Prato Reaction: Fullerene, Carbon Nanotube, Azomethine Ylide . Surhone LM, Tennoe MT, Hessonow SF. Betascript Publishing; Beau Bassin: 2010
- 8a Georgakilas V, Bourlinos A, Gournis D, Tsoufis T, Trapalis C, Mateo-Alonso A, Prato M. J. Am. Chem. Soc. 2008; 130: 8733 . Georgakilas V., Demeslis A., Ntararas E., Kouloumpis A., Dimos K., Gournis D., Kocman M., Otyepka M., Zboril R.; Adv. Funct. Mater.; 2015, 25: 1481
- 8b Yao Z, Braidy N, Botton GA, Adronov A. J. Am. Chem. Soc. 2003; 125: 16015
- 8c Campidelli S, Sooambar C, Lozano Diz E, Ehli C, Guldi DM, Prato M. J. Am. Chem. Soc. 2006; 128: 12544
- 8d Pantarotto D, Partidos CD, Graff R, Hoebeke J, Briand J.-P, Prato M, Bianco A. J. Am. Chem. Soc. 2003; 125: 6160
- 8e Mulvey JJ, Feinberg EN, Alidori S, McDevitt MR, Heller DA, Scheinberg DA. Int. J. Nanomed. 2014; 9: 4245
- 9 Vázquez E, Prato M. ACS Nano 2009; 3: 3819
- 10 Calcio Gaudino E, Tagliapietra S, Martina K, Barge A, Lolli M, Terreno E, Lembo D, Cravotto G. Org. Biomol. Chem. 2014; 12: 4708
- 11 Koutsioukis A, Belessib V, Georgakilas V. Green Chem. 2021; 23: 5442
- 12 250 °C was also tested, with lower functionalization; see: Paiva MC, Simon F, Novais RM, Ferreira T, Proença MF, Xu W, Besenbacher F. ACS Nano 2010; 4: 7379
- 13 The preparation of functionalized multiwalled CNTs was studied at 250 °C for 3 h in the absence of a solvent, giving one pyrrolidine per 22 carbon atoms, approximately.
- 14 Brunetti FG, Herrero MA, Muñoz J. deM, Giordani S, Díaz-Ortiz Á, Filippone S, Ruaro G, Meneghetti M, Prato M, Vázquez E. J. Am. Chem. Soc. 2007; 129: 14580
- 15a Salice P, Maity P, Rossi E, Carofiglio T, Menna E, Maggini M. Chem. Commun. 2011; 47: 9092
- 15b Salice P, Rossi E, Pace A, Maity P, Carofiglio T, Menna E, Maggini M. J. Flow Chem. 2014; 4: 79
- 16 Ferrándiz-Saperas M, Ghisolfi A, Cazorla-Amorós D, Nájera C, Sansano JM. Chem. Commun. 2019; 55: 7462
- 17 These nanotubes were purchased from Cheap Tubes Inc., Cambridgeport, VT, and they contained some double-walled CNTs.
- 18 Functionalization of SWCNTs; General Procedure A pressure tube equipped with a 1.2 atm valve was charged with a 1 mg/mL suspension of SWCNTs in NMP (40 mL) and the appropriate freshly prepared imino ester 1 (0.8 mmol). The mixture was subjected to microwave irradiation to maintain a temperature of 100 °C for 2 h. The resulting mixture was then centrifuged for 40 min at 7000 rpm, and the functionalized nanotubes were collected, redispersed in EtOAc (10 mL), and recentrifuged (30 min, 7000 rpm): this process was repeated three times. Eventually, the product was dried at a reduced pressure for 24 h. All the samples were characterized (see SI). All the FCNT-3 samples displayed a common peak at 400.1 to 400.7 eV, corresponding to a prolinate nitrogen (see SI).
- 19 Attempts were made to use the carboxylates of rhodium and ruthenium, but we observed leaching of the metals and their low incorporation. Attempts to improve the procedure to form these two metal-supported SWCNTs are currently underway.
- 20 FCNT-Ir: General Procedure The appropriate FCNT-3 was dispersed in acetone (1 mg/mL) and 1 M aq of NaOH was added (1 mL per milligram of nanotubes), and the resulting suspension was stirred at 25 °C for 12 h. The resulting mixture was centrifuged for 40 minutes at 7000 rpm. The functionalized nanotubes were collected, redispersed in MeOH (10 mL), and recentrifuged (30 min, 7000 rpm): this process was repeated three times. The purified functionalized nanotubes (30 mg) were dispersed by ultrasound irradiation in CH2Cl2 (30 mL). [IrCP*Cl2]2 (5 mg) was added, and the suspension was stirred at 25 °C for 18 h under argon. The resulting mixture was centrifuged for 40 minutes at 7000 rpm. The functionalized nanotubes were collected, redispersed in CH2Cl2 (10 mL), and centrifuged again (30 min, 7000 rpm). This process was repeated three times to give a total of 24.75 mg of functionalized FCNT-Ir.
- 21 Marco-Martínez J, Vidal S, Fernández I, Filippone S, Martín N. Angew. Chem. Int. Ed. Engl. 2017; 56: 2136
- 22a Saidi O, Williams JM. J. Top. Organomet. Chem. 2011; 34: 77
- 22b Hintermair U, Campos J, Brewster TP, Pratt LM, Schley ND, Crabtree RH. ACS Catal. 2014; 4: 99
- 23 This process was a little slower than a process using N-heterocyclic carbenes in covalent attachment to CNTs; see: Blanco M, Álvarez P, Blanco C, Jiménez MV, Fernández-Tornos J, Pérez-Torrente JJ, Oro LA, Menéndez R. ACS Catal. 2013; 3: 1307
- 24 Hammond C, Schümperli MT, Conrad S, Hermans I. ChemCatChem 2013; 5: 2983
- 25 Vidal S, Marco-Martínez J, Filippone S, Martín N. Chem. Commun. 2017; 53: 4842