Generation of nitrogen functionalities on activated carbons by amidation reactions and Hofmann rearrangement: Chemical and electrochemical characterization

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Title: Generation of nitrogen functionalities on activated carbons by amidation reactions and Hofmann rearrangement: Chemical and electrochemical characterization
Authors: Mostazo-López, María José | Ruiz-Rosas, Ramiro | Morallon, Emilia | Cazorla-Amorós, Diego
Research Group/s: Materiales Carbonosos y Medio Ambiente | Electrocatálisis y Electroquímica de Polímeros
Center, Department or Service: Universidad de Alicante. Departamento de Química Inorgánica | Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Materiales
Keywords: Nitrogen functionalization | Microporous activated carbon | Amidation reactions | Hofmann rearrangement
Knowledge Area: Química Inorgánica | Química Física
Issue Date: Sep-2015
Publisher: Elsevier
Citation: Carbon. 2015, 91: 252-265. doi:10.1016/j.carbon.2015.04.089
Abstract: Nitrogen functionalization of a highly microporous activated carbon (BET surface area higher than 3000 m2/g) has been achieved using the following sequence of treatments: (i) chemical oxidation using concentrated nitric acid, (ii) amidation by acyl chloride substitution with NH4NO3 and (iii) amination by Hoffman rearrangement. This reaction pathway yielded amide and amine functional groups, and a total nitrogen content higher than 3 at.%. It is achieved producing only a small decrease (20%) of the starting microporosity, being most of it related to the initial wet oxidation of the activated carbon. Remarkably, nitrogen aromatic rings were also formed as a consequence of secondary cyclation reactions. The controlled step-by-step modification of the surface chemistry allowed to assess the influence of individual nitrogen surface groups in the electrochemical performance in 1 M H2SO4 of the carbon materials. The largest gravimetric capacitance was registered for the pristine activated carbon due to its largest apparent surface area. The nitrogen-containing activated carbons showed the highest surface capacitances. Interestingly, the amidated activated carbon showed the superior capacitance retention due to the presence of functional groups (such as lactams, imides and pyrroles) that enhance electrical conductivity through their electron-donating properties, showing a capacitance of 83 F/g at 50 A/g.
Sponsor: This work was supported by the Ministry of Economy and Competitiveness of Spain (MINECO) and FEDER (CTQ2012-31762, MAT2013-42007-P) and Generalitat Valenciana (PROMETEO/2013/038 and PROMETEOII/2014/010). RRR thanks MINECO for ‘Juan de la Cierva’ contract (JCI-2012-12664).
ISSN: 0008-6223 (Print) | 1873-3891 (Online)
DOI: 10.1016/j.carbon.2015.04.089
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2015 Elsevier Ltd.
Peer Review: si
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