Metal-free heterogeneous catalysis is promising in the context of H2 generation. Therefore, establishing structure-activity relationships is a crucial issue to improve the development of more efficient catalysts. Herein, to evaluate the reactivity of the oxygen functionalities in carbonaceous materials, commercial functionalized pyrolytically stripped carbon nanofibers (CNFs) were used as catalysts in the liquid-phase hydrous hydrazine decomposition process and its activity was compared to that of a pristine CNF material. Different oxygenated groups were inserted by treating CNFs with hydrogen peroxide for 1 h (O1-H2O2) and HNO3 for 1 h (O1-HNO3) and 6 h (O6-HNO3). An increase in activity was observed as a function of the oxidizing agent strength (HNO3 > H2O2) and the functionalization time (6 h > 1 h). A thorough characterization of the catalysts demonstrated that the activity could be directly correlated with the oxygen content (O6-HNO3 > O1-HNO3 > O1-H2O2 > CNFs) and pointed out the active sites for the reaction at carbon-oxygen double bond groups (CO and COOH). Systematic DFT calculations supported rationalization of the experimental kinetic trends with respect to each oxygen group (CO, C-O-C, C-OH and COOH).

Effects of oxygen functionalities on hydrous hydrazine decomposition over carbonaceous materials / S. Bellomi, I. Barlocco, S. Tumiati, P. Fumagalli, N. Dimitratos, A. Roldan, A. Villa. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - (2023), pp. 1-7. [Epub ahead of print] [10.1039/D3DT02310A]

Effects of oxygen functionalities on hydrous hydrazine decomposition over carbonaceous materials

S. Bellomi
Primo
;
I. Barlocco;S. Tumiati;P. Fumagalli;N. Dimitratos;A. Villa
Ultimo
2023

Abstract

Metal-free heterogeneous catalysis is promising in the context of H2 generation. Therefore, establishing structure-activity relationships is a crucial issue to improve the development of more efficient catalysts. Herein, to evaluate the reactivity of the oxygen functionalities in carbonaceous materials, commercial functionalized pyrolytically stripped carbon nanofibers (CNFs) were used as catalysts in the liquid-phase hydrous hydrazine decomposition process and its activity was compared to that of a pristine CNF material. Different oxygenated groups were inserted by treating CNFs with hydrogen peroxide for 1 h (O1-H2O2) and HNO3 for 1 h (O1-HNO3) and 6 h (O6-HNO3). An increase in activity was observed as a function of the oxidizing agent strength (HNO3 > H2O2) and the functionalization time (6 h > 1 h). A thorough characterization of the catalysts demonstrated that the activity could be directly correlated with the oxygen content (O6-HNO3 > O1-HNO3 > O1-H2O2 > CNFs) and pointed out the active sites for the reaction at carbon-oxygen double bond groups (CO and COOH). Systematic DFT calculations supported rationalization of the experimental kinetic trends with respect to each oxygen group (CO, C-O-C, C-OH and COOH).
Settore CHIM/03 - Chimica Generale e Inorganica
   One Health Action Hub: task force di Ateneo per la resilienza di ecosistemi territoriali (1H_Hub) Linea Strategica 3, Tema One health, one earth
   1H_Hub
   UNIVERSITA' DEGLI STUDI DI MILANO
2023
26-set-2023
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/1009751
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