Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 20, 2019
Previous Article Next Article

Peroxy self-reaction leading to the formation of furfural

Author affiliations

Abstract

Interest in alternative fuels to petroleum and classical fuels has been growing very rapidly in recent years. Furan and its alkyl derivatives, such as methylfuran (2MF), have been identified as valid alternative biofuels. This study focuses on the self-reaction of the peroxy radical generated in the first oxidation step of 2MF, initiated by Cl atoms at 323 K and 4 Torr. The experiments have been carried out by a multiplexed synchrotron photoionization mass spectrometer (mSPIMS) at the Advanced Light Source (ALS) of Lawrence Berkeley National Laboratory (USA). The presence of a peak at m/z = 96 reveals that furfural is the dominant product of 2MF oxidation. Various reaction mechanisms for furfural formation are proposed here. The potential energy surfaces for singlet and triplet spin states have been mapped using quantum mechanical methods, such as CCSD(T), DFT-B3LYP, and composites models (CBS-QB3), to optimize the products, transition states, and intermediates. Experimental and theoretical results provide evidence that furfural does not form by primary reaction chemistry. Self-reaction of the peroxy radical generated in the first oxidation step of 2MF has been proposed as the pathway leading to the formation of furfural. Among various reaction channels, we indentified some entirely exothermic pathways involving oxygen–oxygen coupling and the formation of ROOOOR Russell intermediates.

Graphical abstract: Peroxy self-reaction leading to the formation of furfural

Back to tab navigation

Supplementary files

Article information


Submitted
11 Dec 2018
Accepted
19 Mar 2019
First published
20 Mar 2019

Phys. Chem. Chem. Phys., 2019,21, 10228-10237
Article type
Paper

Peroxy self-reaction leading to the formation of furfural

A. R. Smith, S. Di Muzio, F. Ramondo and G. Meloni, Phys. Chem. Chem. Phys., 2019, 21, 10228
DOI: 10.1039/C8CP07571A

Social activity

Search articles by author

Spotlight

Advertisements