Theoretical Study of the Decomposition Reactions of 2-Vinylfuran.

With the development of new synthetic methods, 2-vinylfuran (V2F) has become a potential renewable biofuel. In this work, the potential energy surfaces for the V2F unimolecular dissociation reaction, the H-addition reaction, and the H-abstraction reaction were constructed at the G4 level. The temperature- and pressure-dependent rate constants for the relevant reactions on the potential energy surfaces were calculated by solving the master equation based on the transition state theory and Rice-Ramsperger-Kassel-Marcus theory. The results show that the rate constant for the intramolecular H-transfer reaction of V2F with H atoms from the C(5) site to the C(4) site to form 2-vinylfuran-3(2H)-carbene, followed by the decomposition to form h145te3o, is the highest. The rate constants for the H-abstraction reaction of V2F with H atoms were the largest at C(6) on the branched chain, followed by C(7), and the rate constants for the H-abstraction reaction at C(3), C(4), and C(5) on the furan ring were not competitive. Negative temperature coefficient effects are observed for the rate constants of the addition reactions of V2F with H atoms at low pressures, with the H-addition rate constant at the C(5) site being the largest. This work not only provides the necessary rate constants for the reaction mechanism of V2F combustion but also provides theoretical guidance for the practical application of furan-based fuels.

Theoretical and Modeling Study about the Low-Temperature Reaction Mechanism Between Oxymethylene Ether-2 (OME2) Radicals and O2.

Oxymethylene ether-2 (CH3-O-CH2-O-CH2-O-CH3, OME2), a carbon-neutral fuel, was hydrogenated from CO2 captured in air or exhaust gases and reused for synthesis with renewable electricity. In the current work, two different potential energy surfaces (PESs) for the reaction of OME2 radicals with O2 were constructed at the CCSD(T)/CBS//M062X/6-311++G(d,p) level. Based on the Rice-Ramsperger-Kassel-Marcus (RRKM) theory and transition state theory, the temperature- and pressure-dependent rate constants for the relevant reactions on the PES were calculated by solving the master equation. The Arrhenius equation has been used to fit the temperature- and pressure-dependent reaction rate constants. The main reaction channels on the PES are discussed, showing that initial adduct generation and intramolecular H-transfer reactions are the key reaction channels for low-temperature combustion. Among them, the HO2 concerted elimination reaction channel needs to overcome higher energy barriers leading to uncompetitive HO2 concerted elimination reactions. The calculated rate constants were updated to the OME2 combustion model, and the updated model is in considerable agreement with experimentally measured data on the ignition delay time in the shock tube. The present work provides support for further studies on the oxidation reaction of long-chain OME..