Pyrolysis and oxidation of benzene and cyclopentadiene by NOx: a ReaxFF molecular dynamics study.

Benzene (C6H6) and 1,3-cyclopentadiene (c-C5H6) are critical intermediate species in the combustion of fossil fuel and the formation of polycyclic aromatic hydrocarbons (PAHs). This study investigates the underlying mechanisms of pyrolysis and oxidation of C6H6 and c-C5H6 in the presence of O2, NO and NO2, respectively, under combustion conditions via ReaxFF molecular dynamics simulations. The size growth in the pyrolysis system is accompanied by an amorphous nature as well as an increase in the C/H ratio. In the oxidation sytems, NO2 is the most effective in the oxidation of both C6H6 and c-C5H6, followed by NO and O2. In the presence of NOx, O and N radicals generated in the high-temperature decomposition reactions of NO and NO2 are actively involved in the addition and H-abstraction reactions of C6H6 and c-C5H6. Remarkably, the decomposition of NO2 dramatically increases the number of O radicals in the system, which significantly accelerates the ring-opening of C6H6 and c-C5H6 by O-addition and forms linear-C6H6O and C5H6O species, respectively. Afterwards, the formation of -CH2- by H-transfer plays an essential role in the decomposition of linear-C6H6O and -C5H6O. Reaction pathways of O and N radicals with C6H6 and c-C5H6 are reported in detail. The O and N-addition of C6H6 facilitate the decomposition to resonance-stabilized cyclopentadienyl radicals after the restructuring of the C-C bond.

Charge transfer engineering to achieve extraordinary power generation in GeTe-based thermoelectric materials.

By the fine manipulation of the exceptional long-range germanium-telluride (Ge─Te) bonding through charge transfer engineering, we have achieved exceptional thermoelectric (TE) and mechanical properties in lead-free GeTe. This chemical bonding mechanism along with a semiordered zigzag nanostructure generates a notable increase of the average zT to a record value of ~1.73 in the temperature range of 323 to 773 K with ultrahigh maximum zT ~ 2.7. In addition, we significantly enhanced the Vickers microhardness numbers (Hv) to an extraordinarily high value of 247 Hv and effectively eliminated the thermal expansion fluctuation at the phase transition, which was problematic for application, by the present charge transfer engineering process and concomitant formation of microstructures. We further fabricated a single-leg TE generator and obtained a conversion efficiency of ~13.4% at the temperature difference of 463 K on a commercial instrument, which is located at the pinnacle of TE conversion.

CO2 activation and dissociation on In2O3(110) supported PdnPt(4-n) (n = 0-4) catalysts: a density functional theory study.

Converting CO2 into valuable chemicals via catalytic reactions can mitigate both the greenhouse effect and energy shortage problems, thus designing efficient catalysts have attracted considerable attention over the past decades. In this work, a density functional theory (DFT) calculation was carried out to investigate the CO2 activation and dissociation processes on various PdnPt(4-n)/In2O3 (n = 0-4) catalysts. The PdnPt(4-n)/In2O3 models were initially built, and the interface sites of PdnPt(4-n)/In2O3 for CO2 adsorption were confirmed among cluster sites and substrate sites. The CO2 adsorption geometries, charger transfer, and projected density of states (PDOS) were analyzed to study the CO2-PdnPt(4-n)/In2O3 interactions. From the adsorbed *CO2, the transition states (TSs) for CO2 dissociation to form *CO and *O were gained to reveal the characteristics of the activated CO2δ-. Overall, according to the adsorption energy Eads results, the bimetallic PdPt3/In2O3 and Pd3Pt/In2O3 catalysts showed the strongest and weakest CO2 adsorption stabilities, respectively, while the Pd element addition decreases the barriers for CO2 dissociation with the priority order of Pd4 > Pd3Pt > Pd2Pt2 > PdPt3 > Pt4. The Brønsted-Evans-Polanyi (BEP) relation between activation barriers (Eb) and reaction energies E was obtained for the CO2 dissociation mechanism on PdnPt(4-n)/In2O3 catalysts with the equation of E = 0.20Eb + 0.40. Finally, the optimal Pd2Pt2/In2O3 catalyst for CO2 activation and dissociation was proposed. This study provides useful information for CO2 activation and conversation procedures on bimetal-oxide catalysts, and helps to take the optimal design of PdPt/In2O3 catalysts for the CO2 reaction.

Pressure oscillation with destructive effect of flame propagation of a stoichiometric hydrogen-air mixture in a confined space.

In the present work, the formation mechanism of high-intensity combustion with high pressure oscillation and its destructive effects was studied by a newly designed constant volume combustion bomb equipped with a perforated plate. The stoichiometric H2-air mixture was selected as the test fuel because of its high flame propagation velocity with obvious shock wave, which easily leads to a strong pressure oscillation. Two kinds of high-intensity combustion phenomena, including the continuous acceleration of the flame front and end-gas auto ignition, were obtained. The results show that the ultrafast and intense combustion would lead to a high pressure oscillation, consequently caused damage to the experimental device, such as the optical glass and perforated plate. The perforated plate vibrated back and forth in situ forced by the combustion waves. The peak pressure was up to 10.3MPa and maximum amplitude of pressure oscillation was 4.2MPa when the optical glass was damaged. And according to FFT analysis, the frequency of in-cylinder pressure changed because of the combustion mode transition. The present work provides an alternative method to not only grasp the destructive mechanism of knocking combustion, but also understand the destructive effect of the combustion of the hydrogen-air mixture.

Flame temperature theory-based model for evaluation of the flammable zones of hydrocarbon-air-CO2 mixtures.

Theoretical models to evaluate the flammable zones of mixtures made up of hydrocarbon, carbon dioxide and air have been proposed in present study. A three-step reaction hypothesis for hydrocarbon combustion was introduced for predicting the upper flammability limit. The method to predict the parameters at fuel inertization point was put forward as well. Validation of these models has been conducted on existing experimental data reported in the literature, including the cases of methane, propane, propylene and isobutane, and an acceptable precision has been achieved. The average relative differences between the estimated results and experimental ones, except for the results at fuel inertization point, are less than 8.8% and 3.3% for upper and lower flammability limit, respectively. This work also indicated that these models possess practical application capacity and can provide safe prediction limits for nonflammable ranges of hydrocarbon diluted with carbon dioxide.