1-Hexene Ozonolysis across Atmospheric and Combustion Temperatures via Synchrotron-Based Photoelectron Spectroscopy and Chemical Ionization Mass Spectrometry.

This study investigates the complex interaction between ozone and the autoxidation of 1-hexene over a wide temperature range (300-800 K), overlapping atmospheric and combustion regimes. It is found that atmospheric molecular mechanisms initiate the oxidation of 1-hexene from room temperature up to combustion temperatures, leading to the formation of highly oxygenated organic molecules. As temperature rises, the highly oxygenated organic molecules contribute to radical-branching decomposition pathways inducing a high reactivity in the low-temperature combustion region, i.e., from 550 K. Above 650 K, the thermal decomposition of ozone into oxygen atoms becomes the dominant process, and a remarkable enhancement of the conversion is observed due to their diradical nature, counteracting the significant negative temperature coefficient behavior usually observed for 1-hexene. In order to better characterize the formation of heavy oxygenated organic molecules at the lowest temperatures, two analytical performance methods have been combined for the first time: synchrotron-based mass-selected photoelectron spectroscopy and orbitrap chemical ionization mass spectrometry. At the lowest studied temperatures (below 400 K), this analytical work has demonstrated the formation of the ketohydroperoxides usually found during the LTC oxidation of 1-hexene, as well as of molecules containing up to nine O atoms.

Accounting for molecular flexibility in photoionization: case of tert-butyl hydroperoxide.

tert-Butyl hydroperoxide (tBuOOH) is a common intermediate in the oxidation of organic compounds that needs to be accurately quantified in complex gas mixtures for the development of chemical kinetic models of low temperature combustion. This work presents a combined theoretical and experimental investigation on the synchrotron-based VUV single photon ionization of gas-phase tBuOOH in the 9.0 - 11.0 eV energy range, including dissociative ionization processes. Computations consist of the determination of the structures, vibrational frequencies and the energetics of neutral and ionic tBuOOH. The Franck-Condon spectrum for the tBuOOH+ (X+) + e- ← tBuOOH (X) + hν transition is computed, where special treatment is undertaken because of the flexibility of tBuOOH, in particular regarding the OOH group. Through comparison of the experimental mass-selected threshold photoelectron spectra with explicitly correlated coupled cluster calculations and Franck-Condon simulations that account for the flexibility of the molecule, an estimation of the ionization energy is given. The appearance energy of the only fragment observed within the above-mentioned energy range, identified as the tert-butyl C4H9+, is also reported. Finally, the signal branching ratio between the parent and the fragment ions is provided as a function of photon energy, essential to quantify tBuOOH in gas-phase oxidation/combustion experiments via advanced mass spectrometry techniques.

Product Identification in the Low-Temperature Oxidation of Cyclohexane Using a Jet-Stirred Reactor in Combination with SVUV-PEPICO Analysis and Theoretical Quantum Calculations.

Cyclohexane oxidation chemistry was investigated using a near-atmospheric pressure jet-stirred reactor at T = 570 K and equivalence ratio ϕ = 0.8. Numerous intermediates including hydroperoxides and highly oxygenated molecules were detected using synchrotron vacuum ultraviolet photoelectron photoion coincidence spectroscopy. Supported by high-level quantum calculations, the analysis of photoelectron spectra allowed the firm identification of molecular species formed during the oxidation of cyclohexane. Besides, this work validates recently published gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry data. Unambiguous detection of characteristic hydroperoxides (e.g., γ-ketohydroperoxides) and their respective decomposition products provides support for the conventional O2 addition channels up to the third addition and their relative contribution to the cyclohexane oxidation. The results were also compared with the predictions of a recently proposed new detailed kinetic model of cyclohexane oxidation. Most of the predictions are in line with the current experimental findings, highlighting the robustness of the kinetic model. However, the analysis of the recorded slow photoelectron spectra indicating the possible presence of C5 species in the kinetic model provides hints that the substituted cyclopentyl radicals from cyclohexyl ring opening might play a minor role in cyclohexane oxidation. Potentially important missing reactions are also discussed.

Insight into the Ozone-Assisted Low-Temperature Combustion of Dimethyl Ether by Means of Stabilized Cool Flames.

The low-temperature combustion kinetics of dimethyl ether (DME) were studied by means of stabilized cool flames in a heated stagnation plate burner configuration using ozone-seeded premixed flows of DME/O2. Direct imaging of CH2O* chemiluminescence and laser-induced fluorescence of CH2O were used to determine the flame front positions in a wide range of lean and ultra-lean equivalence ratios and ozone concentrations for two strain rates. The temperature and species mole fraction profiles along the flame were measured by coupling thermocouples, gas chromatography, micro-chromatography, and quadrupole mass spectrometry analysis. A new kinetic model was built on the basis of the Aramco 1.3 model, coupled with a validated submechanism of O3 chemistry, and was updated to improve the agreement with the obtained experimental results and experimental data available in the literature. The main results show the efficiency of the tested model to predict the flame front position and temperature in every tested condition, as well as the importance of reactions typical of atmospheric chemistry in the prediction of cool flame occurrence. The agreement on the fuel and major products is overall good, except for methanol, highlighting some missing kinetic pathways for the DME/O2/O3 system, possibly linked to the direct addition of atomic oxygen on the fuel radical, modifying the product distribution after the cool flame.

Isomer-sensitive characterization of low temperature oxidation reaction products by coupling a jet-stirred reactor to an electron/ion coincidence spectrometer: case of n-pentane.

Through the use of tunable vacuum ultraviolet light generated by the DESIRS VUV synchrotron beamline, a jet-stirred reactor was coupled for the first time to an advanced photoionization mass spectrometer based upon a double imaging PhotoElectron PhotoIon COincidence (i2PEPICO) scheme. This new coupling was used to investigate the low-temperature oxidation of n-pentane, a prototype molecule for gasoline or diesel fuels. Experiments were performed under quasi-atmospheric pressure (1.1 bar) with a residence time of 3 s for two equivalence ratios (1/3 and 0.5) with a fuel initial mole fraction of 0.01. The measured time-of-flight mass spectra are in good agreement with those previously obtained with other photoionization mass spectrometers and, like those previous ones, display several m/z peaks for which the related species assignation is ambiguous. This paper shows how the analysis of the coincident mass-tagged Threshold PhotoElectron Spectra (TPES) together with first principle computations, consisting of the determination of the adiabatic ionization energies and the spectra of some products, may assist products' identification. The results mostly confirm those previously obtained by photoionization mass spectrometry and gas chromatography, but also allow a more accurate estimation of the 1-pentene/2-pentene mole fraction ratio. Our data also indicate a higher formation of acetone and methyl ethyl ketone than what is predicted by current models, as well as the presence of products that were not previously taken into account, such as methoxyacetylene, methyl vinyl ketone or furanone. The formation of three, four and five membered ring cyclic ethers is confirmed along with linear ketones: 2- and 3-pentanone. A significant general trend in indicating higher amounts of ketones than are indicated by gas chromatography is noted. Finally, TPES of alkenylhydroperoxides are also provided for the first time and constrains on the isomers identification are provided.

Advancing Lignocellulosic Biomass Fractionation through Molten Salt Hydrates: Catalyst-Enhanced Pretreatment for Sustainable Biorefineries.

Developing a process that performs the lignocellulosic biomass fractionation under milder conditions simultaneously with the depolymerization and/or the upgrading of all fractions is fundamental for the economic viability of future lignin-first biorefineries. The molten salt hydrates (MSH) with homogeneous or heterogeneous catalysts are a potential alternative to biomass pretreatment that promotes cellulose's dissolution and its conversion to different platform molecules while keeping the lignin reactivity. This review investigates the fractionation of lignocellulosic biomass using MSH to produce chemicals and fuels. First, the MSH properties and applications are discussed. In particular, the use of MSH in cellulose dissolution and hydrolysis for producing high-value chemicals and fuels is presented. Then, the biomass treatment with MSH is discussed. Different strategies for preventing sugar degradation, such as biphasic media, adsorbents, and precipitation, are contrasted. The potential for valorizing isolated lignin from the pretreatment with MSH is debated. Finally, challenges and limitations in utilizing MSH for biomass valorization are discussed, and future developments are presented. Cellulose Avicel®PH-101 ZnCl2 ⋅ 4H2O, ZnBr2 ⋅ 4H2O, LiCl ⋅ 8H2O, LiBr ⋅ 4H2O H2SO4, (0.2 M); H3PW12O40 (0.067 M); H4SiW12O40 (0.05 M) T (145-175 °C); Time (30-120 min) Organic solvent (MIBK) LA (94 %) and HMF (3.4 %) Dissolution time: ZnBr2 ⋅ 4H2O<>2O<>2 ⋅ 4H2O<>2O; The highest conversion of pretreated cellulose and yield of glucose were obtained with ZnBr2 ⋅ 4H2O (88 % and 80 %, respectively).

Experimental evidence for the elusive ketohydroperoxide pathway and the formation of glyoxal in ethylene ozonolysis.

Despite decades of research on alkene ozonolysis, the kinetic network of the archetypal case of ethylene (CH2CH2) with ozone (O3) still lacks consensus. In this work, experimental evidence of an elusive diradical pathway is provided through the detection of the 2-hydroperoxyacetaldehyde ketohydroperoxide and its decomposition product, glyoxal.