Photoionization Mass Spectrometry Research Articles

Pyrolysis and kinetic modeling study of tetramethylethylenediamine: A potential green propellant

Tetramethylethylenediamine (TMEDA) is a promising green propellant that has been studied as a substitute for hydrazine. An in-depth study of the TMEDA thermal decomposition mechanism is important for future applications in engines. In this work, pyrolysis experiments of TMEDA were carried out in an atmospheric jet-stirred reactor (JSR) from 610 to 1000 K. Abundant intermediate species were analyzed and quantified by synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) and gas chromatography (GC). The results show that the pyrolysis of TMEDA mainly produces hydrocarbons, amines, imines, and nitriles, among which HCN and C2H5N are the main nitrogen-containing intermediates. Based on the experimental results, a detailed chemical kinetic model for describing the thermal decomposition of TMEDA was updated to improve predictions. The updated model can satisfactorily predict the consumption of TMEDA and the generation of most intermediates. Furthermore, detailed experimental measurements combined with kinetic analysis are used to clarify the decomposition reaction pathways of TMEDA. The rate of production (ROP) analysis indicates that unimolecular C-C bond dissociation is one of the leading consumption pathways of TMEDA, forming the (CH3)2NCH2 radical. In addition, the H-atom abstraction reactions involving CH3 radicals formed by the C-N bond dissociation of (CH3)2NCH2 radicals further promote the consumption of TMEDA. Sensitivity analysis highlights that the unimolecular C-C bond dissociation reaction of TMEDA and the reactions involving CH3 radicals mainly control the pyrolysis behavior of TMEDA. The detailed experimental results and kinetic analysis in this work are expected to contribute valuable references to further research on the combustion mechanism of TMEDA.

Chemical insights into plasma-assisted dry reforming of methane in a nanosecond discharge

The present study explores the chemical kinetics of plasma-assisted dry reforming of methane (340 K, 30 Torr) in a flow reactor activated by a nanosecond pulsed dielectric barrier discharge (DBD). Experiments are conducted with the inlet CO2/CH4 mol ratios varying from 0.4 to 2.8 in CH4/CO2/Ar mixture. Synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) is employed for detailed species measurement of the ions, radicals, and molecules in this system. Eight ions are observed, including CH3+, O+, CH4+, Ar2+, CO+, C2H4+, Ar+, and CO2+. The identification of several intermediate species and products are achieved based on the photoionization efficiency (PIE) spectra, such as methyl radical (CH3), water (H2O), acetylene (C2H2), carbon monoxide (CO), ethylene (C2H4), formaldehyde (CH2O), methanol (CH3OH), ketene (CH2CO), and acetone (CH3COCH3). Species mole fraction profiles as a function of inlet CO2 concentrations are obtained. The present work provides a unique dataset and enriches our understanding of the kinetics of plasma-assisted dry reforming of methane. A kinetic mechanism incorporating plasma reactions and combustion reactions is developed for this system, and its prediction performance of the product selectivity is validated against the experimental data. The main reaction pathways for the consumption of CH4 and CO2 and the formation of products and intermediates are indicated based on the rate of production (ROP) analysis. The ionic reactions are predominant for CH4 consumption, leading to CH4+ and CH5+, while CH4 reactions with electrons and Ar* contribute to CH2 and CH3 formation. CO2 mainly reacts with electrons and Ar*, producing CO, and can also undergo reactions with CH4+ and CH5+, forming HCO2+. The principal formation pathways for H2, CO, CH2O, and CH3OH are discussed. A competition between the discharge pathways and oxygen-containing pathways in CH4/CO2/Ar plasma is proposed.

Revealing the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene sensitized by dimethyl ether

Low to moderate temperature oxidation has been a vital topic in the combustion chemistry due to its critical role in controlling the combustion characteristics such as autoignition and pollutant emissions. Low temperature oxidation kinetics of alkanes and oxygenated biofuels have been widely explored, while that of branched aromatics is poorly understood. This work aims to investigate the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene (TMB, C9H12), which is a multi-branched alkylbenzene with weak low temperature oxidation reactivity. To enhance the low temperature oxidation reactivity of TMB, dimethyl ether (DME) was added to efficiently provide chain initiators. The oxidation experiment of TMB/DME mixture was performed with an atmospheric jet stirred reactor coupled with synchrotron vacuum ultraviolet radiation photoionization mass spectrometry. The negative temperature coefficient (NTC) behavior, as well as featured aromatic intermediates, especially phenyl hydroperoxides and unexpected highly oxygenated molecules (HOMs), were observed in the experiment. The detection of these fingerprint aromatic intermediates provide crucial evidence for revealing the low to moderate oxidation kinetics of TMB. In addition, a kinetic model was developed to provide in-depth kinetic analysis. The results demonstrate that the active chain initiators produced from DME oxidation trigger the low temperature chain-branching reactions of TMB. The chain recycling process is further sustained due to the regeneration of active intermediates such as phenyl hydroperoxides and •OH radicals. Aromatic intermediates with chemical compositions of C9H12Ox and C9H10Ox were measured and identified to be key indicators for the low temperature chemistry of TMB. In particular, the aromatic HOMs (C9H12O6 and C9H10O5) are fingerprint intermediates produced from the third O2 addition and subsequent reactions of TMB. Besides, the sensitivity analysis indicates that the interaction kinetics between TMB and DME by sharing the highly sensitive reactions of hydroperoxides and •OH radicals. The present work extends the conceptual reaction schemes proposed in alkanes towards branched aromatics, especially sequential O2 addition reactions that contributing to the formation of phenyl hydroperoxides and HOMs.

Unveiling radical pathways in the pyrolysis of eugenol: Experimental and computational insights

Understanding the lignin pyrolysis mechanism holds significant importance for enhancing thermochemical conversion processes and advancing the refinement of biofuels. In this paper, a mechanism study was conducted on the pyrolysis of eugenol within the temperature range of 450 to 750 °C, utilizing synchrotron photoionization mass spectrometry coupled with density functional theory. 5-allyl-2-hydroxyphenoxyl radical (m/z 149) and other major radicals were detected experimentally during eugenol pyrolysis for the first time. The cleavage of the O-CH3 bond was confirmed as the main initial unimolecular pyrolysis pathway compared with other hemolysis and isomerization reactions. Radical-assisted bimolecular reactions initiated by CH3 and H atoms, such as ipso substitution and abstraction reactions, were well discussed. Radical-assisted abstractions made the most contribution to the formation of main radicals and products at high temperatures. Furthermore, quinone-type products were determined and their formation pathways were discussed. This research provides insights into eugenol pyrolysis, shedding light on the fundamental mechanisms of thermochemical conversion of lignin.

Experimental and theoretical study of cyclopropanated fuel exo,exo-Tetracyclo[3.3.1.02,4.06,8]nonane pyrolysis in a jet-stirred reactor

Exo,exo-Tetracyclo[3.3.1.02,4.06,8]nonane (exo-TCN), a kind of cyclopropanated fuel with high tension three-membered ring, which has the characteristics of high density, high net heat of combustion and good low-temperature performance, is a potential high-energy-density liquid fuel. To deeply understand its combustion behavior, and lay a foundation for practical application, detailed experimental and theoretical study is necessary. The pyrolysis of exo-TCN was investigated in a jet-stirred reactor at a temperature range of 500–1010 K under atmospheric pressure with a residence time of 2 s. 54 products and intermediates ranging from m/z = 2–204 were identified and quantified by synchrotron vacuum ultraviolet photoionization mass spectrometry and online gas chromatography, the major products were hydrogen, ethylene, benzene, methane, propene, toluene and styrene. The potential energy surfaces of exo-TCN unimolecular decomposition reactions were calculated by quantum chemistry at CBS-QB3 level. It is found that the pyrolysis of exo-TCN experiences three stages. In the first stage, exo-TCN isomerizes into Tricyclo[3.3.1.02,4]non-6-ene (TCN-6) by ring expansion of the three-membered ring. In the second stage, TCN-6 generates two main isomers through ring expansion reactions, and decomposes into pyrolysis products. The third stage is the secondary reaction of the intermediate products. Finally, combined with the experimental results and theoretical calculation, the possible reaction mechanism of exo-TCN pyrolysis was proposed, and the related reaction rate constants were calculated.

Experimental and modeling study of the N, N-dimethylformamide pyrolysis at atmospheric pressure

As a polar solvent, N, N-Dimethylformamide (DMF) is a potential source of volatile organic compounds during industrial processing. The potential energy surface and pressure-dependent rate coefficients of DMF primary and secondary thermal decomposition were theoretically investigated by automatic ab initio calculations. A singlet aminohydroxycarbene route generating CO is found to be the most energetically favored channel among the unimolecular initiation reactions with a tight transition state. A kinetic model was proposed for DMF pyrolysis prediction and validated against the speciation data newly obtained from synchrotron vacuum ultraviolet photoionization mass spectrometry in a flow reactor within 773 K–1048 K and literature data in a jet stirred reactor within 450 K–900 K at atmospheric pressure. Satisfactory agreements were obtained for the major intermediates and products, but the model failed to capture the formation of some oxygenated compounds, possibly due to the missing reaction pathway for bimolecular addition. During pyrolysis, DMF is mainly consumed by the hydrogen abstraction reaction as the relatively high CN bond energy hinders the barrierless homolytic cleavage. Unlike aldehydes where the carbonyl site is favored, H-abstraction from DMF methyl sites is prevalent, although the acylamino group readily undergoes decarbonylation and β-scission forming oxygenated and nitrogenous parts. Consequently, CO and HCN are the major pyrolysis products. Besides, by incorporating essential high temperature kinetics, extended validation was conducted against the available intermediate temperature autoignition delay times (1000–1350 K, 2 bar) and laminar burning velocity data, and the reason for the discrepancy between the model prediction and experiments was inferred according to the sensitivity analyses.

Pyrolysis of Cyclohexane and 1-Hexene at High Temperatures and Pressures—A Photoionization Mass Spectrometry Study

Pyrolysis of Cyclohexane and 1-Hexene at High Temperatures and Pressures—A Photoionization Mass Spectrometry Study

Pyrolysis study of moxa floss with different storage years using online photoionization mass spectrometry

The pyrolysis behaviors of moxa floss with 5–9 storage years were investigated by thermogravimetry (TG) and online synchrotron radiation photoionization mass spectrometry. The online fragment-free mass spectra of moxa floss pyrolysis products were obtained within 300–800 ℃ and characterized as hydrocarbons, nitrogenous and oxygenated compounds. The results indicate that pyrolysis temperature plays a leading role in the low-molecular-weight product distribution, while the storage year has secondary effects. Controlling the pyrolysis temperature in a lower range (<650 ℃) can effectively reduce the generation of benzene, toluene and other harmful substances. Aromatics could be released from the break of large molecules with aromatic structures and formed from the aromatization of small unstructured compounds at high temperatures. At the temperature lower than 400 ℃, short-year samples exhibit a higher intensity of oxygenated compounds. However, with the increase of storage years, nitrogenous heterocyclics such as pyrrole and pyridine are preferably formed at higher temperatures. In addition, increasing the storage year of moxa floss leads the TG curve to exhibit a lower maximum mass loss rate. These results will enrich the understanding of the storage year effect on the beneficial oxygen-containing components generation and the release of harmful components in the moxa floss pyrolysis.

A VUV photoionization study on the gas-phase synthesis of the first five-membered carbon ring - C7H6 isomers

Utilizing synchrotron photoionization and molecular-beam mass spectrometry methodologies, this investigation deciphered the gas-phase reaction of propargyl with vinylacetylene by employing a high-temperature micro reactor within a time scale of tens to hundreds of microseconds, thereby precluding interference from secondary reactions. One of the typical C5-membered cyclic structures, fulvenallene, along with its isomers 1-ethynyl-1,3-cyclopentadiene and 5-ethynyl-1,3-cyclopentadiene, were synthesized. The latter two isomers were detected and identified for the first time within the confines of our experiments. The detailed formation mechanisms of these C7H6 isomers were meticulously examined with the incorporation of quantum computations on the potential energy surfaces and rate constants.

Experimental and Modeling Investigation on the Pyrolysis of n-C10H22 Initiated by C2H5NO2

ABSTRACT To investigate the mechanism of the nitro-alkanes initiation effect on the pyrolysis of hydrocarbons, pyrolysis experiments were conducted on n-C10H22, C2H5NO2, and a binary mixture of both compounds using synchronous vacuum ultraviolet photoionization mass spectrometry. These experiments were performed within a heated flow tube under varying pressure conditions of 30 and 760 Torr. Identifying and measuring pyrolysis species, comprising stable species and radicals, provides insights into the mechanism underlying the pyrolysis and the interaction of n-C10H22 and C2H5NO2. The findings demonstrate that C2H5NO2 can reduce the initial decomposition temperature of n-C10H22, and the acceleration effect on pyrolysis becomes more pronounced with an increase in experimental pressure. The addition of C2H5NO2 also affects the distribution of alkanes, alkenes, dienes, and alkynes. A detailed elementary reaction-dynamics model comprising 223 species and 1730 reactions was established and used to simulate the distribution of C2H5NO2, n-C10H22, major species, and significant intermediates observed in the experiments. The results prove that the developed model exhibits good accuracy in predicting experimental results and enables a detailed analysis of the initiation mechanism of C2H5NO2 on n-C10H22. The impact of C2H5NO2 on the conversion rate and selectivity of pyrolysis products of n-C10H22 is highlighted and elucidated.

Online Exploring the Gaseous Oil Fumes from Oleic Acid Thermal Oxidation by Synchrotron Radiation Photoionization Mass Spectrometry.

Cooking oil fumes are an intricate and dynamic mixture containing a variety of poisonous and hazardous substances, and their real-time study remains challenging. Based on tunable synchrotron radiation photoionization mass spectrometry (SR-PIMS), isomeric/isobaric compounds in the gaseous oil fumes from oleic acid thermal oxidation were determined in real time and distinguished by photoionization efficiency (PIE) curve simulation combined with multiple linear regression (MLR) analysis. A series of common carcinogens such as formaldehyde, acetaldehyde, acrolein, and several unreported chemicals including diethyl ether and formylcyclohexane were successfully characterized. Moreover, time-resolved profiles of certain components in gaseous oil fumes were monitored for 55 h. Distinct evolutionary processes were observed, indicating the consumption and formation of parent molecules, intermediates, and final products.

Recycling of fiber reinforced composites: Online mass spectrometric tracing, offline physicochemical speciation and toxicological evaluation of a pilot plant pyrolytic conversion

The increasing demand for lightweight materials with exceptional stability and durability has resulted in a significant rise in fiber-reinforced plastic (FRP) production. These materials find applications in various fields. However, the exceptional properties and diverse compositional range of FRPs pose challenges to conventional recycling strategies. Pyrolysis has emerged as a highly promising approach for separating the fibers from the polymer matrix. In this study, we employed thermal analysis coupled with high-resolution mass spectrometry to investigate the pyrolysis process. Representative FRP showed a starting decomposition temperature of 300 °C and bisphenol A, styrene, alkenes, and phenols could be identified. The identified parameters were used to operate a pilot plant with a capacity of up to 50 kg/h FRP, and reactor products were directly analyzed with soft photoionization mass spectrometry. The findings demonstrated good agreement between the pilot plant results and laboratory experiments, particularly for smaller compounds (m/z<200). The non-condensable fraction showed a range of 17 to 22 MJ/m3 as lower heating value. Analysis of the recovered fibers (diameter between 6.20 and 8.05 μm) revealed residual coke, but no toxic fibers were detected, according to the World Health Organization's definition. Yet, the organic coating of the fibers contained small amounts of potentially harmful PAHs. A toxicological assessment using a multicellular in vitro model confirmed the low hazardous potential of the recovered fibers. The findings contribute to developing sustainable and environmentally friendly recycling strategies for FRP while addressing important aspects related to the safety and toxicological implications of the resulting chemicals and fibers.

Potassium regulating electronic state of zirconia supported palladium catalyst and hydrogen spillover for improved acetylene hydrogenation

High-selectivity acetylene hydrogenation to produce ethylene is an important issue of removing acetylene impurity in ethylene for industrial polyethylene production. Developing high-efficiency catalyst with excellent ethylene selectivity and catalytic durability is desirable but still challenging. In this work, potassium doped palladium catalysts supported on zirconia with different K contents (Pd/ZrO2-xK) have been developed to catalyze acetylene hydrogenation, the Pd/ZrO2-16K exhibits impressive catalytic performance with acetylene conversion of 100 %, ethylene selectivity of 81 % and high catalytic durability. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), in situ synchrotron radiation photoionization mass spectrometry (SR-PIMS) and density functional theory (DFT) calculations reveal that K doping effectively weakens the adsorption of ethylene by regulating the electronic state of catalyst to improve ethylene selectivity and substantially lowers the barriers of hydrogen activation and transfer reactions to favor hydrogen spillover, thus conferring a remarkably improved durability on the Pd/ZrO2-16K catalysts.

The exploration of pyrolysis characteristics, kinetics and product distribution of Bermuda grass via TG, Py-PIMS and Shuffled Complex Evolution

The pyrolysis behaviors of biomass play an important role in understanding energy utilization. The pyrolysis characteristics, kinetics and product distribution of Bermuda grass were investigated based on thermogravimetric (TG), pyrolysis with photoionization mass spectrometry (Py-PIMS) and Shuffled Complex Evolution algorithm (SCE). The temperature range for weight loss is 450–850 K and the pyrolysis process can be classified into two regions based on the variation of activation energy, with conversion rates of 0.10–0.40 (Region Ⅰ) and 0.40–0.75 (Region Ⅱ). According to the Flynn-Wall-Ozawa (FWO) and Kissinger-Akahria-Sunose (KAS) methods, the mean activation energy values for Region Ⅰ are 126.70 kJ/mol and 124.20 kJ/mol, respectively. while the values for Region Ⅱ are 161.70 kJ/mol and 159.90 kJ/mol, respectively. Then, a three-component parallel reaction model based on the SCE algorithm was proposed and the pyrolysis kinetic parameters were optimized. The results showed the predicted values using the optimized kinetic parameters are well agreeable with experimental data, which shows that the optimized kinetic parameters and the three-component parallel reaction model may be applicable to the Bermuda grass pyrolysis. Moreover, the Py-PIMS results confirmed that the fast pyrolysis products of Bermuda grass included furan derivatives, ketones, cyclopentanones, phenols, aromatic hydrocarbons, acids and esters.

Bimolecular Reaction of Methyl-Ethyl-Substituted Criegee Intermediate with SO2.

Methyl-ethyl-substituted Criegee intermediate (MECI) is a four-carbon carbonyl oxide that is formed in the ozonolysis of some asymmetric alkenes. MECI is structurally similar to the isoprene-derived methyl vinyl ketone oxide (MVK-oxide) but lacks resonance stabilization, making it a promising candidate to help us unravel the effects of size, structure, and resonance stabilization that influence the reactivity of atmospherically important, highly functionalized Criegee intermediates. We present experimental and theoretical results from the first bimolecular study of MECI in its reaction with SO2, a reaction that shows significant sensitivity to the Criegee intermediate structure. Using multiplexed photoionization mass spectrometry, we obtain a rate coefficient of (1.3 ± 0.3) × 10-10 cm3 s-1 (95% confidence limits, 298 K, 10 Torr) and demonstrate the formation of SO3 under our experimental conditions. Through high-level theory, we explore the effect of Criegee intermediate structure on the minimum energy pathways for their reactions with SO2 and obtain modified Arrhenius fits to our predictions for the reaction of both syn and anti conformers of MECI with SO2 (ksyn = 4.42 × 1011 T-7.80exp(-1401/T) cm3 s-1 and kanti = 1.26 × 1011 T-7.55exp(-1397/T) cm3 s-1). Our experimental and theoretical rate coefficients (which are in reasonable agreement at 298 K) show that the reaction of MECI with SO2 is significantly faster than MVK-oxide + SO2, demonstrating the substantial effect of resonance stabilization on Criegee intermediate reactivity.

Accurate Prediction of Adiabatic Ionization Energies for PAHs and Substituted Analogues.

The accurate calculation of adiabatic ionization energies (AIEs) for polycyclic aromatic hydrocarbons (PAHs) and their substituted analogues is essential for understanding their electronic properties, reactivity, stability, and environmental/health implications. This study demonstrates that the M06-2X density functional theory method excels in predicting the AIEs of polycyclic aromatic hydrocarbons and related molecules, rivaling the (R)CCSD(T)-F12 method in terms of accuracy. These findings suggest that M06-2X, coupled with an appropriate basis set, represents a reliable and efficient method for studying polycyclic aromatic hydrocarbons and related molecules, aligning well with the experimental techniques. The set of molecules examined in this work encompasses numerous polycyclic aromatic hydrocarbons from m/z 67 up to m/z 1,176, containing heteroatoms that may be found in biofuels or nucleic acid bases, making the results highly relevant for photoionization experiments and mass spectrometry. For coronene-derivative molecular species with the C6n2H6n chemical formula, we give an expression to predict their AIEs (AIE (n) = 4.359 + 4.8743n-0.72057, in eV) upon extending the π-aromatic cloud until reaching graphene. In the long term, the application of this method is anticipated to contribute to a deeper understanding of the relationships between PAHs and graphene, guiding research in materials science and electronic applications and serving as a valuable tool for validating theoretical calculation methods.

A study on the pyrolysis of n-hexane initiated by 1-nitropropane: Molecular dynamics simulations and SVUV-PIMS experiments

To investigate the influence of 1-nitropropane (1-NP) initiator on the pyrolysis of n-hexane (n-C6H14), molecular dynamics (MD) simulations and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) experiments were used to analyze the pyrolysis processes of n-C6H14 and n-C6H14 with 10 % 1-NP added. ReaxFF MD simulations were used to analyze the pyrolysis rates and product distributions of n-C6H14 and 1-NP/n-C6H14 at different temperatures. The mechanism of action of n-C6H14 pyrolysis initiated by 1-NP was investigated. Additionally, the pyrolysis products of n-C6H14 and 1-NP/n-C6H14 were identified and quantitatively analyzed using the SVUV-PIMS technique. These experimental results were compared with the ReaxFF MD simulation results to validate the reliability of the simulations and to complement each other. The results indicate that the presence of 1-NP promotes the pyrolysis of n-C6H14 and significantly improves the chemical heat sink of the fuel. The chemical heat sink in the 1-NP/n-C6H14 system differs from that in the n-C6H14 system by 28.78 kJ/kg at 2103 K. A significant increase in C2H4 production in the pyrolysis products of n-C6H14 with the addition of 1-NP. The pyrolysis of 1-NP/n-C6H14 yielded approximately twice as much C2H4 as n-C6H14 at 2103 K. The pyrolysis reactions were described by first-order kinetics, and the activation energy for the pyrolysis of 1-NP/n-C6H14 was determined to be 140 kJ/mol, approximately 48 % lower than that of n-C6H14. The composition of the pyrolysis products was confirmed by SVUV-PIMS experiments, which were in good agreement with the ReaxFF MD simulations. The mechanism of pyrolysis of n-C6H14 initiated by 1-NP was elucidated: the NO2 radicals generated by 1-NP react with H radicals of the system to form OH radicals. The primary reaction of n-C6H14 involves the abstraction of H by OH, leading to the formation of C6H13. Subsequently, C6H13 is further decomposed to form 1-C3H7, 1-C4H8, 1-C5H10 and 2-C6H12.

EC/OC-Analysis coupled to Photoionization Mass Spectrometry: A novel approach to the composition of particular matter for epidemiological studies

EC/OC-Analysis coupled to Photoionization Mass Spectrometry: A novel approach to the composition of particular matter for epidemiological studies

Methyl radical chemistry in non-oxidative methane activation over metal single sites

Molybdenum supported on zeolites has been extensively studied as a catalyst for methane dehydroaromatization. Despite significant progress, the actual intermediates and particularly the first C-C bond formation have not yet been elucidated. Herein we report evolution of methyl radicals during non-oxidative methane activation over molybdenum single sites, which leads selectively to value-added chemicals. Operando X-ray absorption spectroscopy and online synchrotron vacuum ultraviolet photoionization mass spectroscopy in combination with electron microscopy and density functional theory calculations reveal the essential role of molybdenum single sites in the generation of methyl radicals and that the formation rate of methyl radicals is linearly correlated with the number of molybdenum single sites. Methyl radicals transform to ethane in the gas phase, which readily dehydrogenates to ethylene in the absence of zeolites. This is essentially similar to the reaction pathway over the previously reported SiO2 lattice-confined single site iron catalyst. However, the availability of a zeolite, either in a physical mixture or as a support, directs the subsequent reaction pathway towards aromatization within the zeolite confined pores, resulting in benzene as the dominant hydrocarbon product. The findings reveal that methyl radical chemistry could be a general feature for metal single site catalysis regardless of the support (either zeolites MCM-22 and ZSM-5 or SiO2) whereas the reaction over aggregated molybdenum carbide nanoparticles likely facilitates carbon deposition through surface C-C coupling. These findings allow furthering the fundamental insights into non-oxidative methane conversion to value-added chemicals.

Study on the thermal oxidation of oleic, linoleic and linolenic acids by synchrotron radiation photoionization mass spectrometry.

Cooking oil fumes contain numerous hazardous and carcinogenic chemicals, posing potential threats to human health. However, the sources of these species remain ambiguous, impeding health risk assessment, pollution control and mechanism research. To address this issue, the thermal oxidation of three common unsaturated fatty acids (UFAs), namely oleic, linoleic and linolenic acids, present in vegetable oils was investigated. The volatile and semi-volatile products were comprehensively characterized by online synchrotron radiation photoionization mass spectrometry (SR-PIMS) with two modes, which were validated and complemented using offline gas chromatography (GC)/MS methods. Tunable SR-PIMS combined with photoionization efficiency curve simulation enabled the recognition of isomers/isobars in gaseous fumes. SR-PIMS revealed over 100 products, including aldehydes, alkenes, furans, aromatic hydrocarbons, etc., such as small molecules of formaldehyde, acetaldehyde, acrolein, ethylene and furan, which are not readily detected by conventional GC/MS; and some unreported fractions, e.g. ketene, 4-ethylcyclohexene and cycloundecene(E), were also observed. Furthermore, real-time monitoring of product emissions during the thermal oxidation of the three UFAs via SR-PIMS revealed that linolenic acid may be the major source of acrolein. SR-PIMS has been demonstrated as a powerful technique for online investigation of cooking oil fumes. This study achieved comprehensive characterization of volatile and semi-volatile products from the thermal oxidation of oleic, linoleic and linolenic acids, facilitating the traceability of species in cooking fumes and aiding in exploring the thermal reactions of different vegetable oils.