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Microkinetic modeling of heterogeneous catalysis serves as an efficient tool bridging atom-scale first-principles calculations and macroscale industrial reactor simulations. Fundamental understanding of the microkinetic mechanism relies on a combination of experimental and theoretical studies. This Perspective presents an overview of the latest progress of experimental and microkinetic modeling approaches applied to gas-solid catalytic kinetics. Then, opportunities and challenges are presented based on recent research progress in gas-solid catalysis and combustion chemistry. For experimental approaches, the importance of ideal catalytic reactors, structured catalysts, and precise elementary rate measurements is emphasized. Additionally, integrating spatiotemporally resolved operando gas-phase diagnostics with surface-adsorbed species characterization methods offers new opportunities for gaining deeper insights into gas-surface reactions. In microkinetic modeling, a hybrid rate parameter evaluation approach that combines first-principles calculations with semiempirical methods, followed by automated mechanism generation and data-driven optimization, opens new avenues for efficiently constructing surface mechanisms. Furthermore, extending microkinetic modeling beyond mean-field approximations allows simulations under realistic catalyst operating conditions. Finally, the critical role of gas-phase mechanisms and comprehensive microkinetic modeling analyses in advancing our fundamental understanding of gas-solid catalytic processes is highlighted.

Orthocarboxylic acids─organic molecules carrying three hydroxyl groups at the same carbon atom─have been distinguished as vital reactive intermediates by the atmospheric science and physical (organic) chemistry communities as transients in the atmospheric aerosol cycle. Predicted short lifetimes and their tendency to dehydrate to a carboxylic acid, free orthocarboxylic acids, signify one of the most elusive classes of organic reactive intermediates, with even the simplest representative methanetriol (CH(OH) 3 )─historically known as orthoformic acid─not previously been detected experimentally. Here, we report the first synthesis of the previously elusive methanetriol molecule in low-temperature mixed methanol (CH 3 OH) and molecular oxygen (O 2 ) ices subjected to energetic irradiation. Supported by electronic structure calculations, methanetriol was identified in the gas phase upon sublimation via isomer-selective photoionization reflectron time-of-flight mass spectrometry combined with isotopic substitution studies and the detection of photoionization fragments. The first synthesis and detection of methanetriol (CH(OH) 3 ) reveals its gas-phase stability as supported by a significant barrier hindering unimolecular decomposition. These findings progress our fundamental understanding of the chemistry and chemical bonding of methanetriol, hydroxyperoxymethane (CH 3 OOOH), and hydroxyperoxymethanol (CH 2 (OH)OOH), which are all prototype molecules in the oxidation chemistry of the atmosphere.

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.

Rationale: 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., Methods: 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., Results: 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., Conclusion: 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., (© 2023 John Wiley & Sons Ltd.)

Selective hydrogenation of carbon monoxide (CO) to higher alcohols (C 2+ OH) is a promising non-petroleum route for producing high-value chemicals, in which precise regulations of both C-O cleavage and C-C coupling are highly essential but remain great challenges. Herein, we report that highly selective CO hydrogenation to C 2-4 OH is achieved over a potassium-modified edge-rich molybdenum disulfide (MoS 2 ) catalyst, which delivers a high CO conversion of 17% with a superior C 2-4 OH selectivity of 45.2% in hydrogenated products at 240 °C and 50 bar, outperforming previously reported non-noble metal-based catalysts under similar conditions. By regulating the relative abundance of edge to basal plane, C 2-4 OH to methanol selectivity ratio can be overturned from 0.4 to 2.2. Mechanistic studies reveal that sulfur vacancies at MoS 2 edges boost carbon-chain growth by facilitating not only C-O cleavage but also C-C coupling, while potassium promotes the desorption of alcohols via electrostatic interaction with hydroxyls, thereby enabling preferential formation of C 2-4 OH., (© 2023. The Author(s).)

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 SiO 2 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 SiO 2 ) 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., (© 2023. Springer Nature Limited.)

Synthetic routes to the 10π Hückel aromatic azulene (C 10 H 8 ) molecule, the simplest polycyclic aromatic hydrocarbon carrying an adjacent five- and seven-membered ring, have been of fundamental importance due to the role of azulene - a structural isomer of naphthalene - as an essential molecular building block of saddle-shaped carbonaceous nanostructures such as curved nanographenes and nanoribbons. Here, we report on the very first gas phase preparation of azulene by probing the gas-phase reaction between two resonantly stabilized radicals, fulvenallenyl and propargyl , in a molecular beam through isomer-resolved vacuum ultraviolet photoionization mass spectrometry. Augmented by electronic structure calculations, the novel Fulvenallenyl Addition Cyclization Aromatization (FACA) reaction mechanism affords a versatile concept for introducing the azulene moiety into polycyclic aromatic systems thus facilitating an understanding of barrierless molecular mass growth processes of saddle-shaped aromatics and eventually carbonaceous nanoparticles (soot, interstellar grains) in our universe., Competing Interests: The authors declare no competing interest., (This journal is © The Royal Society of Chemistry.)

Initiators can accelerate the pyrolysis of hydrocarbon fuels, thereby reducing the required reaction temperature in the hypersonic vehicle heat exchanger/reactor. Nitro-alkanes are considered as efficient initiators due to their lower energy barrier of the C-N bond cleavage reaction. To research the mechanism of the initiation effect of nitro-alkanes on the decomposition of hydrocarbon fuel, synchrotron radiation vacuum ultraviolet photoionization-mass spectrometry (SVUV-PIMS) was employed to experimentally study the pyrolysis of n -C 10 H 22 , 1-C 3 H 7 NO 2 , and their binary mixtures in a flow tube under pressures of 30 and 760 Torr. The species identified and measured in the experiments included alkanes, alkenes, dialkenes, alkynes, nitrogen oxides, benzene, and free radicals, which revealed the mechanism of n -decane and 1-C 3 H 7 NO 2 pyrolysis, as well as the interactions of the two fuels. Experiments show that the presence of 1-C 3 H 7 NO 2 reduces the initial decomposition temperature of n -C 10 H 22 , and the increased pressures could achieve a stronger promoting effect on the conversion of n -C 10 H 22 . A detailed kinetic model containing 1769 reactions and 278 species was established and validated based on the mole fraction distributions of n -C 10 H 22 , major pyrolysis species, and important intermediates measured in pure fuel and initiated pyrolysis. The kinetic model can accurately predict the experimental data, and the mechanism of 1-C 3 H 7 NO 2 -initiated pyrolysis of n -C 10 H 22 is analyzed with the model. The effect of 1-C 3 H 7 NO 2 on the consumption of n -C 10 H 22 and selectivity of cracked products is highlighted., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Gallium-modified HZSM-5 zeolites are known to increase aromatic selectivity in methanol conversion. However, there are still disputes about the exact active sites and the aromatic formation mechanisms over Ga-modified zeolites. In this work, in situ synchrotron radiation photoionization mass spectrometry (SR-PIMS) experiments were carried out to study the behaviors of intermediates and products during methanol conversion over Ga-modified HZSM-5. The increased formaldehyde (HCHO) yield over Ga-modified HZSM-5 was found to play a key role in the increase in aromatic yields. More HCHO was deemed to be generated from the direct dehydrogenation of methanol, and Ga 2 O 3 in Ga-modified HZSM-5 was found to be the active phase. The larger increase in aromatic production over Ga-modified HZSM-5 after reduction‒oxidation treatment was found to be the result of redispersed Ga 2 O 3 with smaller size generating a larger amount of HCHO. This study provides some new insights into the internal driving force for promoting the production of aromatics over Ga-modified HZSM-5., (© 2022. The Author(s).)

Soft photoionization molecular-beam mass spectrometry (PI-MBMS) using synchrotron vacuum ultraviolet (SVUV) light has been significantly developed and applied in various fields in recent decades. Particularly, the tunability of SVUV light enables two-dimensional measurements, i.e. mass spectrum and photoionization efficiency spectrum measurements, affording isomer distinguishment in complex reaction processes. Many key intermediates have been successfully detected in combustion and catalysis reactions with the help of the state-of-the-art SVUV-PI-MBMS, promoting the understanding of the chemical mechanisms. Herein, we present a brief review of the instrumentation of beamline and PI-MBMS machines at the current synchrotron user facility Hefei Light Source II and exemplify the advantages of the SVUV-PI-MBMS method with recent applications in combustion and catalysis research, especially in probing key reaction intermediates. Future opportunities with the next generation synchrotron light source and bench-top light source have also been discussed.

Unravelling the generation of complex organic molecules (COMs) on interstellar nanoparticles (grains) is essential in establishing predictive astrochemical reaction networks and recognizing evolution stages of molecular clouds and star-forming regions. The formation of COMs has been associated with the irradiation of interstellar ices by ultraviolet photons and galactic cosmic rays. Herein, we pioneer the first incorporation of synchrotron vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry (SVUV-PI-ReTOF-MS) in laboratory astrophysics simulation experiments to afford an isomer-selective identification of key COMs (ketene (H 2 C═CO); acetaldehyde (CH 3 CHO); vinyl alcohol (H 2 C═CHOH)) based on photoionization efficiency (PIE) curves of molecules desorbing from exposed carbon monoxide-methane (CO-CH 4 ) ices. Our results demonstrate that the SVUV-PI-ReTOF-MS approach represents a versatile, rapid methodology for a comprehensive identification and explicit understanding of the complex organics produced in space simulation experiments. This methodology is expected to significantly improve the predictive nature of astrochemical models of complex organic molecules formed abiotically in deep space, including biorelated species linked to the origins-of-life topic.

Non-thermal plasma (NTP) catalysis is considered one of the most promising technologies to address a wide range of energy and environmental needs, such as carbon dioxide (CO 2 ) conversion, NH 3 synthesis, and volatile organic compounds (VOCs) removal. A systematic approach to optimizing NTP systems benefits from understanding VOCs' fundamental NTP destruction behavior and analyzing the correlations between molecular structures and conversion and selectivity. Herein, the mechanical performance of the toluene destruction in NTP is examined and compared with benzene bearing a similar molecular structure. Different experimental and theoretical techniques are applied, including synchrotron vacuum ultraviolet photoionization mass spectrometry(SVUV-PIMS), thermochemistry, and quantum chemistry. Comparatively, toluene is more readily destroyed under the same NTP conditions than benzene. More intriguingly, the distribution of the decomposition species is significantly different. The theoretical calculations reveal that the abundant methyl radicals generated in toluene decomposition mainly lead to the various species distribution. These radicals promote some reactions, such as the decomposition of o-benzoquinone, one of the key intermediates, thus leading to new reaction pathways and products different from benzene. Finally, the critical mechanistic steps of toluene decomposition under the present non-thermal plasma conditions are established, which include the interactions between toluene and electrons or reactive radicals, the cleavage of the aromatic ring, and the various reaction pathways involving of methyl radicals. This study presents an effective approach to elucidate the distinct fundamental reaction mechanisms arising from subtle structural differences, offering new insights into the underlying plasma chemistry crucial for advancing various promising environmental and energy applications of non-thermal plasma systems., Competing Interests: The authors declare that they have no conflicts of interest in this work., (© 2022 The Authors. Publishing Services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd.)

Featuring high olefin selectivity, hexagonal boron nitride (h-BN) has emerged recently as an attractive catalyst for oxidative dehydrogenation of propane (ODHP). Herein, we report that dispersion of vanadium oxide onto BN facilitates the oxyfunctionalization of BN to generate more BO x active sites to catalyze ODHP via the Eley-Rideal mechanism and concurrently produce nitric oxide to initiate additional gas-phase radical chemistry and to introduce redox VO x sites to catalyze ODHP via the Mars-van Krevelen mechanism, all of which promote the catalytic performance of BN for ODHP. As a result, loading 0.5 wt % V onto BN has doubled the yield of light alkene (C 2 -C 3 ) at 540-580 °C, and adding an appropriate concentration of NO in the reactants further enhances the catalytic performance. These results provide a potential strategy for developing efficient h-BN-based catalysts through coupling gas-phase and surface reactions for the ODHP process., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Sufficient experimental evidence has suggested that polycyclic aromatic hydrocarbons are the building blocks of carbonaceous nanostructures in combustion and circumstellar envelops of carbon-rich stars, but their fundamental formation mechanisms remain elusive. By exploring the reaction kinetics of phenylacetylene with 1-naphthyl/4-phenanthryl radicals, we provide compelling theoretical and experimental evidence for a novel and self-consistent hydrogen-abstraction phenylacetylene-addition (HAPaA) mechanism. HAPaA operates efficiently at both low and high temperatures, leading to the formation, expansion, and nucleation of peri-condensed aromatic hydrocarbons (PCAHs), which are otherwise difficult to synthesis via traditional hydrogen-abstraction acetylene/vinylacetylene-addition pathways. The HAPaA mechanism can be generalized to other α-alkynyl PCAHs and thus provides an alternative covalent bond bridge for PCAH combination via an acetylene linker. The proposed HAPaA mechanism may contribute toward a comprehensive understanding of soot formation, carbonaceous nanomaterials synthesis, and the origin and evolution of carbon in our galaxy.

Non-thermal Plasma (NTP) catalysis is considered as one of the most promising technologies to address a wide range of environmental needs, such as volatile organic compounds (VOCs) and NOx removal. To meet the updated environmental emission standard, the NTP catalysis reaction system needs to be better understood and further optimized. In this work, the degradation process of benzene in NTP, which is still regarded as a "black box" process, was explored by synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). For the first time, we observed over 20 representative species by PIMS and identified their structures accurately by photoionization efficiency (PIE) spectra. Phenol, acetylene and acrolein were recognized as the three main products. More intriguingly, concentration profiles demonstrated that a large amount of acrolein and also several higher-order products, which were usually neglected in previous research, were produced during the NTP destruction process. The details of the benzene degradation reaction mechanism, were finally established by the combination of SVUV-PIMS results, thermochemistry and theoretical calculations. This work helps to complete the mechanistic picture of plasma chemistry, which may be helpful on raveling the more complicated NTP catalysis mechanism in the future therefore contributing to design of improved NTP system for environmental applications., (Copyright © 2021 Elsevier B.V. All rights reserved.)

We study the conformers of the ethyl peroxy radical (C 2 H 5 O 2 ), the simplest peroxy radical having more than one conformer, by combining synchrotron radiation vacuum ultraviolet (VUV) photoionization mass spectrometry with theoretical calculations. The ethyl peroxy radical is formed in a microwave discharge flow tube through the reaction of the ethyl radical (C 2 H 5 ) with oxygen molecules, where C 2 H 5 is generated via the hydrogen-abstraction reaction of ethane with fluorine atoms. Two kinds of C 2 H 5 + , originating from photoionization of C 2 H 5 and from dissociative photoionization of C 2 H 5 O 2 , whose cation is not stable, have been identified and separated in photoionization mass spectra. The photoionization spectrum corresponding to C 2 H 5 O 2 is obtained and assigned with Franck-Condon calculations. The present findings show that the gauche conformer ( G -C 2 H 5 O 2 ) of C 2 H 5 O 2 has favorable Franck-Condon factors in the ionization transitions, whereas the contribution of the trans conformer ( T -C 2 H 5 O 2 ) to the photoionization spectrum is minor or negligible due to its large geometric changes in the photoionization process. Moreover, the reason for the instability of C 2 H 5 O 2 + and its detailed dissociation mechanisms have been unraveled with the aid of the calculated potential energy curves.

Atomically dispersed metal catalysts maximize atom efficiency and display unique catalytic properties compared with regular metal nanoparticles. However, achieving high reactivity while preserving high stability at appreciable loadings remains challenging. Here we solve the challenge by synergizing metal-support interactions and spatial confinement, which enables the fabrication of highly loaded atomic nickel (3.1 wt%) along with dense atomic copper grippers (8.1 wt%) on a graphitic carbon nitride support. For the semi-hydrogenation of acetylene in excess ethylene, the fabricated catalyst shows extraordinary catalytic performance in terms of activity, selectivity and stability-far superior to supported atomic nickel alone in the absence of a synergizing effect. Comprehensive characterization and theoretical calculations reveal that the active nickel site confined in two stable hydroxylated copper grippers dynamically changes by breaking the interfacial nickel-support bonds on reactant adsorption and making these bonds on product desorption. Such a dynamic effect confers high catalytic performance, providing an avenue to rationally design efficient, stable and highly loaded, yet atomically dispersed, catalysts., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

Polycyclic aromatic hydrocarbons (PAHs) play a crucial role in soot inception, interstellar evolution, and nanomaterial synthesis. Although several mechanisms, such as hydrogen-abstraction acetylene/vinylacetylene addition, have previously been proposed, PAH formation and growth are not yet fully understood. We propose an alternate PAH growth mechanism wherein propargyl radical reacts with butadiyne to form larger radicals containing newly fused aromatic rings. Butadiyne is an important intermediate in hydrocarbon oxidation and carbon rich stars, while propargyl is one of the most important resonantly stabilized radicals that persists for long times. Our proposed mechanism is validated by quantum chemical calculations, elementary reaction experiments, laminar flame analysis, and kinetic modeling. Our findings challenge the conventional wisdom that radical site regeneration, being central to PAH growth, requires sequential hydrogen elimination and/or abstraction. In our proposed mechanism, PAH growth does not depend on abundant free radical consumption, and could, therefore, help explain carbonaceous nanoparticle coalescence in radical-deficient reaction environments.

Photoionization cross sections (PICSs) for the products of the reaction from CN with toluene, including benzonitrile and o/m/p-cyanotoluene, were obtained at photon energies ranging from ionization thresholds to 14 eV by tunable synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Theoretical calculations based on the frozen-core Hartree-Fock approximation and Franck-Condon simulations were carried out to cross-verify the measured PICS. The results show that the photoionization cross sections of benzonitrile and cyanotoluene isomers are similar. The generalized charge decomposition analysis was used to investigate the components of the highest occupied molecular orbital (HOMO) and HOMO-1. It was found that the HOMO and HOMO-1 of benzonitrile and cyanotoluene isomers are dominated by the features of the benzene ring, indicating that the substitution of CN and methyl has a minor influence on the PICS of the studied molecules. The reported PICS on benzonitrile and cyanotoluene isomers in the present work could contribute to the near-threshold PIMS experiments and determine the ionization and dissociation rates in interstellar space for these crucial species. The theoretical analysis on characteristics of molecular orbitals provides clues to estimating the PICS of similar substituted aromatic compounds.

Online monitoring of the volatile compounds during the tea roasting process is crucial to find the optimum roasting conditions and improve the quality of green tea. In this work, synchrotron radiation photoionization mass spectrometry (SR-PIMS) was utilized to online monitor the evolved gaseous compounds during the tea roasting process. By virtue of "soft" ionization and fast data acquisition characteristics of SR-PIMS, dozens of aroma compounds including alcohols, aldehydes, furans, and nitrogen- and sulfur-containing species were detected and identified in real time. Moreover, 5-hydroxymethylfurfural (5-HMF), the key intermediate of Maillard reactions, was found with high sensitivity. Evolution processes of all the products could be observed via the time- and temperature-resolved profiles in N 2 and the air. Dehydration was found to be the first step during roasting. Oxygen in the air was found to accelerate the formation rate of various stable species and intermediates in the course of the thermal treatment of fresh green tea. The formation mechanisms of evolved compounds such as three sulfur-containing compounds, i.e., dimethyl sulfide, hydrogen sulfide, and methanethiol, could be proposed according to the step-by-step formation process. The time-resolved results were demonstrated to be applicable in the evaluation of different roasting processes by statistical analysis. The optimum tea roasting temperature and duration are proposed to be around 200 °C and 1000 s.

This work reports an experimental and kinetic modeling investigation on laminar premixed flame of p -xylene at 0.04 atm and equivalence ratios of 0.75, 1.0, and 1.79. Intermediates such as the p -xylyl radical, p -xylylene, and styrene, as well as polycyclic aromatic hydrocarbons (PAHs), were detected by using synchrotron vacuum ultraviolet photoionization mass spectrometry. Based on our previous aromatic kinetic model, a detailed kinetic model of p -xylene combustion was developed, and the model was validated against the present flame structure data. Model analysis work was also performed in order to reveal the important reactions in p -xylene decomposition and oxidation. The H-abstraction reactions leading to the p -xylyl radical are found to control the consumption of p -xylene in all the three flames. In the rich flame, p -xylyl mainly suffers the H-elimination and isomerization reactions, which produce p -xylylene and the o -xylyl radical, respectively. The further decomposition reactions of the o -xylyl radical contribute to the production of styrene, which is another important C 8 intermediate observed in the rich flame. In the stoichiometric and lean flames, p -xylyl mainly suffers the oxidation reactions by O, which give p -methylbenzaldehyde as major product. The growth pathways of PAHs in the rich flame were also investigated in this work. Indenyl, indene, naphthalene, and phenanthrene were observed as the abundantly produced bicyclic and tricyclic PAHs due to the existence of direct formation pathways from the decomposition of p -xylyl radical.

Direct analysis of chemical components in fresh cigarette smoke in real time is a challenging task. In this work, by using a novel continuous cigarette-pushing and smoke-introducing setup combined with synchrotron radiation photoionization mass spectrometry (SR-PIMS), the photoionization mass spectra of fresh gaseous cigarette sidestream smoke (SSS) from the combustion of solid tobacco could be recorded in real time, and the photoionization efficiency (PIE) curves of each mass peak could be obtained for the first time. Hence, lots of well-known chemical components and even isomers could be identified by their discriminated onsets or PIE curve simulation. Moreover, diimine, 2 H -azirine, and sulfur monoxide, which have never been reported in cigarette smoke, were observed in cigarette SSS, and even two intermediates, ethenol and propen-2-ol, anticipated to exist were actually observed and distinguished. To increase the qualification accuracy, a new simulation method based on multiple linear regression (MLR) was developed and applied for the PIE curve simulation, where qualification mistakes caused by subjective judgements could be eliminated as far as possible.

The pyrolysis of chlorobenzene (C 6 H 5 Cl) at 760 Torr was studied in the temperature range of 873-1223 K. The pyrolysis products including intermediates and chlorinated aromatics were detected and quantified via synchrotron radiation photoionization mass spectrometry. Furthermore, the photoionization cross sections of chlorobenzene were experimentally measured. On the basis of the experimental results, the decomposition pathways of chlorobenzene were discussed as well as the generation and consumption pathways of the main products. Benzene is the main product of chlorobenzene pyrolysis. Chlorobiphenyl (C 12 H 9 Cl), dichlorobiphenyl (C 12 H 8 Cl 2 ), and chlorotriphenylene (C 18 H 11 Cl) predominated in trace chlorinated aromatic products. Chlorobenzene decomposed initially to form two radicals [chlorophenyl (·C 6 H 4 Cl) and phenyl (·C 6 H 5 )] and the important intermediate o -benzyne ( o -C 6 H 4 ). The propagation processes of chlorinated aromatics, including polychlorinated naphthalenes and polychlorinated biphenyls, were mainly triggered by chlorobenzene, chlorophenyl, and benzene via the even-numbered-carbon growth mechanism. Besides, the small-molecule products such as acetylene (C 2 H 2 ), 1,3,5-hexatriyne (C 6 H 2 ), and diacetylene (C 4 H 2 ) were formed via the bond cleavage of o -benzyne ( o -C 6 H 4 ).

Rationale: Aromatic hydrocarbons play an important role in the formation and growth of polycyclic aromatic hydrocarbon (PAH) and soot particles. Measurements of their absolute photoionization cross-sections (PICSs), that benefit the quantitative investigation of mass spectrometry, are still lacking, however., Methods: PICSs of some aromatic hydrocarbons were measured with tunable synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Nitric oxide and benzene were chosen as standard references for PICS calibration, since their photoionization cross-sections are well documented in the literature. Binary liquid mixtures of the investigated molecules and their specific solvents were used in the measurements., Results: The investigated aromatics include naphthalene, phenanthrene, 1-methylnaphthalene, indene, 2-/3-/4-methylphenylacetylene, 2-methylindene, diphenylacetylene, 1-/2-ethynylnaphthalene and acenaphthylene. Photo-induced fragments from the molecules were also observed with increasing photon energy., Conclusions: Based on our measurements and literature data, PICSs of most aromatic molecules have very similar values beyond their ionization energies. However, molecules that contain the phenylacetylene structure have PICSs higher than other aromatics., (© 2020 John Wiley & Sons, Ltd.)

A high-pressure reactor was designed and coupled to synchrotron radiation photoionization mass spectrometry (SR-PIMS), which realizes the molecular-beam sampling and detection of gaseous products of high-pressure reactions. The reaction pressure can be controlled by varying the size of the pinhole of the pressure-bearing pipe. As tested by the Fischer-Tropsch synthesis (FTS) catalyzed by Co/SiO 2 at 230 °C, the reaction pressure of our setup can reach 1.3 MPa with a pinhole size of 50 µm and 0.16 MPa with a pinhole size of 150 µm. The FTS products were successfully online detected by SR-PIMS, and the photoionization efficiency spectra of selected products were acquired for unambiguous identification of the detected signals. Meanwhile, time-resolved SR-PIMS spectra were acquired with a temporal resolution of 10 s. The characterization results demonstrate that the product distribution (C 2 -C 4 , C 5 -C 11 , and C 12+ ) of FTS depends on the reaction pressure, where a high pressure facilitates the formation of long-chain hydrocarbons. With the advantages of detecting unstable intermediates and distinguishing isomers, this setup will be useful for fundamental studies of high-pressure heterogeneous catalytic reactions.

Although hexagonal boron nitride (h-BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas-phase methyl radicals (CH 3 . ) in the ODHP reaction over boron-based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV-PIMS), which uncovers the existence of gas-phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C-H activation of propane, while C 2 and C 1 products can be formed via both surface-mediated and gas-phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron-based catalysts., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

HCHO has been confirmed as an active intermediate in the methanol-to-hydrocarbon (MTH) reaction, and is critical for interpreting the mechanisms of coke formation. Here, HCHO was detected and quantified during the MTH process over HSAPO-34 and HZSM-5 by in situ synchrotron radiation photoionization mass spectrometry. Compared with conventional methods, excellent time-resolved profiles were obtained to study the formation and fate of HCHO, and other products during the induction, steady-state reaction, and deactivation periods. Similar formation trends of HCHO and methane, and their close correlation in yields suggest that they are derived from disproportionation of methanol at acidic sites. In the presence of Y 2 O 3 , the amount of HCHO changes, affecting the hydrogen-transfer processes of olefins into aromatics and aromatics into cokes. The yield of HCHO affects the aromatic-based cycle and the formation of ethylene, indicating that ethylene is mainly formed from the aromatic-based cycle., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Desorption electrospray ionization (DESI) mass spectrometry imaging (MSI) can simultaneously record the 2D distribution of polar biomolecules in tissue slices at ambient conditions. However, sensitivity of DESI-MSI for nonpolar compounds is restricted by low ionization efficiency and strong ion suppression. In this study, a compact postphotoionization assembly combined with DESI (DESI/PI) was developed for imaging polar and nonpolar molecules in tissue sections by switching off/on a portable krypton lamp. Compared with DESI, higher signal intensities of nonpolar compounds could be detected with DESI/PI. To further increase the ionization efficiency and transport of charged ions of DESI/PI, the desorption solvent composition and gas flow in the ionization tube were optimized. In mouse brain tissue, more than 2 orders of magnitude higher signal intensities for certain neutral biomolecules like creatine, cholesterol, and GalCer lipids were obtained by DESI/PI in the positive ion mode, compared with that of DESI. In the negative ion mode, ion yields of DESI/PI for glutamine and some lipids (HexCer, PE, and PE-O) were also increased by several-fold. Moreover, nonpolar constituents in plant tissue, such as catechins in leaf shoots of tea, could also be visualized by DESI/PI. Our results indicate that DESI/PI can expand the application field of DESI to nonpolar molecules, which is important for comprehensive imaging of biomolecules in biological tissues with moderate spatial resolution at ambient conditions.

Pyrolytic kinetics of indene was studied in a flow reactor at 30 and 760 Torr. Indene and its decomposition products, as well as polycyclic aromatic hydrocarbons (PAHs), were measured with synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Five literature models were selected to reproduce the experimental data and analyze the reaction kinetics of indene. The experimental and predicted results illustrate that an indenyl radical is the dominant decomposition intermediate and also the main contributor to the further growth of aromatic rings in the pyrolysis of indene. The indene consumption process needs further precise characterization, especially the subsequent dissociation reactions of indanyl and indenyl radicals. A self-recombination reaction of the indenyl radical and the combination reactions between indenyl and other radicals are found to be necessary for the efficient formation of large PAHs. The absence of these pathways leads to the underprediction of experimental measurements. In contrast, literature models adopting indenyl global reactions for PAH formation generally overestimate the system reactivity. Proper radical combination pathways proposed in a future model should consider not only the PAH formation efficiency but also its impact on system reactivity.

The hydrogen-deficient and oxygen-rich nature of lignocellulosic biomass prohibits effective conversions of biomass to fuels and chemicals via catalytic pyrolysis due to significant coking of the catalysts. Co-feeding of biomass feedstock with hydrogen-rich and oxygen-deficient thermoplastics could improve the process. Herein, thermal and catalytic co-pyrolysis of cellulose and polyethylene (PE) was studied via thermogravimetry combined with an online photoionization time-of-flight mass spectrometry (PI-TOF-MS). No notable synergetic effect was found in the thermal co-pyrolysis process while a considerable synergetic effect was observed during the catalytic co-pyrolysis. In the case of catalytic pyrolysis, co-feeding of cellulose with PE significantly improved the aromatic formation. Detailed reaction intermediates and products were detected by PI-TOF-MS and the process of aromatization could be ascribed to aromatization of small oxygenates and olefins, as well as Diels-Alder reaction and dehydration by HZSM-5. Moreover, this study provides a reliable tool for screening and optimizing of catalytic co-pyrolysis., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The thermal decomposition of furfural is investigated in a flow tube reactor at 30 Torr by synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) at temperatures from 1023 to 1273 K. Over 20 kinds of pyrolysis products, including short-lived radicals, stable oxygen-containing compounds, and hydrocarbons, are identified from the scanning photoionization efficiency (PIE) spectra. Vinylketene (CH 2 ═CH-CH═C═O), which has been shown to be an important primary product, is also directly observed. The possible steps of hydrogen atom addition and hydrogen atom abstraction in the thermal decomposition of furfural are studied by theoretical calculations at the CBS-QB3 level. In addition to unimolecular decomposition, hydrogen atom addition followed by ring opening can lead to the production of vinylketene.

n-Butanol is a promising renewable biofuel and has a lot of advantages as a gasoline additive compared with ethanol. Though the combustion of pure n-butanol has been extensively investigated, the chemical structures of large hydrocarbons doped with n-butanol, especially for aromatic fuels, are still insufficiently understood. In this work, rich premixed toluene/n-butanol/oxygen/argon flames were investigated at 30 Torr with synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). The blending ratio of n-butanol was varied from 0 to 50%, while the equivalence ratio was maintained at a quite rich value (1.75) for the purpose of studying the influence of n-butanol on the aromatic growth process. Flame species including radicals, reactive molecules, isomers and polycyclic aromatic hydrocarbons (PAHs) were identified and their mole fraction profiles were measured. A kinetic model of toluene/n-butanol combustion was developed from our recently reported toluene and n-butanol models. It is observed that the production of most toluene decomposition products and larger aromatics was suppressed as the blending ratio of n-butanol increases. Meanwhile, the addition of n-butanol generally enhanced the formation of most observed C2-C4 hydrocarbons and C1-C4 oxygenated species. The rate of production (ROP) analysis and experimental observations both indicate that the interaction between toluene and n-butanol in their decomposition processes mainly occurs at the formation of small intermediates, e.g. acetylene and methyl. In particular, the interaction between toluene and n-butanol in methyl formation influences the formation of large monocyclic aromatics such as ethylbenzene, styrene and phenylacetylene, making their maximum mole fractions decay slowly upon increasing the blending ratio of n-butanol compared with toluene and benzyl. The increase of the blending ratio of n-butanol reduces the formation of key PAH precursors such as benzyl, fulvenallenyl, benzene, phenyl and propargyl, which leads to a remarkable reduction in the formation of PAHs.

Rationale: The goal of this work is to employ extractive atmospheric pressure photoionization mass spectrometry (EAPPI-MS) to characterize the constituents in traditional Chinese herbal medicine (TCHM) directly without chromatographic separation., Methods: Sample was placed in 4 mL of methanol/water (v/v, 3:1) in the nebulization cell, and then the ultrasonic nebulizer was switched on. The ultrasonic nebulization system allows the simultaneous sample extraction and introduction of extract aerosols. The extract aerosols were vaporized in a transfer tube. Mixed with a gaseous dopant, vaporized analytes were ionized through ambient photon-induced ion-molecule reactions, and were mass-analyzed by high-resolution time-of-flight mass spectrometry (TOF-MS)., Results: The major ingredients including alkaloids, flavonoids, amino acids, saccarides, ginsenosides, lignans and terpenoids were readily detected. Compared with electrospray ionization (ESI), EAPPI allowed the ionization of a wider range of compounds, which is desirable for the integral characterization of TCHMs containing numerous constituents. The significant discrepancies for both alkaloids and terpenoids in tripterygium glycoside tablets from two different manufacturers could be simultaneously reflected from EAPPI mass spectra., Conclusions: Our results demonstrate that EAPPI-MS can be regarded as a supplementary ambient method for the fast and comprehensive analysis of TCHMs, which is important for the quality control and safety assurance of these products., (Copyright © 2017 John Wiley & Sons, Ltd.)

Solvent and ion source pressure were two important factors relating to the photon induced ion-molecule reactions in low pressure photoionization (LPPI). In this work, four anabolic steroids were analyzed by LPPI mass spectrometry. Both the ion species present and their relative abundances could be controlled by switching the solvent and adjusting the ion source pressure. Whereas M •+ , MH + , [M - H 2 O] + , and solvent adducts were observed in positive LPPI, [M - H] - and various oxidation products were abundant in negative LPPI. Changing the solvent greatly affected formation of the ion species in both positive and negative ion modes. The ion intensities of the solvent adduct and oxygen adduct were selectively enhanced when the ion source pressure was elevated from 68 to 800 Pa. The limit of detection could be decreased by increasing the ion source pressure. Graphical Abstract ᅟ.

Extractive atmospheric pressure photoionization (EAPPI) mass spectrometry was designed for rapid qualitative and quantitative analysis of chemicals in complex matrices. In this method, an ultrasonic nebulization system was applied to sample extraction, nebulization, and vaporization. Mixed with a gaseous dopant, vaporized analytes were ionized through ambient photon-induced ion-molecule reactions, and were mass-analyzed by a high resolution time-of-flight mass spectrometer (TOF-MS). After careful optimization and testing with pure sample solution, EAPPI was successfully applied to the fast screening of capsules, soil, natural products, and viscous compounds. Analysis was completed within a few seconds without the need for preseparation. Moreover, the quantification capability of EAPPI for matrices was evaluated by analyzing six polycyclic aromatic hydrocarbons (PAHs) in soil. The correlation coefficients (R (2) ) for standard curves of all six PAHs were above 0.99, and the detection limits were in the range of 0.16-0.34 ng/mg. In addition, EAPPI could also be used to monitor organic chemical reactions in real time. Graphical Abstract ᅟ.

An undulator-based vacuum ultraviolet (VUV) beamline (BL03U), intended for combustion chemistry studies, has been constructed at the National Synchrotron Radiation Laboratory (NSRL) in Hefei, China. The beamline is connected to the newly upgraded Hefei Light Source (HLS II), and could deliver photons in the 5-21 eV range, with a photon flux of 10(13) photons s(-1) at 10 eV when the beam current is 300 mA. The monochromator of the beamline is equipped with two gratings (200 lines mm(-1) and 400 lines mm(-1)) and its resolving power is 3900 at 7.3 eV for the 200 lines mm(-1) grating and 4200 at 14.6 eV for the 400 lines mm(-1) grating. The beamline serves three endstations which are designed for respective studies of premixed flame, fuel pyrolysis in flow reactor, and oxidation in jet-stirred reactor. Each endstation contains a reactor chamber, an ionization chamber where the molecular beam intersects with the VUV light, and a home-made reflectron time-of-flight mass spectrometer. The performance of the beamline and endstations with some preliminary results is presented here. The ability to detect reactive intermediates (e.g. H, O, OH and hydroperoxides) is advantageous in combustion chemistry research.

A novel ultrasonic nebulization extraction/low-pressure photoionization (UNE-LPPI) system has been designed and employed for the rapid mass spectrometric analysis of chemicals in matrices. An ultrasonic nebulizer was used to extract the chemicals in solid sample and nebulize the solvent in the nebulization cell. Aerosols formed by ultrasonic were evaporated by passing through a transferring tube, and desolvated chemicals were ionized by the emitted light (10.6 eV) from a Krypton discharge lamp at low pressure (∼68 Pa). First, a series of semi/non-volatile compounds with different polarities, such as polycyclic aromatic hydrocarbons (PAHs), amino acids, dipeptides, drugs, nucleic acids, alkaloids, and steroids were used to test the system. Then, the quantification capability of UNE-LPPI was checked with: 1) pure chemicals, such as 9,10-phenanthrenequinone and 1,4-naphthoquinone dissolved in solvent; 2) soil powder spiked with different amounts of phenanthrene and pyrene. For pure chemicals, the correlation coefficient (R(2)) for the standard curve of 9,10-phenanthrenequinone in the range of 3 ng-20 μg mL(-1) was 0.9922, and the measured limits of detection (LOD) was 1 ng ml(-1). In the case of soil powder, linear relationships for phenanthrene and pyrene from 10 to 400 ng mg(-1) were obtained with correlation coefficients of 0.9889 and 0.9893, respectively. At last, the feasibility of UNE-LPPI for the detection of chemicals in real matrices such as tablets and biological tissues (tea, Citrus aurantium peel and sage (Salvia officinalis) leaf) were successfully demonstrated., (Copyright © 2015 Elsevier B.V. All rights reserved.)