Transfer Learning Approach to Multitarget Temperature-Dependent Reaction Rate Prediction.

Accurate prediction of temperature-dependent reaction rate constants of organic compounds is of great importance to both atmospheric chemistry and combustion science. Extensive work has been done on developing automated mechanism generation systems but the lack of quality reaction rate data remains a huge bottleneck in the application of highly detailed mechanisms. Machine learning prediction models have been recently adopted to alleviate the data gap in thermochemistry and have great potential to do the same for kinetic data with the recent release of quality reaction rate data compilations.

Analysis of pyrolysis index and reaction mechanism in microwave-assisted ex-situ catalytic co-pyrolysis of agro-residual and plastic wastes.

Catalytic and non-catalytic microwave-assisted co-pyrolysis of biomass with plastics was performed to understand the interactions. An ex-situ configuration was adopted for performing catalytic co-pyrolysis experiments with ZSM-5 as a catalyst. Co-pyrolysis promoted cracking of vapors resulting in enhanced gas yields.

The effect of hydrogen bonding on the reactivity of OH radicals with prenol and isoprenol: a shock tube and multi-structural torsional variational transition state theory study.

The presence of two functional groups (OH and double bond) in C methyl-substituted enols (, isopentenols), such as 3-methyl-2-buten-1-ol (prenol) and 3-methyl-3-buten-1-ol (isoprenol), makes them excellent biofuel candidates as fuel additives. As OH radicals are abundant in both combustion and atmospheric environments, OH-initiated oxidation of these isopentenols over wide ranges of temperatures and pressures needs to be investigated. In alkenes, OH addition to the double bond is prominent at low temperatures (, below ∼700 K), and H-atom abstraction dominates at higher temperatures.

Yttrium stabilization and Pt addition to Pd/ZrO catalyst for the oxidation of methane in the presence of ethylene and water.

Catalytic oxidation is the most efficient method of minimizing the emissions of harmful pollutants and greenhouse gases. In this study, ZrO-supported Pd catalysts are investigated for the catalytic oxidation of methane and ethylene. Pd/YO-stabilized ZrO (Pd/YSZ) catalysts show attractive catalytic activity for methane and ethylene oxidation.

Reaction kinetics of 1,4-cyclohexadienes with OH radicals: an experimental and theoretical study.

This work presents the OH-initiated oxidation kinetics of 1,4-cyclochexadiene (1,4-CHD). The temperature dependence of the reaction was investigated by utilizing a laser flash photolysis flow reactor and laser-induced fluorescence (LPFR/LIF) technique over the temperature range of 295-438 K and a pressure of ∼50 torr. The kinetics of the reaction was followed by measuring the LIF signal of OH radicals near 308 nm.

Study of the Effect of Research Octane Number on the Auto-Ignition of Lubricant Oil Surrogates (-Hexadecane).

Engine oil is considered one of the sources for pre-ignition in downsized boosted direct injection spark-ignited engines. When interacting with fuel sprayed in the combustion chamber, engine oil forms an ignitable mixture and can cause an ignition event before firing the spark plug. Because high research octane number (RON) fuels are difficult to auto-ignite and tend to suppress the knock in an internal combustion engine, studying their interaction with engine oil is essential.

The kinetics of the reactions of Br atoms with the xylenes: an experimental and theoretical study.

This work reports the temperature dependence of the rate coefficients for the reactions of atomic bromine with the xylenes that are determined experimentally and theoretically. The experiments were carried out in a Pyrex chamber equipped with fluorescent lamps to measure the rate coefficients at temperatures from 295 K to 346 K. Experiments were made at several concentrations of oxygen to assess its potential kinetic role under atmospheric conditions and to validate comparison of our rate coefficients with those obtained by others using air as the diluent.

Noncatalytic Oxidative Coupling of Methane (OCM): Gas-Phase Reactions in a Jet Stirred Reactor (JSR).

Oxidative coupling of methane (OCM) is a promising technique for converting methane to higher hydrocarbons in a single reactor. Catalytic OCM is known to proceed via both gas-phase and surface chemical reactions. It is essential to first implement an accurate gas-phase model and then to further develop comprehensive homogeneous-heterogeneous OCM reaction networks.

Inception of Carbonaceous Nanostructures via Hydrogen-Abstraction Phenylacetylene-Addition Mechanism.

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.

Continuous Butadiyne Addition to Propargyl: A Radical-Efficient Pathway for Polycyclic Aromatic Hydrocarbons.

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.

Biomass as source for hydrochar and biochar production to recover phosphates from wastewater: A review on challenges, commercialization, and future perspectives.

Excessive phosphate run-off with total phosphorus concentration greater than 20 μg P L triggers the growth of harmful algal species in waterbodies and potentially leads to eutrophication. This has severe negative implications on aquatic environment and impacts human health. The annual economic impact of harmful algal blooms is reported to be as high as $25 million for public health and commercial fishery sector, $29 million for recreation/tourism sector and $2 million for monitoring and management.

New Particle Formation and Growth from Dimethyl Sulfide Oxidation by Hydroxyl Radicals.

Dimethyl sulfide (DMS) is produced by plankton in oceans and constitutes the largest natural emission of sulfur to the atmosphere. In this work, we examine new particle formation from the primary pathway of oxidation of gas-phase DMS by OH radicals. We particularly focus on particle growth and mass yield as studied experimentally under dry conditions using the atmospheric simulation chamber AURA.

Early Chemistry of Nicotine Degradation in Heat-Not-Burn Smoking Devices and Conventional Cigarettes: Implications for Users and Second- and Third-Hand Smokers.

Nicotine exposure results in health risks not only for smokers but also for second- and third-hand smokers. Unraveling nicotine's degradation mechanism and the harmful chemicals that are produced under different conditions is vital to assess exposure risks. We performed a theoretical study to describe the early chemistry of nicotine degradation by investigating two important reactions that nicotine can undergo: hydrogen abstraction by hydroxyl radicals and unimolecular dissociation.

Synthesis of core-shell copper-graphite submicronic particles and carbon nano-onions by spark discharges in liquid hydrocarbons.

Spark discharge in hydrocarbon liquids is considered a promising method for the synthesis of various nanomaterials, including nanocomposites. In this study, copper-carbon particles were synthesized by generating spark discharges between two Cu electrodes immersed in heptane, cyclohexane, or toluene. The synthesized particles were characterized using scanning electron microscopy, high-resolution transmission electron microscopy, and selected area electron diffraction.

Efficient alkane oxidation under combustion engine and atmospheric conditions.

Oxidation chemistry controls both combustion processes and the atmospheric transformation of volatile emissions. In combustion engines, radical species undergo isomerization reactions that allow fast addition of O. This chain reaction, termed autoxidation, is enabled by high engine temperatures, but has recently been also identified as an important source for highly oxygenated species in the atmosphere, forming organic aerosol.

Calcium Looping: On the Positive Influence of SO and the Negative Influence of HO on CO Capture by Metamorphosed Limestone-Derived Sorbents.

The CO capture performance of sorbents derived from three distinct limestones, including a metamorphosed limestone, is studied under conditions relevant for calcium looping CO capture from power plant flue gas. The combined and individual influence of flue gas HO and SO content, the influence of textural changes caused by sequential calcination/carbonation cycles, and the impact of CaSO accumulation on the sorbents' capture performance were examined using bubbling fluidized bed reactor systems. The metamorphosed limestone-derived sorbents exhibit atypical capture behavior: flue gas HO negatively influences CO capture performance, while limited sulfation can positively influence CO capture, with space time significantly impacting CO and SO co-capture performance.

A droplet reactor on a super-hydrophobic surface allows control and characterization of amyloid fibril growth.

Methods to produce protein amyloid fibrils, in vitro, and in situ structure characterization, are of primary importance in biology, medicine, and pharmacology. We first demonstrated the droplet on a super-hydrophobic substrate as the reactor to produce protein amyloid fibrils with real-time monitoring of the growth process by using combined light-sheet microscopy and thermal imaging. The molecular structures were characterized by Raman spectroscopy, X-ray diffraction and X-ray scattering.

Author Correction: Absolute spectroscopy near 7.8 μm with a comb-locked extended-cavity quantum-cascade-laser.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Synthesis of Copper and Copper Oxide Nanomaterials by Pulsed Electric Field in Water with Various Electrical Conductivities.

Nanomaterial synthesis is a hot research subject that has been extensively studied in the last two decades. Recently, plasmas in liquid systems have been proposed as an efficient means of synthesizing various types of nanomaterials. The formation processes implicate many physical and chemical phenomena that take place at the electrode surface, as well as in the plasma volume, which renders it difficult to fully understand the underlying mechanisms.

Collision Efficiency Parameter Influence on Pressure-Dependent Rate Constant Calculations Using the SS-QRRK Theory.

The system-specific quantum Rice-Ramsperger-Kassel (SS-QRRK) theory ( , , 2690) is suitable to determine rate constants below the high-pressure limit. Its current implementation allows incorporating variational effects, multidimensional tunneling, and multistructural torsional anharmonicity in rate constant calculations. Master equation solvers offer a more rigorous approach to compute pressure-dependent rate constants, but several implementations available in the literature do not incorporate the aforementioned effects.

Data Science Approach to Estimate Enthalpy of Formation of Cyclic Hydrocarbons.

In spite of increasing importance of cyclic hydrocarbons in various chemical systems, studies on the fundamental properties of these compounds, such as enthalpy of formation, are still scarce. One of the reasons for this is the fact that the estimation of the thermodynamic properties of cyclic hydrocarbon species via cost-effective computational approaches, such as group additivity (GA), has several limitations and challenges. In this study, a machine learning (ML) approach is proposed using a support vector regression (SVR) algorithm to predict the standard enthalpy of formation of cyclic hydrocarbon species.

QCL-Based Dual-Comb Spectrometer for Multi-Species Measurements at High Temperatures and High Pressures.

Rapid multi-species sensing is an overarching goal in time-resolved studies of chemical kinetics. Most current laser sources cannot achieve this goal due to their narrow spectral coverage and/or slow wavelength scanning. In this work, a novel mid-IR dual-comb spectrometer is utilized for chemical kinetic investigations.

Separation and Detection of meta- and ortho-Substituted Benzene Isomers by Using a Water-Soluble Pillar[5]arene.

Efficient and energy-saving separation of benzene isomers bearing a diverse range of functional groups is a great challenge due to their overlapping physicochemical properties. Here, we report the successfully use of a water-soluble pillar[5]arene (WP5) as a multifunctional material for the separation and detection of meta/ortho-substituted benzene isomers in water. A liquid-liquid extraction strategy was used for the separation of these benzene isomers based on their different affinity for WP5 in water.

Gas-to-Liquid Phase Transition of PAH at Flame Temperatures.

Significant evidence has shown that soot can be formed from polycyclic aromatic hydrocarbon (PAH) in combustion environments, but the transition of high molecular PAH from the gas phase to soot in a liquid or solid state remains unclear. In this study, the relationships between the boiling points of various planar PAHs and their thermodynamic properties are systematically investigated, to find a satisfactory marker for the phase transition event. Temperature-dependent thermodynamic properties, including entropy, specific heat capacity, enthalpy, and Gibbs free energy, are simultaneously calculated for PAHs, using density functional theory and three composite compound methods.

Kinetics of the benzyl + HO and benzoxyl + OH barrierless association reactions: fate of the benzyl hydroperoxide adduct under combustion and atmospheric conditions.

Radical-radical association reactions are challenging to address theoretically due to difficulties finding the bottleneck that variationally minimizes the reactive flux. For this purpose, the variable reaction coordinate (VRC) formulation of the variational transition state theory (VTST) represents an appropriate tool. In this work, we revisited the kinetics of two radical-radical association reactions of importance in combustion modelling and poly-aromatic hydrocarbon (PAH) chemistry by performing VRC calculations: benzyl + HO2 and benzoxyl + OH, both forming the adduct benzyl hydroperoxide.