Excited Radicals Research Articles

Vibrational State-Resolved Differential Cross Sections of the F + CH4 → HF + CH3 Reaction at the Collision Energies of 3.1-13.8 kcal/mol.

We report a high-resolution crossed molecular beam experiment investigating the reaction dynamics of the F + CH4 → HF + CH3 reaction across a broad range of collision energies (3.1-13.8 kcal/mol). By using time-sliced velocity map imaging within the crossed molecular beam apparatus, we obtain correlated angular distributions and branching ratios for various product pairs (CH3(ν), HF(ν')). The resolved reactive rainbow-like features that display a distinct bulge in the angular distribution in different channels reveal the formation of vibrationally ground and excited states of the methyl radical accompanied by different rovibrationally excited HF products. These findings suggest distinct reaction dynamics for channels leading to vibrationally excited methyl radicals compared to those forming ground-state methyl radicals.

Electron Attachment to the Nucleobase Uracil in Diethylene Glycol: The Signature of a Doorway.

The cellular environment plays a significant role in low energy electron-mediated radiation damage to genetic materials. In this study, we have modeled the effect of the bulk medium on electron attachment to nucleobases in diethylene glycol (DEG) using uracil as a test case, in accordance with recent experimental work on the observation of dissociative quasi-free electron attachment to nucleoside via excited anion radical in solution (in DEG). Our EOM-CCSD-based quantum mechanical/molecular mechanical (QM/MM) simulations indicate that the electron scavenging by uracil in DEG is much slower than that observed in the aqueous medium due to its viscosity. This work also establishes that a doorway mechanism exists in uracil microsolvated and bulk solvated with DEG, with the dipole-bound state and solvent-bound state acting as doorway states, respectively.

Anthraquinones as organophotoredox catalysts for atom transfer radical polymerization via sequential absorption of visible light

AbstractAnthraquinones have been used as the organophotoredox catalysts to catalyze metal‐free atom transfer radical polymerization (ATRP) under visible light irradiation. Polymers with different molecular weight and molecular weight distribution were obtained under different reaction conditions. The “living”/controlled nature of the polymerization was confirmed by the kinetic study, light on/off experiment and the block copolymer synthesis. The anthraquinones are found to catalyze ATRP via redox mechanism via sequential absorption of visible light. Evidence supported by control experiments showed that the excited anthraquinone radical anion or semiquinone anion generated by photo‐induced single electron reduction or subsequent protonation and further reduction were responsible for the initiation/activation of the polymerization.

Quantifying the thermal effect and methyl radical production in nanosecond repetitively pulsed glow discharges applied to a methane-air flame

In this work, we investigated non-equilibrium plasma produced by nanosecond repetitively pulsed glow discharges applied across a lean premixed methane-air flame. The flame is stationary, axisymmetric, and laminar. The discharges are applied on the symmetry axis crossing the reactant gases, flame front, and product gases, allowing phase-locked averaged measurements and comparisons with axisymmetric numerical simulations. The thermal effect and methyl radical production are quantified in the discharge in the reactant gas region. One-dimensional, two-beam, hybrid, femtosecond-picosecond, coherent anti-Stokes Raman scattering is used to acquire spatial and temporal profiles of temperature and oxygen-to-nitrogen concentration ratio. Photo-fragmentation laser-induced fluorescence is used to acquire quantitative two-dimensional profiles of methyl radicals in the discharge providing the first quantitative imaging of methyl produced ahead of a flame by plasma-induced methane dissociation. The spatial profiles of temperature and oxygen-to-nitrogen concentration ratio are in steady state, indicating that individual discharges have an insignificant heating effect. Upper and lower bounds of the produced mole fraction of methyl radicals in the plasma are obtained due to uncertainties in the collisional quenching rates of excited state methylidyne radicals in the plasma. The discharges produce a maximum of 600–1100 ppm of methyl radicals upstream of the flame front within 25 ns. This amount is similar to the predicted methyl mole fraction for the flame without plasma and thus represents a significant chemical perturbation to the reactants upstream of the flame front. The produced methyl follows an exponential decay in the first microsecond after the discharge with a decay constant of 8 µs close to the flame, and 0.8 µs further from the flame. The decay then deviates from the exponential curve and the methyl persists for tens of microseconds. The results suggest that for the tested configuration, the thermal effect of individual discharges through fast gas heating is negligible, while active chemical species are produced in large quantities in the reactant gases, upstream of the flame front.

Detection of vibrationally excited hyroxyl radicals by absorption of the DFB diode laser radiation at the transition (ν = 3) ← (ν = 1)

Using a DFB laser diode at 1509.3 nm the OH(v = 1) formed in the reaction O(1D) + H2O was detected by absorption at the transition (v = 3)←(v = 1). The advantage of the method is the ability to obtain reliable data on absolute concentrations of vibrationally excited radicals. The spectrum of transient absorption near Q(3/2) line of 2Π3/2 term was recorded. At a pressure of 8 Torr He, the rotation distribution was found to be in thermal equilibrium. The yields of OH(v = 1) and OH(v = 2) in the chemical reaction were determined. The rate constants of vibrational relaxation of OH(v = 1) on H2O and SF6 were measured.

Improvement of mechanical properties by cold plasma treatment of bonded surfaces

In nature, matter is found in solid, liquid or gaseous form. At very high temperatures, molecules can absorb an enormous amount of energy, causing them to move in a disordered way. With the absorbed energy, they can dissociate into atoms, and because of their disordered motion, these molecules or atoms can split into ions and electrons. Excessive heating of matter is therefore always accompanied by ionisation, leaving the medium electrically neutral. This ionised state is known as plasma. It is sometimes called the fourth state of matter. Plasmas are therefore mixtures of neutral and/or excited ions, electrons, atoms, radicals or demodules with an internal energy above the neutral state. Sources of plasma can be as follows: naturally occurring in the ionosphere; produced by nuclear reactions; generated by a hyperfrequency source; formed by direct heating followed by confinement in a region of space by a magnetic field; and produced by electrical discharges. Plasma is characterised by the state of its components: density, which is defined by the number of particles per unit volume; kinetic temperature; and degree of ionisation. Plasma can be thermal or out of thermal equilibrium, or 'cold plasma'. Cold plasma is formed, for example, when a gas passes through strong electric fields - electrons are dissociated from the molecules and the gas becomes electrically conductive and glows blue. The paper describes the equipment used to create cold plasma, which was used to treat different surfaces. After treatment, they were bonded with different adhesives and tested for tensile strenght. An improvement in the mechanical properties mentioned above was observed when the surfaces to be bonded were treated with cold plasma compared to surfaces bonded normally. When the impact of cold plasma treatment on elongation, or ε, is examined, it is found that for Fiber Wood samples, cold plasma treatment considerably boosts elongation, increasing it from 0.35% for untreated samples to 0.81% for samples treated with cold plasma. For samples that have been treated with cold plasma, the average value increases significantly from 0.03% to 0.63% when ArbofillFichte material is used. In addition, the application of cold plasma treatment to the surfaces results in an increase in the modulus of elasticity. For example, the modulus of elasticity doubles for Arbofill Fichte samples, going from 113.56MPa for untreated samples to 227.43MPa for cold plasma treated samples; for Fiber Wood, it increases from an average value of 789.52MPa for untreated samples to an average value of 931.62MPa for treated samples.

Picosecond reactions of excited radical ion super-reductants

Classical photochemistry requires nanosecond excited-state lifetimes for diffusion-controlled reactions. Excited radicals with picosecond lifetimes have been implied by numerous photoredox studies, and controversy has arisen as to whether they can actually be catalytically active. We provide direct evidence for the elusive pre-association between radical ions and substrate molecules, enabling photoinduced electron transfer beyond the diffusion limit. A strategy based on two distinct light absorbers, mimicking the natural photosystems I and II, is used to generate excited radicals, unleashing extreme reduction power and activating C(sp2)―Cl and C(sp2)―F bonds. Our findings provide a long-sought mechanistic understanding for many previous synthetically-oriented works and permit more rational future photoredox reaction development. The newly developed excitation strategy pushes the current limits of reactions based on multi-photon excitation and very short-lived but highly redox active species.

Positive cooperativity in binding: Spectroscopic characterization and dissociation energy of the anisole…(CH4)2 complex

We have previously reported on the spectroscopy and binding energy of the anisole…methane complex, which exhibits a dual mode of binding that involves both CH/O and CH/π interactions. In this work, we seek to examine cooperativity in binding through a study of the isolated anisole-(methane)2 complex, using a combination of experiments that include mass-selected two-color resonant two-photon ionization spectroscopy (2CR2PI), two-color appearance potential (2CAP) measurements, and velocity mapped ion imaging (VMI) augmented with a complementary theoretical characterization. Using 2CAP and VMI, we derive the dissociation energies of the complex in ground (S0), excited (S1), and cation radical (D0) states. The experimental values from the two methods are in excellent agreement and are compared with selected theoretical values calculated using DFT and ab initio methods. The data show that the dissociation energy increases by some 10 % for the second methane relative to the first, with this trend being consistent across all three electronic states, indicating a cooperative binding effect where the initial solvation turns on binding of a second methane onto the opposite face. This lies in contrast to the aniline-(methane)2 complex, where recent studies have shown a negativity cooperativity, and these trends are examined.

Cyclodextrin-boosted photocatalytic oxidation for efficient bisphenol A removal

Wastewater contains various high-risk trace organic pollutants, such as antibiotics and endocrine disruptors, which seriously restrict wastewater reuse. Cyclodextrin-based functional materials show great potential in the removal of trace pollutants because of their adsorption catalytic synergy. Clarifying the synergistic mechanism of cyclodextrin in oxidation is the key issue in confined catalytic oxidation process design. In this work, we fabricated a BiOIO3@BiOBr/β-CD heterojunction photocatalyst to study the synergistic mechanism of cyclodextrin in the photocatalytic oxidation process. The synergistic mechanism of cyclodextrin was investigated by combining radical chemistry, electrochemistry, spectroscopy, and time-dependent density functional theory. Results showed that the excited intermediate free radicals played an important role in promoting the photocatalytic degradation process. The heterojunction photocatalyst loaded with β-cyclodextrin (β-CD) at the electronic end (C[Cat.] = 0.2 mg/mL) removed about 97% of bisphenol A (BPA) within 30 min, and the first-order kinetic constant (kCDBIB = 0.112 min−1) was about twice that of the unloaded β-CD (kBIB = 0.057 min−1). Cyclodextrin loading improved the photocatalytic performance of the heterojunction and stimulated the intermediate to increase the free radical yield and regulate the reaction path.

Doubly Spiro-Conjugated Chiral Carbocycles Exhibiting SOMO-HOMO Inversion in Persistent Radical Cations.

Persistent chiral organic open-shell systems have captured growing interest due to their potential applications in organic spintronic and optoelectronic devices. Nevertheless, the integration of configurationally stable chirality into an organic open-shell system continues to pose challenges in molecular design. The π-extended skeleton incorporated in spiro-conjugated carbocycles can provide robust chiroptical properties and a significant stabilization of the excited and ionic radical states. However, this approach has been relatively less explored in the design of persistent organic open-shell systems. We report here the (S,S)-, (R,R)-, and meso-isomers of doubly spiro-conjugated carbocycles featuring flat and rigid carbon-bridged para-phenylenevinylene (CPV) of different conjugation lengths connected by two spiro-carbon centers, which we denote D-spiro-CPV for its quasi-dimeric structure. Our synthetic method based on a double lithiation cyclization approach enables facile production of D-spiro-CPV. D-spiro-CPVs exhibit circularly polarized luminescence (CPL) with high fluorescence quantum yields (ΦFL) resulting in a high CPL brightness of 21 M-1 cm-1 and also exhibit high thermal and photostability. The monoradical cation of D-spiro-CPV absorbing near-infrared light is notably persistent, exhibiting a half-life of 570 h under ambient conditions due to doubly spiro-conjugative stabilization. Theoretical and electrochemical studies indicate the radical cation of D-spiro-CPVs presents a non-Aufbau electron filling, exhibiting inversion of the energy level of the singly occupied molecular orbital (SOMO) and the highest (doubly) occupied molecular orbitals with the SOMO level even below the HOMO-1 level (double SHI effect). Our discoveries provide valuable insights into non-Aufbau molecules and the development of configurationally stable, optically active persistent radicals.

Activating the synergistic effect in Ni-Co bimetallic MOF for enhanced plasma-assisted ammonia synthesis

Plasma-assisted ammonia synthesis (PAAS) can produce ammonia using highly energetic, electronically excited nitrogen and Hydrogen radicals at low temperatures and atmospheric pressure, which has been regarded as a prospective alternative to the Haber − Bosch process. PAAS can exclusively use renewable power (solar, wind, etc.) to achieve green, decentralized and efficient ammonia synthesis. However, current catalysts for PAAS are suffering from low efficiency, poor stability and cyclability. Herein, we demonstrate a one-step hydrothermal synthesis of Ni-Co bimetallic metal–organic frameworks (MOFs) for PAAS. Attributed to the amplified gas transport capability and bimetallic coupling, the Ni-Co-MOF exhibits significantly improved PAAS performance: 88.21 μmol g−1·min−1, above 30 % increase over 5 wt% Ni/Al2O3. The high stability of Ni-Co-MOF under the harsh electric field enables its durable performance (36 h) and excellent cyclability (24 cycles). Finally, to determine the viability of PAAS for industrial applications, we construct a hypothetical zero-carbon ammonia plant using only renewable energy sources, and the outcomes indicate that PAAS has significant competitiveness for future ammonia production.

The Potential of Cold Plasma-Based Seed Treatments in Legume–Rhizobia Symbiotic Nitrogen Fixation: A Review

The use of cold plasma (CP) seed treatment is an emerging agricultural technology that exhibits the potential to enhance nodulation and symbiotic nitrogen fixation (SNF) in legumes. CP is composed of a diverse mixture of excited atoms, molecules, ions, and radicals that have the potential to affect the physical properties of the seed and influence gene expressions that could have a lasting impact on the nodulation, SNF, growth, and yield of legumes. The direct participation of the CP in the nodulation process and its correlation with the escalation of nodules and SNF is still not fully understood. This review discussed four areas in the nodulation and SNF process that can directly or indirectly affect CP seed treatments: root–rhizobia signal exchange pathways, root/shoot growth and development, phytohormone production, and the nitrogen fixation process. We also discuss the potential challenges and future research requirements associated with plasma technology to enhance SNF in legumes.

Experimental investigation on combustion and emission characteristics of non-premixed ammonia/hydrogen flame

The use of ammonia and hydrogen as fuels to decarbonise the heavy transport industry has attracted worldwide attention. In this work, a swirl-enhanced combustion test rig has been built to investigate the combustion and emission characteristics of non-premixed ammonia/hydrogen flames. The blowoff limits were first examined to ensure that a range of stable flames could be achieved. Emissions containing nitric oxide (NO), nitrous oxide (NO2), ammonia slip (NH3) and unburnt hydrogen (H2) were then measured with a variety of global equivalence ratios, hydrogen blending ratios, inlet gas temperature, swirl numbers and combustion chamber insulation conditions. The structure of non-premixed ammonia/hydrogen flames and the relationship between excited hydroxyl radicals (OH*) and NO emission were revealed using OH* chemiluminescence profiles. The stable non-premixed ammonia/hydrogen flames were achieved when the hydrogen blending ratio was greater than 20%. The optimal emission performance was achieved under stoichiometric conditions, as determined by combustion efficiency. The insulation conditions of the combustor wall played a key role in the emission results, as significant growth of NO and NO2 as well as a reduction of ammonia slip were found. Although a lower swirl number improved the flame stability range, the increases in NO and NO2 emissions were observed.

Effect of UV-LED Wavelength on Reactive Species Photogeneration from Dissolved Organic Matter

The photogeneration of reactive species from dissolved organic matter (DOM) plays a crucial role in the photochemical and photobiochemical processes in natural aquatic systems. However, the impact of the ultraviolet (UV) wavelength on the photogeneration of reactive species by different sources of DOM remains unclear. In this study, UV light at four wavelengths (365 nm, 310 nm, 280 nm, and 260 nm) provided by UV-LEDs were irradiated onto three types of DOM: humic acid (HA), fulvic acid (FA), and effluent organic matter (EfOM). Three reactive species produced by DOM, including excited triplet-state DOM (3DOM*), singlet oxygen (1O2), and hydroxyl radicals (•OH), were determined. UV365 proved to be the most efficient wavelength for generating 1O2 and •OH, with formation rates of 3.47 × 10−6 M s−1 and 1.67 × 10−8 M s−1, respectively, with the addition of FA and EfOM. The highest steady-state concentrations of all three reactive species were also generated under UV365, reaching 3.00 × 10−13 M (3DOM*) and 1.64 × 10−11 M (1O2) with the FA addition, and 1.44 × 10−10 M (•OH) with the EfOM. Across the different DOM sources, UV365 obtained the maximum quantum yields of reactive species, indicating the stronger effect of UV365 on inducing the photosensitization of DOM compared to the other shorter wavelengths. This study expands our understanding of the photochemistry of DOM in aquatic environments.

Polyoxometalate-dependent Photocatalytic Activity of Radical-doped Perylenediimide-based Hybrid Materials.

Inorganic-organic hybrid materials are a kind of multiduty materials with high crystallinity and definite structures, built from functional inorganic and organic components with highly tunable photochemical properties. Perylenediimides (PDIs) are a kind of strong visible light-absorbing organic dyes with π-electron-deficient planes and photochemical properties depending on their micro-environment, which provides a platform for designing tunable and efficient hybrid photocatalytic materials. Herein, four radical-doped PDI-based crystalline hybrid materials, Cl4-PDI⋅SiW12O40 (1), Cl4-PDI⋅SiMo12O40 (2), Cl4-PDI⋅PW12O40 (3), and Cl4-PDI⋅PMo12O40 (4), were attained by slow diffusion of polyoxometalates (POMs) into acidified Cl4-PDI solutions. The obtained PDI-based crystalline hybrid materials not only exhibited prominent photochromism, but also possessed reactive organic radicals under ambient conditions. Furthermore, all hybrid materials could be easily photoreduced to their radical anions (Cl4-PDI⋅-), and then underwent a second photoexcitation to form energetic excited state radical anions (Cl4-PDI⋅-*). However, experiments and theoretical calculations demonstrated that the formed energetic Cl4-PDI⋅-* showed unusual POM-dependent photocatalytic efficiencies toward the oxidative coupling of amines and the iodoperfluoroalkylation of alkenes; higher photocatalytic efficiencies were found for hybrid materials 1 (anion: SiW12O40 4-) and 2 (anion: SiMo12O40 4-) compared to 3 (anion: PW12O40 3-) and 4 (anion: PMo12O40 3-). The photocatalytic efficiencies of these hybrid materials are mainly controlled by the energy differences between the SOMO-2 level of Cl4-PDI⋅-* and the LUMO level of the POMs. The structure-photocatalytic activity relationships established in present work provide new research directions to both the photocatalysis and hybrid material fields, and will promote the integration of these areas to explore new materials with interesting properties.

Structure, variability, and origin of the low-latitude nightglow continuum between 300 and 1800 nm: evidence for HO2 emission in the near-infrared

Abstract. The Earth's mesopause region between about 75 and 105 km is characterised by chemiluminescent emission from various lines of different molecules and atoms. This emission was and is important for the study of the chemistry and dynamics in this altitude region at nighttime. However, our understanding is still very limited with respect to molecular emissions with low intensities and high line densities that are challenging to resolve. Based on 10 years of data from the astronomical X-shooter echelle spectrograph at Cerro Paranal in Chile, we have characterised in detail this nightglow (pseudo-)continuum in the wavelength range from 300 to 1800 nm. We studied the spectral features, derived continuum components with similar variability, calculated climatologies, studied the response to solar activity, and even estimated the effective emission heights. The results indicate that the nightglow continuum at Cerro Paranal essentially consists of only two components, which exhibit very different properties. The main structures of these components peak at 595 and 1510 nm. While the former was previously identified as the main peak of the FeO “orange arc” bands, the latter is a new discovery. Laboratory data and theory indicate that this feature and other structures between about 800 and at least 1800 nm are caused by emission from the low-lying A′′ and A′ states of HO2. In order to test this assumption, we performed runs with the Whole Atmosphere Community Climate Model (WACCM) with modified chemistry and found that the total intensity, layer profile, and variability indeed support this interpretation, where the excited HO2 radicals are mostly produced from the termolecular recombination of H and O2. The WACCM results for the continuum component that dominates at visual wavelengths show good agreement for FeO from the reaction of Fe and O3. However, the simulated total emission appears to be too low, which would require additional mechanisms where the variability is dominated by O3. A possible (but nevertheless insufficient) process could be the production of excited OFeOH by the reaction of FeOH and O3.

Efficacy of argon cold atmospheric pressure plasma jet on hospital surface decontamination and its impact on the surface property

The emergence of antimicrobial resistance has become a major contributor to healthcare-associated infections. Recently, the cold atmospheric pressure plasma jet (CAPJ) discharges have garnered attention of the researchers globally for their novel antimicrobial property. This research evaluated the effectiveness of an in-house developed CAPJ on the inactivation of multidrug-resistant (MDR) E. coli and S. aureus artificially inoculated over stainless steel and aluminium test surfaces. A greater than ∼5 log10 reduction of E. coli, whereas reduction of ∼3.4–4.6 log10 for S. aureus on the test surfaces was achieved on 180 s CAPJ exposure. Extremely low D- values (in the range of ∼27–63 s) were recorded for both isolates. In addition, this study assessed the impact of repeated CAPJ exposure on surface property, by replicating the process of hospital surface decontamination. Surface properties such as wettability, roughness, and elemental composition varied non-linearly on repetitive Ar CAPJ exposure on test surfaces. It was observed that the identified gas-phase species such as excited atoms (Ar I, and O I), positive ions (NO+, O2 +, OH+, O+, N2 +, Ar+, etc), negative ions (N2O2 −, N2O3 −, NO3 −, NO2 −, etc), radical RONS (OH•), and non-radical RONS (O I, NO+, OH+, N2O3 −, NO3 −, NO2 −, etc) would contribute to bacterial load reduction on the test surface along with any alteration in surface characteristic. There may be chemical and physical processes involved in the above activity. This investigation into understanding the effects of CAPJ surface decontamination on surface properties would aid in determining its potential applications in healthcare settings.

Enhancing lithium-ion battery safety: Investigating the flame-retardant efficacy of bis(2,2,2-trifluoroethyl) carbonate during ethyl methyl carbonate combustion

Bis(2,2,2-trifluoroethyl) carbonate (BtFEC) is a candidate fire suppressant for lithium-ion batteries (LIBs). The high flammability of the electrolyte is the reason behind the frequent fire incidents reported with LIBs. These incidents are due to various factors, such as a default in the conception of the battery or operational abuse. The flame-retardant effectiveness of BtFEC was investigated by measuring its effect on the oxidation of ethyl methyl carbonate (EMC), a common LIB electrolyte component. Laminar flame speed (LFS) measurements for EMC-BtFEC in air mixtures were carried out at 403 K, 1 atm, for equivalence ratios (ϕ) between 0.8 and 1.4, and with 0.5 % vol. BtFEC. Additional measurements were made at ϕ = 1.1 with BtFEC addition ranging from 0.1 up to 1.4 % vol. To further understand the combustion chemistry of the EMC-BtFEC system, ignition delay times (time at the maximum peak production of the excited radical OH*) and CO time histories were measured in a shock tube with temperatures ranging from 1217 to 1732 K, at near-atmospheric pressure (1.24–1.42 atm), and for three equivalence ratios (ϕ = 0.5, 1.0, and 2.0). These new results constitute an experimental database that was used to evaluate the performance of a model assembled for both BtFEC and EMC using previous work from our group. The updated, detailed chemical kinetics mechanism presented in this study consists of 237 species and 1630 reactions. Sensitivity, rate-of-production, and reaction pathway analyses permitted the oxidation of the BtFEC-EMC system to be described. A flame sensitivity analysis exhibited the significant effect from the reactions H + CF2O ⇆ HF + CFO and CF3 + H ⇆ CF2 + HF, which consume H radicals that are involved in the branching reaction H + O2⇆ OH + O, ultimately reducing the LFS. This study shows that improvements in the base fluorine chemistry are still necessary to obtain better agreement with the experiments, especially at the speciation level.

An experimental and kinetic study of OH(A2Σ+) formation and quenching in ammonia-hydrogen-air flames

This work provides a kinetic and experimental investigation of excited radical OH(2Σ+) (also referred to as OH*) in NH3H2-air flames. A counterflow burner is used to stabilize laminar diffusion flames over wide ranges of ammonia fraction in the fuel blend (0.2 ≤ xNH3 ≤ 0.8) and strain rate (40 ≤ a ≤ 200/s). Using an intensified camera or a spectrometer coupled to a Cassegrain optical system, spatially resolved and spatially integrated OH(A2Σ+-X2Π) chemiluminescence intensities are measured. These data are used to challenge a kinetic mechanism largely developed from existing literature schemes. Measurements and simulations show that two distinct OH* peaks exist in spatially resolved profiles for intermediate ammonia fractions in the fuel blend. Sensitivity analyses identified that reactions N2O+H=N2+OH* and H+O+M=OH*+M, respectively pertinent to NH3 and H2 oxidation routes, are responsible for the formation of OH*. The proposed kinetic mechanism gives a remarkable portrait of the empirical data recorded in diffusion flames as well as in premixed NH3H2-air flames from the literature. Nevertheless, the contribution of reaction N2O+H=N2+OH* in the formation of OH* in the peak closest to the fuel side of diffusion flames is consistently overpredicted. Consequently, the frequency factor of the N2O+HN2+OH* reaction is adjusted to A = 1.35 × 1014 cm3mol−1s−1, which significantly improves predictions of spatially integrated and spatially resolved OH* intensities for all the diffusion and premixed flames examined.

Modified surfatron device to improve microwave-plasma-assisted generation of RONS and methylene blue degradation in water

Microwave-induced plasmas generated at atmospheric pressure are very attractive for a great variety of applications since they have a relatively high electron density and can generate large amounts of reactive species. Argon plasmas can be sustained inside dielectric tubes but are radially contracted and exhibit filamentation effects when the diameter of the tube is not narrow enough (over 1.5 mm). In this work, we describe a new approach for creating microwave (2.45 GHz) plasmas under atmospheric pressure conditions by using a surfatron device and power from 10 W. This modified design of the reactor enables the sustenance of non-filamented argon plasmas. These new plasmas have a higher gas temperature and electron density than the plasma generated in the original surfatron configuration. The new design also allows for the maintenance of plasmas with relatively high proportions of water, resulting in the generation of larger quantities of excited hydroxyl radicals (·OH*). Thus, this novel configuration extends the applicability of microwave-induced plasmas by enabling operation under new conditions. Finally, the degradation of methylene blue (MB) in aqueous solutions has been assessed under different initial dye concentrations and argon flow conditions. The new plasma produces a substantial increase in hydrogen peroxide and nitrate concentrations in water and leads to a noteworthy enhancement in MB degradation efficiency. The introduction of water into the plasma produces a minor additional improvement.