Heterogeneous Reaction Mechanism Research Articles

DEVELOPMENT OF AN ENERGY-SAVING TECHNOLOGY FOR THE PRODUCTION OF SYNTHETIC METHANE FROM CARBON DIOXIDE. 1. RESEARCH OF KINETICS AND MACRO-KINETICS OF THE SABATIER REACTION ON MODIFICATIONS OF THE SERIAL NI/Α-AL2O3 CATALYST GIAP-3-6N

This study presents the results of laboratory research of kinetics and mechanisms of heterogeneous catalytic reactions of hydrogenation of carbon dioxide to carbon monoxide and methane through the Sabatier reaction on modifications of the serial Ni/α-Al2O3 catalyst GIAP-3-6N manufactured in Ukraine. The research was carried out on a laboratory bench using a classic glass gradientless reactor with internal piston stirring, which provides kinetic equations at the level of physicochemical constants of the reactions under consideration. A detailed analysis and review of the literature in the areas of kinetic research of our interest was carried out. A detailed comparison of the kinetic parameters obtained by us for the powder (kinetic) form of contact with a nickel content of 7.5 % (NiO = 7.5 %) with a similar and one of the best foreign analogs containing nickel, Katalco 57-4 (NiO = 15−18 %), produced by the British chemical and metallurgical company Johnson Matthey, was performed. The results of the research confirmed almost equal parameters of the kinetic activity of the compared catalysts in the reactions of hydrogenation of carbon dioxide with hydrogen, including the «Sabatier» reaction, which made it possible to propose a similar mechanism of the processes, calculate the reaction rate constants and their activation energy, propose (determine) kinetic equations for design of reactors and processes, both with the loading of a domestic catalyst and its replacement with a foreign analog. Kinetic equations will be used in the development of multi-ton synthesis gas plants for the production of methanol, ammonia, and synthetic methane, as well as carbon-free e-fuel for internal combustion engines that meet modern climate requirements. Bibl. 28, Fig. 4, Tab. 6.

Simultaneous tracking of ultrafast surface and gas-phase dynamics in solid-gas interfacial reactions.

Real-time detection of intermediate species and final products at the surface and near-surface in interfacial solid-gas reactions is critical for an accurate understanding of heterogeneous reaction mechanisms. In this article, an experimental method that can simultaneously monitor the ultrafast dynamics at the surface and above the surface in photoinduced heterogeneous reactions is presented. This method relies on a combination of mass spectrometry and femtosecond pump-probe spectroscopy. As a model system, the photoinduced reaction of methyl iodide on and above a cerium oxide surface is investigated. The species that are simultaneously detected from the surface and gas-phase present distinct features in the mass spectra, such as a sharp peak followed by an adjacent broad shoulder. The sharp peak is attributed to the species detected from the surface, while the broad shoulder is due to the detection of gas-phase species above the surface, as confirmed by multiple experiments. By monitoring the evolution of the sharp peak and broad shoulder as a function of the pump-probe time delay, transient signals are obtained that describe the ultrafast photoinduced reaction dynamics of methyl iodide on the surface and in the gas-phase. Finally, SimION simulations are performed to confirm the origin of the ions produced on the surface and in the gas-phase.

Promises of MOF‐Based and MOF‐Derived Materials for Electrocatalytic CO2 Reduction

AbstractElectrocatalytic CO2 reduction (ECR) powered by renewable electricity is a promising technology to mitigate carbon emissions and lessen the dependence on fossil fuels toward a carbon‐neutral energy cycle. Metal–organic frameworks (MOFs) and their derivatives, due to their excellent intrinsic activity, have emerged as promising materials for the ECR to high‐demand products. However, challenges such as unsatisfactory energy efficiency, selectivity, and relatively low production rates hinder their industrial scalability. Here, a comprehensive and critical review is presented that summarizes the state‐of‐the‐art progress in MOF‐based and MOF‐derived CO2 electroreduction catalysts from design and functionality perspectives. The fundamentals of CO2 reduction reaction (CO2RR) over heterogeneous catalysts, reaction mechanisms, and key challenges faced by ECR are described first to establish a solid foundation for forthcoming in‐depth analyses. MOF's building blocks, properties, and shortcomings pertinent to ECR including low conductivity and stability, are systematically discussed. Moreover, comprehensive discussions are provided on MOF‐based and MOF‐derived catalysts design, fabrication, characterization, and CO2RR activity to pinpoint the intricate structure‐property‐performance relationship. Finally, promising recommendations are put forward for enhancing MOF electrocatalysts activity, selectivity, and durability. This work may serve as a guideline for developing high‐performance MOF‐related catalysts for CO2RR, benefiting researchers working in this growing and potentially game‐changing area.

Assessment of Nocturnal NOx Heterogeneous Reaction Mechanisms in the Community Multiscale Air Quality (CMAQ) Model

AbstractNitrogen oxides (NOx) have adverse human health impacts and play a central role in the production of ozone and PM2.5. Nighttime heterogeneous chemistry regulates the nocturnal reservoirs and sinks of NOx such as N2O5 removal and ClNO2 production. However, existing parameterizations of nocturnal NOx heterogeneous chemistry in air quality models do not capture the variability in observations. Here, we implemented for the first time in the Community Multiscale Air Quality (CMAQ) model the Gaston N2O5 uptake (γ(N2O5)) mechanism that accounts for the role of particulate organic matter in regulating N2O5 uptake and the Staudt ClNO2 yield (Φ(ClNO2)) mechanism that includes the role of reactive solutes in suppressing ClNO2 production. With the Gaston and Staudt parameterizations, the coarse mode contributed modestly to N2O5 loss (17.2%) but significantly to ClNO2 production (60.3%), highlighting the impact of coarse mode chemistry. The Gaston γ(N2O5) parameterization in the fine mode increased agreement between modeled N2O5 concentration and observations (RMSEnew = 0.37ppb) compared to the model default (RMSEdefault = 0.43ppb). The Gaston γ(N2O5) parameterization was overall biased low due to underestimates in modeled particle oxygen to carbon ratio (O:C). The Staudt Φ(ClNO2) parameterization resulted in further underestimation (NMBnew = −73.7%) compared to the model default (NMBdefault = −37.9%) because of underestimation of fine mode particle chloride concentration. We expect that the updated parameterizations may more accurately capture the mean state and variability in γ(N2O5) and Φ(ClNO2) under conditions where model particulate O:C and chloride are better represented.

Deciphering orbital hybridization in heterogeneous catalysis

AbstractThe catalytic coordinate is essentially the evolving frontier orbital interaction while feeding with catalytic materials and adsorbates under proper reaction conditions. The heterogeneous catalytic reaction mechanism involves the initial adsorption and activation of reactants, subsequent intermediate transformation, final target product desorption, and regeneration of catalytic materials. In these catalytic processes, interaction modulations in terms of orbital hybridization/coupling allow an intrinsic control on both thermodynamics and kinetics. Concerned charge transfer and redistribution, orbital splitting and rearrangement with specific orientation, and spin change and crossover pose a formidable challenge on mechanism elucidation; it is hard to precisely correlate the apparent activity and selectivity, let alone rational modulations on it. Therefore, deciphering the orbital couplings inside a catalytic round is highly desirable and the dependent descriptor further provides in‐depth insights into catalyst design at the molecule orbital level. This review hopes to provide a comprehensive understanding on orbital hybridizations, modulations, and correlated descriptors in heterogeneous catalysis.

The recent progress of cathode materials for heterogeneous electro-Fenton reactions

As one of environmentally friendly and efficient oxidation techniques, the electro-Fenton (EF) processes allow to remove and mineralize organic pollutants. However, the transitional EF processes require an acidic environment, adding ferrous ions, treatment of iron sludge, and costly solution pH adjustment. Heterogeneous EF (hetero-EF) processes enable EF to function over a broad working pH region and recycle across multiple reaction rounds which reduces overall cost and displays great potential for practical engineering applications. Here, this work reviewed the reported cathode materials for the hetero-EF processes. We firstly described the mechanisms of homogeneous and heterogeneous EF reactions. Then, we summarized different types of cathode materials for hetero-EF reactions, including metal-free carbon materials, transition metal single-atom catalysts (SACs)/carbon materials, alloys catalysts/carbon materials, metal compounds/carbon materials and other materials. Finally, we overviewed the challenges and proposal strategies of hetero-EF technique in order to expand its wide-scale applicability and practical significance for advanced wastewater treatment.

Distinctive Heterogeneous Reaction Mechanism of ClNO2 on the Air-Water Surface Containing Cl.

The heterogeneous reaction of nitryl chloride (ClNO2) on the air-water surface plays a significant role in the chloride lifecycle. The air-water surface is ubiquitous on ice surfaces under supercooled conditions, affecting the uptake and heterogeneous reaction processes of trace gases. Previous studies suggest that ClNO2 is formed on Cl-doped ice surfaces following the N2O5 uptake. Herein, a distinctive heterogeneous reaction mechanism of ClNO2 is suggested on an air-water surface containing Cl under supercooled conditions using combined classic molecular dynamics (MD) and Born-Oppenheimer MD simulations. It is found that N2O5 dissociates into a NO2+ and NO3- ionic pair on the top air-water surface. In the top layer of the surface containing barely any Cl-, NO2+ proceeds through hydrolysis and produces H3O+ and HNO3. Thus, surface acidification appears because of H3O+ yields. With NO2+ diffusion to the deep layer of the surface, NO2+ reacts with Cl- and forms ClNO2. Note that ClNO2 formation competes with NO2+ hydrolysis, and the rate of ClNO2 formation is 27.7[Cl-] larger than that of NO2+ hydrolysis. Afterward, the reaction of ClNO2 with Cl- becomes barrierless with the catalysis by H3O+, which is not feasible on a neutral surface. Cl2 is thus generated and escapes into the atmosphere (low solubility of Cl2), contributing to the Cl radical. The proposed mechanism bolsters the current understanding of ClNO2's fate and its role in Cl chemistry in extremely cold environments like the Arctic and other high-latitude regions in wintertime.

Numerical study on hydrogen heterogeneous reaction characteristic in a micro catalytic combustor with blunt body

A numerical investigation has been conducted to explore the effect of an inserted blunt body on the heterogeneous reaction (HTR) characteristics in a micro-catalytic combustor operating with premixed hydrogen/air. The two-dimensional numerical model incorporates a comprehensive heterogeneous reaction mechanism of hydrogen employed by experimental verification. The influences of blockage ratio at various inlet velocities have been investigated to obtain optimized design parameters of the combustor. The findings of this research highlight analysis of the positive influence of an inserted blunt body within the combustor, including enhancement of chemical reaction rate and hydrogen conversion ratio. Numerical results shows that the gaseous mixture between the blunt body and catalytic surface noticed a considerable velocity increase, leading to a greater adsorption–desorption of bulk species on the catalytic surface. At the same inlet velocity, the hydrogen conversion ratio gradually increases with higher blockage ratios. When the blockage ratio is less than or equal to 0.6, the average inner wall temperature is positively affected by the increased blockage ratio. However, the effect becomes negative at higher blockage ratios (0.8). The Pr (Prandtl number) number near the gas–solid interface adjacent to the blunt body initially decreases and then increases, while Nu/Nu0 (Nusselt number) and Pe (Peclet number) exhibit an initial increase followed by a decrease. The presence of the blunt body leads to a reduction in the cross-sectional area of the channel, causing an acceleration in fluid velocity near the blunt body and exerting an impact on the boundary layer near the gas–solid interface. This indicates that the addition of the blunt body reduces the boundary layer thickness and enhances the mass and heat transfer characteristics in the region. The study reveal that as the blockage ratio increases, the overall field synergy of the combustor initially increases and then decreases. The peak field synergy is attained at an optimal blocking ratio of 0.6. The findings of this study have important implications for the design of micro-scale combustors.

CALCULATION OF THERMODYNAMIC AND KINETIC PARAMETERS OF CATALYTIC CRACKING REACTIONS ON LEWIS AND BRØNSTED ACID SITES

Link for citation: Nazarova G.Y., Ivashkina E.N., Maltsev V.V. Calculation of thermodynamic and kinetic parameters of catalytic cracking reactions on Lewis and Brønsted acid sites. Bulletin of the Tomsk Polytechnic University. Geo Аssets Engineering, 2023, vol. 334, no. 7, рр. 214-225. In Rus. The relevance of the research is caused by the emerging necessity of developing a mathematical model to optimize the heterogeneous process of catalytic cracking. This tools should take into account both the chemical transformations of a wide range of hydrocarbon groups (different feedstock types), as well as the stages of adsorption, reactants diffusion, conversion of hydrocarbons on the catalyst surface, acid characteristics and pore size of the catalysts. The study of the hydrocarbon conversion patterns on Lewis or Brønsted acid sites using quantum-chemical modeling methods allow us to quantify the thermodynamic parameters of reactants adsorption, the kinetic parameters of carbocations formation and cracking on acid sites. These results are necessary to develop a mathematical model based on the of heterogeneous catalytic reaction mechanism. The aim of this work is to identify the level of quantum chemical theory and to determine the thermodynamic and kinetic parameters of reactants adsorption, carbenium ions formationand hydrocarbons cracking on Lewis and Brønsted acid sites. Methods: quantum-chemical modeling methods to optimize the molecular geometry of reactants and products of catalytic cracking reactions, calculate vibrational frequencies, thermodynamic parameters of adsorption and catalytic cracking of hydrocarbons and heteroatomic compounds with the participation of Bronsted and Lewis acid sites. Results. The chosen level of quantum-chemical theory allowed obtaining the results that are consistent with the laws of the process and the experimental reactivity of hydrocarbons in cracking reactions on acid catalysts. The thermodynamic parameters of the adsorption of C6–C16 hydrocarbons and thiophenes on Lewis and Brønsted acid sites were identified. We found that during the cracking of n-hexane on the Lewis acid site, the reaction is limited by the carbenium ion formation stage.The activation energy of this stage was 281,3 kJ/mol whereas the value for the cracking stage was 277,2 kJ/mol. Further study shows that the activation energy of carbenium ion formation from izohexane and C8–C10 alkanes with normal structure on the Lewis acid site was 257,6 and 279,2…277,9 kJ/mol. The most energetically favorable is the formation of carbocation from hexene at Brønsted acid sites (76,59 kJ/mol). The results of the work will be used to create a mathematical model of a heterogeneous process based on the Langmuir–Hinshelwood equations.

Recent Developments in Direct C-H Functionalization of Quinoxalin-2(1H)-Ones via Heterogeneous Catalysis Reactions.

In recent years, Web of Science has published nearly one hundred reports per year on quinoxalin-2(1H)-ones, which have attracted great interest due to their wide applications in pharmaceutical and materials fields, especially in recyclable heterogeneous catalytic reactions for direct C-H functionalisation. This review summarises for the first time the methods and reaction mechanisms of heterogeneous catalytic reactions of quinoxalin-2(1H)-ones, including six major types of heterogeneous catalysts involved. The heterogeneous reactions of quinoxalin-2(1H)-ones are summarised by classifying different types of catalytic materials (graphitic phase carbon nitride, MOF, COF, ion exchange resin, piezoelectric materials, and microsphere catalysis). In addition, this review discusses the future development of heterogeneous catalytic reactions of quinoxalin-2(1H)-ones, including the construction of C-B/Si/P/RF/X/Se bonds by heterogeneous catalytic reactions, the enrichment of heterogeneous catalysts such as metal oxides, graphene-based composites, doped metal nanoparticles, and molecular sieve-based porous materials, asymmetric synthesis, and other areas. The aim of this review is to contribute to the development of green and sustainable heterogeneous reaction methods for quinoxalin-2(1H)-ones with applications in materials chemistry and pharmacology.

DFT study of mercury adsorption on Al2O3 with presence of HCl

mercury emission control from flue gas is a crucial issue for environment protection. Alumina is an important alkali metal oxide for mercury adsorption in particulate, meanwhile is the potential adsorbent for mercury removal. The cognition on mercury heterogeneous reaction mechanism with alumina in presence of hydrogen chloride is inadequate. In this work, the DFT calculation was applied to detect mercury's chlorides adsorption on α-Al2O3 (001) surface, the Bader charge analysis was used to estimate electron transfer and the transition state theory was used to clarify reaction pathway and energy barrier, besides, the kinetic analysis based on Gibbs free energy was conducted to study the impact of temperature on chemical reaction. The results show that Hg can be captured by weak chemisorption on α-Al2O3 (001) surface with the adsorption energy of −56.37 kJ/mol, HgCl, HgCl2 are intensively bonded on surface with adsorption energies of −276.90 kJ/mol and −231.87 kJ/mol, the surface unsaturated Al and O atoms are the active sites. Charge transfer and PDOS analysis prove that the forming of covalent bonding is responsible for Hg species adsorption. Two possible reaction pathways of Hg oxidization to HgCl2 are discussed, in which a smaller energy barrier of 0.1 eV implies the dominant pathway 1 via Eley-Rideal mechanism: two adsorbed HCl molecules dissociate on surface and then react with one Hg atom. High temperature can promote the reaction rate constants of pathway 1 and 2, but is only favorable for reducing energy barrier of pathway 2.

Dynamic biomass char porosity during gasification: Model compared with data

This investigation presents a new biomass char porosity model as a function of char conversion during gasification and compares it with entrained-flow data from poplar, corn stover and switchgrass particles reacting with H2O, CO2, and combinations of both at temperatures of 1050–1350 °C. The experimental data include particle temperature, mass, size, and shape combined with porosity, BET surface area, geometric specific surface area and SEM images of char vascular structure. The new theoretical model describes char porosity changes during char conversion and the model indicates that porosity increases monotonically, consistent with the data. The vascular char structure remains intact even at the highest conversions and this structure effectively transports reactants and products through the particle, with reactions occurring on the walls of these vascular vessels, referred to here as vascules. The investigation shows that char porosity most strongly depends on average vascule diameter which, in turn, increases with increasing conversion. This investigation extends current understanding of the mechanism of heterogeneous biomass char reactions (gasification and oxidation) under kinetically controlled conditions. This work concludes that (1) kinetically controlled biomass gasification involves reactions on the walls of vascules with small contributions from the nanopores or even mesopores; (2) char porosity increases monotonically with increasing char conversion in the kinetically and internal transport-controlled regimes; and (3) observed porosity behaviors correspond the predicted behaviors.

New insight into the mechanism of ferric hydroxide-based heterogeneous Fenton-like reaction.

The heterogeneous Fenton-like reaction (HeFR) has always been a research focus for environmental applications. However, it has long been difficult to reach a consensus on the reaction mechanism because the process of metal ions dissolution and its role were not well understood. In this paper, we propose the courses of organics-mediated coordination or/and reduction dissolution of ferric hydroxide to initiate the autocatalytic kinetics of phenol degradation and illustrate it through density functional theory (DFT) and experiments. With the increase of hydrogen peroxide concentration, the degradation of phenol changes from autocatalytic kinetics to first-order kinetics. Furthermore, a novel "limit segmentation method" initiated by us indicates that homogeneous reaction plays a decisive role in the phenol degradation process. The dominant roles of the reactive organics in both iron dissolution and the iron cycle and of the homogeneous reaction in the whole degradation process in the ferric hydroxide-based HeFR system are brand-new insights that pave the pathway for future research.

Silver nanostructure-modified graphite electrode for in-operando SERRS investigation of iron porphyrins during high-potential electrocatalysis.

In-operando spectroscopic observation of the intermediates formed during various electrocatalytic oxidation and reduction reactions is crucial to propose the mechanism of the corresponding reaction. Surface-enhanced resonance Raman spectroscopy coupled to rotating disk electrochemistry (SERRS-RDE), developed about a decade ago, proved to be an excellent spectroscopic tool to investigate the mechanism of heterogeneous oxygen reduction reaction (ORR) catalyzed by synthetic iron porphyrin complexes under steady-state conditions in water. The information about the formation of the intermediates accumulated during the course of the reaction at the electrode interface helped to develop better ORR catalysts with second sphere residues in the porphyrin rings. To date, the application of this SERRS-RDE setup is limited to ORR only because the thiol self-assembled monolayer (SAM)-modified Ag electrode, used as the working electrode in these experiments, suffers from stability issues at more cathodic and anodic potential, where H2O oxidation, CO2 reduction, and H+ reduction reactions occur. The current investigation shows the development of a second-generation SERRS-RDE setup consisting of an Ag nanostructure (AgNS)-modified graphite electrode as the working electrode. These electrodes show higher stability (compared to the conventional thiol SAM-modified Ag electrode) upon exposure to very high cathodic and anodic potential with a good signal-to-noise ratio in the Raman spectra. The behavior of this modified electrode toward ORR is found to be the same as the SAM-modified Ag electrode, and the same ORR intermediates are observed during electrochemical ORR. At higher cathodic potential, the signatures of Fe(0) porphyrin, an important intermediate in H+ and CO2 reduction reactions, was observed at the electrode-water interface.

Effect of inserted baffles on hydrogen heterogeneous reaction in planar catalytic micro combustor

Heterogeneous reaction characteristics of premixed H2/Air mixture are numerically investigated in micro combustor with coating platinum (Pt) catalyst on the inner wall. The well-designed combustor with the inserted baffle is committed to improving the transport of bulk species on the catalytic surface, therefore enhancing the fuel conversion ratio. A two-dimensional numerical model with detailed heterogeneous reaction mechanism is developed and verified. In this work, the numerical results reveal that the heterogeneous reaction rate and fuel conversion ratio are significantly improved in the combustor with inserted baffle. The velocity of gaseous mixture swiftly increases between the baffle and catalytic surface, resulting in the increasing adsorption-desorption of bulk species on the catalytic surface. The main influencing factors of inserted baffle body comprise of slit width between two ribs in the same row (W), rib length (L), distance between adjacent baffles row (D), number of baffle row (n) which are studied to obtain a set of optimized parameters of baffle in the well-designed combustor. The optimized parameters of the baffle are W = 0 mm, L = 0.4 mm, D = 4 mm and n = 4, which are employed in the combustor to obtain a high hydrogen conversion ratio. Moreover, the effect of different inlet velocities and equivalent ratios of the mixture on the heterogeneous reaction characteristics are carried out in the designed combustor. As the designed combustor performs well, and the improvement effect of the optimized baffle gradually increases together with the inlet velocity, particularly for high inlet velocity (7 m/s). The promotion effects of baffle in the designed combustor are presented when the rich and lean fuel are adopted at inlet velocity of 7 m/s. Finally, the relative parameters of this work can serve as a reference and guidance for the design of micro scale combustor.

Impacts of the COVID-19 lockdown on atmospheric oxidizing capacity and secondary aerosol formation over the Beijing-Tianjin-Hebei region in Winter-Spring 2020

By using WRF-Chem coupled with a heterogeneous reaction mechanism for sulfate formation, this study investigated the impact of meteorological condition and emission changes on chemical species, atmospheric oxidizing capacity (AOC), and secondary aerosol formation during the COVID-19 lockdown period from 23 January to April 8, 2020, focusing on a severe haze event on 7–14 February. The model with the new sulfate formation scheme reasonably reproduces the spatial-temporal distribution of meteorological variables and chemical species, and significantly improves predictions for both sulfate and SO2 concentrations, as well as for PM2.5, ammonium, and nitrate to some extent. It is found that the adverse meteorological conditions were the main cause for the haze event formation, whereas emission reduction due to the lockdown somewhat decreased PM2.5 concentration on average in the Beijing-Tianjin-Hebei (BTH) region. Compared with the same period in 2019, increased surface air temperature and relative humidity (RH) and decreased planetary boundary layer height (PBLH) facilitated accumulation of pollutants and formation of secondary aerosols during the haze episode in 2020, whereas the emission reduction due to the lockdown led to decreases in SO2, NO2, primary PM2.5 (PPM2.5), black carbon (BC), primary organic aerosols (POA), nitrate and ammonium concentrations, but increases in O3, sulfate and secondary organic aerosol (SOA) concentrations, due to the combined effect of changes in emissions and AOC. Gas and aqueous phase oxidation of SO2 accounted for approximately 24% of sulfate formation, while the heterogeneous reaction of Mn-catalytic oxidation of SO2 on aerosol surfaces dominated sulfate formation (76%) during the haze episode in the BTH region. Both adverse meteorological conditions and emission reductions increased heterogeneous sulfate formation rate mainly through altering aerosol surface area (ASA), pH, and Mn2+ concentration. Chemical species varied diversely during the three subperiods before (Period-1, 15–22 January) and during the lockdown (Period-2, 23 January to 5 March and Period-3, 6 March to 8 April) over the BTH. NO2 concentration firstly decreased and then rebounded, whereas O3 concentration increased gradually from the Period-1 to Period-3. All aerosols except SOA decreased throughout the lockdown period, whereas SOA peaked in the Period-2 due to its strong sensitivity to increasing AOC. Sulfate concentration decreased from the Period-1 to Period-2, mainly due to more adverse meteorological conditions in the Period-1, although sulfate increased slightly due to increasing AOC in the Period-2. The large difference in the direction and magnitude of species variations during the COVID-19 lockdown indicates the complex interplay among meteorology, emission, and chemistry.

Synergistic removal of ammonia nitrogen by UV photo-electrocatalytic process: Heterogeneous reaction pathways and mechanism

UV photo-electrocatalytic process has emerged as a promising approach for the abatement of ammonia nitrogen in wastewater. However, the radical chemistry for ammonia nitrogen removal in this process requires further clarification. The heterogeneous reaction pathways and mechanism of ammonia nitrogen oxidation in the UV photo-electrocatalytic process were investigated in this study. Photocurrents of the Ti/RuO2-IrO2-TiO2 electrodes with good electrocatalytic behavior were enhanced by UV radiation. Compared with the electrocatalytic process, the removal rates of ammonia nitrogen were improved by 12.4%∼20% at the Cl− concentration of 50 mM in the photo-electrocatalytic process. The ammonia nitrogen was mainly transferred into N2, meanwhile, the formation of nitrogenous by-products, active chlorine, and chloramines was inhibited in the photo-electrocatalytic process. The contribution of UV radiation was to photo-decompose the active chlorine and chloramines, generating free radicals. The removal efficiency of ammonia nitrogen reached more than 64% after the elimination of free radicals. The electro-generated HOCl was the principal species for ammonia nitrogen removal, and the synergistic effect for the acceleration of ammonia nitrogen oxidation resulted from the photo-generated chlorine radicals. This investigation provides insight into the electrochemistry, photochemistry, and radical chemistry for the heterogeneous catalytic degradation of ammonia nitrogen by UV photo-electrocatalytic process.

Performance and mechanism of co-doped Ce–Mn perovskite for degradation of tetracycline via heterogeneous photocatalysis coupled PMS oxidation

In this work, CeMn1-xMxO3 (M = Cu, Fe and Co) perovskites were synthesized and used as efficient heterogeneous catalyst for degrade of tetracycline chloride (TC-HCl) via photocatalysis coupled peroxymonosulfate (PMS) oxidation under visible-light illumination. Metal doping significantly improved the catalytic activity of perovskites. The CeMn0.6Co0.4O3/PMS/Vis system demonstrated excellent performance that 96.4% of 60 mg/L of TC-HCl was degraded within 30 min with a high reaction rate constant of 0.136 min−1, which is about 4.3 times higher than that of CeMnO3, and almost 4.4 times higher than that of pure PMS. Results confirmed the addition of Co led to mixed valence states of Mn (III)/Mn (Ⅳ) and Co (II)/Co (III) in the perovskite structure, promoting the electron transfer from the CeMn0.6Co0.4O3 to PMS. Moreover, CeMn0.6Co0.4O3 exhibited good stability over a wide pH range (3.0–11.0). The rapid transformation of Co (II)/Co (III) redox pairs is critical for PMS activation as the limiting step. Superoxide radicals (•O2−), electron (e−) and sulfate radical (SO4−•) were the dominant oxidative species responsible for removing TC-HCl. This work proposed some new insights to understand the heterogeneous reaction mechanism during PMS oxidation and photocatalytic process and promote the development of perovskites catalyst for removal of organic pollutants.

Color and spectral characteristics of long-lived meteor trail formed by the Tunka bolide

The paper addresses color characteristics and possible spectral composition of emission of a long-lived (~40 min) meteor trail of uncommon geometry, which was formed due to the bolide passage in the Tunka Valley on November 17, 2017. Analysis of dynamics of RGB channels of the meteor trail colored image shows that during the first ~8 minutes the meteor trail emission might have been contributed by the ionization trail. The ionization trail was formed by particles of the meteor matter neutral and ionized components that were heated to high temperatures on the surface of the main meteoroid and separated from it. We also examine the discussed mechanism of heterogeneous chemical reactions occurring on the surface of meteoric dust (FeS, FeO, etc.) with participation of atoms and molecules of atmospheric gases. The yellowish color of the Tunka bolide meteor trail was assumed to be determined, first of all, by the emission of molecular nitrogen N₂ band within the 570–750 nm spectral range (the first positive system) and/or enhancement of NO*₂ continuum in heterogeneous chemical reactions. The meteor trail emission spectrum should also include relatively bright atomic lines and molecular bands of the meteoric matter and atmospheric gases FeI, MgI, CaI, SiI, NaI, FeO and SO₂, OI, OH, etc.

Цветовые и спектральные характеристики долгоживущего метеорного следа, образованного Тункинским болидом

The paper addresses color characteristics and possible spectral composition of emission of a long-lived (~40 min) meteor trail of uncommon geometry, which was formed due to the bolide passage in the Tunka Valley on November 17, 2017. Analysis of dynamics of RGB channels of the meteor trail colored image shows that during the first ~8 minutes the meteor trail emission might have been contributed by the ionization trail. The ionization trail was formed by particles of the meteor matter neutral and ionized components that were heated to high temperatures on the surface of the main meteoroid and separated from it. We also examine the discussed mechanism of heterogeneous chemical reactions occurring on the surface of meteoric dust (FeS, FeO, etc.) with participation of atoms and molecules of atmospheric gases. The yellowish color of the Tunka bolide meteor trail was assumed to be determined, first of all, by the emission of molecular nitrogen N₂ band within the 570–750 nm spectral range (the first positive system) and/or enhancement of NO*₂ continuum in heterogeneous chemical reactions. The meteor trail emission spectrum should also include relatively bright atomic lines and molecular bands of the meteoric matter and atmospheric gases FeI, MgI, CaI, SiI, NaI, FeO and SO₂, OI, OH, etc.