OH Reaction Research Articles

Investigation of cyclopentene + OH and cyclopentene thermal decomposition reactions

This study presents the first high-temperature measurements of cyclopentene+OH→k1Products reaction over 856 – 1258 K and 1.03 – 4.33 bar. The determined rate coefficients of k1 exhibited Arrhenius temperature dependence with an activation energy ∼ 3.3 kcal mol−1 and negligible pressure dependence. Rate coefficients of OH + cyclopentene are faster than OH + 1-pentene but comparable to OH + 2-pentene, highlighting the significance of allylic CH bonds in these reactions. At 1258 K, our rate coefficient is ∼ 30 % slower than the average room-temperature measurement, indicating the role of OH-addition pathways at low temperatures. Site-specific rate coefficients and branching ratios are determined, with H-abstraction at the allylic CH site accounting for ∼68 % of the reaction and alkylic CH bond contributing ∼22 %. Our measured k1 may be given as (unit: cm3molecule−1s−1):k1=1.64×10−10e(−1660T)Cyclopentene decomposition reaction (cyclopentene→k2cyclopentadiene+H2) is studied over 1186–1472 K and 1.17 – 1.38 bar. Time-resolved yields of the product, cyclopentadiene, are monitored using a sensitive UV laser diagnostic near 220 nm. Absorption cross-sections of cyclopentadiene, measured in two separate mixtures, showed weak positive temperature dependence (8.7 – 9.8 × 10−18 cm2molecule−1) over 961 – 1326 K. Our rate coefficients of k2 exhibited a positive Arrhenius temperature dependence with an activation energy of ∼ 54.7 kcal mol−1. At 1300 K, the decomposition of cyclopentene proceeds 5.5 and 28 times faster than that of cyclopentadiene and cyclopentane, respectively. Our measured k2 may be expressed as (unit: s−1):k2=2.55×1012e(−27,527.6T)The pentagonal structure of cyclopentene influences its H-abstraction and decomposition reactions distinctively. While H-abstraction by OH follows a mechanism akin to cyclohexene and linear alkenes, with comparable rate coefficients at allylic CH bonds, the penta-ring structure significantly impacts the decomposition mechanism. Cyclopentene decomposition predominantly produces cyclopentadiene and H2 in a ring-conserving manner, differing from the cleavage of allylic-alkylic CC bonds in the decompositions of 1-alkenes and cyclohexene.

Experimental Study of the Reaction of OH Radicals with Carbonyl Sulfide between 365 and 960 K: Kinetics and Products

Reaction OH + OCS ® products (1) has been studied in a discharge–flow reactor combined with modulated molecular beam mass spectrometry. The reaction rate constant has been determined under pseudo-first-order conditions through monitoring OH decays in a high excess of OCS: k1 = (2.35 ± 0.25) × 10−12 exp(−(2144 ± 56)/T) cm3 molecule−1 s−1 at T = 365–960 K (the uncertainties represent precision at the 2σ level, the total 2σ relative uncertainty including statistical and systematic errors on the rate constant being 20% at all temperatures). The rate constant of reaction (1) was found to be similar at a total helium pressure of 1, 2, and 8 torr at around 500 K. The SH radical was identified as the primary product of the reaction, and its yield was determined to be about 100% at T = 500 and 750 K. The kinetic and mechanistic data from the present study are compared to previous experimental and theoretical work.

New Instrument for Time-Resolved OH and HO2 Quantification in High-Pressure Laboratory Kinetics Studies.

We have constructed a new time-resolved high-pressure fluorescence assay by gas expansion (HP-FAGE) apparatus, optimized for the detection of OH and HO2 radicals in complex gas-phase reactions. The new instrument fills a gap in the existing experimental toolkit for chemical kinetics by enabling the quantification of two key reactive species with microsecond time resolution from high-pressure sources, which was previously not attainable. The HP-FAGE is interfaced with a flow reactor, designed for pressures up to 100 bar and temperatures up to 1000 K, in which reactions are initiated by laser photolysis of radical precursors at repetition rates of 1-10 Hz. The HP-FAGE samples gas out of the reactor into a miniature FAGE chamber, where OH is detected by resonant laser-induced fluorescence using a time-delayed probe laser pulse. HO2 is converted to OH via reaction with NO and then detected by OH fluorescence. The novel FAGE design places the probe region very close to the gas expansion, minimizing the transport time of sampled molecules and resulting in time resolution better than 20 μs for both OH and HO2. We calibrate the sensitivity of HP-FAGE, validate its performance with measurements of well-known reaction kinetics (OH + CH4, OH + OH, OH + HO2, and HO2 + HO2), and discuss prospects for its future use.

Dual-level strategy for quantitative kinetics for the reaction between ethylene and hydroxyl radical.

The atmospheric reactions are mainly initiated by hydroxyl radical (OH). Here, we choose the C2H4 + OH reaction as a model reaction for other reactions of OH with alkenes. We use the GMM(P).L//CCSD(T)-F12a/cc-pVTZ-F12 theoretical method as the benchmark results close to the approximation of CCSDTQ(P)/CBS accuracy to investigate the C2H4 + OH reaction. The rate constants for the C2H4 + OH reaction at high-pressure limit were calculated by using the dual-level strategy. It integrates the transition state theory rate constant calculated by GMM(P).L//CCSD(T)-F12a/cc-pVTZ-F12 with the canonical variational transition state theory containing small-curvature tunneling (CVT/SCT) calculated by using the M11-L functional method with the MG3S basis set. The rate constants of C2H4 + OH at different pressures were obtained by using both the system-specific quantum Rice-Ramsperger-Kassel (SS-QRRK) theory and master equation method. The calculated results uncover that both the calculated rate constants at different pressures and temperatures are quantitatively consistent with the values obtained by the experimental measurements in the C2H4 + OH reaction. We find that the post-CCSD(T) contributions to the barrier height for the C2H4 + OH reaction are significant with the calculated value of -0.38 kcal/mol. We also find that the rate determining step is only dominated by the tight transition state under atmospheric conditions, whereas previous investigations indicated that the rate constants were controlled by both the loose and tight transition states in the C2H4 + OH reaction. The present findings unravel that it is an important factor for the effect of torsional anharmonicity on quantitative kinetics.

Co-N-C axially coordination regulated H2O2 selectivity via water medicated recombination of solute •OH: A new route

The cobalt, earth abundant transition metal, embedded in nitrogen doped carbon material as single atom site (Co-N-C) has been manifested as promising electrochemical oxygen reduction reaction (ORR) catalyst, however the unsatisfying production selectivity has hampered its widespread applications. Herein, the H2O2 selectivity of Co-N-C catalyst has been tailored with Co axial functional groups. Thermodynamically, the selectivity is regulated due to the fine-tuning of the adsorption of the key reaction intermediates (ΔG*OOH), and five functional groups, including −O, –OH, –CN, −CH3 and −SO3, endow the Co-N-C catalyst with superior H2O2 selectivity. Importantly, we unravel a new water medicated recombination of solute •OH reaction pathway for H2O2 production, which was the result of dissociation of *HOOH in explicit water environment. That is, two •OH species reaction in the liquid environment which originated from the creaking of *OOH intermediates due to the weakened O-O bond by the interaction with surrounding water. This study provides foundational understanding for the ORR catalytic mechanism at the electrochemical interface and opens up new avenues for rational design of targeted high efficiency electrocatalysts.

Photochemical behaviour and toxicity evolution of phenylbenzoate liquid crystal monomers in water

Liquid crystal monomers (LCMs) are a group of emerging pollutants that pose potential environmental risks because of their ubiquitous occurrence and toxicity. Understanding their environmental transformation is essential for assessing the ecological risk. In this study, we investigated the photochemical transformation kinetics, mechanism, and photo-induced toxicity of three phenylbenzoate LCMs in water. Their apparent photolytic rate constants were within (0.023 – 0.058) min-1, and the half-lives were < 30.0 min, showing lower persistence in water. Dissolved organic matter significantly inhibited their photolysis because of light-shielding effect and quenching of excited triplet states of LCMs. Their photolysis mainly occurred through excited triplet states, and the reactive oxygen species (i.e., ⋅OH, 1O2 and ⋅O2-) contributed to their degradation. The main photolysis pathways were ester bond cleavage, ⋅OH substitution/addition, and defluorination. Experiments and computational simulation revealed that some ·OH addition/substitution products have similar toxicity with LCMs. Additionally, the ∙OH reaction rate constants (kOH) of LCMs were determined to be > 1 × 109 M-1 s-1, evidence for their high reactivity toward ⋅OH. We have further developed reliable methods to estimate kOH of other phenylbenzoate-like LCMs with quantum chemical calculations. These results are useful for understanding the transformation and fate of LCMs in aquatic environments.

A large role of missing volatile organic compound reactivity from anthropogenic emissions in ozone pollution regulation

Abstract. There are thousands of volatile organic compound (VOC) species in ambient air, while existing techniques can only detect a small part of them (approximately several hundred). The large number of unmeasured VOCs prevents us from understanding the photochemistry of ozone and aerosols in the atmosphere. The major sources and photochemical effects of these unmeasured VOCs in urban areas remain unclear. The missing VOC reactivity, which is defined as the total OH reactivity of the unmeasured VOCs, is a good indicator for constraining the photochemical effect of unmeasured VOCs. Here, we identified the dominant role of anthropogenic emission sources in the missing VOC reactivity (accounting for up to 70 %) by measuring missing VOC reactivity and tracer-based source analysis in a typical megacity in China. Omitting the missing VOC reactivity from anthropogenic emissions in model simulations will remarkably affect the diagnosis of sensitivity regimes for ozone formation, overestimating the degree of VOC-limited regimes by up to 46 %. Therefore, a thorough quantification of missing VOC reactivity from various anthropogenic emission sources is urgently needed for constraints of air quality models and the development of effective ozone control strategies.

Comparative Study on the H-Abstraction Reactions of Isopropyl Acetate and Propyl Acetate by HO2 and OH Radicals.

Isopropyl acetate (IPA) and propyl acetate (PA) are recognized as promising biofuels suitable for applications as fuel additives and biodiesel models. The H-abstraction reactions with radicals stand out as the fundamental initiating reactions in the combustion kinetic models for IPA and PA. In the present work, the kinetic calculations of IPA and PA plus HO2 and OH radicals were investigated at M06-2X/cc-pVTZ//G4, M08-HX/maug-cc-pVTZ, and CCSD(T)/jul-cc-pVTZ levels. The thermodynamic calculations were obtained based on the G4 and CBS-APNO methods. Rate coefficients were calculated using both transition state theory and canonical variational transition state theory with tunneling correction at the temperature range of 250-2000 K. The total rate constants for the IPA + OH system were fitted as follows: k = 0.4674 × T3.927 exp(2128/T) (cm3 mol-1 s-1), and for the PA + OH system, the total rate constants were determined using the following equation: k = 0.0161 × T4.373 exp(2220/T) (cm3 mol-1 s-1). The rate coefficients of IPA + OH reactions determined based on the M08-HX/maug-cc-pVTZ level effectively replicate the experimental data, while H-abstraction rate coefficients of PA + OH by the CCSD(T)/jul-cc-pVTZ method accurately reproduce the experimental data. Refining the H-abstraction rate coefficients in the kinetic mechanism of PA, as proposed by Dayma et al. [Proc. Combust. Inst. 37 (2019) 429-436], has been achieved through incorporating the present calculated data, leading to the development of a revised mechanism. The validation of the updated mechanism against jet-stirred reactor data is presented, showcasing its effective performance in predicting JSR data.

Experimental and Theoretical Study of the OH-Initiated Degradation of Piperidine under Simulated Atmospheric Conditions.

The OH-initiated photo-oxidation of piperidine and the photolysis of 1-nitrosopiperidine were investigated in a large atmospheric simulation chamber and in theoretical calculations based on CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ quantum chemistry results and master equation modeling of the pivotal reaction steps. The rate coefficient for the reaction of piperidine with OH radicals was determined by the relative rate method to be kOH-piperidine = (1.19 ± 0.27) × 10-10 cm3 molecule-1 s-1 at 304 ± 2 K and 1014 ± 2 hPa. Product studies show the piperidine + OH reaction to proceed via H-abstraction from both CH2 and NH groups, resulting in the formation of the corresponding imine (2,3,4,5-tetrahydropyridine) as the major product and in the nitramine (1-nitropiperidine) and nitrosamine (1-nitrosopiperidine) as minor products. Analysis of 1-nitrosopiperidine photolysis experiments under natural sunlight conditions gave the relative rates jrel = j1-nitrosoperidine/jNO2 = 0.342 ± 0.007, k3/k4a = 0.53 ± 0.05 and k2/k4a = (7.66 ± 0.18) × 10-8 that were subsequently employed in modeling the piperidine photo-oxidation experiments, from which the initial branchings between H-abstraction from the NH and CH2 groups, kN-H/ktot = 0.38 ± 0.08 and kC2-H/ktot = 0.49 ± 0.19, were derived. All photo-oxidation experiments were accompanied by particle formation that was initiated by the acid-base reaction of piperidine with nitric acid. Primary photo-oxidation products including both 1-nitrosopiperidine and 1-nitropiperidine were detected in the particles formed. Quantum chemistry calculations on the OH initiated atmospheric photo-oxidation of piperidine suggest the branching in the initial H-abstraction routes to be ∼35% N1, ∼50% C2, ∼13% C3, and ∼2% C4. The theoretical study produced an atmospheric photo-oxidation mechanism, according to which H-abstraction from the C2 position predominantly leads to 2,3,4,5-tetrahydropyridine and H-abstraction from the C3 position results in ring opening followed by a complex autoxidation, of which the first few steps are mapped in detail. H-abstraction from the C4 position is shown to result mainly in the formation of piperidin-4-one and 2,3,4,5-tetrahydropyridin-4-ol, whereas H-abstraction from N1 under atmospheric conditions primarily leads to 2,3,4,5-tetrahydropyridine and in minor amounts of 1-nitrosopiperidine and 1-nitropiperidine. The calculated rate coefficient for the piperidine + OH reaction agrees with the experimental value within 35%, and aligning the theoretical numbers to the experimental value results in k(T) = 2.46 × 10-12 × exp(486 K/T) cm3 molecule-1 s-1 (200-400 K).

Accurate Kinetic Studies of OH + HO2 Radical-Radical Reaction through Direct Measurement of Precursor and Radical Concentrations with High-Resolution Time-Resolved Dual-Comb Spectroscopy.

The radical-radical reaction between OH and HO2 has been considered for a long time as an important reaction in tropospheric photochemistry and combustion chemistry. However, a significant discrepancy of an order of magnitude for rate coefficients of this reaction is found between two recent experiments. Herein, we investigate the reaction OH + HO2 via direct spectral quantification of both the precursor (H2O2) and free radicals (OH and HO2) upon the 248 nm photolysis of H2O2 using infrared two-color time-resolved dual-comb spectroscopy. With quantitative and kinetic analysis of concentration profiles of both OH and HO2 at varied conditions, the rate coefficient kOH+HO2 is determined to be (1.10 ± 0.12) × 10-10 cm3 molecule-1 s-1 at 296 K. Moreover, we explore the kinetics of this reaction under conditions in the presence of water, but no enhancement in the kOH+HO2 can be observed. This work as an independent experiment plays a crucial role in revisiting this prototypical radical-radical reaction.

Characterization and source apportionment of volatile organic compounds in Hong Kong: A 5-year study for three different archetypical sites

Initial success has been achieved in Hong Kong in controlling primary air pollutants, but ambient ozone levels kept increasing during the past three decades. Volatile organic compounds (VOCs) are important for mitigating ozone pollution as its major precursors. This study analyzed VOC characteristics of roadside, suburban, and rural sites in Hong Kong to investigate their compositions, concentrations, and source contributions. Here we show that the TVOC concentrations were 23.05 ± 13.24, 12.68 ± 15.36, and 5.16 ± 5.48 ppbv for roadside, suburban, and rural sites between May 2015 to June 2019, respectively. By using Positive Matrix Factorization (PMF) model, six sources were identified at the roadside site over five years: Liquefied petroleum gas (LPG) usage (33%–46%), gasoline evaporation (8%–31%), aged air mass (11%–28%), gasoline exhaust (5%–16%), diesel exhaust (2%–16%) and fuel filling (75–9%). Similarly, six sources were distinguished at the suburban site, including LPG usage (30%–33%), solvent usage (20%–26%), diesel exhaust (14%–26%), gasoline evaporation (8%–16%), aged air mass (4%–11%), and biogenic emissions (2%–5%). At the rural site, four sources were identified, including aged air mass (33%–51%), solvent usage (25%–30%), vehicular emissions (11%–28%), and biogenic emissions (6%–12%). The analysis further revealed that fuel filling and LPG usage were the primary contributors to OFP and OH reactivity at the roadside site, while solvent usage and biogenic emissions accounted for almost half of OFP and OH reactivity at the suburban and rural sites, respectively. These findings highlight the importance of identifying and characterizing VOC sources at different sites to help policymakers develop targeted measures for pollution mitigation in specific areas.

Predicting pressure-dependent rate constants for the furan + OH reactions and their impact under tropospheric conditions.

In this work, we have evaluated the influence of temperature and pressure on the mechanism of furan oxidation by the OH radical. The stationary points on the potential energy surface were described at the M06-2X/aug-cc-pVTZ level of theory. In the kinetic treatment at the high-pressure limit (HPL), we have combined the multistructural canonical variational theory with multidimensional small-curvature tunneling corrections and long-range transition state theory. The system-specific quantum Rice-Ramsperger-Kassel theory was employed to estimate the pressure-dependent rate. In the HPL, the OH addition on the α carbon is the dominant pathway in the mechanism, producing a product via the ring-opening process, also confirmed by the product branching ratio calculations. The overall rate constant, obtained by a kinetic Monte Carlo simulation, reads the form koverall=5.22×10-13T/3001.10⁡exp1247(K/T) and indicates that the furan oxidation by OH radicals is a pressure-independent reaction under tropospheric conditions.

Time-resolved FRS detection of OH radical for chemical reactions rate measurement

The time-resolved Faraday rotation spectroscopy method with a DFB diode laser at 1434 nm was used to detect the hydroxyl radical OH in the first overtone region. Experiments were made at the most intense Q(3/2) line of the 2Π3/2 electronic term. The sufficient concentration for radical measurement is 2 × 1012 cm−3, with the resolving time approximately 10−6 s. This resolution is sufficient for studying fast chemical reactions, which was demonstrated by measuring the rate constant of the OH and dimethylsulfide reaction.

Experimental and kinetic study of ammonia oxidation and NOx emissions at elevated pressures

To investigate the effects of pressure and equivalence ratio on ammonia oxidation and the emission of NOx, experiments were conducted in a flow reactor at atmospheric pressure and 5.0 MPa between 600 and 1250 K, with equivalence ratios ranging from 0.125 to 1.0. In addition, a kinetic model applicable to ammonia oxidation under high-pressure conditions was developed and validated against the performance of other recently published kinetic models with reference to several parameters associated with the ammonia oxidation and the emission of NOx under high-pressure conditions. The developed model was also validated against previously published experimental data collected under high-pressure conditions, and it can accurately capture the data obtained. The study found that the increase in pressure and oxygen content significantly enhanced the reactivity of NH3 and consequently resulted in increased NO and N2O concentrations at low temperatures. Based on a kinetic analysis using the developed model, the HO2 content was identified as the key factor influencing the difference in reactivity between atmospheric and high pressure. Sensitivity analysis revealed that H + O2 (+M) = HO2 (+M) inhibits NH3 consumption at atmospheric pressures but has a promoting effect at high pressures, because at high pressures the reaction generates a significant amount of HO2 radicals at low temperatures, increasing the reaction activity and reducing the onset temperature of ammonia oxidation. The H2NO system becomes even more critical under higher pressure, as more NH2 and O2 are converted to H2NO and NO. H2NO, NO, and N2O act as chain carriers in the reaction sequence, converting NH2 and O2 to OH and NO and accelerating the process of ammonia oxidation. At the same time, higher pressure enhances the NOx formation pathway due to the large amount of HO2 generated. However, as temperatures increase, O and OH radicals increase and DeNOx pathways dominate, resulting in lower NO and N2O contents. In the context of the equivalence ratios, the increase in the O2 content enhances the generation of HO2, leading to a greater tendency for NH2 to be converted in the NH2 + HO2 = HNO + H2O and NH2 + HO2 = H2NO + OH reaction pathways to HNO and H2NO, respectively. The HNO and H2NO produced are subsequently converted to NOx.

Theoretical Insights into the Gas-Phase Oxidation of 3-Methyl-2-butene-1-thiol by the OH Radical: Thermochemical and Kinetic Analysis.

3-Methyl-2-butene-1-thiol ((CH3)2C═CH-CH2-SH; MBT) is a recently identified volatile organosulfur compound emitted from Cannabis sativa and is purported to contribute to its skunky odor. To understand its environmental fate, hydroxyl radical (•OH)-mediated oxidation of MBT was conducted using high-level quantum chemical and theoretical kinetic calculations. Three stable conformers were identified for the title molecule. Abstraction and addition pathways are possible for the MBT + OH radical reaction, and thus, potential energy surfaces involving H-abstraction and •OH addition were computed at the CCSD(T)/aug-cc-pV(T+d)Z//M06-2X/aug-cc-pV(T+d)Z level of theory. The barrier height for the addition of the OH radical to a C atom of the alkene moiety, leading to the formation of a C-centered MBT-OH radical, was computed to be -4.1 kcal mol-1 below the energy of the starting MBT + OH radical-separated reactants. This reaction was found to be dominant compared to other site-specific H-abstraction and addition paths. The kinetics of all the site-specific abstraction and addition reactions associated with the most stable MBT + OH radical reaction were assessed using the MESMER kinetic code between 200 and 320 K. Further, we considered the contributions from two other conformers of MBT to the overall reaction of MBT + OH radical. The estimated global rate coefficient for the oxidation of MBT with respect to its reactions with the OH radical was found to be 6.1 × 10-11 cm3 molecule-1 s-1 at 298 K and 1 atm pressure. The thermodynamic parameters and atmospheric implications of the MBT + OH reaction are discussed.

The quasi-classical trajectory study of vibrational mode-specific dynamics of the multi-channel reaction OH− + CH3F

The vibrational mode-specific dynamics of the multiple channel reaction, OH− + CH3F, namely the effects of excitations of the CF stretching (v1), CH3 rocking (v3), CH3 umbrella (v4), CH3 deformation (v5), CH symmetric stretching (v7) and CH asymmetric stretching (v8) as well as the OH stretching (vOH) on the reactivity of different product channels, were investigated by running extensive quasi-classical trajectories on a latest accurate full-dimensional potential energy surface. Integral cross sections (ICS), differential cross sections (DCS), product state populations, and product energy distributions for different vibrational excitation modes were calculated and analyzed. The Sudden Vector Projection model is also employed to rationalize these dynamic results.

Glutathione degradable manganese-doped polydopamine nanoparticles for photothermal therapy and cGAS-STING activated immunotherapy of lung tumor

Photothermal therapy (PTT), which utilizes nanomaterials to harvest laser energy and convert it into heat to ablate tumor cells, has been rapidly developed for lung tumor treatment, but most of the PTT-related nanomaterials are not degradable, and the immune response associated with PTT is unclear, which leads to unsatisfactory results of the actual PTT. Herein, we rationally designed and prepared a manganese ion-doped polydopamine nanomaterial (MnPDA) for immune-activated PTT with high efficiency. Firstly, MnPDA exhibited 57.2% photothermal conversion efficiency to accomplish high-efficiency PTT, and secondly, MnPDA can be stimulated by glutathione (GSH) to the release of Mn2+, and it can produce ·OH in a Fenton-like reaction with the overexpressed H2O2 and stimulate the cyclic GMP-AMP synthase-stimulator of interferon genes (cGAS-STING) pathway. These two synergistically can effectively remove lung tumor cells that have not been ablated by PTT, resulting in an 86.7% tumor suppression rate under laser irradiation of MnPDA in vivo, and further significantly activated the downstream immune response, as evidenced by an increased ratio of cytotoxic T cells to immunosuppressive Treg cells. Conclusively, the GSH degradable MnPDA nanoparticles can be used for photothermal therapy and cGAS-STING-activated immunotherapy of lung tumors, which provides a new idea and strategy for the future treatment of lung tumors.

Experimental and simulation study of inert gas mixture inhibiting coal spontaneous combustion

To explore the mechanism of inhibiting spontaneous combustion of coal by mixed gases, the low-temperature oxidation characteristics of coal under different components of mixed gases were analyzed. ESR and FTIR experiments were used to investigate the effects of different gas mixtures on the activity of coal during low-temperature oxidation and the oxidation reaction of coal surface functional groups. The mechanism of chemical oxygen inhibition of mixed gas was studied by density functional theory. The results show that the larger the CO2 component in the mixed gas, the higher the ability to inhibit coal oxidation. The concentration of free radicals in coal under dry air condition is higher than that under inert mixed gas condition during oxidation heating at 30–230 °C. The oxidation ability of –CH3, –OH and oxygen-containing functional groups in the mixed gas reaction is inhibited. Through quantum chemistry calculation, it is found that the mixed gas increases the activation energy of free radicals and reduces the heat release of the reaction. This study provides theoretical reference for coal mine thermal disaster.

Optimizing Intermediate Adsorption on Pt Sites via Triple-Phase Interface Electronic Exchange for Methanol Oxidation.

For the most commonly applied platinum-based catalysts of direct methanol fuel cells, the adsorption ability toward reaction intermediates, including CO and OH, plays a vital role in their catalytic activity and antipoisoning in anodic methanol oxidation reaction (MOR). Herein, guided by a theoretical mechanism study, a favorable modulation of the electronic structure and intermediate adsorption energetics for Pt active sites is achieved by constructing the triple-phase interfacial structure between tin oxide (SnO2), platinum (Pt), and nitrogen-doped graphene (NG). From the strong electronic exchange at the triple-phase interface, the adsorption ability toward MOR reaction intermediates on Pt sites could be efficiently optimized, which not only inhibits the adsorption of CO* on active sites but also facilitates the adsorption of OH* to strip the poisoning species from the catalyst surface. Accordingly, the resulting catalyst delivers excellent catalytic activity and antipoisoning ability for MOR catalysis. The mass activity reaches 1098 mA mg-1Pt, 3.23 times of commercial Pt/C. Meanwhile, the initial potentials and main peak for CO oxidation are also located at a much lower potential (0.51 and 0.74 V) against commercial Pt/C (0.83 and 0.89 V).

Theoretical Study on the Mechanisms and Kinetics of Atmospheric Oxidation of Tetrafluoropropyne and Its Analogues.

Tetrafluoropropyne (C3F4) is a potential dielectric in various electrical insulating equipment to replace the most potent industrial greenhouse gas, sulfur hexafluoride. Atmospheric oxidation of C3F4 by OH radicals in the presence of molecular O2 has been investigated theoretically in order to clarify the lifetime and degradation products at mechanistic and kinetic aspects. Energetic minimum-energy pathways for the C3F4 + OH/O2 reactions were calculated in detail using various theoretical methods including density functional M06-2X and CCSD for geometries, CBS-QB3, CCSD(T), and multireference RS2 with extrapolation to the complete basis-set limit for energies. It has been demonstrated that the C3F4 + OH reaction takes place via the bifurcated C-O addition/elimination routes leading to CF3C(OH)═CF and CF3C═C(OH)F radical adducts, where the latter is more preferable in view of the difference in barrier heights (1.3 vs 0.3 kcal/mol), followed by H-migration, HF-elimination, and C-C and C-F bond fission. The atmospheric lifetime of C3F4 was estimated to be about 13 days, which is indicative of a very short-lived substance in the atmosphere. Further degradation of the energy-rich C3F4OH* intermediates by O2 takes place spontaneously in view of the successive barrier-free and highly exothermic pathways, producing a variety of fluorinated acids, anhydrides, biacetyls, and regenerating OH radicals. For comparison, the reactions of C3H4, CF3CCH, and CH3CCF with OH radicals were examined to clarify the F-substitution effect. It is revealed that the reactivity of fluoropropynes could be either reduced by CF3 or enhanced by atomic F attached to the acetylenic carbon. The present work provides a fundamental understanding of the reactions of fluoroalkynes with OH/O2. The use of C3F4 as a promising eco-friendly gaseous dielectric alternative to SF6 has been supported.