O2 Reaction Research Articles

Hematite (Fe2O3)-modified biopolymer for Rhodamine B degradation under visible light

This study deals with the preparation of a novel biomaterial by incorporating the hematite α-Fe2O3 onto crushed leaves of the Washingtonia filifera palm tree in their raw state and in extracted cellulose from the same plant. The incorporation of α-Fe2O3 was accomplished by hydrothermal route at 200 °C. The palm leaves, extracted cellulose, and synthesized products were characterized by thermal analysis (TG) and FT-IR spectroscopy. The latter revealed peaks at 524 and 449 cm−1 for the synthesized material, attributed to vibrational deformation of the inorganic Fe-O bond. In contrast to the TG profile of raw palm leaves, the thermogram of the composite degrades in a single step at 343 °C. This one-step decomposition clearly indicates the chemical modification of our cellulose matrix and confirms the successful incorporation of the hematite α-Fe2O3 into the lignocellulose. The second part is devoted to α-Fe2O3 working as sensitizer in photocatalysis, it was characterized optically (Eg = 1.94 eV) and electrochemically with a flat band potential of −0.53 VSCE. The conduction band (−0.73 V SCE ) is more cathodic than the potential of the O2/O2 •− couple (−0.52 V SCE ) and should reduce dissolved oxygen into reactive O2 •− radical. The as-prepared materials were successfully tested in the photocatalytic degradation of Rh B (10 ppm) and the result gave an abatement of 60% on α-Fe2O3/lignocellulose under visible light irradiation (LED lamp) with a flux of 23 mW cm−2. The kinetic obeys a first-order model with a half photocatalytic-life of ∼ 7 h.

Value-Added Electrolysis Hydrogen Production Via Methanol Oxidation over a Synergetic Pt1-W Dual-Site Catalyst

Electrochemical water splitting is a promising way of generating hydrogen for future sustainable green energy source technology options to replace nonrenewable and environmentally pollutant hydrocarbon energy sources. However, due to its high overpotential in oxygen evolution reaction (OER) and low-value product O2, some candidate anodic reactions with low potential should be proposed to replace OER, such as alcohol oxidation. Unlike fuel cell applications, partial oxidation is preferred to achieve high-value products rather than complete oxidation. For this purpose, we design a synergistic effect Pt1-W site on the dual-doped TiO2 support (Ti0.8W0.2NxOy) to catalyze alkaline methanol oxidation and gain 90% selectivity of formate production. Comparing the case of the Pt nanoparticles (69% selectivity of formaldehyde), the Pt single-atom catalyst controls selectivity and enhances the reactivity and stability attributed to the strong catalyst-support interaction. As a result, this work shows a novel strategy for electrochemical hydrogen production at far lower anodic potential by designing a stable and efficient Pt-based single-atom catalyst.

Revealing the Functionality of Li2CO3 in the Li-Metal SEI Via Study of Gas-Reacted Li Films

The solid electrolyte interphase (SEI) governs transport and reactivity at lithium interfaces, so its structure and composition are essential factors in improving the cyclability of next-generation lithium-metal anodes (1). An ideal SEI should passivate Li against continuous reactions with electrolyte while promoting facile transport of Li+ ions. However, achieving these properties is challenging, in part because our understanding of the relative desirability of different SEI materials is often based on qualitative relationships between characterization and cell performance; quantitative experimental conductivity (2, 3) and stability (4) measurements are limited. As a further complication, the highly reductive conditions (-3.04 V vs SHE) and the complex nanoscale structure of the SEI can lead to markedly different behavior in practical contexts compared to bulk environments (2, 5, 6). In previous work, our group developed techniques to synthesize single-component, nanoscale films of LiF and Li2O on Li, enabling direct measurements of their transport properties and reactivity in relevant electrolytes (6-8). Here, we turn to Li2CO3, which has a mixed reputation as an SEI material. While many papers assert its desirability based on high ionic conductivity (9-12), others raise concerns related to reductive instability (13-15).In this work, we synthesized Li2CO3 films via sequential reactions of O2 and CO2 on polished lithium surfaces at slightly elevated temperature (175-200°C). Scanning electron microscopy (SEM) and air exposure tests showed that the prepared films are conformal, tens of nanometers thick, and relatively pinhole-free. Fourier transform infrared spectroscopy (FTIR) was used to confirm the speciation of the films, and titration-based quantification yielded insights into their composition. We found that the formation of Li2CO3 is associated with generation of Li2O and Li2C2, confirming that the reductive instability of Li2CO3 results in the evolution of a more reduced inner SEI layer at the Li | Li2CO3 interface. We also studied the stability of films at the SEI | electrolyte interface, performing electrolyte soak tests then assessing native SEI evolution using FTIR and titration-based quantification of LiF. We found that Li2CO3 is poorly-passivating in fluorinated electrolytes, leading to continuous formation of native SEI. However, in 1M LiClO4 PC electrolyte, the Li2CO3 film remains intact, enabling the use of electrochemical impedance spectroscopy (EIS) to study film transport properties. This analysis reveals an ionic conductivity of ~4-8 nS/cm, which is substantially greater than ionic conductivities previously measured in Li2O (~1 nS/cm) and LiF (~0.5 nS/cm) (6). Together, these results show that though Li2CO3 has some stability limitations, it could promote facile Li+ ion transport as a stable meso-SEI layer in less-fluorinated electrolytes.This work was funded by the 2022-2023 ECS Toyota Young Investigator Fellowship award. References E. Peled and S. Menkin, Journal of The Electrochemical Society, 164, A1703 (2017).S. Lorger, K. Narita, R. Usiskin and J. Maier, Chemical Communications, 57, 6503 (2021).P. Lu and S. J. Harris, Electrochemistry Communications, 13, 1035 (2011).B. S. Parimalam, A. D. MacIntosh, R. Kadam and B. L. Lucht, Journal of Physical Chemistry C, 121, 22733 (2017).S. Shi, Y. Qi, H. Li and L. G. Hector, (2013).R. Guo and B. M. Gallant, Chemistry of Materials, 32, 5525 (2020).R. Guo, D. N. Wang, L. Zuin and B. M. Gallant, Acs Energy Letters, 6, 877 (2021).M. F. He, R. Guo, G. M. Hobold, H. N. Gao and B. M. Gallant, Proceedings of the National Academy of Sciences of the United States of America, 117, 73 (2020).E. Plichta, S. Slane, M. Uchiyama, M. Salomon, D. Chua, W. B. Ebner and H. W. Lin, J. Electrochem. Soc., 136, 1865 (1989).D. Aurbach, A. Zaban, Y. Gofer, E. Ely, I. Weissman, O. Chusid and O. Abramson, Recent studies of the lithium-liquid electrolyte interface Electrochemical, morphological and spectral studies of a few important systems, in Journal of Power Sources, p. 76 (1995).T. Osaka, T. Momma, Y. Matsumoto and Y. Uchida, Journal of Power Sources, 68, 497 (1997).J. Besenhard, M. W. Wagner, M. Winter, A. D. Jannakoudakis, P. D. Jannakoudakis and E. Theodoridou, Journal of Power Sources, 413 (1993).K. Leung, F. Soto, K. Hankins, P. B. Balbuena and K. L. Harrison, Journal of Physical Chemistry C, 120, 6302 (2016).N. Tian, C. Hua, Z. Wang and L. Chen, Journal of Materials Chemistry A, 3, 14173 (2015).B. Han, Z. Zhang, Y. C. Zou, K. Xu, G. Y. Xu, H. Wang, H. Meng, Y. H. Deng, J. Li and M. Gu, Advanced Materials, 33 (2021). Figure 1

(Invited) Mechanical Properties of Proton Exchange Membranes for Water Electrolysis Applications

Water electrolysers are critical to the advancement of sustainable hydrogen technologies. A key component of proton-exchange membrane water electrolysers (PEMWE) is the ionomer membrane which transports protons and water from the anode to the cathode and physically separates the H₂ and O₂ reaction products. Importantly, the barrier properties of the membrane must be maintained at high differential pressure over the lifetime of the PEMWE. To help predict the mechanical durability and operational safety of the PEMWE, it is important to understand the mechanical properties of the PEM as a function of temperature, differential pressure, and time.The main component of a typical modern PEM is a perfluorosulfonic acid (PFSA) ionomer. PFSAs have a hydrophobic perfluorinated backbone with pendant perfluorinated side chains terminating in sulfonic acid groups. The general chemical structure of PFSAs is understood to result in phase separation into hydrophilic, sulfonate-rich domains that act as transport pathways and hydrophobic, tetrafluoroethylene-rich domains that impart thermomechanical stability. In PEMWE applications, short-side chain PFSAs are a promising alternative to the benchmark Nafion, a long-side chain PFSA. At a given ion-exchange capacity (IEC), the ratio of perfluorinated backbone to sulfonic acid side chain increases as the side chain length decreases. Thus, short-side chain PFSAs may be more thermomechanically stable while maintaining good proton and water transport necessary for PEMWE efficiency.In this work, the mechanical properties of short-side chain PFSAs are investigated as a function of IEC, temperature, differential pressure, and time. Particular focus is given to compressive mechanical measurements to simulate the conditions experienced by the membrane in PEMWE applications. The findings are expected to help inform the design of next-generation membranes for hydrogen technology applications.

Role of Ammonia in Aerosol Liquid Water, pH, and Secondary Inorganic Aerosols Formation at an Ammonia-rich City in Changzhou

Ammonia （NH3） is an important alkaline reactive nitrogen, which, as a precursor of fine particulate matter, raises public health issues. In this study, online NH3, SO2, NO2, PM2.5, and its water-soluble inorganic ions were detected to deduce the influence of NH3 on aerosol liquid water content （AWC） and aerosol pH, including the formation of water-soluble secondary ions in PM2.5 in winter in Changzhou, an ammonia-rich city in the Yangtze River Delta area in winter. The results showed that NH4+ mainly existed in the form of NH4NO3 and （NH4）2SO4, and the remaining NH4+ existed as NH4Cl. Owing to the NH3-NH4+ buffer system, the aerosol pH values were found at 4.2 ± 0.4, which was positively correlated with the NH3 content. The aerosol pH value variation narrowed with the increase in PM2.5 concentration and tended to be between 4 to 5. AWC increased exponentially with the increase in humidity and SNA content, among which NH4NO3, （NH4）2SO4, and NH4Cl contributed 58.5%, 18.4%, and 8.3%, respectively, due to their hygroscopicity. Aerosol pH, AWC, and NH3-NH4+ conversion promoted the gas-to-particle conversion of SO2 and NO2. In Changzhou, rich NH3-NH4+ were found to maintain relatively high pH values, push up AWC, and promote the heterogeneous reaction of SO2, whereas NO3- generation was dominated by a homogeneous reaction, which was accelerated by NH3. According to the simulation results, relatively noticeable changes in aerosol pH and AWC could be found by the reduction of up to 30% of NH3.

Singlet Oxygen Photophysics: From Liquid Solvents to Mammalian Cells.

Molecular oxygen, O2, has long provided a cornerstone for studies in chemistry, physics, and biology. Although the triplet ground state, O2(X3Σg-), has garnered much attention, the lowest excited electronic state, O2(a1Δg), commonly called singlet oxygen, has attracted appreciable interest, principally because of its unique chemical reactivity in systems ranging from the Earth's atmosphere to biological cells. Because O2(a1Δg) can be produced and deactivated in processes that involve light, the photophysics of O2(a1Δg) are equally important. Moreover, pathways for O2(a1Δg) deactivation that regenerate O2(X3Σg-), which address fundamental principles unto themselves, kinetically compete with the chemical reactions of O2(a1Δg) and, thus, have practical significance. Due to technological advances (e.g., lasers, optical detectors, microscopes), data acquired in the past ∼20 years have increased our understanding of O2(a1Δg) photophysics appreciably and facilitated both spatial and temporal control over the behavior of O2(a1Δg). One goal of this Review is to summarize recent developments that have broad ramifications, focusing on systems in which oxygen forms a contact complex with an organic molecule M (e.g., a liquid solvent). An important concept is the role played by the M+•O2-• charge-transfer state in both the formation and deactivation of O2(a1Δg).

Trapping an Elusive Fe(IV)-Superoxo Intermediate Inside a Self-Assembled Nanocage in Water at Room Temperature.

Molecular cavities that mimic natural metalloenzymes have shown the potential to trap elusive reaction intermediates. Here, we demonstrate the formation of a rare yet stable Fe(IV)-superoxo intermediate at room temperature subsequent to dioxygen binding at the Fe(III) site of a (Et4N)2[FeIII(Cl)(bTAML)] complex confined inside the hydrophobic interior of a water-soluble Pd6L412+ nanocage. Using a combination of electron paramagnetic resonance, Mössbauer, Raman/IR vibrational, X-ray absorption, and emission spectroscopies, we demonstrate that the cage-encapsulated complex has a Fe(IV) oxidation state characterized by a stable S = 1/2 spin state and a short Fe-O bond distance of ∼1.70 Å. We find that the O2 reaction in confinement is reversible, while the formed Fe(IV)-superoxo complex readily reacts when presented with substrates having weak C-H bonds, highlighting the lability of the O-O bond. We envision that such optimally trapped high-valent superoxos can show new classes of reactivities catalyzing both oxygen atom transfer and C-H bond activation reactions.

A Transcriptomic Analysis of Bottle Gourd-Type Rootstock Roots Identifies Novel Transcription Factors Responsive to Low Root Zone Temperature Stress.

The bottle gourd [Lagenaria siceraria (Molina) Standl.] is often utilized as a rootstock for watermelon grafting. This practice effectively mitigates the challenges associated with continuous cropping obstacles in watermelon cultivation. The lower ground temperature has a direct impact on the rootstocks' root development and nutrient absorption, ultimately leading to slower growth and even the onset of yellowing. However, the mechanisms underlying the bottle gourd's regulation of root growth in response to low root zone temperature (LRT) remain elusive. Understanding the dynamic response of bottle gourd roots to LRT stress is crucial for advancing research regarding its tolerance to low temperatures. In this study, we compared the physiological traits of bottle gourd roots under control and LRT treatments; root sample transcriptomic profiles were monitored after 0 h, 48 h and 72 h of LRT treatment. LRT stress increased the malondialdehyde (MDA) content, relative electrolyte permeability and reactive oxygen species (ROS) levels, especially H2O2 and O2-. Concurrently, LRT treatment enhanced the activities of antioxidant enzymes like superoxide dismutase (SOD) and peroxidase (POD). RNA-Seq analysis revealed the presence of 2507 and 1326 differentially expressed genes (DEGs) after 48 h and 72 h of LRT treatment, respectively. Notably, 174 and 271 transcription factors (TFs) were identified as DEGs compared to the 0 h control. We utilized quantitative real-time polymerase chain reaction (qRT-PCR) to confirm the expression patterns of DEGs belonging to the WRKY, NAC, bHLH, AP2/ERF and MYB families. Collectively, our study provides a robust foundation for the functional characterization of LRT-responsive TFs in bottle gourd roots. Furthermore, these insights may contribute to the enhancement in cold tolerance in bottle gourd-type rootstocks, thereby advancing molecular breeding efforts.

In-situ inhibition mechanism of SO3 formation over MoS2 modified V2O5/TiO2 catalyst within selective catalytic reduction process

The utilization of commercial vanadium-titanium based catalysts (V2O5/TiO2) within the selective catalytic reduction (SCR) process is a prominent contributor to the emergence of sulfur trioxide (SO3) in coal-fired boiler environments. The direct modification of vanadium-titanium based catalysts has big potential to be an efficacious strategy for in-situ inhibiting SO3 formation. This research evaluates the effectiveness of MoS2 modified V2O5/TiO2 catalyst on SO2 oxidation under diverse conditions, using controlled condensation for SO3 collection. The results showed that V2O5-MoS2/TiO2 catalysts outperformed conventional V2O5/TiO2 catalysts in inhibiting the oxidation from SO2 to SO3 between 200 and 400 °C, with optimal performance at 350 °C. No significant effect was observed on the catalytic oxidation of SO2 when the O2 concentration was lower than that of SO2, whereas the introduction of appropriate quantities of NO promoted the generation of SO3. The excessive inclusion of NH3 nearly doubled the SO3 generation rate, increasing it from 0.284 % to 0.434 %. The NO and NH3 mixture markedly reduced SO3 generation to 0.085 % at a 62 mL/min mixture concentration, just 30 % of the rate without the mixture. Following the reaction of SO2 and O2, the reacted catalyst exhibited reduced pore volume, enhanced thermochemical stability, and lower susceptibility to SO2 catalytic oxidation. The addition of low-valence sulfur improves catalyst reducibility, reduces V5+–OH reactions in various atmospheres, and decreases the formation of sulphate and gaseous SO3. The Mo-S-Mo group also effectively prevents the formation of HSO4− intermediates. Additionally, MoS2 reacts with SO3 via a reduction reaction, significantly lowering the SO3 levels. Finally, in diverse atmospheric conditions, the catalysts maintained their V5+ content and catalytic efficiency, thus improving SCR performance stability.

Promoting Proton Donation through Hydrogen Bond Breaking on Carbon Nitride for Enhanced H2O2 Photosynthesis.

Photocatalytic H2O2 production has attracted much attention as an alternative way to the industrial anthraquinone oxidation process but is limited by the weak interaction between the catalysts and reactants as well as inefficient proton transfer. Herein, we report on a hydrogen-bond-broken strategy in carbon nitride for the enhancement of H2O2 photosynthesis without any sacrificial agent. The H2O2 photosynthesis is promoted by the hydrogen bond formation between the exposed N atoms on hydrogen-bond-broken carbon nitride and H2O molecules, which enhances proton-coupled electron transfer and therefore the photocatalytic activity. The exposed N atoms serve as proton buffering sites for the proton transfer from H2O molecules to carbon nitride. The H2O2 photosynthesis is also enhanced through the enhanced adsorption and reduction of O2 gas toward H2O2 on hydrogen-bond-broken carbon nitride because of the formation of nitrogen vacancies (NVs) and cyano groups after the intralayer hydrogen bond breaking on carbon nitride. A high light-to-chemical conversion efficiency (LCCE) value of 3.85% is achieved. O2 and H2O molecules are found to undergo a one-step two-electron reduction pathway by photogenerated hot electrons and a four-electron oxidation process to produce O2 gas, respectively. Density functional theory (DFT) calculations validate the O2 adsorption and reaction pathways. This study elucidates the significance of the hydrogen bond formation between the catalyst and reactants, which greatly increases the proton tunneling dynamics.

The characteristics and mechanism NO formation during hydroxylated fuels/NH3 oxidation in oxy-fuel atmospheres

Oxy-fuel combustion, as an important technology to realize CCUS in the field of combustion, needs to control the generation of pollutants such as NOx while realizing CO2 capture, and the conversion of fuel-N to N2 is crucial. Previous experiments have provided insights into the influence of different atmospheres on NO during oxy-fuel combustion of alcohols. However, the specific reaction mechanism underlying how the atmosphere and hydroxyl fuels impact NO generation through the free radical pool remains unclear. In this study, the formation and reduction of NO during the oxidation of CH3OH/NH3 and C2H5OH/NH3 in O2/CO2, O2/H2O and O2/CO2/H2O atmospheres with oxy-fuel condition were investigated by simulation. In the NO generation stage, different H2O, CO2, O2 and fuel types have little effect on the peak of NO although they change the NH3→NO reaction path. In the process of NO reduction, stage 1 is the main reaction phase of NO→N2, and both CO2 and H2O are beneficial for the reduction of NO. But the reduction of NO by H2O was more pronounced. In the case of simultaneous addition of H2O and CO2, the reducing effect of H2O and CO2 alone on NO was attenuated. On the other hand, the reduction effect exerted by H2O and CO2 was stronger in high than in low oxygen-fuel ratio, stronger in C2H5OH than in CH3OH. The reduction of NO by H2O and CO2 is based on the general equation NO→N2+O2. H2O is used to promote the reaction in the positive direction by consuming O2 to convert it to H and OH, so that more of the element O is converted to OH than O2 to inhibit the production of NO. The CO2 contributes to the formation of less O2 during the reduction of N2 from NO by promoting reaction NO + N→O + N2, while the additional OH increases the "capacity" of O2 in the NO→N2+O2 reaction.

Intermediates involved in the reduction of SO2: insight into the mechanism of sulfite reductases.

Sulfite reductases (SiRs) catalyze the reduction of SO32- to H2S in biosynthetic sulfur assimilation and dissimilation of sulfate. The mechanism of the 6e-/6H+ reduction of SO32- at the siroheme cofactor is debated, and proposed intermediates involved in this 6e- reduction are yet to be spectroscopically characterized. The reaction of SO2 with a ferrous iron porphyrin is investigated, and two intermediates are trapped and characterized: an initial Fe(III)-SO22- species, which undergoes proton-assisted S-O bond cleavage to form an Fe(III)-SO species. These species are characterized using a combination of resonance Raman (with 34S-labelled SO2), EPR and DFT calculations. Results obtained help reconcile the different proposed mechanisms for the SiRs.

Degradation of the neonicotinoid insecticide imidacloprid by ozonation and the E-peroxone process: Mechanisms, transformation products, and toxicity

In this study, degradation of the neonicotinoid insecticide imidacloprid (IMI) by ozonation and the E-peroxone process was investigated. Results show that IMI is an O3-refractory compound with second-order rate constants for the reaction with O3 and •OH (kO3,IMI and k•OH,IMI) being 3.9 and 3.95 × 109 M−1 s−1 at pH 7, respectively. Due to its low O3 reactivity, IMI was only abated by < 20 % in a selected groundwater during ozonation with typical ozone doses applied in water treatment (1–5 mg/L). In comparison, the E-peroxone process considerably enhanced IMI removal efficiency to > 80 % under similar reaction conditions. During both ozonation and the E-peroxone process, IMI was mainly abated by •OH oxidation. The reaction mechanism of IMI with •OH was investigated with quantum computations, which show that H-abstraction at H23 site was the most favorable pathway. Sixteen transformation products (TPs) generated from IMI degradation were identified using various chromatographic and mass-spectrometric techniques. The acute and chronic toxicities of IMI and its TPs to different aquatic organisms were evaluated with Microtox bioassay and the ECOSAR program, which indicate that some TPs (e.g., TP2–TP5 and TP7–TP9) are even more toxic than IMI to aquatic organisms (e.g., daphnia). The results of this study suggest that IMI along with its TPs should be sufficiently abated during water treatment, and the E-peroxone process provides an efficient option to upgrade conventional ozonation for enhanced IMI abatement.

ClSO and ClSO2 photochemistry: Implications for the Venusian atmosphere.

The electronic structure and spectroscopy of ClSOx (x = 1 and 2) isomers were investigated using coupled cluster theory and multireference interaction methods. In this study, the equilibrium geometry and harmonic vibrational frequencies of these isomers in their ground electronic state were shown. Our analysis of the vertical excitation energy and potential energy surface showed the photochemical instability of ClSO for wavelengths below 280nm. Furthermore, the photodissociation of ClSO was unlikely to cause the formation of diatomic ClS. At the same time, ClSO could form atomic chlorine and SO as a result of photodissociation through the repulsive states. In the case of ClSO2, a novel weakly bound Cl-SO2 isomer was identified, indicating the potential influences on the chlorine and SO2 reactions. The potential energy surface of the most stable ClSO2 isomer also indicated the potential production of SO2 in both its ground and excited states. In addition, the electronic spectrum of ClSO2 was predicted to be broad, with numerous significant peaks in the near-UV‒Vis range. Valuable new insights into the chemical role of chlorine and sulfur in Venus's atmosphere were provided, along with a discussion of a potential mechanism contributing to the H2O and SO2 depletion in Venus's atmosphere.

Baeyer-Villiger oxidation of cyclohexanone catalyzed by bifunctional Mg2Fe layered double hydroxide

Mg2Fe layered double hydroxide was prepared by the coprecipitation method and was used as an efficient catalyst for the Baeyer–Villiger oxidation of cyclohexanone to caprolactone in the presence of molecular oxygen and benzaldehyde. The obtained catalyst was characterized by XRD, FTIR, SEM, TG, XPS, and Hammett indicator method. The effects of solvent, benzaldehyde dosage. reaction temperature, O2 flow rate, catalyst dosage, and reaction time on the reaction were examined. Mg2Fe-LDH catalyst shows good catalytic results in the catalytic process which could also selectively convert a variety of cyclic ketone derivatives to their corresponding lactone with high yields. A series of controlled experiments were conducted to reveal the reaction mechanism. The results imply that the catalyst is bifunctional, possessing both alkalinity and redox properties. The alkalinity of Mg2Fe-LDH catalyzes the oxygen transfer from perbenzoic acid to cyclohexanone, iron with its highest oxidation state could catalyze the autoxidation of benzaldehyde to perbenzoic acid. In addition, the catalysts can be reused at least five times without significant decrease in catalytic activity.

A novel formulation representation regarding the equilibrium constant subject to reaction between N2 and O2

Nitrogen (N2) and oxygen (O2) are the two main components in the air. Here, we report a novel formulation representation concerning the chemical equilibrium constant regarding the reaction of N2 and O2. It depends only on the standard experimental data subject to four molecular constants of N2, O2 and NO, while the conventional calculation schemes involve application of multiple experimental spectroscopic data or calorimetric data. Comparing two sets of experimentally measured data respecting the equilibrium constant with the theoretical prediction results obtained from the developed formulation and provided in the previous literature, we validate the reliability of the proposed prediction model. The mean absolute deviations between two experimental data sets and the predicted results from the proposed formulation are 2.983 % and 4.047 %, respectively, and the corresponding deviations of the same experimental measurements from the previous theoretical values reported in the literature are 11.07 % and 33.53 %, respectively.

The ultra-thin flexible graphite/epoxy bipolar plates adjusted by different surface tension modifiers and application in the fuel cell stack

The graphite-resin composite bipolar plates prepared by the traditional hybrid pressing process exhibit poor conductivity, processability, and wettability due to the graphite flake layer being covered by resin, hindering the formation of a continuous conductive network, which significantly constrains their promotion and application in the field of proton exchange membrane fuel cells (PEMFC). In this paper, an ultra-thin flexible graphite/epoxy composite bipolar plates (BPs) with a thickness of only 0.775 mm is prepared followed by a process of flexible graphite preforming and impregnation curing. The hydrophilicity-modified BPs surface has a contact angle of 59.01° as well as flexural and compressive strengths of 11 MPa and 4 MPa and possesses a high in-plane conductivity of 380 S/cm and a low in-plane specific resistance of 6 mΩ cm2. The electrostack test results show that the hydrophilic runner channel is more conducive to the diffusion and spreading of H2O generated from the cathode-side reduction reaction in the flow channel, so that O2 smoothly passes through the gas diffusion layer to participate in the reduction reaction of O2, and exhibits higher electric power at high current density, while the hydrophobically modified BPs has relatively poor overall performance due to ohmic losses.

Contrast and Complexity in the Low-Temperature Kinetics of CN(v = 1) with O2 and NO: Simultaneous Kinetics and Ringdown in a Uniform Supersonic Flow.

Bimolecular rate coefficients were determined for the reaction CN(v = 1) + NO and O2 using continuous wave cavity ringdown spectroscopy in a uniform supersonic flow (UF-CRDS). The well-matched time scales for ringdown and reaction under pseudo-first-order conditions allow for the use of the SKaR method (simultaneous kinetics and ringdown) in which the full kinetic trace is obtained on each ringdown. The reactions offer an interesting contrast in that the CN(v = 1) + NO system is nonreactive and proceeds by complex-mediated vibrational relaxation, while the CN(v = 1) + O2 reaction is primarily reactive. The measured rate coefficients at 70 K are (2.49 ± 0.08) × 10-11 and (10.49 ± 0.22) × 10-11 cm3 molecule-1 s-1 for the reaction with O2 and NO, respectively. The rate for reaction with O2 is a factor 2 lower than previously reported for v = 0 in the same temperature range, a surprising result, while that for NO is consistent with extrapolation of previous high-temperature measurements to 70 K. The latter is also discussed in light of theoretical calculations and measurements of the rate constants for the association reaction in the high-pressure limit. The measurements are complicated by the presence of a metastable population of high-J CN formed by photolysis of the precursor BrCN, and a kinetic model is developed to treat the competing relaxation and reaction. It is particularly problematic for reactions at low temperatures where the rotational relaxation and reaction have similar rates, precluding a reliable determination of the rate coefficients at 30 K. Also presented are important modifications to the data acquisition and control for the instrument that have yielded considerably enhanced stability and throughput.

Unraveling the Solvent Regulation in the Heteroatom-Doped Endohedral Gold Clusters: A Theoretical Study on the Electronic Properties and O2 Activation.

Liquid-phase synthesis of atomically precise nanoclusters has experienced rapid development recently, where polar solvents are indispensable in such a process. However, the regulation effect of solvents on the structural and electronic properties of different metal clusters and cluster assembly materials is still not well understood. Herein, a comprehensive density functional theory calculation has been performed to explore the solvation effect on heteroatom-doped endohedral gold clusters that always have remarkable stabilities and tunable electronic structures. The solvation free energy of the M@Au12 clusters (M = Cr, Mo, W, Co, Rh, Ir, Cu, Ag, and Au) was found to be related to the charge distribution of the central doped-atom M and the outer Au12 cage. Moreover, the aqueous solvent was observed to be able to increase the adsorption capacity of M@Au12 to O2 following the activation of O2 through the charge transfer from M@Au12 to O2, in which the transferred electrons occupy the π antibonding orbital of O2. In addition, the water solvent can also improve the hydrogenation reaction of O2 to form OOH over M@Au12, where the activation energy barrier for this process is very low with the participation of the solvent. Considering the importance of solvents in the liquid-phase synthesis of atomically precise clusters, these findings highlighted here could provide valuable theoretical guidance in potential applications of functional gold nanoclusters, especially in the liquid-phase cluster catalysis.

A Common Bottleneck for Metal Oxidation by Molecular Oxygen Across Size Regimes: Kinetics of Atomic Lanthanide Cations (La+-Lu+) with O2.

Kinetics of the lanthanide cations (Ln+ = La+-Lu+ excluding Pm+) reacting with molecular oxygen were measured in a selected-ion flow tube apparatus from 300 to 600 K. Where exothermic, these reactions occur efficiently, producing LnO+ + O. The reactions display positive temperature dependences consistent with Arrhenius equation behavior and show small activation energies (0-2 kJ mol-1) that are strongly correlated to promotion energies of the Ln+ atoms. Reanalysis of literature data on neutral Ln + O2 reactions show a similar correlation with slightly larger activation energies (0-10 kJ mol-1). The data are explained by a common mechanism controlling oxidation by molecular oxygen in these systems, as well as in gas-phase reactions of transition metal and posttransition metal cluster anions, neutral clusters deposited on surfaces, and for oxygen incident on metal surfaces. It is posited that across these systems, the height of an early barrier along the reaction coordinate is predictable based on knowledge of the electronic states of the reactants and may be used to either promote or inhibit oxygen activation.