Oxygen Molecules Research Articles

Enhancing directional thermal conductivity in hexagonal boron nitride reinforced epoxy composites through robust interfacial bonding

AbstractEstablishing a robust interfacial bond between hexagonal boron nitride (h‐BN) plates and the epoxy matrix is essential for enhancing heat transfer, which is difficult because of h‐BN's low‐surface energy, tendency to clump together, and the chemical inertness of the epoxy matrix. This research shows different techniques for treating the surface of h‐BN fillers by applying acids and thermal processes to activate the surface. The silanization process was used to increase the silane content on the surface of activated h‐BN in order to make it more compatible with the epoxy matrix. X‐ray photoelectron spectroscopy analysis revealed silicon peaks (Si2s peak at 150.1 eV and Si2p peak at 100.3 eV) in the spectrum of silane‐treated samples. Heat treatment resulted in the production of more oxygen molecules on the shell of h‐BN compared to the acid treatment. Here, the primary focus was on examining how surface treatment affects thermal conductivity (TC) performance in both in‐plane and through‐thickness paths. There was an increase in the epoxy's TC perpendicular to the plane, going from 0.21 to 0.47 (W/mK), showing a remarkable 123.8% enhancement by adding 10 wt% of silane‐modified‐thermal treated h‐BN particles. The improvement resulted from effectively silanizing the exterior boundary of h‐BN particles, enhancing connection and distribution in the epoxy matrix. Surface modification of h‐BN‐epoxy composites improves TC, leading to better heat conduction in thermal management systems, benefiting industries like aerospace, automotive, and energy systems.Highlights Silanization of h‐BN for better filler‐matrix bonding leading to improved heat transfer Boosting thermal conductivity in the through‐thickness direction with surface‐modified h‐BN Significant improvement in through‐thickness thermal conductivity with treated h‐BN. Thermal treatment of h‐BN produced better oxygenation than acid treatment. Application in aerospace and automotive through improved heat transfer.

Temperature-Dependent Oxidation Behavior of Silicon Carbide Surface: Reactive Molecular Dynamics Simulations.

The high-temperature oxidation mechanism of silicon carbide (SiC) is crucial for designing thermal protection systems in aircraft. This study explored the oxidative chemical reaction processes and mechanism on SiC surface and interfaces within the temperature range of 300-2300 K by using reactive molecular dynamics simulation. The oxygen impact on the silica (SiOx) growth of the SiC surface was analyzed, which shows a progressive increase of silica thickness. The simulation results indicated that the oxidation process of SiC was a typical passive oxidation mechanism. With the environmental temperature rising and oxygen impact, the increase of oxidation thickness on the SiC surface undergoes three oxidizing reaction processes: little chemical adsorption of oxygen molecules on the initial surface, rapid oxidation of silicon and carbon, and dramatic oxidation of the interface between the oxidation layer and SiC. Additionally, this work studied the mechanism of oxidation thickness growth and chemical diffusion of oxygen. The oxidation rate is weakened according to the oxygen atom diffusion barrier effect of silica repulsion. Moreover, the kinetic parameters were statistically calculated by fitting the growth of Si-O bonds and their reaction rate constants. Subsequently, the activation energy and pre-exponential factors were derived by using the Arrhenius equation to model the chemical reaction kinetics of the thermal oxidation process. The chemical reaction behaviors of the two stages could be concluded as follows: (i) in stage I, the initial oxidation is reaction rate limiting; (ii) in stage II, SiC oxidation is limited by both the oxidation reaction rate and the oxygen diffusion coefficient of the oxidation layer. The activation energy of stage II increased compared with stage I due to the oxygen atoms diffusion barrier between the oxidation layers. This study on the oxidation and ablation mechanism of the SiC surface at the atomic scale would provide insight into understanding thermal oxidation behavior and the design of ceramic materials.

Atmospheric pressure plasma jet interacting with a droplet on dielectric surface

Abstract The chemical processes at plasma–liquid interface has become a crucial point for plasmas’ various applications. In this study, the interaction between atmospheric pressure plasma jet and different-scale droplets were investigated by both experiments and modeling. The interaction transited from ‘annular’ mode to ‘solid’ mode when plasma involved with different size of droplets. As the droplet size increased, the high-field region moved from the plasma jet head to the gap between plasma jet head and droplet vertex surface. Additionally, the time averaged surface fluxes of the main active species were analyzed. For the flux of singlet oxygen (1O2), both small and medium-scale droplets reached the maximum value in the central region of the droplets, while for large-scale droplet, the maximum value was observed in the edge region of the droplet. This was due to the fact that, compared to small and medium-scale droplet, the edges of large-scale droplet are closer to the He–Air mixed boundary layer, where more oxygen molecules were provided in the gas environment, leading to enhanced electron collision reactions with oxygen molecules. The cause for these behaviors were also analyzed and discussed. This work shed light on the interaction mechanism for plasma–liquid interactions, which provides significant guidance for plasma medical or water treatment applications.

A near-infrared triggered multi-functional indocyanine green nanocomposite with NO gas release function inducing improved photothermal therapy

The integration of photothermal and near-infrared (NIR) imaging capabilities of indocyanine green (ICG) small molecules has attracted considerable attention in tumor diagnosis and treatment. However, the abnormal upregulation of cellular heat shock proteins (HSPs) induced by photothermal therapy (PTT) enhances cellular heat resistance, thereby severely affecting the efficacy of PTT. In this study, to address the impact of HSPs on the efficacy of PTT while obtaining high-quality NIR fluorescence imaging in the NIR region, we designed a targeted peptide@ICG nanofluorescent probe encapsulated in liposomes. The introduced cRGD targeting peptide not only possesses tumor-targeting capabilities but also features LA as the last amino acid in the targeting peptide, which can generate nitric oxide (NO) under reactive oxygen species (ROS) triggering. It can happen under 808 nm single-light source NIR light, and the guanidine group in the peptide decomposes and combines with singlet oxygen molecules to generate NO gas molecules, thereby exerting an elevated photothermal effect by inhibiting the expression of HSP70. In addition, the nanoprobes enable deep imaging and treatment of glioma in situ and can be combined with a laser speckle contrast imaging (LSCI) system for multimodal imaging. This composite probe demonstrates synergistic tumor therapeutic effects of photodynamic therapy (PDT), PTT, and gas therapy, offering a promising strategy for cancer treatment.

Line-shape parameters of the oxygen first rotational triplet

A lines shape of the first triplet of rotational band of oxygen molecule was studied beyond the Voigt profile in the framework of the quadratic approximation of speed dependence of collision relaxation rate. Recordings of the lines broadened by O2 and N2 were obtained at room temperature using two fundamentally different spectrometers, in particular, a video spectrometer and a spectrometer with radio-acoustic detection of absorption. A set of line-shape parameters was determined based on the line recording analysis. Data accuracy and reliability was evaluated from a comparative analysis of the parameters obtained from different techniques and with previous data.

Metal–Organic Skeleton-Derived W-Doped Ga2O3-NC Catalysts for Aerobic Oxidative Dehydrogenation of N-Heterocycles

N-heterocycles with quinoline structures hold significant importance within the chemical and pharmaceutical industries. However, achieving their efficient transformations remains a vital yet challenging endeavor. Herein, a series of W-doped Ga2O3-NC catalysts were synthesized using a Ga-MOF-derived strategy through a simple solvothermal method, with a remarkably high activity and selectivity towards the oxidative dehydrogenation of N-heterocycles. Furthermore, the MOF-derived W-doped Ga2O3-NC catalysts exhibit remarkable substrate tolerance and recyclability. The outstanding catalytic activity was attributed to the robust synergistic interaction between the W species and the Ga2O3-NC carrier, which facilitates the activation of hydrogen atoms in the C-H and C=N bonds on both the oxygen molecule and the substrate to produce H2O2. Additionally, the solvent effect of methanol can significantly enhance dehydrogenation due to its strong ability to donate and accept protons of hydrogen bonding. The present work provides a new approach to MOF-derived non-precious metal catalysts for achieving the efficient oxidation dehydrogenation of N-heterocycles.

Effects of Ionomer Film Thickness and Water Content on Oxygen Permeation Properties of PEFC Cathode Catalyst

In order to promote the widespread use of Polymer Electrolyte Fuel Cell (PEFC), enhancing cell performance is necessary. One significant factor affecting cell performance is the oxygen permeability in the ionomer, which depends on its nano-scale structure. In this study, to investigate the relationship between structures of catalyst layers and cell performances, we analyzed the effects of film thickness and water content on the oxygen permeation properties of ionomer in the cathode catalyst layer of PEFC using molecular dynamics simulations. We constructed a system in which oxygen molecules permeated ionomer on a platinum (Pt) surface. We found that sulfonic acid groups have a significant effect on oxygen permeation in low water content conditions.

Enhanced gas sensing performance of ZnO and Pt-doped ZnO nanostructured films by chemical spray pyrolysis

This study focuses on the preparation and characterization of zinc oxide (ZO) and platinum-doped zinc oxide (Pt-ZO) nanostructured thin films using the chemical spray pyrolysis technique. Structural and morphological properties of the films were investigated via X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). To understand the semiconducting nature and carrier dynamics, UV-Vis spectroscopy, electrical conductivity measurements, and a static gas sensing system were employed. The films exhibited crystallization in the hexagonal wurtzite structure with a preferred orientation along the (002) plane. FESEM images revealed the presence of small bright particles, particularly abundant in the 5 wt% Pt-doped ZO thin film, indicating the presence of platinum catalysts. Electrical conductivity measurements confirmed the semiconducting nature of the films. Optical parameters such as band gap and absorption index were obtained from UV-Vis spectroscopy. Gas sensing performance towards liquefied petroleum gas (LPG) showed that the 5 wt% Pt-doped ZO thin film exhibited a high response (69.9) to a 50 ppm concentration of LPG at 350 °C. The gas response and recovery times were observed to be 8 s and 12 s, respectively. These results are attributed to interactions between LPG molecules and adsorbed oxygen species on the sensor surface. Platinum atoms on the oxide surface facilitate the formation of oxygen vacancies and the dissociation of oxygen molecules at low temperatures, leading to increased adsorption and reaction with LPG molecules. This results in significant changes in the sensor's resistance, thereby amplifying the sensor response. The findings demonstrate the potential of Pt-doped ZO thin films for practical gas sensing applications.

Metal-doped nanocages (Fe-Si76, Fe-C76, and Fe-Al38N38) as potential catalysts for ozone decomposition to oxygen molecules

Metal-doped nanocages (Fe-Si76, Fe-C76, and Fe-Al38N38) as potential catalysts for ozone decomposition to oxygen molecules

Effect of Cu doping on morphology and properties of calcium ferrite and its application as oxygen carrier in chemical looping hydrogen production

Chemical looping hydrogen production with inherent CO2 capture has been widely recognized as a clean and efficient approach to high-purity hydrogen production because of the ultra-pure H2 product without any purification facilities. It is crucial to develop oxygen carriers with better performance to improve fuel conversion and hydrogen production efficiency. The potential of Ca2Fe2O5 in steam converting has been confirmed. However, its lower oxygen transfer capacity, that is, it tends to produce lower fuel conversion in fuel reactors, which will limit its practical application. Here, we report the development of Cu-doped Ca2Fe2O5-based oxygen carriers using sol-gel technology. The effects of B-site substitution of Cu element on the morphological properties and redox properties of Ca2Fe2-xCuxO5 (x = 0, 0.1, 0.25, 0.5, 1) oxygen carriers were evaluated based on experiments and density functional theory calculations. The results show that Cu doping not only elevated the surface oxygen content and enhanced the oxygen activity of the oxygen carriers, but also increased the Fe3+ at the B-site, thus enhanced their binding ability with oxygen molecules. Vacancy formation was a rate-determining step in the chemical looping hydrogen production (CLH), and Cu-doped Ca2Fe2O5 reduced the energy of oxygen vacancy formation. In the CLH process, the doping of Cu significantly improved the hydrogen productivity and fuel conversion rate. The fuel conversion rate was positively correlated with the doping amount of Cu. When x = 1, Ca2Fe2-xCuxO5 had the maximum fuel conversion rate, and its average conversion was 54.2% more than that of undoped Ca2Fe2O5. Ca2Fe2-xCuxO5 with x = 0.25 was the most suitable for CLH with the highest H2 yield, which was 20.3% more than that of Ca2Fe2O5. Moreover, its properties remained stable over multiple redox cycles with high activity and stability for CO-CLH.

Bimetallic MOFs-Derived Metal Oxides Co3O4/SnO2 Microspheres for Ultrahigh Response n-Butanol Gas Sensors.

The construction of p-n heterojunctions is expected to be one of the effective means to improve gas sensitivity. In this research, p-n heterojunctions are successfully constructed by metal oxides derived from metal-organic frameworks (MOFs). MOFs-derived bimetallic Co3O4/SnO2 microspheres are prepared by precipitation. Gas-sensing performance shows that the Co3O4/SnO2 sensor exhibits an extremely high response (Ra/Rg = 641) to 20 ppm of n-butanol at 200 °C, which is 19 times that of pristine SnO2. It can detect n-butanol gas at low concentrations, has good selectivity to alcohol gas, and reduces the interference of benzene gas. The improved gas sensitivity can be attributed to the formation of a stable heterojunction between Co3O4 and SnO2, resulting in a greater resistance change of Co3O4/SnO2. Co3O4/SnO2 inherits the characteristic of high specific surface area of MOFs, which provides abundant sites for the reaction of the target gas and oxygen molecules. Finally, the gas-sensing mechanism of the Co3O4/SnO2-based sensor is discussed in detail.

A new catalyst derived from the sulfur-doped metal-organic framework for Fenton-like reaction

Fenton-like reaction exhibits considerable advantages in the remediation of pollutants. To fabricate an efficient catalyst becomes an issue concerning the performance enhancement in Fenton-like reaction. Herein, S-Fe-MOF-400 which was derived from a sulfur-doped metal-organic framework (Fe-MOF), was newly prepared and exhibited high ability for H2O2 activation during Fenton-like reaction. The results showed that the sulfurization effectively reduced the charge transfer resistance (Rct) of S-Fe-MOF-400, and facilitated the charge transfer, consequently enhancing the catalytic performance of S-Fe-MOF-400 in the Fenton-like reaction. XRD analysis revealed that FeS2 was the predominant reactive component in S-Fe-MOF-400 with a regular cubic structure and pronounced crystallinity. Additionally, the presence of low-valent sulfur ensured the availability of Fe (II), thereby facilitating the occurrence of the Fenton reaction. Under optimal conditions, the removal efficiency of pollutants reached 86.7 % within 60 min, resulting in total organic carbon (TOC) removal efficiency at 40.6 %. Quenching experiments and electron paramagnetic resonance (EPR) detections revealed that •OH, 1O2, and O2•− synergistically participated in the Fenton-like reaction, with •OH being the primary active species. The activation process of H2O2 induced by S-Fe-MOF-400 mainly yielded hydroxyl radicals and superoxide radicals. The 1O2 was generated through two following pathways: (i) the transformation of superoxide and hydroxyl radicals, and (ii) the conversion of natural oxygen molecules (O2). This current study illustrated the significant potential for the application of sulfur-modified Fe-MOF in the Fenton-like reaction for pollutant removal.

Quantitative analysis of the density of states distribution in N-type polymer filed-effect transistor

In the advancement of polymer field-effect transistors, both p-type and n-type polymer transistors are indispensable because they are the basic components of complementary metal oxide semiconductor (CMOS) logic circuitry. The scarcity of research on the interface properties of n-type polymer transistors, particularly regarding their density of state (DOS) distribution hinders the device modeling and further optimization of n-type polymer transistor. Consequently, the focus on understanding and investigating n-type polymer transistors interface properties holds substantial value and relevance, as it fills a critical knowledge gap in the polymer transistors. In view of this, an n-type poly((N,N0-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-5,50-(2,29-bisthiophene)) (N2200) polymer transistor was fabricated and a dynamic quantitative measurement method was utilized to investigate the DOS distribution of polymer transistors. Comparative analyses were conducted on the drain current (ID), carrier charge (Q), and DOS with varying pulse fall times (Tf). Variations in pulse fall times revealed significant differences in the DOS near the edge of the lowest unoccupied molecular orbital (LUMO), with a maximum DOS of 8 × 1013 cm−2 eV−1 observed at Tf = 1000 μs and a maximum of 2 × 1013 cm−2 eV−1 at Tf = 100 μs. By using different Tf, an effective method was successfully utilized for analyzing the effects of water and oxygen molecules on the DOS distribution of n-type polymer transistors.

Single-Pot Reaction of Novel Fused Indolizine Derivatives.

An unprecedented fused hexacyclic indolizine derivative generated by a single-pot reaction has been developed. This model overcomes the use of catalysts, inefficient atom economy, low yields, and limitations of lengthy steps. Density functional theory calculations reveal the reaction mechanism in which the oxygen molecule plays a crucial role in trapping the penultimate zwitterionic or biradical intermediate to generate the observed products.

Enhancing Carrier Behavior via Controlled Molecular Film Formation Engineering Leads to Significant Improvement in Electroluminescence

The quality of organic thin films critically influences carrier dynamics in organic semiconductors. In neat/doped films, even tiny voids can be penetrated by water or oxygen molecules to create charge‐trap states called water/oxygen‐induced traps that significantly hinder carrier mobility. While the water/oxygen‐induced traps in non‐doped films and crystalline states have been investigated comprehensively, there is a lack of thorough examination regarding their properties in the doped state. Therefore, there is a high demand for a molecular design strategy that effectively modulates the molecular stacking behavior in doped films and practical devices and enhances the quality of these films. Herein, we proposed a versatile molecular design principle that enables the formation of "nano‐cluster" structures on both the surface and interior of doped films in target molecule 10‐(4‐(4,6‐diphenyl‐1,3,5‐triazin‐2‐yl)phenyl)‐1'‐(4‐fluorophenyl)‐10H‐spiro[acridine‐9,9'‐xanthene] (DspiroO‐F‐TRZ), which is modified with a fluorophenyl group. These "nano‐cluster" structures exhibit more uniform shapes within doped films and effectively reduce defective state densities while enhancing carrier injection and transport properties, ultimately improving device performance. Notably, TADF‐OLED based on DspiroO‐F‐TRZ demonstrates nearly twice as much efficiency as its control counterpart due to contributions from 'nano‐cluster' structure enhancements toward improved electroluminescence performance.

Enhancing Carrier Behavior via Controlled Molecular Film Formation Engineering Leads to Significant Improvement in Electroluminescence.

The quality of organic thin films critically influences carrier dynamics in organic semiconductors. In neat/doped films, even tiny voids can be penetrated by water or oxygen molecules to create charge-trap states called water/oxygen-induced traps that significantly hinder carrier mobility. While the water/oxygen-induced traps in non-doped films and crystalline states have been investigated comprehensively, there is a lack of thorough examination regarding their properties in the doped state. Therefore, there is a high demand for a molecular design strategy that effectively modulates the molecular stacking behavior in doped films and practical devices and enhances the quality of these films. Herein, we proposed a versatile molecular design principle that enables the formation of "nano-cluster" structures on both the surface and interior of doped films in target molecule 10-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-1'-(4-fluorophenyl)-10H-spiro[acridine-9,9'-xanthene] (DspiroO-F-TRZ), which is modified with a fluorophenyl group. These "nano-cluster" structures exhibit more uniform shapes within doped films and effectively reduce defective state densities while enhancing carrier injection and transport properties, ultimately improving device performance. Notably, TADF-OLED based on DspiroO-F-TRZ demonstrates nearly twice as much efficiency as its control counterpart due to contributions from 'nano-cluster' structure enhancements toward improved electroluminescence performance.

Phosphorus heteroatom doped BiOCl as efficient catalyst for photo-piezocatalytic degradation of organic pollutant and unveiling the mechanism: Experiment and DFT calculation

A novel phosphorus heteroatom doped bismuth oxychloride (P-BiOCl) catalyst was synthesized and the photo-piezocatalytic degradation of rhodamine B dye performances were explored under the ultrasound vibration and light illumination. The P-BiOCl exhibited excellent photo-piezocatalytic degradation activity, such as an ultra-high reaction kinetic rate constant of 0.3961 min−1, efficient degradation efficiency (94.7 % within 8 min) and excellent stability compared to solely piezocatalysis and photocatalysis. More impressively, these outstanding performances of P-BiOCl exceeded pure BiOCl and most other catalytic materials systems. The relevant experimental and density functional theory (DFT) calculation results were exhibited to clarify enhanced photo-piezocatalytic mechanism. The introduction of P heteroatom could reduce the bandgap of BiOCl, modulate electronic structure and charge redistribution, provide novel electron channel to promote electron transfer and restrain charge carriers recombination. Additionally, P-doped could also enhance the adsorption of oxygen and water molecules, promote intrinsic catalytic activity, leading to the increased production of active free radicals ·O2– and ·OH, thus significantly boosting the efficiency of organic pollutant degradation. This work provides a comprehensive understanding of heteroatom doping enhancing photo-piezocatalytic activity and presents a potential new strategy for designing highly efficient catalysts for wastewater treatment.

Unveiling Na2-Eosin Y-Catalyzed and Water-Assisted Visible-Light Activation of Oxygen Molecules for the Dicarbonylation of Pyrazole Amines.

A novel approach employing visible light-mediated activation of triplet oxygen molecules has been established. The reaction occurs at room temperature between pyrazole amine and phenylglyoxal monohydrate in the presence of Na2-eosin Y. Water played the dual role of solvent and reagent/additive. Photoactivation of triplet oxygen species was used to demonstrate the initiation of the hydrogen atom transfer (HAT) process. The conversion of the reaction mixture was found to be dependent on the amount of water present. Control experiments confirmed the importance of light, the photocatalyst, oxygen, the base, and water. The process tolerated various substitutions in both pyrazole amine and phenylglyoxal derivatives, enabling the synthesis of various dicarbonylpyrazole amines 15 and pyrazolooxazine derivatives 16 in moderate to good yields. 2 equiv of phenylglyoxal 10 gave a different reaction pathway, yielding highly diastereoselective pyrazolooxazine derivatives, confirmed by X-ray diffraction analysis. Collectively, this sustainable and environmentally friendly synthetic technique offers a promising method for the efficient preparation of pyrazole-based heterocyclic compounds. The high regioselectivity observed during the formation of trans-tetrahydropyrazolo[3,4-d][1,3]oxazine has been clarified through computational methods. These investigations emphasize the underlying factors and mechanisms that encourage the formation of this specific product, providing valuable insights into the reaction's selectivity and efficiency.

Unravelling the effect of oxidation/reduction sites for photocatalytic H2O2 production

Metal/semiconductor heterostructures have been widely used to drive photochemical reactions. However, understanding of the synergies between them is still limited. In this study, we discovered that under ultraviolet (UV) light, rather than visible (Vis) excitation, the redox active sites oxidize adsorbed water and reduce oxygen molecules more efficiently. In this paper, the comprehensive mechanism of Ag@TiO2 photocatalysis of H2O2 has been elucidated and confirmed their synergies in photocatalytic reactions, through in situ characterization and theoretical calculation. Our findings provide insights into the key factors that influence the difference of photoactivity in UV and Vis light, thus having important implications for the design of solar energy conversion materials as well as environmental purification materials.

Superhydrophilic Surface Creation and Its Temporal Transition to Hydrophobicity on Copper via Femtosecond Laser Texturing

We analyzed a process to fabricate a superhydrophilic surface on copper by forming various laser-induced periodic surface structures (LIPSS) using a Ti/sapphire femtosecond laser. For these structured surfaces, the correlation between the surface structure and the wetting characteristics was analyzed by scanning electron microscopy, atomic force microscopy, and contact angle (CA) measurement. X-ray photoelectron spectroscopy (XPS) was also employed to analyze variation of the elemental composition of the surfaces. The laser treatment produced micro/nanostructures composed of ripples whose length and width are in microscale and nanoscale, respectively. At specific conditions, the CA of a water droplet was reduced to less than 1°. The superhydrophilcity is attributed to the effect of nanoholes and nanoclusters, which consist of copper (II) oxide and copper hydroxide, having a hydrophilic effect on LIPSS. However, the pristine superhydrophilic surface spontaneously became hydrophobic after being exposed to air at room temperature for about 10 days. According to XPS analysis, the surface’s transition to hydrophobic is attributed not only to the decomposition of Cu(OH)2 but also to the adsorption of oxygen molecules and/or airborne organic molecules containing carbon, which further influences the wettability.