O2 Molecules Research Articles

Waste Polyethylene-Derived Carbon Dots: Administration of Metal-Free Oxidizing Agents for Tunable Properties and Photocatalytic Hyperactivity.

The possibility of converting waste plastics into carbon dots (CDs) with 100% efficiencies using KMnO4 has emerged as a significant discovery in mitigating plastic pollution and upcycling. However, the lack of tunability of their properties, viz. aerial O2 harvesting, light-induced autophagy, and photoactivity using air as a free oxidant, has remained a bottleneck. Besides, the toxicity of KMnO4 makes the process less sustainable. Attempting to bridge these gaps, herein, we demonstrate the preparation of CDs using polyethylene with enormous controllability of their properties by utilizing less-toxic and metal-residue-free oxidizers, e.g., H2O2, HNO3, HClO4, and NaClO. We obtain structurally diverse CDs with controllable luminescent quantum yields (∼0.5-8%), excitonic lifetimes (1.3-2.3 ns), and binding energies (147-290 meV). These CDs exhibit a hugely extended range of molecular O2 harvesting (∼405-650 μM) with different amounts of strongly and weakly surface-bound O2 molecules within an estimated ratio of ∼0.77-2.51. Autophagy varied from 14 days to a nearly "no-autophagy" show. We efficiently utilized their oxygen harvesting and photocatalytic abilities to synthesize imine compounds from the corresponding amines in the open air (rate constant of ∼0.055 min-1), surpassing the literature efficiencies achieved using an O2 flow and noble metals. Notably, due to oxygen harvesting by CDs, no additional rate enhancement was observed after O2 purging, establishing the role of CDs in making free air an excellent oxidizing agent.

Process Model for SiC Oxidation for a Large Range of Conditions

A comprehensive process model for 4H‐SiC oxidation is created and calibrated against a very large collection of experimental data. The model reproduces measured oxide thickness for Si‐face, C‐face, and a‐face SiC wafers, in the temperature range 950–1500 °C, in the pressure range 0.25–4.0 atm, in the thickness range 3–1600 nm, and for SiC doping ranging between 1019 cm−3 n‐type and 1019 cm−3 p‐type. The model is based on the Massoud model: Oxidation is driven by oxidants (O2, H2O) which are present in the gas phase, diffuse through the oxide, and form SiO2 at the oxide–SiC interface. For thin oxides, the interface reaction rate includes empirical correction terms which add to the oxidation rate, and which asymptotically approach zero with increasing oxide thickness. For dry oxidation, a remarkable dependence on the O2 partial pressure is discovered: For thick oxides, the oxidation rate scales linearly with the pressure, but the correction term for thin oxides scales with the square root of the pressure. This suggests that the atomistic processes responsible for the fast initial growth of oxides involve the splitting of O2 molecules into two O atoms.

Ab initio study of Ti-doped C3N nanosheet as COCl2, O3, and HCN gas sensor

In the present study, we designed the pristine C3N and Ti-doped C3N nanosheets to investigate the geometrical, electrical, and optical properties using density functional theory calculation. The negative value of the cohesive energy of both nanosheets indicates the structures are energetically stable. Ti-doping in C3N results in a conductor-to-semiconductor transition with a band gap of 0.15 eV. We studied the adsorption of COCl2, O3, and HCN gas molecules on the designed structures. The adsorption energy for COCl2, O3, and HCN gases significantly increased to −8.63, −9.80, and −5.98 eV respectively after Ti-doping. A significant variation in the band gap of Ti-doped C3N is observed due to gas adsorption. The complex structures show a high absorption coefficient of over 104 cm−1 in the visible range with a significant red/blue shifting of absorption peaks. The study proves the Ti-doped C3N to be a potential candidate for sensing COCl2, O3, and HCN gases.

Kinetic Study and Reaction Mechanism of the Gas-Phase Thermolysis Reaction of Methyl Derivatives of 1,2,4,5-Tetroxane.

Tetroxane derivatives are interesting drugs for antileishmaniasis and antimalaric treatments. The gas-phase thermal decomposition of 3,6,-dimethyl-1,2,4,5-tetroxane (DMT) and 3,3,6,6,-tetramethyl-1,2,4,5-tetroxane (acetone diperoxide (ACDP)) was studied at 493-543 K by direct gas chromatography by means of a flow reactor. The reaction is produced in the injector chamber at different temperatures. The resulting kinetics Arrhenius equations were calculated for both tetroxanes. Including the parent compound of the series 1,2,4,5-tetroxane (formaldehyde diperoxide (FDP)), the activation energy and frequency factors decrease linearly with the number of methyl groups. The reaction mechanisms of ACDP and 3,6,6-trimethyl-1,2,4,5-tetroxane (TMT) decomposition have been studied by means of the DFT method with the BHANDHLYP functional. Our calculations confirm that the concerted mechanism should be discarded and that only the stepwise mechanism occurs. The critical points of the singlet and triplet state potential energy surfaces (S- and T-PES) of the thermolysis reaction of both compounds have been determined. The calculated activation energies of the different steps vary linearly with the number of methyl groups of the methyl-tetroxanes series. The mechanism for the S-PES leads to a diradical O···O open structure, which leads to a C···O dissociation in the second step and the production of the first acetaldehyde/acetone molecule. This last one yields a second C···O dissociation, producing O2 and another acetone/acetaldehyde molecule. The O2 molecule is in the singlet state. A quasi-parallel mechanism for the T-PES from the open diradical to products is also found. Most of the critical points of both PES are linear with the number of methyl groups. Reaction in the triplet state is much more exothermic than the singlet state mechanism. Transitions from the singlet ground state, S0 and low-lying singlet states S1-3, to the low-lying triplet excited states, T1-4, (chemical excitation) in the family of methyl tetroxanes are also studied at the CASSCF/CASPT2 level. Two possible mechanisms are possible here: (i) from S0 to T3 by strong spin orbit coupling (SOC) and subsequent fast internal conversion to the excited T1 state and (ii) from S0 to S2 from internal conversion and subsequent S2 to T1 by SOC. From these experimental and theoretical results, the additivity effect of the methyl groups in the thermolysis reaction of the methyl tetroxane derivatives is clearly highlighted. This information will have a great impact for controlling these processes in the laboratory and chemical industries.

Fe-doped BN monolayer: A single-atom catalyst for efficient formaldehyde oxidation

Formaldehyde (HCHO) is a ubiquitous air pollutant, and the prolonged inhalation poses a serious threat to human health, thus it is imperative to develop HCHO oxidation catalysts with high activity. FeNx-based catalysts have shown brilliant catalytic performance due to their unique electronic structures. In this work, the active FeN3 site is designed by doping Fe atom at the B-vacancy in BN monolayer without introducing additional N atoms. Our first principles calculation results show that the Fe atom has good dispersibility, dynamical stability and thermal stability on the BN monolayer. Two oxidation mechanisms (Langmuir-Hinshelwood and Eley-Rideal) of HCHO on Fe-doped BN monolayer are investigated to explore the possible reaction pathways. The dissociation of O2 molecule is identified as the rate-limiting step, and the lowest energy barrier is 0.99 eV. Moreover, the excellent desorption behaviors of the produced CO2 and H2O molecules on substrate (small desorption energy of 0.20 and 0.75 eV, and short desorption time of 2.39 × 10−9 and 4.64 s) enable this catalyst to maintain high activity during the reaction cycle. Our results suggest the feasibility of Fe-doped BN monolayer for the catalytic oxidation of HCHO and broaden the application of BN-based single-atom catalysts.

Defective Diamane: A Superior Sensor for Toxic Gases Capture and Detection with Excellent Selectivity, Sensitivity, and Reversibility at Room Temperature.

The toxic gases emitted from industrial production have caused significant damage to the environment and human health, necessitating efficient gas sensors for their detection and removal. In this work, first-principles calculations are employed to investigate the potential application of diamanes for high-performance toxic gas sensors. The results show that nine gas molecules (CO, CO2, NO, NO2, NH3, SO2, N2, O2, and H2O) are physisorbed on pristine diamane by weak van der Waals interactions. After introducing H/F defects, diamane can effectively capture specific toxic gases (CO, NO, NO2, and SO2) in the presence of interfering gases (N2, O2, and H2O), suggesting excellent selectivity and anti-interference ability. Orbital hybridization and significant charge redistribution between gas molecules and defective diamane dominate the enhanced adsorbate-substrate interactions. More importantly, the high sensitivity and good reversibility of defective diamane for detecting CO, NO, and SO2 molecules enable its reuse as a superior resistance-type gas sensor. Our calculations provide valuable insights into the potential of defective diamane for detecting toxic gases and shed light on the practical application of novel carbon-based materials in the gas-sensing field.

Electric Field Generated at the Millisecond Pulse-Polarized Interface Facilitates the Electrolytic Conversion of SO2 into H2S.

Interfacial electric field holds significant importance in determining both the polar molecular configuration and surface coverage during electrocatalysis. This study introduces a methodology leveraging the varying electric dipole moment of SO2 under distinct interfacial electric field strengths to enhance the selectivity of the SO2 electroreduction process. This approach presented the first attempt to utilize pulsed voltage application to the Au/PTFE membrane electrode for the control of the molecular configuration and coverage of SO2 on the electrode surface. Remarkably, the modulation of pulse duration resulted in a substantial inhibition of the hydrogen evolution reaction (HER) (FEH2 < 3%) under millisecond pulse conditions (ta = 10 ms, tc = 300 ms, Ea = -0.8 V (vs Hg/Hg2SO4), Ec = -1.8 V (vs Hg/Hg2SO4)), concomitant with a noteworthy enhancement in H2S selectivity (FEH2S > 97%). A comprehensive analysis, incorporating in situ Raman spectroscopy, electrochemical quartz crystal microbalance, COMSOL simulations, and DFT calculations, corroborated the increased selectivity of H2S products was primarily associated with the inherently large dipole moment of the SO2 molecule. The enhancement of the interfacial electric field induced by millisecond pulses was instrumental in amplifying SO2 coverage, activating SO2, facilitating the formation of the pivotal intermediate product *SOH, and effectively reducing the reaction energy barrier in the SO2 reduction process. These findings provide novel insights into the influences of ion and molecular transport dynamics, as well as the temporal intricacies of competitive pathways during the SO2 electroreduction process. Moreover, it underscores the intrinsic correlation between the electric dipole moment and surface-molecule interaction of the catalyst.

Remarkable improvement in photocatalytic activity of g-C3N4 for NO oxidation through surface hydroxylation

The nitrogen oxide emissions originating from combustion pose significant risks to the environment. Photocatalysis is considered an efficient and environmentally friendly strategy to alleviate this problem. Graphitic carbon nitride (g-C3N4) is regarded as one of the most promising organic photocatalytic materials for environmental purification. However, its small specific surface area, weak adsorption and high recombination rate of charge carriers result in low intrinsic photocatalytic activity. To overcome these obstacles, a hydrothermal treatment of dicyandiamide-derived g-C3N4 (DCN) at different temperatures (140–200 °C) was employed to enhance the photocatalytic activity for NO oxidation. The experimental results demonstrated a significant improvement in the photocatalytic oxidation removal rate of NO after a hydrothermal treatment. The optimal photocatalyst, DCN-180, treated at 180 °C, demonstrated the highest NO removal efficiency (65.0 %), which is twice the value of pristine DCN (32.5 %). Additionally, the formation of the toxic intermediate NO2 was effectively suppressed during the reaction. Photoelectrochemical tests revealed that DCN-180 exhibited higher photocurrent density and smaller impedance radius compared to the untreated g-C3N4 sample. Moreover, density functional theory (DFT) calculations confirmed that the DCN-180 sample showed a stronger ability to adsorb O2 and NO. The enhanced photocatalytic NO oxidation performance of DCN-180 has been primarily attributed to its enlarged specific surface area (from 10.7 to 35.5 m2 g−1), local polarization effect, reduced interfacial charge transfer resistance, and improved adsorption abilities for NO and O2 molecules. This study provides valuable insights for designing and preparing highly efficient g-C3N4 based photocatalysts through surface modification for photocatalytic NO purification.

Two-dimensional Mo3-TiS2 monolayer hosting high moisture resistance and abundant surface-chemisorbed oxygen for effective detection of SF6 decomposition gases: Atomic-scale study

Monitoring the SF6 decomposition gas (DPA) by gas sensors can be used to predict the operating status of power equipment, and the sensitivity performance of gas sensors is deeply influenced by the humidity resistance and surface oxygen adsorption performance of their sensing materials. The present research aims to explore a high‐valence transition‐metal ion doped transition metal dichalcogenide (TMD) monolayer that hosts high moisture resistance and abundant surface-chemisorbed oxygen suitable for detecting DPA. Using first-principles methods, the adsorption behavior of three representative types of gases (HF, SO2, and CO2) in DPA, H2O, and O2 on Mo3-TiS2 monolayer are considered. Our results show that SO2 and CO2 molecules are adsorbed above the Mo3 cluster through chemical adsorption, while HF molecule is physically adsorbed. The desorption times for SO2 and CO2 on Mo3-TiS2 adsorbent are 9.89 s at 348 K and 34.96 s at 398 K, respectively. Introducing dopant Mo3 resulted in better anti-humidity performance of TiS2, as the force of Mo3-TiS2 monolayer towards H2O molecule is weakened compared to the intrinsic adsorption system. Additionally, Mo3-TiS2 monolayer exhibits an exceptionally high affinity for O2 molecule, leading to the rupture of chemical bond in O2, and the chemisorbed oxygen ions are acquired through the charge transfer between Mo3 cluster and O2 molecule. The computational findings in this article offer theoretical backing for advancing the development of gas sensors utilizing Mo3-TiS2 and its utilization in the realm of DPA detection.

A Highly Charged Positive Cage Causes Simultaneous Enhancement of Type‐II and O2‐Independent‐Type‐I Photodynamic Therapy via One‐/Two‐Photon Stimulation and Tumor Immunotherapy via PANoptosis and Ferroptosis

To solve the oxygen dependence problem of photodynamic therapy (PDT), it is critical to explore photosensitizers that do not rely on O2 molecule to generate reactive oxygen species (ROS). Herein, a stable cationic metal‐organic cage [Pd6(RuLoz3)8](BF4)28 (MOC‐88) that possesses high +28 charges is designed. The cage‐confined positive microenvironment enables efficient generation of hydroxyl radicals and improved yield of the singlet oxygen under one‐/two‐photon excitation, showing excellent performance to concurrently enhance Type‐II and O2‐independent‐Type‐I PDT. Moreover, the effective ROS production and robust lipid peroxidation trigger a series of signaling pathways (inflammasome, cyclic guanosine monophosphate–adenosine monophosphate synthase stimulator of interferon genes, and NF‐κB) to evoke PANoptosis and ferroptosis in tumor cells, enabling MOC‐88 to simultaneously cause the loss of cell membrane integrity, release a series of inflammatory cytokines and damage‐associated molecular patterns, stimulate the maturation and antigen presentation ability of dendritic cells, and ultimately activate T‐cell‐dependent adaptive immunity in vivo to inhibit tumor growth.

Quantifying Drivers of Seasonal and Interannual Variability of Dissolved Oxygen in the Canada Basin Mixed Layer

AbstractAnalysis of dissolved oxygen (O2) in the Arctic's surface ocean provides insights into gas transfer between the atmosphere‐ice‐ocean system, water mass dynamics, and biogeochemical processes. In the Arctic Ocean's Canada Basin mixed layer, higher O2 concentrations are generally observed under sea ice compared to open water regions. Annual cycles of O2 and O2 saturation, increasing from summer through spring and then sharply declining to late summer, are tightly linked to sea ice cover. The primary fluxes that influence seasonal variability of O2 are modeled and compared to Ice‐Tethered Profiler O2 observations to understand the relative role of each flux in the annual cycle. Findings suggest that sea ice melt/growth dominates seasonal variations in mixed layer O2, with minor contributions from vertical entrainment and atmospheric exchange. While the influence of biological activity on O2 variability cannot be directly assessed, indirect evidence suggests relatively minor contributions, although with significant uncertainty. Past studies show that O2 molecules are expelled from sea ice during brine rejection; sea ice cover can then inhibit air‐sea gas exchange resulting in winter mixed layers that are super‐saturated. Decreasing mixed layer O2 concentrations and saturation levels are observed during winter months between 2007 and 2019 in the Canada Basin. Only a minor portion of the decreasing trend in wintertime O2 can be attributed to decreased solubility. This suggests the O2 decline may be linked to more efficient air‐sea exchange associated with increased open water areas in the winter sea ice pack that are not necessarily detectable via satellite observations.

Oxidation and mineralization rates of harmful organic chemicals in hydroxyl radical induced reactions

In most of advanced oxidation processes (AOPs) used to destroy harmful organic chemicals in water/wastewater hydroxyl radical (•OH) reactions oxidize (increasing the oxygen/carbon ratio in the molecules) and mineralize (transforming them to inorganic molecules, H2O, CO2, etc.) these contaminants. In this paper, we used the radiolysis of water to produce •OH and characterised the rate of oxidation and mineralization by the dose dependences of the Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC) content values. Analysis of the dose dependences for 34 harmful organic compounds showed large differences in the oxidation and mineralization rates and these parameters are characteristic to the given group of chemicals. E.g., the rate of oxidation is relatively low for fluoroquinolone antibiotics; it is high for β-blocker medicines. Mineralization rates are low for both fluoroquinolones and β-blockers. The one-electron-oxidant •OH in most cases induces two − four-electron-oxidations. Most of the degradation takes place gradually, through several stable molecule intermediates. However, based on the results it is likely, that some part of the oxidation and mineralization takes place parallel. The organic radicals formed in •OH reactions react with several O2 molecules and release several inorganic fragments during the radical life cycle.

The role of CO on initial oxidation behavior of α-U(001) surface: A first principles study

A first-principles approach based on density-functional theory has been used to investigate the corrosion resistance of alpha-U in the CO environment. Calculations show that O2 molecules spontaneously dissociate on the uranium surface, and the two O atoms formed by dissociation tend to adsorb on the hole sites and bind to the surface in the form of a U–O bond to emit a large amount of heat. The CO molecules occur on the surface of uranium as a non-dissociative chemical. The mechanism of CO inhibiting the adsorption of O2 molecules stems from the fact that CO molecules occupy the optimal adsorption sites. Another inhibition mechanism, the combination of C atoms and O atoms to form bonds and consume oxygen atoms, has little effect on uranium corrosion.

Anisotropic CO adsorption and enhanced O2 activation on defective TiS2 monolayer: A DFT study

This study employs density functional theory (DFT) calculations to investigate the adsorption behaviour of CO and O2 on a defective TiS2 monolayer. The primary objective is to evaluate the potential of TiS2 for gas sensing and catalytic applications. By exploring the adsorption of CO and O2 on a monolayer with a sulfur vacancy, this study provides significant new insights into their interaction mechanisms and energetics. The DFT simulations showed that the adsorption of the CO molecule is anisotropic (i.e., orientation dependent) with higher adsorption energy for the carbon end (Ti-CO) -0.63 eV than the oxygen end (Ti-OC) -0.16 eV. In both scenarios, the CO molecule bond length does not change significantly. In contrast, the adsorption of O2 molecule is the strongest with the highest adsorption energy of -3.25 eV. The defective TiS2 monolayer exhibits notable catalytic properties through the elongation of the O-O bond from 1.21 Å to 1.47 Å, comparable to the O-O bond length in peroxides (∼ 1.45 Å). Additionally, the adsorption mechanism is explained in variation observed in Density of States (DOS), Partial Density of States (PDOS), and Mulliken charges, thus establishing its potential for gas sensing and catalytic applications.

Determining the influence of relative humidity on the working parameters of a gas sensor based on zinc oxide

This paper investigates the dependence of operating parameters of a gas sensor based on zinc oxide obtained by the method of direct current magnetron sputtering. The production of gas sensor films was carried out using a VUP-5M vacuum unit with an original material-saving magnetron. The study of the dependence of the working parameters of the gas sensor was carried out under standard conditions. It was found that with increasing humidity, the electrical resistance of the gas sensor decreases and, accordingly, the sensitivity to the target gas decreases. A significant reaction of the gas sensor to an increase in humidity was observed in the range of 65–80 % relative humidity. The mechanism of influence of relative humidity on the sensitivity of a gas sensor based on ZnO was investigated. The change in resistance of the gas sensor is caused by trapped electrons on adsorbed oxygen molecules on the surface of the sensitive layer. The capture of electrons from the conduction zone leads to bending of the conduction zone and an increase in the space charge zone, respectively, to a change in the resistance of the sensitive layer of the gas sensor. In the atmosphere, when O2 molecules are adsorbed on the ZnO surface, they remove an electron from the conduction band. The reaction of oxygen adsorbed on the ZnO surface with reducing gases and the replacement of adsorbed oxygen with other molecules changes the bending of the conduction band and reduces the area of space charge. Adsorption of water on the surface of zinc oxide occurs according to the dissociation mechanism, which consists in the adsorption of steam molecules or hydroxyl groups with the subsequent displacement of previously adsorbed oxygen and free electrons and, accordingly, leads to a decrease in the sensitivity of the gas sensor. In addition, the adsorption of water vapor (H2O) molecules leads to less chemisorption of oxygen species on the ZnO surface due to the reduction of the surface area, which is responsible for the sensor response. Approaches to reduce the influence of relative humidity on the sensitivity of a gas sensor based on zinc oxide have been proposed

Atomic Confinement Empowered CoZn Dual-Single-Atom Nanotubes for H2O2 Production in Sequential Dual-Cathode Electro-Fenton Process.

Single-atom catalysts (SACs) are flourishing in various fields because of their 100% atomic utilization. However, their uncontrollable selectivity, poor stability and vulnerable inactivation remain critical challenges. According to theoretical predictions and experiments, a heteronuclear CoZn dual-single-atom confined in N/O-doped hollow carbon nanotube reactors (CoZnSA@CNTs) is synthesized via spatial confinement growth. CoZnSA@CNTs exhibit superior performance for H2O2 electrosynthesis over the entire pH range due to dual-confinement of atomic sites and O2 molecule. CoZnSA@CNTs is favorable for H2O2 production mainly because the synergy of adjacent atomic sites, defect-rich feature and nanotube reactor promoted O2 enrichment and enhanced H2O2 reactivity/selectivity. The H2O2 selectivity reaches ∼100% in a range of 0.2-0.65V versus RHE and the yield achieves 7.50M gcat -1 with CoZnSA@CNTs/carbon fiber felt, exceeding most of the reported SACs in H-type cells. The obtained H2O2 is converted directly to sodium percarbonate and sodium perborate in a safe way for H2O2 storage/transportation. The sequential dual-cathode electron-Fenton process promotes the formation of reactive oxygen species (•OH, 1O2 and •O2 -) by activating the generated H2O2, enabling accelerated degradation of various pollutants and Cr(VI) detoxification in actual wastewater. This work proposes a promising confinement strategy for catalyst design and selectivity regulation of complex reactions.

Benzene Oxidation in Air by an Amine-Functionalized Metal-Organic Framework-Derived Carbon- and Nitrogen-Loaded Zirconium Dioxide-Supported Platinum Catalyst.

To learn more about the behavior of amine (NH2)-functionalized metal-organic framework (MOF)-derived noble metal catalysts in the removal of aromatic volatile organic compounds in air, benzene oxidation at low temperatures has been investigated using 0.2-, 0.8-, and 1.5%-platinum (Pt)/Universitetet i Oslo (UiO)-66-NH2. The benzene conversion (XB) of x%-Pt/UiO-66-NH2-R under dry conditions (175 °C) was 23% (x = 0.2%) < 52% (x = 0.8%) < 100% (x = 1.5%): 'R' suffix denotes reduction pretreatment using a hydrogen (10 vol %) and nitrogen mixture at 300 °C for the generation of metallic Pt (Pt0) sites and simultaneous partial MOF decomposition into carbon- and nitrogen-loaded zirconium dioxide. The prominent role of reduction pretreatment was apparent in benzene oxidation as 1.5%-Pt/UiO-66-NH2 did not exhibit catalytic activity below 175 °C (dry condition). The promotional role of moisture in benzene oxidation by 1.5%-Pt/UiO-66-NH2-R was evident with a rise in the steady-state reaction rate (r) at 110 °C (21 kPa molecular oxygen (O2)) from 1.3 × 10-3 to 5.0 × 10-3 μmol g-1 s-1 as the water (H2O) partial pressure increased from 0 to 1.88 kPa. In contrast, the activity was lowered with increasing RH due to catalyst poisoning by excess moisture (r (110 °C) of 6.6 × 10-04 μmol g-1 s-1 at 2.83 kPa H2O (21 kPa O2)). Kinetic modeling suggests that XB proceeds through the Langmuir-Hinshelwood mechanism on the Pt/UiO-66-NH2-R surface (dissociative O2 chemisorption and the involvement of two oxygen species in benzene oxidation). According to the density functional theory simulation, the carbon and nitrogen impurities are to make the first XB step (i.e., hydrogen migration from the benzene molecule to the substrate) energetically favorable. The second hydrogen atom from the benzene molecule is also extracted effectively, while the oxygen derived from O2 facilitates further XB. The Pt0 sites dissociate the O2 and H2O molecules, while the product of the latter, i.e., free hydrogen and hydroxyl, makes the subsequent XB steps energetically favorable.

Modulated bandgap and gas adsorption behavior on two-dimensional SrAl2S4 monolayer: Potential applications for photovoltaic and energy storage

The structure of a novel two-dimensional layered material SrAl2S4 monolayer has been proposed, and its kinetic and thermodynamic stability has been confirmed. Researches have shown that SrAl2S4 monolayer is a semiconductor material with a bandgap of 1.630 eV for PBE and 2.798 eV for HSE06 at the ground state. Under biaxial strain, SrAl2S4 monolayer can complete the transition from a direct bandgap semiconductor to an indirect bandgap semiconductor, and its bandgap can vary between 0.187 eV and 1.712 eV. In addition, We have considered the adsorption behavior of SrAl2S4 monolayer for hydrogen and oxygen molecules, and the results show that SrAl2S4 monolayer adsorbed H2 molecules remains a direct bandgap semiconductor, whereas SrAl2S4 monolayer adsorbed O2 molecules show indirect bandgap semiconductor properties. At the same time, the adsorption of O2 molecules causes a flat band near the Fermi level, which increases the electrical conductivity. The few charges transfer observed between the SrAl2S4 monolayer and gas molecules confirms that the adsorption process of gas molecules on SrAl2S4 monolayer is physical adsorption. The tunable bandgap characteristics and good adsorption behavior of hydrogen and oxygen exhibited by SrAl2S4 monolayer make it a promising candidate material in the fields of photovoltaics and energy storage.

Moisture‐Induced High‐Quality Perovskite Film in Air for Efficient Solar Cells

The quality of perovskite light‐harvesting layer is known to be the most critical factor for the performance of perovskite solar cells (PSCs). Herein, a facile ambient air‐aging process (AAP, 20%–30% RH) is adopted to realize the fabrication of high‐quality Cs0.15FA0.75MA0.1PbI3 perovskite films, thereby upgrading device performance. We find that the perovskite crystallinity after AAP for 10 d is greatly intensified, with large grain size and preferred crystal orientation along (110) and (220) planes. Comparative studies on the Ag‐based devices employing the perovskite films upon exposing to different atmospheres, i.e., dry N2, dry O2, N2, and H2O (20%–30% RH) and ambient air (20%–30% RH), demonstrate that H2O molecules in air rather than O2 molecules induce an effective defect passivation that holds the multiple functions in enhancing the quality of perovskite film, inhibiting the nonradiative recombination, prolonging the carrier lifetime, and improving the energy level matching, etc. Moreover, the positive effect of H2O in ambient atmosphere on cell performance is irreversible and remains even if moisture escapes. Finally, the average power conversion efficiency (PCE) of device based on the AAP‐induced film is increased from 18.24 ± 1.49 to 21.34 ± 0.76, with the champion PCE up to 22.60%. Also, the device with AAP exhibits better moisture resistance capability. Herein, it offers a viable AAP‐induced route for the perovskite films with superb optoelectronic properties that can be subsequently extended to the design and construction of other photovoltaic devices for practical application.

Plasma atomic layer etching of ruthenium by oxygen adsorption-removal cyclic process

Ruthenium (Ru) is a next-generation metal interconnect material, and the demand for precise etching is on the rise. This study explores anisotropic atomic layer etching (ALE) of Ru, utilizing various oxygen adsorption methods (O radical, oxygen plasma, or O2 molecule) and two types of plasma sources: inductively coupled plasma (ICP) and ion beam source. Through ICP ALE, an etch per cycle (EPC) of ∼ 1.5 Å/cycle was achieved using oxygen plasma for adsorption. For ion beam ALE, EPC values of ∼ 0.8 Å/cycle were obtained using oxygen radical, and ∼ 0.4 Å/cycle through physisorption using oxygen molecule without plasma generation. The higher EPC with the ICP ALE was attributed to spontaneous etching during oxygen adsorption during the oxygen plasma generation. Conversely, the lower EPC with ion beam ALE during oxygen adsorption using O2 molecule without plasma generation resulted from nonuniform oxidation of Ru during the adsorption step. Among the three ALE methods, optimal Ru ALE with 100 % ALE synergy was achieved with ion beam ALE, likely due to the absence of ion bombardment during oxygen adsorption and the precise Ar+ ion energy for removing RuOx formed on the surface.