Adsorption Of Molecules Research Articles

Label-Free Single-Molecule Electrical Sensor for Ultrasensitive and Selective Detection of Iodide Ions in Human Urine.

Herein, a label-free single-molecule electrical sensor was first proposed for the ultrasensitive and selective detection of iodide ions in human urine. Single-molecule conductance measurements in different halogen ion solutions via scanning tunneling microscopy break junction (STM-BJ) clearly revealed that I- ions strongly affect the stability and displacement distance (Δz) distribution of molecular junctions. Theoretical calculations prove that the specific adsorption of I- ions modifies the surface properties and weakens the molecular adsorption. Furthermore, the average conductance peak area versus the logarithm of the I- ion concentration has a very good linear relationship in the range of 5 × 10-6 to 5 × 10-10 M, with a correlation coefficient of 0.99. This quantitative analysis remains valid in the presence of interfering ions of SO42-, ClO4-, Br-, and Cl- as well as interfering molecules of ascorbic acid, uric acid, dopamine, and cysteine. A cross-comparison of the human urine detection results of this single-molecule electrical sensor with those of the clinical method of As3+-Ce4+ catalytic spectrophotometry revealed an average difference of 0.9%, which decreased the detection time of 2 h with the traditional method to approximately 15 min. This work proves the promising practical potential of the single-molecule electrical technique for relevant clinical analysis.

L-cystine adsorption on a pyrite (100) surface exposed to O2 and CO2 atmospheres by near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS)

Pyrite surfaces were exposed to oxygen or carbon dioxide atmospheres in a controlled manner at different pressures at the NAPP end station of the CIRCE beamline at the ALBA Synchrotron Light Source to simulate various primitive terrestrial environments, confirming the occurrence of surface oxidation and characterise the chemical species formed. After preliminary gas pretreatment to prepare the substrate, the dimeric amino acid molecule L-cystine was dosed onto the pyrite substrate under UHV conditions, representing the first time that an amino acid was successfully sublimated and adsorbed in situ on a surface at the NAPP-CIRCE beamline. The intense nitrogen feature and molecular disulphide bridge as a molecular fingerprint, confirmed the successful adsorption of L-cystine on the pretreated pyrite surfaces under both O2 and CO2 atmospheres, although the oxidation process differed. Our results using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) at the ALBA synchrotron source help to clarify how different environments can favour or inhibit molecular adsorption and modify biomolecule-surface interactions. Furthermore, it could explain the high reactivity of pyrite surfaces to organic molecules, even after exposure to an oxidising atmosphere, thus inhibiting further reactions and provide insight relevant to the field of prebiotic chemistry.

Chemoinformatics for corrosion science: Data-driven modeling of corrosion inhibition by organic molecules.

This paper reviews the application of machine learning to the inhibition of corrosion by organic molecules. The methodologies considered include quantitative structure-property relationships (QSPR) and related data-driven approaches. The characteristic features of their key components are considered as applied to corrosion inhibition, including datasets, response properties, molecular descriptors, machine learning methods, and structure-property models. It is shown that the most important factors determining their choice and application features are: (1) the small or very small size of datasets, (2) the mechanism of corrosion inhibition associated with the adsorption of inhibitor molecules on the metal surface, and (3) multifactorial conditioning and noisiness of response property. On this basis, the application of machine learning to the inhibition of corrosion of materials based on iron, aluminum, and magnesium is considered. The main trends in the development of QSPR and related data-driven modeling of corrosion inhibition are discussed, the shortcomings and common errors are considered, and the prospects for their further development are outlined.

Constructing 2D Porous ZnO Gas Sensors Based on Polyvinylpyrrolidone-Assisted Zn-MOF Nanosheets for NO2 Detection.

Two-dimensional (2D) ZnO nanomaterials are promising for gas sensing, because of their large surface area, abundant active sites, and rapid charge transfer. However, it is challenging to prepare 2D ZnO nanosheet gas sensors with high sensing performance, due to the tight interlayer stack and low adsorptive property of ZnO for NO2 molecules. Herein, we synthesized Zn-MOF nanosheets employing polyvinylpyrrolidone (PVP) as the structure-directing agent, further through pyrolysis of the Zn-MOF to obtain 2D ZnO nanosheet gas sensors. As anticipated, the 2D ZnO gas sensors exhibited high sensitivity and selectivity for NO2, and the optimal sample could achieve a response value of 162 at the working temperature of 160 °C, which is 10 times higher than that of pristine ZnO. Meanwhile, experimental and DFT results showed that PVP plays critical roles in the lateral lattice growth of 2D Zn-MOF nanosheets, while the existence of PVP makes the ZnO gas sensors with rich porous property and more oxygen vacancy after the pyrolysis process, which promoted the adsorption, activity, and surface reaction for NO2 molecules. It provides a new approach for the application of 2D ZnO nanosheets in the NO2 detection field.

Mitigation effect of a biodegradable surfactant N,N,N-trimethyl-2-(((hexadecyloxy)carbonyl)oxy)ethan-1-aminiumiodide for mild steel corrosion in 5% HCl: Experimental and theoretical insights

A cleavable cationic surfactant having carbonate linkage, N,N,N-trimethyl-2-(((hexadecyloxy)carbonyl)oxy)ethan-1-aminiumiodide referred to as THC was synthesised and characterized employing elemental analysis, FT-IR (Fourier Transform Infrared Spectroscopy), 1H NMR (Nuclear Magnetic Resonance) and 13C NMR. The extent of corrosion inhibition of THC was for the first time studied experimentally and theoretically on mild steel (MS) substrate in 5 % HCl solution at temperatures 303, 313, 323, 333, 343, 353 K. Experimental investigations include gravimetric analysis, potentiodynamic polarization (PDP) and electrochemical impedance analysis (EIS). THC provided maximum inhibition efficiency of 93.2 % at concentration of 1×10−4 M at 303 K which was further raised to 98.1 % at 353 K. PDP studies reveal that given surfactant is mixed type inhibitor. Surface studies such as contact angle measurement, AFM (Atomic Force Microscopy), SEM-EDX (Scanning Electron Microscope-Energy Dispersive X-ray Analysis), and XPS (X-ray Photoelectron Spectroscopy) were employed to justify the adsorption of inhibitor molecules on MS surface. Furthermore, biodegradability test on THC was done to support the environment friendly nature of the surfactant.

Triggering Asymmetric Layer Displacement Polarization and Redox Dual-Sites Activation by Inside-Out Anion Substitution for Efficient CO2 Photoreduction.

Sluggish bulk charge transfer and barren catalytic sites severely hinder the CO2 photoreduction process. Seeking strategies for accelerating charge dynamics and activating reduction and oxidation sites synchronously presents a huge challenge. Herein, an inside-out chlorine (Cl) ions substitution strategy on the layered polar Bi4O5Br2 is proposed for achieving layer structure-dependent polarization effect and redox dual-sites activation. Cl ions in the bulk phase shrink the halogen layer interspace by 8‰, triggering asymmetric [Bi4O5]2+ layer displacement polarization, prolonging the average photocharge lifetime to 201.8ps. Meanwhile, surface substituted Cl ions enhance the electron-donating capability of neighboring Bi atoms, activating the intrinsic Bi reduction sites, and increasing H2O molecule adsorption on nearby intrinsic O oxidation site (cal. by 0.105eV), also self-donating as an alien oxidation site. Besides, Cl upshifts the p-band center closer to the Fermi level, facilitating the reactant adsorption. Therefore, the energy barrier for CO2 activation and rate-limiting *COOH intermediate formation steps are significantly decreased. Without cocatalysts and sacrificial reagents, inside-out Cl-substituted Bi4O5Br2 delivers a remarkable CO2-to-CO photoreduction rate of 50.18µmol g-1 h-1, being one of the state-of-the-art catalysts. This finding offers insights into exploiting polarization at the molecular-level and enhances understanding of catalytic site activation.

Preparation and Performance Study of Zinc Dibenzyl Dithiocarbamate Self‐Assembled Film on Electrodeposited Cu–Ni Alloy Surface

ABSTRACTThis study developed a green and efficient surface protection method for Cu–Ni alloys. A zinc dibenzyl dithiocarbamate film was prepared on the surface of electrodeposited Cu–Ni alloys using the self‐assembly method to improve the material's corrosion resistance in seawater. The influence of zinc dibenzyl dithiocarbamate concentration and self‐assembly time on the corrosion resistance of the self‐assembled films was investigated through electrochemical testing. The findings revealed that at a zinc dibenzyl dithiocarbamate concentration of 10 mmol/L and a self‐assembly time of 20 min, the self‐assembled film exhibited the most robust corrosion resistance, achieving a maximum corrosion inhibition efficiency of 97.70%. The self‐assembly and adsorption mechanism of zinc dibenzyl dithiocarbamate were explored using molecular dynamics simulations and adsorption isotherms. The protective effect of self‐assembled films was visually observed through salt spray testing. Zinc dibenzyl dithiocarbamate self‐assembled film technology has high application prospects in the field of marine anti‐corrosion.

Reversible Tuning Electrical Properties in Ferroelectric SnS with NH3 Adsorption and Desorption.

Two-dimensional (2D) ferroelectrics usually exhibit instability or a tendency toward degradation when exposed to the ambient atmosphere, and the mechanism behind this phenomenon remains unclear. To unravel this affection mechanism, we have undertaken an investigation utilizing NH3 and two-dimensional ferroelectric SnS. Herein, the adsorption and desorption of NH3 molecules can reversibly modulate the electrical properties of SnS, encompassing I-V curves and transfer curves. The response time for NH3 adsorption is approximately 1.12 s, which is much quicker than that observed in other two-dimensional materials. KPFM characterizations indicate that air molecules' adsorption alters the surface potentials of SiO2, SnS, metal electrodes, and contacts with minimal impact on the electrode contact surface potential. Upon the adsorption of NH3 molecules or air molecules, the hole concentration within the device decreases. These findings elucidate the adsorption mechanism of NH3 molecules on SnS, potentially fostering the advancement of rapid gas sensing applications utilizing two-dimensional ferroelectrics.

Environmental Impact of Synthetic Dyes on Groundwater in Malaysia: Sources, Distribution, Transport Mechanisms, and Mitigation Strategies

Synthetic dyes, extracted from natural sources like insects, plants, coal, and ochre, have become prevalent due to their advantages over natural dyes. However, their production has led to increased environmental pollution, particularly in groundwater. Groundwater contamination from synthetic dyes occurs through advection, dispersion, and retardation. This review aims to highlight the environmental impacts of synthetic dyes on groundwater, elucidate the mechanisms of dye transport, and propose effective strategies for monitoring and mitigating contamination. Urban runoff carries dyes from surfaces such as roofs, parking lots, and roads into stormwater systems, while agricultural runoff transports dyes from products like soil conditioners, fertilizers, and seed coatings into water bodies. In groundwater, dyes move through the aquifer via advection, dispersion, and retardation, all influenced by groundwater flow and geological conditions. The advection process involves the bulk movement of groundwater carrying dissolved dyes, while dispersion causes dyes to spread and dilute over time and distance. Retardation, which involves the adsorption of dye molecules onto soil particles, slows dye movement, prolonging their presence in groundwater. Understanding the sources, distribution, and movement of synthetic dyes in groundwater is crucial for developing strategies to protect water resources and reduce environmental and health impacts. The extensive use of dyes in industrial and domestic activities necessitates comprehensive monitoring and management to ensure sustainable groundwater quality.

Paper-Based Analytical Devices Based on Amino-MOFs (MIL-125, UiO-66, and MIL-101) as Platforms towards Fluorescence Biodetection Applications

In this study, we designed three promising platforms based on metal–organic frameworks (MOFs) to develop paper-based analytical devices (PADs) for biosensing applications. PADs have become increasingly popular in field sensing in recent years due to their portability, low cost, simplicity, efficiency, fast detection capability, excellent sensitivity, and selectivity. In addition, MOFs are excellent choices for developing highly sensitive and selective sensors due their versatility for functionalizing, structural stability, and capability to adsorb and desorb specific molecules by reversible interactions. These materials also offer the possibility to modify their structure and properties, making them highly versatile and adaptable to different environments and sensing needs. In this research, we synthesized and characterized three different amino-functionalized MOFs: UiO-66-NH2 (Zr), MIL-125-NH2 (Ti), and MIL-101-NH2 (Fe). These MOFs were used to fabricate PADs capable of sensitive and portable monitoring of alkaline phosphatase (ALP) enzyme activity by laser-induced fluorescence (LIF). Overall, amino-derivated MOF platforms demonstrate significant potential for integration into biosensor PADs, offering key properties that enhance their performance and applicability in analytical chemistry and diagnostics.

Novel tempo oxidized polyvinyl alcohol/ cellulose nanocrystal-based nanocomposite membrane for malachite green dye removal.

In this study, in-situ modification by TEMPO oxidation was performed after nanocomposite synthesis to improve its properties toward dye molecule removal. The unoxidized and oxidized polymeric-based nanocomposite was denoted as PNC6 and PNC6O respectively. The nanocomposites were characterized using FESEM, FTIR, contact angle, XRD and BET analysis. Measurements of swelling ratio and chemical stability were also performed to provide insight into the durability of the nanocomposites. The effects of changing variables included contact duration, pH of aqueous solution, initial pollutant concentration, and temperature were observed. The kinetic study showed that the experimental data is best fitted with pseudo-second-order kinetics (R2 = 0.988 and 0.997 respectively), whereas on observing isotherm data, in both unoxidized and oxidized nanocomposite it fits well with Langmuir isotherm (R2 = 0.951 and 0.993 respectively). In addition, the effects on Gibb's free energy, Enthalpy, and Entropy were measured in terms of thermodynamic characteristics, it was established that dye molecules adsorption mechanism is endothermic and spontaneous in behaviour. To check regeneration tendency of the nanocomposite seven consecutive adsorption desorption cycles were run and about 90% and 80%, regeneration ability could be seen in an unoxidized state (PNC6) and an oxidized state (PNC6O) respectively upto 5th cycle after that the tendency get reduced. This study suggests that this novel polymeric nanocomposite can be employed as an efficient and relatively inexpensive adsorbent for dye removal from aqueous solutions.

Theoretically design of 2D penta-BN2/penta-Graphene wdW heterostructure for NO gas sensing implications: a first-principles study

As air pollution becomes more and more serious, the detection of harmful gas of NO has become an urgent need in daily life. In this paper, the electronic and gas-sensing properties of penta-BN2/penta-Graphene heterojunction (P-BN2/P-G) are studied by density functional theory and non-equilibrium Green's function method. The analysis results indicate that the P-BN2/P-G heterojunction has metallic properties. The electronic structures in combination with the adsorption behavior shows that the P-BN2/P-G heterojunction can chemically adsorb NO gas molecules, and there is obvious charge transfer, indicating that it has high gas sensitivity to NO gas. In addition, the sensing performance of the gas sensor constructed by NO adsorption on upper, middle and lower layers of the P-BN2/P-G heterojunction is deeply studied. Transport calculations show that when NO is adsorbed on the upper and middle layers of the P-BN2/P-G heterojunction-based gas sensor, the current of the device decreases significantly. When adsorbed on the lower layer, the current shows a trend of first decreasing and then increasing. Under a bias of 0.1 V, the gas sensitivity can reach up to 49% when NO is adsorbed in the middle layer, which is substantially higher than that of the P-BN2 monolayer device. It can be seen that the gas sensitivity is significantly improved after forming the heterojunction. In addition, the bias transport spectrum and scattering state can reveal the change in device current caused by the adsorption of NO gas molecules, thereby clarifying its microscopic mechanism. Finally, all the findings indicate that penta-based materials can be used as a very promising gas-sensitive material for detecting NO.

Nano-MnOx prepared by redox method for toluene oxidation removal from air

Catalytic oxidation is an efficient VOCs removal technology with great potential and development advantages. The key to the oxidative elimination of VOCs lies in the development and application of the catalyst with high efficiency. In this work, the nano-MnOx catalysts were prepared by redox method and the catalytic oxidation performance of toluene was studied. The calcination temperature could effectively change the surface chemical composition and the nano-MnOx catalyst structures, which could effectively regulate the number of active centers on the catalyst surface to improve the adsorption, activation, and oxidation ability of the nano-MnOx catalysts for toluene molecules. The nano-MnOx catalyst dominated by the MnO2 phase, which was prepared at the calcination temperature of 400 °C, had a high specific surface area, developed porosity, abundant reactive oxygen species, and oxygen vacancies. The structural characteristics are conducive to the adsorption, activation, and oxidation of toluene molecules, and thus exhibited excellent toluene catalytic oxidation activity. At the reaction temperature of 140 °C, the toluene oxidation conversion was as high as 99.4 %, and the toluene conversion remained above 96.6 % after experiencing a 690 min stability test.

Electrochemical, surface, and theoretical investigations of palm kernel shell extract as an effective inhibitor for carbon-steel corrosion in 1M HCl solution.

Herein, we employed palm kernel shell extract (PKSE) as an eco-friendly inhibitor for carbon steel in acidic-induced corrosion. The corrosion inhibition of PKSE on carbon steel in 1M HCI solution was investigated by electrochemical impedance spectroscopy, weight loss, and potentiodynamic polarization measurements. The surface was characterized by scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy. Moreover, the elastic modulus and hardness tests were conducted. Weight loss measurements revealed that the optimum concentration of inhibitors is 500ppm with 95.3% inhibition efficiency in 1M HCl solution. Electrochemical results showed that the inhibitor could exhibit excellent corrosion inhibition performance and displayed mixed-type inhibition. The electrochemical impedance spectroscopy analysis shows that the inhibition performance increases by increasing the concentration of PKSE. The surface studies ensure the PKSE effectiveness in carbon steel surface damage reduction. Also, the adsorption of PKSE molecules on the carbon steel surface occurs according to the Langmuir isotherm model. The primary goal of this investigation was the utilization of palm kernel shell extract as corrosion inhibitor for 1018 low carbon steel in 1M HCl solution, which highlights its novelty. The present results will be helpful to uncover the versatile importance of palm kernel shell compounds in the corrosion inhibition process.

Molecular Simulation of Cyclohexane in Nanoporous Materials: Adsorption of Conformers and Coadsorption with Water and Carbon Dioxide.

Molecular simulation is used to investigate the adsorption of an organic molecule and its different conformers into various nanoporous adsorbents. In more detail, we perform grand canonical Monte Carlo simulations to determine the adsorption isotherms for cyclohexane with its three conformers (chair, boat, and twisted boat) at three different temperatures into a molecular model of active carbons and two metal-organic frameworks (MOFs) (Cu-BTC and Al-Fum). By considering the adsorption of each conformer separately, we show that the adsorption isotherms are weakly dependent on the molecular conformation. When considering the concomitant adsorption of the three conformers under realistic conditions (to verify the population of each conformer in bulk mixtures), we show that the chair conformer is predominantly adsorbed in each material. However, such favorable adsorption mostly reflects the fact that this conformer has the largest population in the bulk mixture under the same thermodynamic conditions. On the contrary, with an increase in the cyclohexane gas pressure, the adsorption of boat and twisted boat conformers increases, while that of the chair conformer decreases as packing (entropy) effects become predominant during confinement. The adsorption of cyclohexane in the active carbon and MOF materials is also considered in the presence of water and CO2 atmospheres. In the case of the Al-fumarate material, the material is found to be strongly organophilic so that water and CO2 adsorption are negligible, and cyclohexane adsorption is not affected by competitive adsorption under any considered thermodynamic condition. On the contrary, for the active carbon and Cu-BTC material, competitive adsorption between cyclohexane and water or CO2 is observed even if cyclohexane adsorption remains preferred. While the different molecules coexist in the adsorbed phase at low pressures, increasing the cyclohexane pressure beyond 103 Pa promotes cyclohexane adsorption concomitantly with water and/or CO2 desorption.

Temperature-induced evolution of CuOx clusters in CuOx/TiO2 catalyst for boosting auto-exhaust oxidation

Developing non-noble metal oxides, replacing platinum group catalysts for auto-exhaust purification, where their usage amount exceeds 40 % of global demand, remains a challenge. Herein, we presented a combined approach on the synthesis and application of robust CuOx/TiO2 catalysts with ultra-fine CuOx clusters (ca. 1 nm). The strong interaction between CuOx and TiOx induces favorable interfacial charge accumulation, facilitating the extraction of the interfacial oxygen atoms in Cu2-x-O-Ti4-y chains and the surface lattice oxygen on CuOx clusters. Isotope 18O2 experiments and DFT calculations jointly confirmed that these oxygen atoms preferentially participate in the oxidation through the Mars-van Krevelen mechanism below 250 °C. The resulted oxygen vacancies facilitate the adsorption and activation of O2 molecules, which will participate the oxidation above 250 °C through Eley-Rideal mechanism. The increase in the temperature also drives the synergy of active oxygen species in the interfacial Cu2-x-O-Ti4-y bond chains and on CuOx clusters, cooperatively promoting the conversion of NO to NO2. As a result, the CuOx/TiO2 catalyst exhibits exceptional catalytic performance in soot oxidation, with a four-fold higher reaction rate (4.17 μmol g−1 min−1) than that of single-atom Cu₁-TiO2 catalyst. Such findings provide a novel strategy for the advancement of Cu-based cluster catalysts in environmental applications.

A first-principles study of the effects of temperature on the atomic and electronic structures of Mg-montmorillonite with H2O molecule adsorption

The interaction between water and soft rock rich in clay minerals is one of the main factors causing damage in soft rock tunnel engineering. The effects of temperature on the atomic structure and water absorption capacities of clay minerals cannot be ignored. In the present study, the influence of temperature on the microstructure of Mg-montmorillonite and the thermal stability of the Mg-montmorillonite (010) surface were calculated based on density functional theory. Furthermore, the adsorption properties of H2O molecules within different coverages (0 < Θ ≤ 1.0 ML) on the (010) surface were investigated in the temperature range of 0–900 K. First, the volume of Mg-montmorillonite expanded significantly with increasing temperature along the z-axis direction. The surface energy of the Mg-montmorillonite (010) surface decreased with increasing temperature, indicating that the high temperature weakened the interatomic interactions on the surface. Moreover, the calculations demonstrated that H2O molecules could still be stably adsorbed on the Mg-montmorillonite (010) surface at different temperatures, and the order of stable adsorption configurations for a single H2O molecule was hollow > bridge > interlayer bridge > top sites. With increasing coverage of H2O molecules, the adsorption energies increased for the top sites, while decreased for the bridge, hollow, and interlayer bridge sites at high temperature. In addition, the changes in atomic structure and electronic characteristics during water absorption were further explored by calculating the ICOHP, PDOS, and lattice relaxation.

Study on the effect of spatial adsorption orientation on the preferential selection mechanism of dust suppression surfactants

Surfactants are widely used in the field of coal dust control. However, the dust suppression effect of different surfactants varies significantly, and the preferential selection mechanism of dust suppressants for mining is not clear. In this study, the water/surfactant/lignite system was constructed by molecular simulation to investigate the adsorption behavior of surfactants with different structures on the lignite surface at the molecular level. The reasons for the differences in the wettability adsorption of sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), fatty alcohol polyoxyethylene ether-9 (AEO-9), and alkyl polyglycoside (APG1214) on the lignite surface were also investigated based on the quantum chemical calculations and macroscopic experimental analysis. The results showed that the adsorption orientation of surfactant molecules at the solid–liquid interface exerted a pivotal influence on the surface wettability of lignite. According to molecular orbital and electrostatic potential analysis, surfactant molecules with LUMO distributed in the tail chain were more inclined to form a positive adsorption orientation than that concentrated in the polar headgroups; and the stronger the interaction between the polar headgroups and the coal surface with the like charge, the more stable the adsorption of surfactant molecules with the positive arrangement at the interface was. Furthermore, the stronger potential difference between SDS molecules and the hydroxyl-rich structure of the APG1214 molecules are conducive to the formation of hydrogen bonds with water molecules. Wettability experiments showed that the ability of surfactants to improve the wettability of coal dust was positively correlated with the adsorption orientation.

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.

Boosting photocatalytic nitrogen fixation performance by adjusting the intramolecular D-A structure and band gap of thiophene-based COFs

Herein, we successfully synthesized two photoactive donor–acceptor (D-A) covalent organic frameworks by incorporating electric-deficient triazine and electric-rich benzotrithiophene moieties into the framework. The introduction of sulfur atom and triazine unit significantly change the intrinsic band gap of JLNU-COFs, this leads to an expanded range of light absorption, encompassing wavelengths from ultraviolet to visible. The narrow band gap of JLNU-311 allows for efficient utilization of visible light while maintaining the thermodynamic activity required for nitrogen reduction within appropriate energy bands. JLNU-311 modified with strong electron absorbing groups has higher activity to NH3 production without co-catalyst or sacrificial agent, and yield can reach 325.6 µmol/g/h. Theoretical calculation further confirm that acceptor structure can effectively regulate the band gap width, promote the adsorption, dissociation and protonation of N2 molecules on JLNU-COFs, and thus reduce the energy barrier of photocatalytic nitrogen reduction reaction (PNRR). Therefore, this study provides an effective strategy for design of active nitrogen fixing photocatalysts.