Search Results (216)

Metallic glass, as an emerging catalytic material, possesses an atomic structure characterized by long-range disorder and short-range order, which creates abundant and accessible active sites that enhance the adsorption and reactivity toward pollutant molecules, particularly dye compounds. In treating highly colored and recalcitrant Reactive Black 5 (RB5) dye wastewater, Mo₅₁Fe₃₄B₁₅ metallic glass wire demonstrate outstanding catalytic degradation performance within a conventional Fenton-like system. Under acidic conditions (pH = 2), the material exhibits a degradation rate constant of 0.698 min⁻¹ for a 20 ppm RB5 dye solution, achieving a degradation efficiency of 98.8% within 10 min. After 10 consecutive cycles, the efficiency remains at 95%, and throughout 15 cycles, it consistently maintains a performance level above 90%. As the reaction proceeds, the degradation rate gradually decreases, primarily due to the accumulation of corrosion products on the catalyst surface, which are predominantly composed of MoO₃ and Fe₂O₃. During the degradation process, metallic Mo⁰ and Fe⁰ serve as electron donors that facilitate the decomposition of H₂O₂, generating highly reactive hydroxyl radicals (•OH). These radicals attack the chromophoric structure of the dye, leading to its structural disruption and enabling rapid decolorization. Full article

This paper develops mathematical apparatus for the modeling of the electronic structure of semiconductor nanoparticles and the description of sensor response of the layers constructed on their base. The developed technique involves solutions of both the direct and inverse problems. The direct problem involves of the two coupled sets of differential equations, at fixed values of physical parameters. The first of them is the set of equations of chemical kinetics which describes processes occurring at the surface of a nanoparticle. The second involves an equation describing electron concentration distribution inside a nanoparticle. The inverse problem consists of the determination of physical parameters (essentially, reactions rate constants) which provide a good approximation of experimental data when using them to find the solution of the direct problem. The mathematical novelty of this paper is the application of—for the first time, to find the solution of the inverse problem—the new gradient-free optimization methods based on low-rank tensor train decomposition and modern machine learning paradigm. Sensor effect was measured in a dedicated set of experiments. Comparisons of computed and experimental data on sensor effect were carried out and demonstrated sufficiently good agreement. Full article

Efficient recycling of polyamide 6 (PA6) requires selective depolymerization routes that recover monomers under moderate conditions. This study investigates microwave-assisted acid hydrolysis of four PA6 waste streams, two oligomer-rich residues (WS-13, WS-24), an industrial fiber (C-fiber), and a commercial resin (C-resin) to elucidate degradation kinetics, activation energies, and product yields. Thermogravimetric analysis revealed multi-step solid-state decomposition, while microwave hydrolysis (125–200 °C, 15–60 min, 400 W) demonstrated strong dependence on acid type. HCl achieved complete conversion, whereas phosphoric and formic acids exceeded 95%. Kinetic analysis under H₃PO₄ followed pseudo-first-order behavior, with rate constants (0.015–0.141 min⁻¹ at 200 °C) and activation energies reflecting feedstock structure: 53.1 kJ mol⁻¹ (WS-13), 56.5 kJ mol⁻¹ (WS-24), 87.1 kJ mol⁻¹ (C-resin), and 99.9 kJ mol⁻¹ (C-fiber). Monomer yields varied by substrate: WS-13 achieved 62.4% at 200 °C and 45 min (ACA 46%, CPL 16%), WS-24 yielded 62.0% (primarily ACA), C-fiber reached 69.7% (ACA-dominant), and C-resin produced 53.8%. These results show that oligomer-rich wastes are kinetically favored for rapid hydrolysis at lower energy cost, while C-fiber maximizes aminocaproic acid recovery. Overall, microwave-assisted hydrolysis provides a selective, energy-efficient pathway for PA6 circularity, offering design parameters for reactor operation and process optimization. Full article

To impart high flame resistance, enhanced thermal stability, and low dielectric properties to epoxy resin while maintaining good mechanical behaviors for high-end applications, a monomer (BZPN) containing the characteristic structure of benzoxazine, phthalonitrile, and trifluoromethyl was prepared and added into the Bisphenol A-type epoxy resin (DGEBA)/Dapsone (DDS) combination. The glass transition temperature (T_g) and carbon yield under a nitrogen atmosphere at 800 °C were found to significantly increase from 155 °C, 17.2% to 236 °C, 50.3%, respectively, for the neat EP/DDS and the BZPN-containing material. The UL-94 flammability rating achieved V-0 level when the BZPN content was 19.2 wt.% (EP-BZ-1). The thermal decomposition and flame retardancy mechanism were explored by TGA-FTIR, Raman, and XPS analysis. The fluorine-containing products were found in both the gas phase and the char residue, implying that the •CF₃ radicals played an important role in promoting the flame-retardant behaviors through a radical trapping mechanism. The dielectric constant and dielectric loss of the materials decreased as anticipated. In addition, mechanical testing of carbon fiber-reinforced composites showed that the BZPN-containing resin presented equivalent mechanical behaviors to the neat EP/DDS resin. The synthesized BZPN was proved to be an effective and promising additive for the epoxy-based composite. Full article

The paper describes the conversion of carbon dioxide into methanol in a chemical reactor under standard operating conditions. Electro-analytical techniques, cyclic voltammetry, and chrono-amperometry characterize the process. The electrochemical redox reaction develops using various catalyzers to evaluate the performance of the carbon dioxide conversion into methanol process under variable chemical conditions. The results of the applied technique showed an incomplete redox reaction with an electronic change of z = 2.84 on average, below the ideal number, z = 6, that may be due to methanol decomposition (reverse reaction) because the system operates with a reaction constant above the equilibrium value. The methanol production may improve by draining the methanol/water solution from the chemical reactor to reduce the methanol concentration in the electrochemical cell, shifting the forward reaction towards the formation of methanol, increasing the electron change number, which approaches the ideal value, and improving the methanol production efficiency. The draining process shows a significant increase in methanol formation, which depends on the draining flow rate and the catalyzer type. A simulation process shows that if we operate in optimum conditions, with no methanol decomposition through a reverse reaction, the redox reaction fulfills the ideal condition of maximum electronic change. The experimental tests validate the simulation results, showing a relevant increase in the electron change number with values up to z = 4.2 for optimum draining flow rate conditions (0.2 L/s). The experimental results show a relative increase factor of 4.7 in methanol production, meaning we can produce more than four times more methanol compared with no draining techniques. The data analysis shows that the draining flow rate has a threshold of 0.2 L/s, beyond which the extent of the reaction reverses, reducing the methanol formation due to a chemical reaction disequilibrium. The paper concludes that using the draining method, the methanol production mass rate increases significantly from an average value of 20.9 kg/h for non-draining use, considering all catalyzer types, to a range between 91.9 kg/h and 104.3 kg/h, depending on the flow rate. Averaging all values for different flow rates and comparing with the non-draining case, we obtain an absolute methanol production mass rate of 77 kg/h, meaning an incremental percentage of 469.1%, more than four times the initial production. Although the proposed methodology looks promising, applying this procedure on an industrial scale may suffer from restrictions since the chemical reactions intervening in the methanol formation do not perform linearly. According to experimental tests, the best option among the six catalyzers used for methanol production is the plain copper, with copper oxides (Cu₂O, CuO) and copper Sulphur (CuS) as feasible alternatives. Full article

Accurate peak detection in the frequency domain is fundamental to reliable range estimation in Frequency-Modulated Continuous-Wave (FMCW) radar systems, particularly in challenging conditions characterized by a low signal-to-noise ratio (SNR) and phase noise impairments. This paper presents a comprehensive comparative analysis of five peak detection algorithms: FFT thresholding, Cell-Averaging Constant False Alarm Rate (CA-CFAR), a simplified Matrix Pencil Method (MPM), SVD-based detection, and a novel Learned Thresholded Subspace Projection (LTSP) approach. The proposed LTSP method leverages singular value decomposition (SVD) to extract the dominant signal subspace, followed by signal reconstruction and spectral peak analysis, enabling robust detection in noisy and spectrally distorted environments. Each technique was analytically modeled and extensively evaluated through Monte Carlo simulations across a wide range of SNRs and oscillator phase noise levels, from $-100$ dBc/Hz to $-70$ dBc/Hz. Additionally, real-world validation was performed using a custom-built harmonic FMCW radar prototype operating in the 2.4–2.5 GHz transmission band and 4.8–5.0 GHz harmonic reception band. Results show that CA-CFAR offers the highest resilience to phase noise, while the proposed LTSP method delivers competitive detection performance with improved robustness over conventional FFT and MPM techniques. Furthermore, the hardware feasibility of each algorithm is assessed for implementation on a Xilinx FPGA platform, highlighting practical trade-offs between detection performance, computational complexity, and resource utilization. These findings provide valuable guidance for the design of real-time, embedded FMCW radar systems operating under adverse conditions. Full article

This study evaluated the synergistic effects of microbial decomposition agents and deep rotary tillage on rice straw decomposition, soil nutrient dynamics, and microbial communities in paddy fields of southern China. A two-factor randomized block experiment was conducted, with straw decomposition dynamics modeled using a modified Olson decay model, and microbial communities were assessed via high-throughput sequencing and network analysis. The combined treatment significantly increased the decomposition rate constant, reduced the time for 50% decomposition to 81 days, and enhanced soil nutrient availability, especially total nitrogen, phosphorus, and potassium. Microbial richness, diversity, and network complexity were also improved. Structural equation modeling indicated that nutrient availability, rather than microbial α-diversity, was the main driver of decomposition processes. These findings suggest that integrating microbial agents with deep tillage offers an effective strategy for optimizing straw return, improving soil fertility, and enhancing microbial functional resilience in rice systems. Full article

A composite photocatalyst of ceria–cadmium supported on mesoporous SBA-15 silica was synthesized and employed for the aqueous methylene blue (MB) degradation. The composites were prepared using an incipient wetness impregnation technique and a conventional sol–gel approach with triblock copolymer P123 as a structure-directing agent for SBA-15 preparation, enabling the uniform dispersion of CeO₂ and Cd species within the SBA-15 framework. The physicochemical properties of both CeO₂/SBA-15 and Cd-CeO₂/SBA-15 composites were analyzed using small-angle and wide-angle XRD, FT-IR spectroscopy, SEM, TEM, EDX spectroscopy, N₂ physisorption at 77 K, and UV-Vis spectroscopy. The findings revealed that the SBA-15 support retained its well-ordered hexagonal mesostructure in both the ceria–SBA-15 and SBA-15-supported cadmium–ceria (Cd-CeO₂) composites. The highest degradation efficiency of 96.40% was achieved under optimal conditions, and kinetic analysis using the Langmuir–Hinshelwood model indicated that the MB degradation process followed pseudo-first-order kinetics, with a strong correlation coefficient (R² = 0.9925) and a rate constant (k) of 0.02532 min⁻¹. Under irradiation, the Cd-CeO₂/SBA-15 composites exhibited superior photocatalytic activity compared to the pristine components, owing to the synergistic interaction between ceria and cadmium, enhanced light absorption, and improved charge carrier separation. The recyclability test demonstrated that the degradation efficiency decreased slightly from 96.40% to 94.86% after three cycles, confirming the stability and reusability of Cd-CeO₂/SBA-15 composites. The photocatalytic process demonstrated a favorable electrical energy per order (EE/O) value of 281.8 kWh m⁻³, indicating promising energy efficiency for practical wastewater treatment. These results highlight the excellent photocatalytic performance and durability of the synthesized Cd-CeO₂/SBA-15 composites, making them promising candidates for facilitating the photocatalytic decomposition of MB and other dye molecules in water treatment applications. Full article

The development of high-performance photocatalysts is vital for combating water pollution and microbial contamination. In this study, visible-light-active Z-scheme heterojunction nanocomposites composed of Co₃O₄ and Nb₂O₅ (CNNC) were synthesized via co-crystallization and subsequent high-pressure annealing to enhance photocatalytic and antimicrobial performance. Structural and optical analyses via XRD, FESEM, TEM, XPS, and PL confirmed the heterojunction formation between porous Co₃O₄ nanoparticles (CONP) and columnar orthorhombic Nb₂O₅ nanoparticles (NONP). The CNNC exhibited significantly improved photocatalytic activity, achieving degradation efficiencies of 95.1% for methylene blue, 72.6% for tetracycline, and 90.0% for Congo red within 150 min. Kinetic studies showed that CNNC’s rate constants were 367% and 466% of those of CONP and NONP, respectively. Moreover, CNNC demonstrated a strong antibacterial effect on Staphylococcus aureus and Escherichia coli with ZOI values of 9.3 mm and 6.8 mm, respectively. Mechanistic analysis revealed that the Z-scheme charge-transfer pathway improved charge separation and reduced electron–hole recombination, contributing to the promoted photocatalytic efficiency. The nanocomposite also showed robust stability and recyclability over five times. These results highlight the promise of CNNC as a bifunctional, visible-light-driven photocatalyst for pollutant decomposition and microbial control. Full article

The practical implementation of transition state theory (TST) commonly assumes equivalence between theoretical and experimentally determined rate constants, represented by Arrhenius parameters—the activation energy and pre-exponential factor. Here, we employed the General Rate Equation (GRE) to analyse solid–gas-phase thermolysis in two paradigms: mass loss (e.g., calcite decomposition) and mass gain (e.g., methane pyrolysis leading to solid carbon formation). By partitioning the Gibbs free energy of activation into forwards and reverse contributions, plus an additional term accounting for concurrent physical phenomena (notably nucleation and diffusion-viscosity effects), we derived an empirical universal expression relating both Arrhenius parameters and $∆G^{+}$ across 500–1500 K. We further demonstrate the utility of the isokinetic temperature for interpreting cases where only Kinetic Compensation or Enthalpy–Entropy Compensation effects are observed. This framework unifies kinetic and thermodynamic descriptions of complex thermolysis processes. Full article

When frequency-modulated continuous-wave (FMCW) laser radar (Ladar) is employed for three-dimensional imaging, the echo signal is susceptible to modulation nonlinearity and platform vibration due to modulation and the short wavelength. These effects cause main-lobe widening, side-lobe elevation, and positional shift, which degrades distance detection accuracy. To solve these problems, this paper proposes a compensation method combining multiple synchrosqueezing transform (MSST), equal-phase interval resampling, and high-order ambiguity function (HAF). Firstly, variational mode decomposition (VMD) is applied to the optical prism signal to eliminate low-frequency noise and harmonic peaks. MSST is used to extract the time–frequency curve of the optical prism. The nonlinearity in the transmitted signal is estimated by two-step integration. An internal calibration signal containing nonlinearity is constructed at a higher sampling rate to resample the actual signal at an equal-phase interval. Then, HAF compensates for high-order vibration and residual phase error after resampling. Finally, symmetrical triangle wave modulation is used to remove constant-speed vibration. Verifying by actual data, the proposed method can enhance the main lobe and suppress the side lobe about 1.5 dB for a strong reflection target signal. Natural-target peaks can also be enhanced and the remaining peaks are suppressed, which is helpful to extract an accurate target distance. Full article

A device was developed to study the evolution of fluorescence spectra as a function of time. A previously designed fluorimeter based on the diode array mini-spectrometer CM12880MA was used. The control and measurement were carried out by programming a SAM21D microcontroller. Considerations regarding the optimization of acquisition speed, memory, and computer interface have been analyzed and optimized. As a result, a very versatile device with great adaptability, reduced dimensions, portability, and a low budget (under EUR 500) has been built. The sensitivity, controlled by the integration time of the photodiodes, can be adjusted between 10 µs and 20 s, thus allowing sampling times ranging from 10 ms to more than 10 h. Under these conditions, chemical rate constants from 20 s⁻¹ to 10⁻⁸ s⁻¹ can be experimentally determined. It has a very wide operating range for the kinetic rate constant determination, over six orders of magnitude. As proof of the system performance, the oxidation reaction of Thiamine in a basic medium to form fluorescent Thiochrome has been employed. The evolution of the emission spectrum has been followed, and the decomposition rate constant has been measured at 2.1 × 10⁻³ s⁻¹, a value which matches those values reported in the literature for this system. A Thiochrome calibration curve has also been performed, obtaining a detection limit of 13 nM, consistent with literature data. Additionally, the stability of Thiochrome has been tested, being the photo-decomposition rate constants 1.8 × 10⁻⁴ s⁻¹ and 3.0 × 10⁻⁷ s⁻¹, in the presence and absence of UV light (365 nm), respectively. Finally, experiments have been designed to obtain, in a single measurement, the values of both rate constants: the formation of Thiochrome from Thiamine and its photo-decomposition under UV light to a non-fluorescent product. The rate constant values obtained are in good agreement with those previously obtained through independent experiments under the same experimental conditions. These results show that, under these conditions, Thiochrome can be considered an unstable intermediate in a chemical reaction with successive stages. Full article

With the advancement of new synthetic techniques, 5-Methyl-2-ethylfuran (5-MEF) has emerged as a promising renewable biofuel. In this study, the potential energy surfaces for the unimolecular dissociation reaction, H-addition reaction, and H-abstraction reaction of 5-MEF were mapped at the CBS-QB3 level. The temperature- and pressure-dependent rate constants for these reactions on the potential energy surfaces were determined by solving the master equation, using both transition state theory and Rice–Ramsperger–Kassel–Marcus theory. The results showed that the dissociation reaction of the C(6) site on the branched chain of 5-MEF has the largest rate constant and is the main decomposition pathway, while the dissociation reaction of the H atom on the furan ring has a lower rate constant and is not the main reaction pathway. In addition, the dissociation of H atoms on the branched chain and intramolecular H-transfer reactions also have high-rate constants and play an important role in the decomposition of 5-MEF. H-addition reactions mainly occur at the C(2) and C(5) sites, and the generation of the corresponding products through β-breakage becomes the main reaction pathway. With the increase in temperature, the H-addition reaction at the C(2) site gradually changes to a substitution reaction, dominating the formation of C₂H₅ and 2-methylfuran. Full article

This study investigates the impact of nickel doping on the thermal and combustion properties of ammonium perchlorate/carboxymethyl cellulose (AP/CMC) composites. Through comprehensive SEM-EDS, FTIR, XRD, DSC, TGA, and burning rate analyses, significant improvements in the structural and functional characteristics of the AP/CMC-Ni composite were observed compared to those of pure AP and AP/CMC composites. The SEM-EDS analysis revealed that nickel incorporation resulted in thicker and more irregular CMC fibers, indicating substantial morphological changes. The FTIR spectroscopy showed shifts in the O-H and C=O stretching bands, pointing to interactions between nickel ions and CMC functional groups. The XRD patterns highlighted a decrease in crystallinity and the presence of NiO phases, confirming the successful integration of nickel into the CMC matrix. The thermal analysis demonstrated that nickel doping significantly lowered the decomposition temperature of the AP/CMC composite, as evidenced by DSC, and enhances the thermal degradation process, as shown by TGA. The AP/CMC-Ni composite exhibited a higher burning rate across all of the tested pressures, highlighting the catalytic effect of nickel in improving the combustion efficiency. The burning rate for AP/CMC follows the power-law expression with constants a = 2.34 and n = 0.499, while for AP/CMC-Ni, the constants are a = 3.35 and n = 0.475. This study highlights the essential role of nickel doping in facilitating the decomposition of AP within the AP/CMC composite. By lowering the decomposition temperature, nickel enhances the overall combustion process, making the AP/CMC-Ni composite more efficient for applications requiring controlled thermal decomposition. These findings provide valuable insights for the design and development of high-performance composite materials in advanced industrial applications. Full article

Evaluating the air purification performance of photocatalytic materials typically requires complex gas decomposition tests involving expensive analytical equipment and lengthy testing periods. In this study, photocatalytic performance evaluation methods involving resazurin (Rz) ink and fluorescence probe techniques were investigated as alternatives to conventional gas decomposition tests. TiO₂ films with varying performance levels were fabricated by controlling TiO₂ slurry concentration and the amount of photocatalyst deposited through spin coating. Photocatalytic performances of the synthesised films were then evaluated using the acetaldehyde decomposition method, Rz ink test, and fluorescence probe method for measuring OH radical generation. The acetaldehyde decomposition rate constants showed high correlation with both the Rz colour change rate in modified-pH ink (R² = 0.91) and the OH radical concentration (R² = 0.98). Conventional Rz ink testing for high-performance materials showed rapid colour changes, indicating its limited applicability. Our modified-pH Rz ink enabled facile analysis by ensuring controlled reactivity. Both the modified Rz ink method, which enables quantitative evaluation within five minutes even for high-performance materials, and the fluorescence probe method are suitable as reliable screening tools for photocatalytic air purification materials. These simplified evaluation methods will aid in developing more efficient photocatalysts and advancing environmental purification technologies. Full article