Search Results (329)

The fabrication and application of single-site heterogeneous reaction centers are new frontiers in chemistry. Single-site heterogeneous reaction centers are analogous to metal centers in enzymes and transition-metal complexes: they are charged and decorated with ligands and would exhibit superior reactivity and selectivity in chemical conversion. Such high reactivity would also result in significant response, such as a band gap or resistance change, to approaching molecules, which can be used for sensing applications. As a proof of concept, the electronic structure and reaction pathways with NO and NO₂ of Au(I) fragments dispersed on phosphorene (Pene) were investigated with first-principle-based calculations. Atomic-deposited Au atoms on Pene (Au₁-Pene) have hybridized Au states in the bulk band gap of Pene and a decreased band gap of 0.14 eV and would aggregate into clusters. Passivation of the Au hybrid states with -OH and -CH₃ forms thermodynamically plausible HO-Au₁-Pene and H₃C-Au₁-Pene and restores the band gap to that of bulk Pene. Inspired by this, HO-Au₁-Pene and H₃C-Au₁-Pene were examined for detection of NO and NO₂ that would react with -OH and -CH₃, and the resulting decrease of band gap back to that of Au₁-Pene would be measurable. HO-Au₁-Pene and H₃C-Au₁-Pene are highly sensitive to NO and NO₂, and their calculated theoretical sensitivities are all 99.99%. The reaction of NO₂ with HO-Au₁-Pene is endothermic, making the dissociation of product HNO₃ more plausible, while the barriers for the reaction of CH₃-Au₁-Pene with NO and NO₂ are too high for spontaneous detection. Therefore, HO-Au₁-Pene is not eligible for NO₂ sensing and CH₃-Au₁-Pene is not eligible for NO and NO₂ sensing. The calculated energy barrier for the reaction of HO-Au-Pene with NO is 0.36 eV, and the reaction is about thermal neutral, suggesting HO-Au-Pene is highly sensitive for NO sensing and the reaction for NO detection is spontaneous. This work highlights the potential superior sensing performance of transition-metal fragments and their potential for next-generation sensing applications. Full article

This study investigates the structure of a metal hydride (MH) cartridge as a hydrogen storage tank for small-scale fuel cells (FCs). This cartridge is designed to be stacked and used in layers, allowing flexible capacity adjustment according to demand. MH enables compact and safe hydrogen storage for small-scale fuel cell (FC) applications due to its high energy density and low-pressure operation. However, because hydrogen desorption from MH is an endothermic reaction, an external heat supply is required for stable performance. To enhance both the heat transfer efficiency and cartridge usability, we propose a heat supply method that utilizes waste heat from an air-cooled proton-exchange membrane fuel cell (PEMFC). The proposed cartridge incorporates four cylindrical MH tanks that require uniform heat transfer. Therefore, we proposed the tank arrangements within the cartridge to minimize the non-uniformity of heat transfer distribution on the surface. The flow of exhaust air from the PEMFC into the cartridge was analyzed using computational fluid dynamics (CFD) simulations. In addition, an empirical correlation for the Nusselt number was developed to estimate the heat transfer coefficient. As a result, it was concluded that the heat utilization rate of the exhaust heat flowing into the cartridge was 13.2%. Full article

The metallurgical industry has been constantly changing over the past decades. On the one hand, there has been the modernization and improvement of production efficiency, and on the other hand, we have seen a reduction in the negative impact on the environment. The possibility of using alternative materials and the circular economy is significant in this area. In the present work, research was carried out to determine the usefulness of biomass in the form of fruit seeds for the recycling processes of metal-bearing raw materials, including slags from copper production processes, which are characterized by a much higher metal content than ores of this metal. The main carbon-bearing material/reducer used in the process is metallurgical coke. The transformation of the European metal industry has been observed in recent years. To carry out the physicochemical characterization of the tested material, a research methodology was adopted using tools to determine the stability of behavior at high temperatures, chemical composition, and volatile components. Thermodynamic analysis was carried out, indicating the theoretical course of reactions of individual system components and thermal effects, allowing a determination of whether the assumed reactions are endothermic or exothermic. The planned research ends with the reduction process in conditions similar to those carried out in industrial conditions. Enforced by the guidelines for reducing CO₂ emissions, it contributes to a significant reduction in the demand for coke. This paper addresses the issue of determining the feasibility of using selected bioreducers, including cherry stones, to verify their suitability in the process of reducing copper oxides. The study used copper slag with a composition similar to slags generated at the copper production stage in a flash furnace. The results obtained in reducing copper content above 98 wt. % indicate the great potential of this type of bioreducer. It should be noted that, unlike conventional fossil fuels, the use of cherry stones to reduce copper slag can be considered an environmentally neutral method of carbon offset. The resulting secondary slag is a waste product that can be stored and disposed of without harmful environmental effects due to its low lead content. An additional advantage is the relatively wide availability of cherry stones. Full article

The potential of dry reforming methane (DRM) to convert two greenhouse gases concurrently is drawing interest from around the world. This research focused on developing supported nickel catalysts for the DRM, utilizing stabilized zirconia (SZ31107), which contains 5% SiO₂, as the support material. To promote the catalysts with a 5 wt.% Ni concentration, we used varying gallium loadings, specifically 0.1, 0.25, 0.5, 0.75, and 1 wt.%. After a detailed analysis, characterization was performed using X-ray diffraction, N₂-physorption, temperature-programmed reduction/desorption techniques, thermogravimetry, and Raman spectroscopy. The optimal DRM performance, achieved at 700 °C with a 1:1 CH₄:CO₂ feed, was recorded for the catalyst that has 0.25 wt.% Ga. The catalyst demonstrated remarkable average conversion rates of 56% for CH₄ and 66% for CO₂ after 300 min at 700 °C, with an H₂:CO ratio of 0.84. Activity was further enhanced by raising the temperature to 800 °C, which resulted in an 87% CO₂ conversion and an 80% CH₄ conversion. Studies on the catalyst’s long-term stability revealed a slow deactivation. With computed activation energies of 28,009 J/mol for CH₄ conversion and 21,875 J/mol for CO₂ conversion, temperature-programmed reaction tests conducted over the best catalyst demonstrated the DRM reaction’s endothermic character. Small additions of Ga encouraged the creation of more graphitic carbon structures, according to Raman spectroscopy of spent catalysts; the ideal catalyst had the lowest I_D/I_G ratio. These results suggest that the 5Ni+0.25Ga/SZ31107 catalyst is a promising candidate for large-scale syngas and hydrogen production. Full article

Traditional designs often ignore the effect of catalyst particle shape, which suffers from capturing detailed local flow hydrodynamics, mass transport and reaction behaviors, and further significantly affects reactor phenomena. This study aims to perform particle-resolved computational fluid dynamics (CFD) simulations to investigate the influence of operating conditions and various catalyst particle shapes on fixed-bed reactor performance. Three important industrial reaction systems, including methanol to dimethyl ether, CO₂ hydrogenation to methanol, and levulinic acid esterification, are discussed in fixed-bed reactors. The numerical results demonstrate that reactor performance varies from the important interactive contributions of hydrodynamics characteristics and reaction behaviors. Specifically, exothermic reactions such as methanol to dimethyl ether and CO₂ hydrogenation to methanol are characterized by a gradual increase in temperature along the reactor height, while endothermic reactions such as valeric acid esterification exhibit a gradual decrease in temperature along the reactor height. For the methanol to dimethyl ether system, the increase in operating temperature leads to a decrease in axial methanol concentration, as well as an improvement in axial dimethyl ether concentration. However, the change in methanol molar concentration has little influence on its conversion. Furthermore, reactor phenomena strongly vary from the different catalyst shapes. The numerical results demonstrate that the fixed bed with hollow cylinders facilitates a more uniform flow distribution, whereas the fixed bed with solid cylinders achieves higher conversion rates within a specific temperature range (483.15 K to 523.15 K). This research provides valuable insights for fixed-bed reactor optimized design, emphasizing the need for precise control over temperature, feed rate, and catalyst configuration to improve reactant conversion in industrial applications. Full article

Among biomass gasification syngas cleaning methods, non-catalytic reforming emerges as a sustainable and high-efficiency alternative. This study employed integrated experimental analysis and kinetic modeling to examine non-catalytic reforming processes of biomass-derived producer gas utilizing a synthetic tar mixture containing representative model compounds: naphthalene (C₁₀H₈), toluene (C₇H₈), benzene (C₆H₆), and phenol (C₆H₅OH). The experiments were conducted using a high-temperature fixed-bed reactor under varying temperatures (1100–1500 °C) and equivalence ratios (ERs, 0.10–0.30). The results obtained from the experiment, namely the measured mole concentration of H₂, CO, CH₄, CO₂, H₂O, soot, and tar suggested that both reactor temperature and O₂ content had an important effect. Increasing the temperature significantly promotes the formation of H₂ and CO. At 1500 °C and a residence time of 0.01 s, the product gas achieved CO and H₂ concentrations of 28.02% and 34.35%, respectively, while CH₄, tar, and soot were almost entirely converted. Conversely, the addition of O₂ reduces the concentrations of H₂ and CO. Increasing ER from 0.10 to 0.20 could reduce CO from 22.25% to 16.11%, and H₂ from 13.81% to 10.54%, respectively. Experimental results were used to derive a kinetic model to accurately describe the non-catalytic reforming of producer gas. Furthermore, the maximum of the Root Mean Square Error (RMSE) and the Relative Root Mean Square Error (RRMSE) between the model predictions and experimental data are 2.42% and 11.01%, respectively. In particular, according to the kinetic model, the temperature increases predominantly accelerated endothermic reactions, including the Boudouard reaction, water gas reaction, and CH₄ steam reforming, thereby significantly enhancing CO and H₂ production. Simultaneously, O₂ content primarily influenced carbon monoxide oxidation, hydrogen oxidation, and partial carbon oxidation. Full article

In this study, a Zn-Mn ferrite soft magnetic material (Mn_0.6Zn_0.4Fe₂O₄) was successfully prepared from a spent Zn-Mn battery using a novel multi-step process involving bioleaching, co-precipitation, and boiling reflux. The green Zn–Mn ferrite exhibited optimal magnetic properties, with Ms, Mr, and Hc values of 68.9 emu/g, 4.7 emu/g, and 53.6 Oe, respectively. The adsorption kinetics and isotherms of Cd (II), As (III), and Pb (II) in wastewater on Mn_0.6Zn_0.4Fe₂O₄ were subsequently investigated. The sorption dosages of Cd (II), As (III), and Pb (II) were 22.9 mg/g, 8.7 mg/g, and 33.9 mg/g, respectively. The pseudo-second-order kinetic model provided a fitting correlation with the experimental data. The adsorption process exhibited a good correlation with the Langmuir model, with R² = 0.997, and the q_m and b values were 33.44 mg/g and 2.43 L/mg, respectively. The sorption rates followed the sequence Pb (II) > Cd (II) > As (III). On increasing the temperature, the saturated adsorption capacity of the Cd (II), As (III), and Pb (II) increased, thus indicating that the adsorption reaction was endothermic, with the corresponding activation energy (Ea) values determined to be 9.5 KJ/mol, 32.2 KJ/mol, and 1.4 KJ/mol, respectively. Full article

Non-stoichiometric skinnerite Cu_3+mSbS₃ (−0.04 ≤ m ≤ 0.04) was synthesized via mechanical alloying and hot pressing. A phase analysis, microstructural characterization, and thermoelectric property evaluation were conducted to investigate the effects of Cu deficiency and excess. An X-ray diffraction of the mechanically alloyed powders confirmed the formation of cubic skinnerite, while the hot-pressed Cu-rich samples contained a secondary phase, identified as cubic tetrahedrite (Cu₁₂Sb₄S₁₃). The lattice constant decreased within the range of 1.0341–1.0347 nm for the non-stoichiometric compositions. The microstructural analysis revealed a skinnerite matrix with tetrahedrite inclusions in the Cu-excess samples. The differential scanning calorimetry showed a single endothermic peak at 876 K for the stoichiometric skinnerite, corresponding to its melting point, whereas the non-stoichiometric samples exhibited additional phase transitions at 814–818 K, and a melting reaction at 873–874 K. The electrical conductivity increased with the temperature, indicating non-degenerate semiconductor behavior. Between 323 and 423 K, the electrical conductivity varied depending on the Cu deficiency or excess, but above 423 K, all the non-stoichiometric samples exhibited higher electrical conductivity than the stoichiometric skinnerite. A positive Seebeck coefficient confirmed p-type conduction in all the samples, while Cu deficiency led to a decrease in the Seebeck coefficient but enhanced the power factor, due to increased electrical conductivity. The Cu_2.98SbS₃ sample exhibited the highest power factor of 0.85 mWm⁻¹K⁻² at 623 K. Although Cu deficiency resulted in increased thermal conductivity due to a higher carrier concentration, the significant enhancement in the power factor led to a maximum dimensionless figure of merit (ZT) of 0.59 at 623 K for Cu_2.98SbS₃, surpassing the ZT of 0.51 for the stoichiometric Cu₃SbS₃. Full article

A series of ionic liquids consisting of anilinium cations with varying alkyl chains and metallic (Sb and Bi) halides as anions have been synthesized and thoroughly characterized by using multinuclear (¹H and ¹³C) NMR, FT-IR, Raman and XPS techniques. They have been exploited as adsorbents for the dye’s removal, such as malachite green, rhodamine B and Sudan II, from the aqueous solution. Various parameters like the effect of stirring rate, pH, reaction time, adsorbent amount and initial dye concentration have been optimized. Both antimony- and bismuth-based ionic liquids exhibit high adsorption efficiencies and have comparable performance for each dye. Kinetic data have been analyzed by applying kinetic models, and the best-fitted model was found to be pseudo-second order with an R² value greater than 0.98. Adsorption capacity has been determined by analyzing the sorption data using the Langmuir and Freundlich equations, and the Langmuir isotherm model has been found to be the best fitting. The maximum adsorption capacities (q_max) derived from the Langmuir isotherm for malachite green, Sudan II and rhodamine B by M-Sb ILs were 217.36, 162.10 and 62.94 mg·g⁻¹, whereas by M-Bi ILs, the adsorption capacities were slightly higher, at 230.18, 170.00 and 64.21 mg·g⁻¹, respectively. Kinetic studies indicated pseudo-second-order behavior (R² > 0.98), while thermodynamic analysis demonstrated an endothermic adsorption, and a spontaneous reaction was carried out by a physisorption process. These findings accentuate the potential of Sb- and Bi-based ionic liquids as efficient and reusable adsorbents for removing dyes from wastewater. Full article

Copper slag, produced in pyrometallurgical processes, has the potential to generate hydrogen through thermolysis, depending on its composition. This manuscript explores the use of copper slag as a highly abundant and low-cost material for thermochemical water splitting using concentrated solar power. Copper slag can undergo endothermic reactions with water vapor at high temperatures, conditions which are favorable for activating hydrogen evolution reactions which can be a potential resource for metal recovery such as magnetite and hematite in the circular economy. While research on copper slag and its components has primarily focused on the recovery of valuable metals and material reuse, its direct application in hydrogen production remains largely unexplored, partly due to historically low interest in hydrogen as an energy source. The vast deposits of copper slag in the Atacama Desert, combined with the growing demand for renewable energy, present a unique opportunity to develop sustainable and cost-effective hydrogen production technologies. Full article

This study presents a comprehensive kinetic and thermodynamic investigation of dried orange peel (OP) combustion, employing thermogravimetric analysis (TGA) and differential thermogravimetry (DTG) at high heating rates (20–80 K min⁻¹). This gap in high heating rate analysis motivates the novelty of present study, by investigating OP combustion at 20, 40, 60, and 80 K min⁻¹ using TGA, to closely simulate rapid thermal conditions typical of industrial combustion processes. Thermal decomposition occurred in three distinct stages corresponding sequentially to the dehydration, degradation of hemicellulose, cellulose, and lignin. Activation energy (E_a) was calculated using six model-free methods—Friedman (FR), Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS), Starink (STK), Kissinger (K), and Vyazovkin (VY)—yielding values between 64 and 309 kJ mol⁻¹. The E_a increased progressively from the initial to final degradation stages, reflecting the thermal stability differences among biomass constituents. Further kinetic analysis using the Coats–Redfern (CR) model-fitting method identified that first-order (F1), second-order (F2), and diffusion-based mechanisms (D1, D2, D3) effectively describe OP combustion. Calculated thermodynamic parameters—including enthalpy (ΔH), Gibbs free energy (ΔG), and entropy (ΔS)—indicated the endothermic and increasingly non-spontaneous nature of the reactions at higher conversions. These findings demonstrate the potential of OP, an abundant agricultural waste product, as a viable bioenergy resource, contributing valuable insights into sustainable combustion processes. Full article

A high-temperature gas plasma scheme using methane/air/K₂CO₃ mixed combustion is proposed for the application background of hypersonic aircraft. The actual combustion temperature was calculated by ANSYS Chemkin Pro software; the various components of the combustion reaction were determined; and the function between temperature and electrical conductivity was established, revealing the variation law of ionization decomposition of K₂CO₃ ionized seeds with gas temperature. At 1500 K, K₂CO₃ ionized seeds are close to complete ionization. Increasing the mass fraction of K₂CO₃ ionized seeds will enhance the endothermic effect of K₂CO₃ seed ionization decomposition. Under the same residual gas coefficient conditions, the combustion equilibrium temperature will correspondingly decrease. The increase in initial combustion temperature results in an approximately linear increase in equilibrium temperature and conductivity. With the increase in initial pressure, the equilibrium temperature of gas shows a logarithmic growth trend, while conductivity gradually decreases and the gradient of change gradually slows down. This study provides a new method for evaluating the ionization characteristics of high-temperature gas plasma formed by potassium carbonate (K₂CO₃) as ionization seed, and hydrocarbon fuel (CxHy) combined with air. Full article

In this study, we report a green, one-step synthesis of fluorescent carbon quantum dots (PET-FCQDs) derived from polyethylene terephthalate (PET) waste using an environmentally friendly pyrolytic method. The PET-FCQDs were systematically characterized using techniques such as UV-Vis spectroscopy, fluorescence spectroscopy, ATR-FTIR, TGA, and fluorescence microscope, confirming their nanoscale size (2–50 nm), rich functional groups and thermal stability. Thermal stability and dynamics evaluated by the Coats–Redfern method showed endothermic reactions with an activation energy of 88.84–125.05 kJ/mol. Density functional theory studies showed a binding energy, highest occupied molecular orbital, lowest unoccupied molecular orbital, and energy gap of −675.39, −5.23, −5.07, and 0.17 eV, respectively. The as-synthesized PET-FCQDs demonstrated excellent optical properties with quantum yield ($\Phi$) of 49.6% and were applied as a dual-mode fluorescent sensing probe for the detection of Pd²⁺, ciprofloxacin (CIP), and fluoxetine (FLX) in aqueous systems via fluorescence quenching and enhancement mechanisms. For Pd²⁺, the fluorescence emission intensity at 470 nm was quenched proportionally to the increasing concentration, while CIP and FLX induced fluorescence enhancement. The Stern–Volmer analysis confirmed strong interaction between the analytes and PET-FCQDs, distinguishing dynamic quenching for Pd²⁺ and static interactions for CIP and FLX. The method exhibited linear detection ranges of 1–10 mg/L for Pd²⁺, 50–150 µg/L for CIP, and 100–400 ng/L for FLX, with corresponding limits of detection (LOD) of 1.26 mg/L, 3.3 µg/L, and 134 ng/L, respectively. Recovery studies in spiked tap water and river water samples demonstrated the practical applicability of PET-FCQDs, although matrix effects were observed, particularly for FLX. This work not only highlights a sustainable route for PET waste upcycling but also demonstrates the potential of PET-FCQDs as cost-effective, sensitive, and versatile fluorescent probes for environmental monitoring of heavy metal ions and pharmaceutical pollutants. Further optimization of the sensing platform could enhance its selectivity and performance in real-world applications. Full article

The removal of methylene blue (MB) cationic dye from aqueous solutions was investigated by applying magnesium molybdate (β-MgMoO₄) as a nanosorbent. The β-MgMoO₄ was synthesized through a simple, rapid, and efficient method. The MB dye removal process was optimized by evaluating various parameters such as temperature, contact time, nanosorbent dosage, pH, and initial cationic dye concentration. The optimal conditions for MB removal were found to be pH 3, with a 99% removal efficiency achieved in just 10 min of contact time, when using an MB cationic dye concentration of 160 ppm. Magnesium molybdate (β-MgMoO₄) showed a maximum adsorption capacity of 356 mg/g, according to Langmuir model-based calculations. The MB dye removal process occurred spontaneously while being favorable and endothermic. The kinetic investigation showed that the pseudo-second-order model accurately represented the reaction kinetics. The thermal regeneration test results indicated that the removal efficiency remained stable even after three consecutive rounds of reuse. A Fourier Transform Infrared (FTIR) spectroscopic analysis confirmed the adsorption and desorption of MB on β-MgMoO₄ and its regeneration. Overall, these results indicate that a β-MgMoO₄ nanosorbent is a favorable and robust adsorbent for the removal of MB cationic dye from wastewater at its maximum capacity. Full article

Hydrogen prereduction of two manganese ores fines was investigated under varied operating conditions in a fluidized bed. The manganese ores used in this study are the Zambian ore and the South African Nchwaneng ore from the Kalahari region. The samples were milled and sized before they were characterized with regard to sphericity, Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) chemical analyses, X-ray diffraction (XRD) analyses and Scanning Electrons Microscope (SEM) analyses. Prereduction experiments were conducted in a laboratory scale fluidized bed with the parameters of interest being minimum fluidization velocity, terminal velocity, elutriation, average bed voidage, residence time, temperature, intrinsic ore properties and cohesive adhesion. Experiments for the determination of fluidization velocity and terminal velocity were conducted at both ambient temperature and elevated temperature ($500 °$C, $550 °$C, $600 °$C, $700 °$C, $800 °$C and $900 °$C), and for varied sample masses (100 g, 300 g and 700 g) and varied particle-size ranges (200–$300 \mathrm{\mu }$m, 300–$425 \mathrm{\mu }$m, 425–$500 \mathrm{\mu }$m and 500–$600 \mathrm{\mu }$m). The experimentally observed minimum fluidization velocities for particles size groupings of [+106–$200 \mathrm{\mu }$m], [+200–$300 \mathrm{\mu }$m], [+300–$425 \mathrm{\mu }$m], [+425–$500 \mathrm{\mu }$m] and [+500–$600 \mathrm{\mu }$m] as well as the mix (20 wt% of each) was comparable with the theoretical minimum fluidization velocity. The fluidized bed was heated to a desired temperature at a rate of $10 °$C/min under argon whilst logging the pressure drop across the bed with increasing temperature. The convectional cooling during the introduction of cold hydrogen as well as the net energy of endothermic and exothermic chemical reactions were observed to result in a temperature drop in the order of 100 to $250 °$C. Thermal mineral transformation under argon was observed to yield iron manganese oxide in the order of 15 to 30 wt/wt%. Prereduction was conducted using hydrogen gas at a desired temperature and terminal velocity. Reduction extent was observed to increase with the increasing temperature and residence time. Increasing reduction temperature beyond $700 °$C was not observed to improve reduction, whereas longer residence time (of up to 40 min) was observed to favor the formation of iron manganese oxide, iron manganese and manganosite. For hydrogen prereduction experiment conducted at $900 °$C, the reactor was observed to be brittle after the experiment. Cohesive adhesion was observed to be more pronounced at $900 °$C. Full article