Stage Of Reaction Research Articles

The stage- and kinetics-dependent regulation of highly ordered sequential reactions by liquid–liquid phase separation

Understanding the reaction kinetics, thermodynamics, and molecular mechanisms of liquid–liquid phase separation (LLPS) holds immense significance in unraveling the cell’s spatiotemporal coordination of metabolic pathways and has the potential to revolutionize diverse fields, including diagnostics and catalysis. However, the current scope of LLPS-based investigations is primarily limited to simplistic models with one or two-step reactions, failing to capture the complexity necessary for comprehending LLPS’s impact on intricate reactions and hindering its widespread practical applications. In this study, we address this limitation by constructing and screening a tailored LLPS system and utilizing complex nucleic acid amplification as a representative example. Our findings reveal a significant departure from the continuous acceleration observed in simple reactions, as the acceleration of complex reactions is highly dependent on the kinetics and reactant concentration of each specific reaction stage. Furthermore, by incorporating LLPS and its stage-specific factors, we demonstrate the development of an LLPS-based molecular diagnostic tool with a shortened detection time, higher efficiency and sensitivity compared to traditional methods. Therefore, this newfound understanding sheds light on the intricate characteristics of LLPS-mediated complex reactions and offers a breakthrough in diagnostic advancements by enabling faster and more accurate detection of target molecules, leveraging LLPS in diagnostic advancements, and driving the unlocking of further potential for LLPS utilization in various fields.

Beyond Catalysts: Exploring Discharge Product Growth and Intrinsic Overpotential in Lithium-Oxygen Batteries.

The lithium-oxygen (Li-O2) battery, renowned for its exceptionally high theoretical energy density, is poised to revolutionize next-generation energy storage systems. However, its practical application depends on overcoming several challenges, particularly the high cathode overpotential, which significantly diminishes the battery's energy efficiency and durability. This study delves into the interactions at the cathode surface during oxygen reduction and evolution reactions (ORR/OER), extending the analysis beyond the initial reaction stages to encompass the extensive charge-discharge process. We introduce and define the concepts of intrinsic equilibrium potential and intrinsic overpotential, demonstrating that these critical parameters are predominantly influenced by the growth of discharge products, rather than the catalysts, thereby underscoring the inherent properties of the battery. This shift in focus from merely enhancing cathode catalysts to understanding and leveraging the intrinsic characteristics of the battery discharge process opens new avenues for optimizing and enhancing the performance of large-scale Li-O2 batteries. Furthermore, our findings indicate potential broader applications to other metal-oxygen systems, paving the way for the design of high-capacity, high-efficiency energy storage technologies.

Effect of additional Al sources on early-age strength of fly ash-based geopolymer containing calcium carbide residue and Glauber’s salt as activators

Alkali-activated materials are more environmentally friendly than cementitious composites and are used in the construction and building sector. However, their intrinsic low early strength under ambient temperatures hinders their practical applicability. More research is needed on the possibilities of increasing early strength at ambient temperatures. In this study, aluminum sulfate (AS) was used as an additional aluminum source to improve the early-age properties of fly ash (FA)-based geopolymers incorporating calcium carbide residue (CCR) and Glauber’s salt (GS) as activators. XRD, TG, SEM, ICP and isothermal calorimetry analyses were carried out to characterize the phase composition, microstructure and hydration process of the prepared materials. The results showed that the 1d strength of AS1-CCR10 was increased by 260.7 % compared with the control material, and the effect on the late strength was negligible. The relative content of AFt increased by 2.97 %, creating a more compact microstructure. During the extraction process, insufficient dissolved Al3+ in the composite led to a decrease in initial strength. In the hydration process, the induction period of AS1-CCR10 was advanced by 40.92 % and that of t50 was advanced by 57.74 %, which accelerated the early reaction rate. However, the Krstulovic-Dabic model could not accurately describe the initial stage of the hydration reaction of composite materials. This study is helpful to broaden the utilization of geopolymer composites and provide a theoretical basis for the preparation and reaction mechanism of alkali-activated materials.

Study on using waste biomass as carbon reducing agent in industrial silicon smelting

In this study, seven types of biomass (coffee husk, macadamia husk, peanut husk, rice husk, rice straw, tobacco straw, and cotton straw) were carbonized at temperatures ranging from 300 °C to 1000 °C. This study explored the potential of these biomass samples as carbon reducing agents for industrial silicon and compared them with charcoal in terms of their proximate analysis, electrical resistivity, and apparent activation energy of the reaction. The results indicated that as the pyrolysis temperature increased, the oxygen content and aliphatic functional groups in biochar gradually decreased, as did the volatiles content, while the proportions of fixed carbon and ash increased. The resistivity decreased upon the removal of volatiles and an increase in the degree of graphitization. At 600 °C, the fixed carbon content of all biochar exceeded 65%, and the fixed carbon content of macadamia husk biochar reached 91.32%, which was higher than that of charcoal (81.44%), the maximum specific surface area was 335.706 m2/g, which was much higher than that of charcoal (5.705 m2/g). Thermogravimetric analysis and kinetic analysis indicated that coffee husk had better reactivity than charcoal. The gasification reactivity of coffee husk was R = 3.1949%/min °C, which was higher than that of charcoal (0.7930 %/min °C). The apparent activation energy during the coking reaction stage was 51.86 kJ/mol, which was lower than that of charcoal (98.9 kJ/mol). Overall, biochar had a suitable fixed carbon and electrical resistivity at 600 °C and can be used as a carbon reducing agent for industrial silicon, among them, macadamia husk with high fixed carbon and coffee husk with high reactivity have greater application potential.

Investigation on effect of different types of inoculants on the solidification of ductile cast iron using thermal analysis

PurposeProducing superior-quality ductile cast iron demands the use of various intricate inoculants. In addition to iron and silicon, these materials also include alloying elements like calcium, barium, cerium, bismuth and zirconium. These elements are effective in minimizing carbide solidification and enhancing the formation of eutectic cells, thereby resulting in improved cast iron quality.Design/methodology/approachThis article discusses the findings of an investigation on how various inoculants impact critical thermal analysis parameters such as undercooling, recalescence and their correlation with the nucleation of graphite nodules and shrinkage tendency.FindingsFor the study, five distinct inoculants with varying active components in their chemical composition were utilized. The particular formulation of the inoculant has a notable impact on the extent of undercooling during the solidifying process of ductile cast iron. Investigation indicates that incorporating inoculant reduces the temperature at which austenite dendrites form and raises the eutectic freezing temperature. Upon analyzing the microstructure, it is found that the inclusion of inoculation led to a rise in the nodule count from 103 to 272 nodules.Originality/valueAn increased graphite factor, which denotes the growth of graphite nodules during the subsequent stage of the eutectic reaction, supports the benefits of inoculation. Ce and Bi-inoculation have increased the growth of graphite nodules in the cast area during solidification compared to other inoculant formulations. This enhanced production helps in decreasing the size of macroporosity.

Prospective life cycle assessment: Identifying the most promising methods for sustainable cellulose nanocrystal production

Concerted endeavors are presently in progress to discern eco-friendlier methods for cellulose nanocrystals (CNC) production, negating the conventional reliance on hazardous concentrated sulfuric acids. Despite the proliferation of methods purported to be environmentally sound, their assertions often lack rigorous scrutiny, relying on theoretical postulations. This study presents the first prospective glimpse into their environmental performance utilizing a life cycle assessment (LCA) methodology from cradle-to-gate. The results transpired that many of the vaunted environmentally-friendly methods resulted in higher environmental loads compared to the traditional method, due to lower conversion rates and higher reaction energy demand. Notably, only specific methods demonstrate lower endpoint impact scores, including deep eutectic solvent extraction (−48 %), ammonium persulfate-assisted oxidation (−62 %), sulfuric acid hydrolysis in glycerol medium (−56 %), and enzymatic hydrolysis (−40 %). Their primary green attributes associate with the utilization of solvents carrying lower climate impact and toxicity level. The reaction stage carries the heaviest burden due to the increased energy required to counteract modest reactivities of the milder solvents. As mitigation strategies, heat integration and by-product recovery for energy generation were explored, resulting in emission reductions of 11–26 % and 41–68 %, respectively, across the proven eco-friendlier methods. This study comprehensively validated a roster of genuinely green candidates, offering a more sustainable prospect than traditional methods and paving the way for large-scale green CNC production.

Characterization of Continuous Neutralization of a Chemical Warfare Agent and Its Simulants.

The persistent threat posed by chemical warfare agents (CWAs) necessitates the development of efficient and safe methods for their neutralization. In this study, we investigated the continuous neutralization of CWAs and their simulants using flow chemistry, which combines the benefits of safety, precise control over reaction parameters, and scalability. We focused on the integration of continuous-flow reactors to achieve controlled and rapid neutralization, thus addressing challenges such as the need for rapid reaction kinetics and the establishment of robust pathways for neutralization. Because the flow-chemistry approach can contribute significantly to the development of neutralization technologies for CWAs, we performed a thorough characterization in terms of reaction kinetics and neutralized product identification. The results demonstrated that the proposed continuous-flow-type neutralization reaction was faster and more efficient than batch-type neutralization reactions. Furthermore, in the early stages of the neutralization reaction, flow-type neutralization not only required less neutralizing agent than batch-type neutralization but was also faster. Thus, the chemical neutralization process proposed in this study can be used as a pragmatic foundation for developing demilitarization methods for CWAs.

Evaluation of hydrogen storage performance of Ti0.25Zr0.25V0.15Nb0.15Ta0.2 high-entropy alloy using calorimetric technique

The features of phase transformations during interaction of BCC-type Ti0.25Zr0.25V0.15Nb0.15Ta0.2 high-entropy alloy (HEA) with hydrogen and the accompanying thermal effects have been examined using the Tian-Calvet calorimetric technique. The alloy was produced by the pendent drop melt extraction method in the form of microfibers and then coated with a thin layer of palladium to eliminate the preliminary high-temperature activation and enable first hydrogenation at room temperature. Two reaction stages were distinguished on the measured heat emission curves. Using XRD data, these stages were attributed to the formation of a BCC-type hydrogen solid solution and a phase transition to FCC-type dihydride phase. Recorded values of the reaction enthalpy decrease in absolute terms from 145 kJ/mol H2 (dilute solid solution) to 73–77 kJ/mol H2 (BCC→FCC) and to 20 kJ/mol H2 (H solution in FCC dihydride). The overall heat emission of the entire process as a whole is 110 kJ/ mol H2. The course of the dehydrogenation process depends strongly on the applied temperature and at 493 K results in the formation of a BCT-type monohydride, which was not detected during hydrogenation. The detailed calorimetric data obtained here significantly change the previously existing ideas about thermal effects during this type HEAs hydrogenation, based on calculations using the Van't-Hoff equation. The reported findings are of special importance for various hydrogen related applications of HEAs

Exploration of the rapid growth of high-molecular-weight oligomers in the later stage of diisocyanate self-polymerization

Diisocyanate trimers are important products in the polyurethane industry. Large amounts of high-molecular-weight oligomers, which change the physical and chemical properties of the final products, are generated in the later stages of the synthesis process. It is important to understand the self-polymerization of high-molecular-weight oligomers. The relationship between this phenomenon and the PDI monomer concentration was first experimentally demonstrated. Then the self-polymerization of pentamethylene diisocyanate (PDI) was investigated via Dmol3 calculations using the linear synchronous transition (LST) and quadratic synchronous transition (QST) methods. Calculations revealed a new synthesis pathway with a reaction energy barrier of 31.548 kcal/mol, leading to the conversion of pentamers into decamers. In the initial stage of the polymerization reaction, the PDI monomer concentration was high, and the reaction followed a step-growth polymerization. However, as the PDI monomer concentration decreased and the PDI pentamer concentration increased in the later stage of the reaction, a new synthesis pathway emerged, leading to the direct synthesis of high-molecular-weight oligomers from the available oligomers. This study further demonstrates the self-polymerization of diisocyanate and provides a comprehensive understanding of its synthesis process. By inhibiting this new pathway can reduce the content of high-molecular-weight oligomers, increase yields, and reduce the product viscosity, all of which are beneficial for chemical process optimization.

Comparison of mineral transformation in CO2 geological storage under CO2–water–sandstone and mudstone reactions

Carbon dioxide (CO2) mineral trapping was considered the most secure and stable mechanism for CO2 geological storage. The previous studies lacked clarity regarding the mechanisms and processes of transformation for various types of minerals involved in CO2–water–sandstone and mudstone reactions during CO2 geological storage. Additionally, it didn't clear the different stages of mineral reactions in reservoir and caprock. We utilized experimental and numerical simulation methods to analyze the mechanisms, processes, and stages of CO2–water–rock reactions involving various types of minerals in the mudstone from Chang 4 + 5 members and the sandstone from Chang 6 member of the Triassic Yanchang Formation in the Ordos Basin. The experimental simulation demonstrated the dissolution of feldspar minerals in sandstone led to precipitate of carbonate, clay, and other minerals. Contrary, mudstone primarily underwent the dissolution of clay minerals and the precipitation of feldspar minerals, whereas carbonate content remained relatively stable. The numerical simulation consisted of experimental results in the short term, but over a longer timescale, The reaction processes of carbonate and clay minerals in the reservoir and caprock dissolved first and then precipitated. Conversely, other minerals behaved oppositely; feldspar minerals continuously dissolved in the reservoir but precipitated first and then dissolved in the caprock. The reaction stages of mineral change in both the reservoir and caprock could be divided into dissolution, rapid precipitation, and stable precipitation. The reservoir's dissolution stage was shorter than the caprock, which entered the stable precipitation stage earlier. With increasing storage time, continuous CO2–water–rock reactions gradually transformed physically sequestered CO2 in the formation into chemically sequestered mineralized CO2.

Dynamics of Cu isotope fractionation during the reactions of pyrite with Cu(I)-bearing hydrothermal fluids

Experimental investigation of the fractionation behavior of Cu isotopes during the replacement of pyrite by Cu-bearing sulfides (chalcopyrite, bornite, and chalcocite) was conducted under hydrothermal conditions. At the initial stages of the replacement reaction, small mounds of product formed on the pyrite surface; these mounds then grew and coalesced, progressively covering the pyrite grains as the reaction proceeded. Chalcopyrite, bornite, and chalcocite formed sequential monomineralic zones from the pyrite reaction front towards the solution. During the early stage of the reaction, Cu isotope fractionation between the solids and the aqueous solution (Δ65Cusolid-aqueous, Δ65Cusolid-aqueous = δ65Cusolid – δ65Cuaqueous) was approximately –0.6 ‰, similar to the calculated equilibrium Cu isotope fractionation factors between Cu-bearing sulfides (chalcopyrite, bornite, and chalcocite) and CuCl2–. However, the Δ65Cusolid-aqueous moved progressively further from equilibrium with prolonged reaction time, with fractionation factors ranging from approximately –0.6 ‰ to –1.2 ‰. We found that significant fractionation of Cu isotopes between the solid products and aqueous solution was mainly controlled by the amount of chalcopyrite that formed in the product layers. We interpret that the Δ65Cusolid-aqueous was controlled by the diffusion of aqueous Cu(I) species among the product layers and the changes in Cu redox state during the precipitation of chalcopyrite. These results imply that the δ65Cu values measured in sulfides from low-temperature hydrothermal deposits may be controlled by the local chemistry of the fluids in product layers that precipitate sulfides. This study highlights the importance of local fluid characteristics, such as redox conditions, metal speciation, and diffusion, in controlling isotope fractionation pathways during non-equilibrium mineral replacement.

Efficient conversion process and mechanism of bromine in bromine-rich saline wastewater

Bromine resources, widely utilized in basic chemical engineering, are considered non-renewable. A substantial amount of Bromine-Rich Saline Wastewater (BRSW), a hazardous waste, is generated during the smelting process of waste printed circuit boards (WPCBs). The efficient conversion of bromine resources is important in BRSW, which contain high concentrations of bromide ions. This study developed a synergistic treatment method utilizing electrolytic manganese anode sludge (EMAS) achieved efficient conversion of Br− to Br2 in BRSW. Optimal technical parameters are determined through single-factor experiments, and the oxidative acid leaching process was optimized using response surface methodology (RSM). The significant influencing factors for Br− conversion were ranked as acidity > anode mud addition amount > temperature > time, resulting in a bromine conversion efficiency of 96.55%. Kinetic studies of bromine conversion in BRSW during the oxidation-acid leaching process indicated a two-stage process: Stage I being a chemical reaction control model and Stage II being a diffusion control model. The reaction mechanism was elucidated, where H+ initially breaks the Mn-O bond in MnO2, exposing O vacancies and forming Mn4+, leading to a redox reaction between free Br− and Mn4+. This research embodies the concept of synergistic solid waste disposal, achieving cost-effectiveness and streamlined preparation of bromine, and providing technical and theoretical support for bromine resource recovery in BRSW.

Time-varying contributions of FeII and FeIII to AsV immobilization under anoxic/oxic conditions: The impacts of biochar and dissolved organic carbon

Engineering black carbon (e.g. biochar) has been widely found in natural environments due to natural processes and extensive applications in engineering systems, and could influence the geochemical processes of coexisting arsenic (AsV) and FeII, especially when they are exposed to oxic conditions. Here, we studied time-varying kinetics and efficiencies of AsV immobilization by solid-phase FeII (FeIIsolid) and FeIII (FeIIIsolid) in FeII-AsV-biochar systems under both anoxic and oxic conditions at pH 7.0, with focuses on the effects of biochar surface and biochar-derived dissolved organic carbon (DOC). Under anoxic conditions, FeII could rapidly immobilize AsV via co-adsorption onto biochar surfaces, which also serves as the dominant pathway of AsV immobilization at the initial stage of reaction (0–5 min) under oxic conditions at high biochar concentrations. Subsequently, with increasing biochar concentrations, FeIIIsolid precipitation from aqueous FeII (FeIIaq) oxidation (5–60 min) starts to play an important role in AsV immobilization but in decreased efficiencies of AsV immobilization per unit iron. In the following stage (60–300 min), FeIIsolid oxidation is suppressed and leads to AsV release into solutions at >1.0 g·L−1 biochar. The decreasing efficiency of AsV immobilization over time is attributed to the gradual release of DOC into solution from biochar particles, which significantly inhibit AsV immobilization when FeIIIsolid is generated from FeIIsolid oxidation in the vicinity of biochar surfaces. Specifically, 4.06 mg·L of biochar-derived DOC can completely inhibit the immobilization of AsV in the 100 μM FeII system under oxic conditions. The findings are crucial to comprehensively understand and predict the behavior of FeII and AsV with coexisting engineering black carbon in natural environments.

Large-area and few-layered 1T′-MoTe2 thin films grown by cold-wall chemical vapor deposition

This study employs cold-wall chemical vapor deposition to achieve the growth of MoTe2 thin films on 4-inch sapphire substrates. A two-step growth process is utilized, incorporating MoO3 and Te powder sources under low-pressure conditions to synthesize MoTe2. The resultant MoTe2 thin films exhibit a dominant 1T′ phase, as evidenced by a prominent Raman peak at 161 cm−1. This preferential 1T′ phase formation is attributed to controlled manipulation of the second-step growth temperature, essentially the reaction stage between Te vapor and the pre-deposited MoO x layer. Under these optimized growth conditions, the thickness of the continuous 1T′-MoTe2 films can be precisely tailored within the range of 3.5–5.7 nm (equivalent to 5–8 layers), as determined by atomic force microscopy depth profiling. Hall-effect measurements unveil a typical hole concentration and mobility of 0.2 cm2 Vs−1 and 7.9 × 1021 cm−3, respectively, for the synthesized few-layered 1T′-MoTe2 films. Furthermore, Ti/Al bilayer metal contacts deposited on the few-layered 1T′-MoTe2 films exhibit low specific contact resistances of approximately 1.0 × 10−4 Ω cm2 estimated by the transfer length model. This finding suggests a viable approach for achieving low ohmic contact resistance using the 1T′-MoTe2 intermediate layer between metallic electrodes and two-dimensional semiconductors.

The Comparison of Catalytic Activity of Carbimazole and Methimazole on Electroreduction of Zinc (II) in Chlorates (VII): Experimental and Molecular Modelling Study.

With the help of electrochemical methods, including CV and EIS, the influence of methimazole, carbimazole, and the concentration of the supporting electrolyte on the kinetics and mechanism of zinc electroreduction on a mercury electrode was compared and analyzed. Moreover, molecular dynamics simulations of zinc/carbimazole and zinc/methimazole solutions were carried out to determine the effect of drugs on the hydration sphere of Zn2+ ions. It was shown that the electroreduction of Zn2+ in the presence of methimazole and carbimazole occurs in two steps and the first one determines the kinetics of the entire process. The presence of both drugs in the solution and the increase in the concentration of the supporting electrolyte reduce the degree of hydration of the depolarizer ions and the hydration of the electrode surface, what is a factor favoring the rate of electroreduction. Based on theoretical studies, the formation of stable complexes between Zn2+ and the molecules of both drugs in a solution was considered unlikely. However, active complexes can be formed between depolarizer ions and molecules adsorbed at the electrode surface. They constitute a bridge facilitating charge exchange during the electrode reaction, revealing the catalytic abilities of methimazole and carbimazole. In the range of cdrug ≤ 1 × 10-3 mol dm-3, carbimazole is a better catalyst, whereas in the range of cdrug ≥ 5 × 10-3 mol dm-3, it is methimazole. The effectiveness of both compounds in catalyzing the first stage of the electrode reaction increases with the increase in the NaClO4 concentration.

Smelting Reduction of HIsarna Slag with Methane

To study the smelting reduction behavior of methane in the HIsarna process, the isothermal reduction experiments of HIsarna slag with 6 wt% of FeO were conducted at the temperatures of 1450, 1475, and 1550 °C, using 5 vol% CH4‐Ar. The effect of the gas injection flow rate on the overall reduction rate was investigated in the range of 0.5–1.5 L min−1. The results confirm that the decomposed carbon black acts as the dominant reductant in the reduction process compared to hydrogen. Increased gas flow rate increases the reaction rate, while temperature shows no significant effect. The reduction process could be described by the JMAEK model: by fixing the gas flow rate at 1.0 L min−1 with different temperatures, the exponent n value is around 1.5, indicating FeO mass transfer is the limiting step since there are sufficient carbon blacks as nucleation sites. The reduction process follows the first‐order model controlled by the reactant concentration with the gas flow rate being at 0.5 L min−1 and in the second reaction stage of the gas flow rate at 1.5 L min−1. The determined activation energy for the methane reduction is 59.8 kJ mol−1.

Study on the thermodynamic mechanism of external magnetic field on gas explosion characteristics

To investigate the thermodynamic mechanism of the magnetic field on the explosion characteristics of gases, experiments were carried out to study the influence of the applied magnetic field of 300 mT on the explosion characteristics of 5.7 % C2H6, 6.5 % C2H4 and 7.7 % C2H2 by volume. CHEMKIN-PRO software was used to simulate the three kinds of gas explosion chain reaction process. The chemical bond strength, stability and bond energy of the three gases were calculated and analyzed by Materials Studio software to derive the strength of chemical bond stability of the three gas molecules in the explosion process. The results show that the magnetic field weakened the breaking rate of CC, CC, and CC, the maximum explosion pressures of C2H6, C2H4, and C2H2 were reduced by 12.14 %, 16.47 %, and 18.71 %. The three gases carbon–carbon bond strength was weaker than the strength of the carbon-hydrogen bond, carbon-hydrogen bond was not easy to break, which in turn reduced the rate of generation of ·H in the chain initiation stage of the cleavage reaction, thus presenting a significant inhibitory effect of the magnetic field on C2H6, C2H4, and C2H2 explosions. The COOP of CC is 0.377 Ha, and the bond energy is 839 KJ/mol, which was greater than CC and CC, so the number of free radicals generated in the C2H2 cleavage reaction was lower, leading to a slower chain reaction rate which led to a stronger inhibitory effect of the magnetic field on C2H2 explosions than that on C2H6 and C2H4.

Multiscale investigation on the formation path of the apatite phase in bioactive glasses

Mesoporous bioactive glasses (MBGs) have been reported as promising biomaterials to stimulate and promote the growth of bones. When exposed to Simulated Body Fluid (SBF), MBGs develop an apatite phase called carbonate hydroxyapatite (H(C)A) on their surfaces that closely mimics the mineral phase of bones. In order to gain deeper insights into the key stages of the surface reactions of two different types of MBGs (58S and 70S30C) soaked in SBF, we have used high energy total X-ray scattering coupled to Pair Distribution Function (PDF) analysis, along with Raman spectroscopy and scanning electron microscopy. This type of coupled analytical approach can ultimately help to unravel the details of the reaction kinetics in the complex calcium phosphate environment around the BGs surfaces. The data obtained in our in-vitro study point to the formation of other intermediate phases like amorphous calcium phosphate (ACP) and calcite (CC), that transform after a specific time into H(C)A depending on the composition of the MBGs, their surface properties and their interaction times with SBF.

Investigation of mechanical, microscopic, and leaching properties of coal-based solid waste geopolymer mortar activated by soda residue and phosphogypsum

In this study, coal-based solid waste geopolymer mortar (SWCB) was prepared by using granulated ground blast-furnace slag (GGBS) and coal gasification coarse slag (CGCS) as precursors, and soda residue (SR) and phosphogypsum (PG) as activators, with gangue sand (GS) utilized as an inert filler. The corresponding compressive strength, fluidity, ion leaching, and microstructure of the developed SWCB were systematically investigated under varying solid contents, binder-to-sand ratios, and activator ratios. The findings suggest that the incorporation of activators promoted the dissolution of the silicon-aluminum phase in GGBS and CGCS into Al(OH)4−, [SiO(OH)3]−, and [SiO2(OH)2]2−, which could subsequently react with the Ca2+ and SO42− released by PG, forming AFt and C-(A)-S-H, thereby playing a crucial role in enhancing matrix strength. AFt was the predominant hydration product in the early reaction stage. The morphology of the AFt phase evolved from needle-like or filamentous to fine and coarse rods as hydration progressed. Initially, the formation of C-(A)-S-H gel increased with rising activator content before decreasing. The optimal synergy between AFt and C-(A)-S-H was observed at an activator content of 30 %. However, the growth of gypsum crystals was hindered when the activator content surpassed 30 %, resulting in a plate-like or columnar morphology. C-(A)-S-H gel exhibited remarkable adsorption capability towards P atoms attributed to intermolecular Van der Waal's forces, enabling simultaneous physical encapsulation of P atoms, while Cl element immobilization was primarily attributed to the contribution of SiOH sites to Cl adsorption.

Insights of sulfur in sulfidated zerovalent iron for activating of dissolved oxygen and CaO2-generated H2O2: Improving iron electron selectivity and utilization

Sulfidated zerovalent iron (S-ZVI) has been extensively used for the degradation of pollutants under anaerobic conditions. However, the investigation of the ability and mechanism of S-ZVI to regulate the catalytic oxidation of pollutants under aerobic conditions has been overlooked. In this study, we revealed the mechanism of enhanced ibuprofen (IBP) degradation by decomposition and activation by S-ZVI under aerobic conditions using CaO2 as a slow-release oxygenate. Specifically, the S-ZVI/CaO2 showed a 2.98-fold increase in rate compared to ZVI/CaO2 within the previous 15 min of reaction. Two reaction stages of enhanced IBP degradation by the S-ZVI/CaO2 system were observed. In the initial stage, the shell layer on the surface of S-ZVI activates dissolved oxygen in water to form H2O2 through a continuous one-electron process. This process effectively prevents the oxidation of ZVI while enhancing the electron selectivity of ZVI and facilitates the decomposition of CaO2, resulting in the production of more H2O2. Subsequently, sulfur on the surface of S-ZVI acts as an electron shuttle in the second stage, facilitating the activation of H2O2 and improving the electron utilization of ZVI. This finding clarifies the mechanism of pollutant degradation by S-ZVI under aerobic conditions and provides a strategy for enhancing pollutant degradation.