All‑Covalent Organic Framework Nanofilms Assembled Lithium‑Ion Capacitor to Solve the Imbalanced Charge Storage Kinetics

Free-standing covalent organic framework(COFs)nanofilms exhibit a remarkable ability to rapidly intercalate/de-intercalate Li^(+) in lithium-ion batteries,while simultaneously exposing affluent active sites in supercapacitors.The development of these nanofilms offers a promising solution to address the persistent challenge of imbalanced charge storage kinetics between battery-type anode and capacitor-type cathode in lithium-ion capacitors(LICs).Herein,for the first time,custom-made COFBTMB-TP and COFTAPB-BPY nanofilms are synthesized as the anode and cathode,respectively,for an all-COF nanofilm-structured LIC.The COFBTMB-TP nanofilm with strong electronegative–CF3 groups enables tuning the partial electron cloud density for Li^(+) migration to ensure the rapid anode kinetic process.The thickness-regulated cathodic COFTAPB-BPY nanofilm can fit the anodic COF nanofilm in the capacity.Due to the aligned 1D channel,2D aromatic skeleton and accessible active sites of COF nanofilms,the whole COFTAPB-BPY//COFBTMB-TP LIC demonstrates a high energy density of 318 mWh cm^(−3) at a high-power density of 6 W cm^(−3),excellent rate capability,good cycle stability with the capacity retention rate of 77%after 5000-cycle.The COFTAPB-BPY//COFBTMB-TP LIC represents a new benchmark for currently reported film-type LICs and even film-type supercapacitors.After being comprehensively explored via ex situ XPS,7Li solid-state NMR analyses,and DFT calculation,it is found that the COFBTMB-TP nanofilm facilitates the reversible conversion of semi-ionic to ionic C–F bonds during lithium storage.COFBTMB-TP exhibits a strong interaction with Li^(+) due to the C–F,C=O,and C–N bonds,facilitating Li^(+) desolation and absorption from the electrolyte.This work addresses the challenge of imbalanced charge storage kinetics and capacity between the anode and cathode and also pave the way for future miniaturized and wearable LIC devices.

“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

Recent progress in thermodynamic and kinetics modification of magnesium hydride hydrogen storage materials

Hydrogen energy has emerged as a pivotal solution to address the global energy crisis and pave the way for a cleaner,low-carbon,secure,and efficient modern energy system.A key imperative in the utilization of hydrogen energy lies in the development of high-performance hydrogen storage materials.Magnesium-based hydrogen storage materials exhibit remarkable advantages,including high hydrogen storage density,cost-effectiveness,and abundant magnesium resources,making them highly promising for the hydrogen energy sector.Nonetheless,practical applications of magnesium hydride for hydrogen storage face significant challenges,primarily due to their slow kinetics and stable thermodynamic properties.Herein,we briefly summarize the thermodynamic and kinetic properties of MgH2,encompassing strategies such as alloying,nanoscaling,catalyst doping,and composite system construction to enhance its hydrogen storage performance.Notably,nanoscaling and catalyst doping have emerged as more effective modification strategies.The discussion focuses on the thermodynamic changes induced by nanoscaling and the kinetic enhancements resulting from catalyst doping.Particular emphasis lies in the synergistic improvement strategy of incorporating nanocatalysts with confinement materials,and we revisit typical works on the multi-strategy optimization of MgH2.In conclusion,we conduct an analysis of outstanding challenges and issues,followed by presenting future research and development prospects for MgH2 as hydrogen storage materials.

Growth kinetics of titanium carbide coating by molten salt synthesis process on graphite sheet surface

The synthesis of carbide coatings on graphite substrates using molten salt synthesis(MSS),has garnered significant interest due to its cost-effective nature.This study investigates the reaction process and growth kinetics involved in MSS,shedding light on key aspects of the process.The involvement of Ti powder through liquid-phase mass transfer is revealed,where the diffusion distance and quantity of Ti powder play a crucial role in determining the reaction rate by influencing the C content gradient on both sides of the carbide.Furthermore,the growth kinetics of the carbide coating are predominantly governed by the diffusion behavior of C within the carbide layer,rather than the chemical reaction rate.To analyze the kinetics,the thickness of the carbide layer is measured with respect to heat treatment time and temperature,unveiling a parabolic relationship within the temperature range of 700-1300℃.The estimated activation energy for the reaction is determined to be 179283 J·mol^(-1).These findings offer valuable insights into the synthesis of carbide coatings via MSS,facilitating their optimization and enhancing our understanding of their growth mechanisms and properties for various applications.

Continuous synthesis of N,N-dicyanoethylaniline in microreactors:Reaction kinetics and process intensification

Cyanoethylation of phenylamine is one of the important steps for the production of dicyanoethyl-based disperse dyes.However,the exothermic nature of this reaction and the inherent instability of intermittent dynamic operation pose challenges in achieving both high safety and reaction efficiency.In this study,a continuous cyanoethylation of phenylamine for synthesizing N,N-dicyanoethylaniline in a microreactor system has been developed.By optimizing the reaction conditions,the reaction time was significantly reduced from over 2 h in batch operation to approximately 14 min in the microreactor,while high conversion and selectivity were maintained.Based on the reaction network constructed,the reaction kinetics was established,and the kinetic parameters were then determined.These findings provide valuable insights into a controllable cyanoethylation reaction,which would be helpful for the design of efficient processes and optimization of reactors.

Kinetics insights into size effects of carbon nanotubes'growth and their supported platinum catalysts for 4,6-dinitroresorcinol hydrogenation

Size effects are a well-documented phenomenon in heterogeneous catalysis,typically attributed to alterations in geometric and electronic properties.In this study,we investigate the influence of catalyst size in the preparation of carbon nanotube(CNT)and the hydrogenation of 4,6-dinitroresorcinol(DNR)using Fe_(2)O_(3)and Pt catalysts,respectively.Various Fe_(2)O_(3)/Al_(2)O_(3)catalysts were synthesized for CNT growth through catalytic chemical vapor deposition.Our findings reveal a significant influence of Fe_(2)O_(3)nanoparticle size on the structure and yield of CNT.Specifically,CNT produced with Fe_(2)O_(3)/Al_(2)O_(3)containing 28%(mass)Fe loading exhibits abundant surface defects,an increased area for metal-particle immobilization,and a high carbon yield.This makes it a promising candidate for DNR hydrogenation.Utilizing this catalyst support,we further investigate the size effects of Pt nanoparticles on DNR hydrogenation.Larger Pt catalysts demonstrate a preference for 4,6-diaminoresorcinol generation at(100)sites,whereas smaller Pt catalysts are more susceptible to electronic properties.The kinetics insights obtained from this study have the potential to pave the way for the development of more efficient catalysts for both CNT synthesis and DNR hydrogenation.

Tuning the crystallinity of titanium nitride on copper-embedded carbon nanofiber interlayers for accelerated electrochemical kinetics in lithium-sulfur batteries

The development of lithium-sulfur(Li-S)batteries is hindered by the disadvantages of shuttling of polysulfides and the sluggish redox kinetics of the conversion of sulfur species during discharge and charge.Herein,the crystallinities of a titanium nitride(TiN)film on copper-embedded carbon nanofibers(Cu-CNFs)are regulated and the nanofibers are used as interlayers to resolve the aforementioned crucial issues.A low-crystalline TiN-coated Cu-CNF(L-TiN-Cu-CNF)interlayer is compared with its highly crystalline counterpart(H-TiN-Cu-CNFs).It is demonstrated that the L-TiN coating not only strengthens the chemical adsorption toward polysulfides but also greatly accelerates the electrochemical conversion of polysulfides.Due to robust carbon frameworks and enhanced kinetics,impressive highrate performance at 2 C(913 mAh g^(-1)based on sulfur)as well as remarkable cyclic stability up to 300 cycles(626 mAh g^(-1))with capacity retention of 46.5%is realized for L-TiN-Cu-CNF interlayer-configured Li-S batteries.Even under high loading(3.8 mg cm^(-2))of sulfur and relatively lean electrolyte(10μL electrolyte per milligram sulfur)conditions,the Li-S battery equipped with L-TiN-Cu-CNF interlayers delivers a high capacity of 1144 mAh g^(-1)with cathodic capacity of 4.25 mAh cm^(-2)at 0.1 C,providing a potential pathway toward the design of multifunctional interlayers for highly efficient Li-S batteries.

Effects of drying methods on the drying kinetics and quality of maize

At present, maize is mostly dried by hot air, and the quality of maize after drying in this way is poor. So it is particularly important to explore the influence of new drying methods on the drying characteristics and quality of maize. Five drying methods, including hot air drying (HAD), vacuum drying (VD), infrared drying (IRD), variable temperature drying (VTD), and vacuum IR drying (VID), were used to analyze the drying rate (DR), moisture ratio (MR), effective moisture diffusion coefficient (Deff), hardness, nutrient composition, color, and microstructure of maize to investigate the effects of different drying methods on the drying kinetics and quality of maize kernels. The results showed that among the five drying methods, the Modified Page drying model could most reflect moisture changes. VTD was better than the other methods in terms of DR, cracking rate, hardness, and crude fat. The highest lysine content in maize was obtained using HAD. The protein content was higher in IRD (p<0.05). The dough characteristics were better in VID and VTD than in IRD. The IRD, VTD, and VID-treated maize had a better color appearance. Microstructure analysis showed that the starch granules of VID, IRD, and VD-treated maize were oval, but large gaps could be found between the granules. The granules were also densely stacked, with most of them relatively intact. Correlation and clustering analysis showed different degrees of correlation between the physicochemical indicators. The overall quality in VTD was the best, followed by VID, whereas HAD and VD showed poorer quality. In terms of economic value and product quality, VTD was the most suitable drying method for maize. This study can provide a theoretical basis for the application of maize drying in the processing industry.

Kinetics and mechanism of the low-energy β-a phase transition of the second kind in 2,4-dinitroanisole

In this work, comprehensive studies of 2,4-dinitroanisole(2,4DNAN) were carried out using powder thermorentgenography of the internal standard. The time of the complete polymorphic transition in the solid phase β→a in 2,4DNAN under various combinations of conditions has been determined. It has been established that, regardless of the season of manufacture of the substance, when it is stored for 8-9months, with a change in ambient temperature from minus 30℃ to plus 30℃, a complete polymorphic transition β→a occurs. When stored in conditions below minus 5℃, polymorphic transition does not occur. When stored in conditions above plus 30℃ in a closed container, polymorphic transition occurs within 3 weeks. The polymorphic transition is accompanied by a decrease in density by 1.3%-1.5% and an increase in melting temperature by 10-12℃, depending on the degree of purity of the starting substance. The activation energy of the molecular rearrangement was 68-70 k J/mol(16.5 ± 3 kcal/mol). The mechanism of polymorphic transition has been evaluated, which is presumably based on internal homodiffusion and energy transfer to the surface of the mass of powder particles and the product. The average activation energy of the polymorphic transition process was 110 ± 6.2 k J/mol(26.2 kcal/mol). In an open container, reactions proceed by a homogeneous mechanism, and in a closed container by a heterogeneous mechanism involving the gas phase.

Synthesis of NaY zeolite from a submolten depolymerized perlite:Alkalinity effect and crystallization kinetics

NaY zeolites are synthesized using submolten salt depolymerized natural perlite mineral as the main silica and alumina sources in a 0.94 L stirred crystallizer.Effects of alkalinity ranging from 0.38 to 0.55(n(Na_(2)O)/n(SiO_(2)))on the relative crystallinity,textural properties and crystallization kinetics were investigated.The results show that alkalinity exerts a nonmonotonic influence on the relative crystallinity and textural properties,which exhibit a maximum at the alkalinity of 0.43.The nucleation kinetics are studied by fitting the experimental data of relative crystallinity with the Gualtieri model.It is shown that the nucleation rate constant increases with increasing alkalinity,while the duration period of nucleation decreases with increasing alkalinity.For n(Na_(2)O)/n(SiO_(2))ratios ranging from 0.38 to 0.55,the as-synthesized NaY zeolites exhibit narrower crystal size distributions with the increase in alkalinity.The growth rates determined from the variations of average crystal size with time are 51.09,157.50,46.17 and 24.75 nm·h^(-1),respectively.It is found that the larger average crystal sizes at the alkalinity of 0.38 and 0.43 are attributed to the dominant role of crystal growth over nucleation.Furthermore,the combined action of prominent crystal growth and the longer duration periods of nucleation at the alkalinity of 0.38 and 0.43 results in broader crystal size distributions.The findings demonstrate that control of the properties of NaY zeolite and the crystallization kinetics can be achieved by conducting the crystallization process in an appropriate range of alkalinity of the reaction mixture.

Improving hydrogen storage thermodynamics and kinetics of Ce-Mg-Ni-based alloy by mechanical milling with TiF_(3)

Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.

Alleviating the sluggish kinetics of all-solid-state batteries via cathode single-crystallization and multi-functional interface modification

The application of Li-rich Mn-based cathodes, the most promising candidates for high-energy-density Liion batteries, in all-solid-state batteries can further enhance the safety and stability of battery systems.However, the utilization of high-capacity Li-rich cathodes has been limited by sluggish kinetics and severe interfacial issues in all-solid-state batteries. Here, a multi-functional interface modification strategy involving dispersed submicron single-crystal structure and multi-functional surface modification layer obtained through in-situ interfacial chemical reactions was designed to improve the electrochemical performance of Li-rich Mn-based cathodes in all-solid-state batteries. The design of submicron single-crystal structure promotes the interface contact between the cathode particles and the solid-state electrolyte,and thus constructs a more complete ion and electron conductive network in the composite cathode.Furthermore, the Li-gradient layer and the lithium molybdate coating layer constructed on the surface of single-crystal Li-rich particles accelerate the transport of Li ions at the interface, suppress the side reactions between cathodes and electrolyte, and inhibit the oxygen release on the cathode surface. The optimized Li-rich cathode materials exhibit excellent electrochemical performance in halide all-solid-state batteries. This study emphasizes the vital importance of reaction kinetics and interfacial stability of Lirich cathodes in all-solid-state batteries and provides a facile modification strategy to enhance the electrochemical performance of all-solid-state batteries based on Li-rich cathodes.

Atomic Ni directional-substitution on ZnIn_(2)S_(4) nanosheet to achieve the equilibrium of elevated redox capacity and efficient carrier-kinetics performance in photocatalysis

It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced into the lattice of hexagonal ZnIn_(2)S_(4) nanosheets(Ni/ZnIn_(2)S_(4))via directionalsubstituting Zn atom with the facile hydrothermal method.The electronic structure calculations indicate that the introduction of Ni atom effectively extracts more electrons and acts as active site for subsequent reduction reaction.Besides the optimized light absorption range,the elevation of Efand ECBendows Ni/ZnIn_(2)S_(4) photocatalyst with the increased electron concentration and the enhanced reduction ability for surface reaction.Moreover,ultrafast transient absorption spectroscopy,as well as a series of electrochemical tests,demonstrates that Ni/ZnIn_(2)S_(4) possesses 2.15 times longer lifetime of the excited charge carriers and an order of magnitude increase for carrier mobility and separation efficiency compared with pristine ZnIn_(2)S_(4).These efficient kinetics performances of charge carriers and enhanced redox capacity synergistically boost photocatalytic activity,in which a 3-times higher conversion efficiency of nitrobenzene reduction was achieved upon Ni/ZnIn_(2)S_(4).Our study not only provides in-depth insights into the effect of atomic directional-substitution on the kinetic behavior of photogenerated charges,but also opens an avenue to the synchronous optimization of redox capacity and carrier-kinetics performance for efficient solar energy conversion.

A Review on Engineering Transition Metal Compound Catalysts to Accelerate the Redox Kinetics of Sulfur Cathodes for Lithium–Sulfur Batteries

Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.

Study on thermal decomposition kinetics of azobenzene-4,4′-dicarboxylic acid by using compensation parameter method and nonlinear fitting evaluation

Recently,azobenzene-4,4'-dicarboxylic acid(ADCA)has been produced gradually for use as an organic synthesis or pharmaceutical intermediate due to its eminent performance.With large quantities put into application in the future,the thermal stability of this substance during storage,transportation,and use will become quite important.Thus,in this work,the thermal decomposition behavior,thermal decomposition kinetics,and thermal hazard of ADCA were investigated.Experiments were conducted by using a SENSYS evo DSC device.A combination of differential iso-conversion method,compensation parameter method,and nonlinear fitting evaluation were also used to analyze thermal kinetics and mechanism of ADCA decomposition.The results show that when conversion rate α increases,the activation energies of ADCA's first and main decomposition peaks fall.The amount of heat released during decomposition varies between 182.46 and 231.16 J·g^(-1).The proposed kinetic equation is based on the Avrami-Erofeev model,which is consistent with the decomposition progress.Applying the Frank-Kamenetskii model,a calculated self-accelerating decomposition temperature of 287.0℃is obtained.

Modeling the Drying Kinetics of Pigeon Pea [Cajanus cajan (L.) Millspaugh]

We set out to model the oven-drying kinetics of a legume known as pigeon pea, harvested in the Bouenza department in the south-west of the Republic of Congo. The drying kinetics of pigeon peas was carried out in an oven under experimental conditions using temperatures of: 50°C, 60°C and 70°C. Seven mathematical models were used to describe pigeon pea drying. During drying, water loss was faster and shorter at 70°C [10.446 g/25 g wet weight (wwb) for 320 min (5.3 h)] compared to 50°C [10.996 g/25 g wet weight (wwb) for 520 min (8.6 h)] and 60°C [10.616 g/25 g wet weight (wwb) for 420 min (7.0 h)] where it was slower and longer. With regard to modeling, and based on the principle of choosing the right model focusing on the high value of R2 and low values of χ2 and RMSE, two models were selected, the Midili model for temperatures of 50°C and 60°C and the Henderson and Pabis model modified for temperature of 70°C showed better results. The R2, χ2 and RMSE values calculated for pigeon pea are 0.99985, 3.93404E-5 and 0.00627;0.9997, 9.245E-5 and 0.00962;0.99996, 1.56332E-5 and 0.00395 respectively at 50°C, 60°C and 70°C.

Thermal Decomposition of Olive-Solid Waste by TGA: Characterization and Devolatilization Kinetics under Nitrogen and Oxygen Atmospheres

Despite the fact that a few countries in the Mediterranean and the Middle East have limited crude oil reserves, they have abundant biomass feedstocks. For instance, Jordan relies heavily on the importation of natural gas and crude oil for its energy needs;but, by applying thermochemical conversion techniques, leftover olive oil can be used to replace these energy sources. Understanding the chemical, physical, and thermal characteristics of raw materials is essential to obtaining the most out of these conversion processes. Thermogravimetric analysis was used in this study to examine the thermal behavior of olive-solid residue (kernel) at three different heating rates (5, 20 and 40 C/min) in nitrogen and oxygen atmospheres. The initial degradation temperature, the residual weight at 500 and 700˚C and the thermal degradation rate during the devolatilization stage (below 400˚C) were all determined. It was found that in N2 and O2 atmospheres, both the initial degradation temperature and the degradation rate increase with increasing heating rates. As heating rates increase in the N2 atmosphere, the residual weight at 500 or 700˚C decreases slightly, but at low heating rates compared to high heating rates in the O2 atmosphere, it decreases significantly. This suggests that a longer lignin oxidation process is better than a shorter one. Coats and Redfern approach was used to identify the mechanism and activation energy for the devolatilization stage of pyrolysis and oxidation reactions. The process mechanism analysis revealed that the model of first-order and second-order reactions may adequately describe the mechanism of heat degradation of the devolatilization step of olive-solid waste for pyrolysis and oxidation processes, respectively.

Optimization of Methylene Blue Dye Adsorption onto Coconut Husk Cellulose Using Response Surface Methodology: Adsorption Kinetics, Isotherms and Reusability Studies

In this study, coconut husk cellulose was employed as a cost-effective and environmentally friendly adsorbent to eliminate methylene blue (MB) dye from aqueous solutions. The successful development of response surface methodology paired with a central composite design (RSM-CCD) enabled the optimization and modelling of the adsorption process. The study investigated the individual and combined effects of three variables (pH, contact time, and initial MB dye concentration) on the adsorption of MB dye onto coconut husk cellulose. The developed RSM-CCD model exhibited a remarkable degree of precision in predicting the removal efficiency of MB dye within the specified experimental parameters. This was demonstrated by the strong regression parameters, with an R2 value of 99.79% and an adjusted R2 value of 99.6%. The study depicted that the optimal parameters for attaining a 98.8827% removal of MB dye using coconut husk cellulose were as follows: an initial MB dye concentration of 30 mg∙L−1, contact time of 120 minutes, and pH 7 at a fixed adsorbent dose of 0.5 g. The Freundlich isotherm model provided the most satisfactory description of the equilibrium adsorption isotherms, suggesting that MB dye adsorption onto coconut husk cellulose occurs on a heterogeneous surface. The experimental results demonstrated a strong agreement with the pseudo-second-order kinetics model, indicating that the number of active sites present on the cellulose adsorbent predominantly influences the adsorption process of MB dye. Additionally, the adsorbent made from coconut husk cellulose exhibited the potential to be reused, as it retained its efficiency for a maximum of three cycles of adsorption of MB dye. The results of this study show that coconut husk cellulose has the potential to be an effective and sustainable adsorbent for removing MB dye from aqueous solutions.

Elimination, Kinetics and Thermodynamics of Fe(II) Ions by Adsorption in Static and Dynamic Conditions on Activated Carbons in Aqueous Media

This work investigated the removal, kinetics and thermodynamics of iron(II) ions (Fe(II)) by adsorption in static and dynamic conditions in aqueous media on activated carbons (AC-i30min, AC-i1h, and AC-i24h), prepared from palm nut shells collected in the city of Franceville to Gabon, using potassium hydroxide (KOH) as the activating agent. Results on the elimination of Fe(II) in static and dynamic adsorption on prepared activated carbons (ACs) showed that the AC-i24h adsorbent has the best Fe(II) adsorption capacities at saturation (Qsat). The Qsat obtained on AC-i24h in static and dynamic conditions (17.87 and 10.38 mg/g, respectively) were higher than those of AC-i30min (13.89 and 5.54 mg/g respectively) and AC-i1h (14.92 and 8.64 mg/g respectively). Moreover, the static adsorption was more effective in the removal of Fe(II) ions in aqueous media in our experimental conditions. The percentage removal (%E) of Fe(II) obtained on prepared activated carbons in static conditions was better than those obtained in dynamic conditions, especially on AC-i24h, where the %E was 89.27% in static and 61.56% in dynamic. In kinetics, results showed that the pseudo-second-order kinetic model best described the adsorption mechanisms of Fe(II) on prepared activated carbons in static adsorption, with mainly of chemisorption on the solid surfaces. However, in dynamic conditions, the pseudo-first-order kinetic model was more suitable. In addition to the weak interactions between Fe(II) and the activated carbon surfaces, strong interactions (chemisorption) were also observed. Also, thermodynamic data obtained on AC-i24h in static adsorption indicated that the adsorption of Fe(II) was spontaneous and increased with temperature (ΔG˚ H˚ = 503.54 KJ/mol).

Comparative investigations of ternary thermite Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3) from pyrolytic,kinetics and combustion behaviors

To develop new energy enhancement energetic materials with great combustion performance and thermal stability,two kinds of ternary thermite,Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3),were prepared and analyzed via mechanical ball milling.The samples were characterized by SEM,XRD,TG-DSC,constant volume and constant pressure combustion experiments.The first exothermic peaks of Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3) appear at 579°C and 564.5°C,respectively.The corresponding activation energies are similar.The corresponding mechanism functions are set as G(a) = [-ln(1-a)]^(3/4) and G(a) =[-ln(1-a)]2/3,respectively,which belong to the Avrami-Erofeev equation.Al/Fe_(2)O_(3)/CuO has better thermal safety.For small dose samples,its critical temperature of thermal explosion is 121.05°C higher than that of Al/Fe_(2)O_(3)/Bi_(2)O_(3).During combustion,the flame of Al/Fe_(2)O_(3)/CuO is spherical,and the main products are FeAl_(2)O_(4) and Cu.The flame of Al/Fe_(2)O_(3)/Bi_(2)O_(3)is jet-like,and the main products are Al_(2)O_(3),Bi and Fe.Al/Fe_(2)O_(3)/Bi_(2)O_(3)has better ignition and gas production performance.Its average ignition energy is 4.2 J lower than that of Al/Fe_(2)O_(3)/CuO.Its average step-up rate is 28.29 MPa/s,which is much higher than 6.84 MPa/s of Al/Fe_(2)O_(3)/CuO.This paper provides a reference for studying the thermal safety and combustion performance of ternary thermite.