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 superca...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.展开更多
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 hyperbo...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.展开更多
Applications of lithium-sulfur(Li-S)batteries are still limited by the sluggish conversion kinetics from polysulfide to Li_(2)S.Although various single-atom catalysts are available for improving the conversion kinetic...Applications of lithium-sulfur(Li-S)batteries are still limited by the sluggish conversion kinetics from polysulfide to Li_(2)S.Although various single-atom catalysts are available for improving the conversion kinetics,the sulfur redox kinetics for Li-S batteries is still not ultrafast.Herein,in this work,a catalyst with dual-single-atom Pt-Co embedded in N-doped carbon nanotubes(Pt&Co@NCNT)was proposed by the atomic layer deposition method to suppress the shuttle effect and synergistically improve the interconversion kinetics from polysulfides to Li_(2)S.The X-ray absorption near edge curves indicated the reversible conversion of Li_(2)Sx on the S/Pt&Co@NCNT electrode.Meanwhile,density functional theory demonstrated that the Pt&Co@NCNT promoted the free energy of the phase transition of sulfur species and reduced the oxidative decomposition energy of Li_(2)S.As a result,the batteries assembled with S/Pt&Co@NCNT electrodes exhibited a high capacity retention of 80%at 100 cycles at a current density of 1.3 mA cm^(−2)(S loading:2.5 mg cm^(−2)).More importantly,an excellent rate performance was achieved with a high capacity of 822.1 mAh g^(−1) at a high current density of 12.7 mA cm^(−2).This work opens a new direction to boost the sulfur redox kinetics for ultrafast Li-S batteries.展开更多
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...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.展开更多
Organosulfur materials containing sulfur-sulfur bonds are an emerging class of high-capacity cathodes for lithium storage.However,it remains a great challenge to achieve rapid conversion reaction kinetics at practical...Organosulfur materials containing sulfur-sulfur bonds are an emerging class of high-capacity cathodes for lithium storage.However,it remains a great challenge to achieve rapid conversion reaction kinetics at practical testing conditions of high cathode mass loading and low electrolyte utilization.In this study,a Li-rich pyrolyzed polyacrylonitrile/selenium disulfide(pPAN/Se_(2)S_(3))composite cathode is synthesized by deep lithiation to address the above challenges.The Li-rich molecular structure significantly boosts the lithium storage kinetics by accelerating lithium diffusivity and improving electronic conductivity.Even under practical test conditions requiring a lean electrolyte(Electrolyte/sulfur ratio of 4.1μL mg^(-1))and high loading(7 mg cm^(-2)of pPAN/Se_(2)S_(3)),DL-pPAN/Se_(2)S_(3)exhibits a specific capacity of 558 mAh g^(-1),maintaining 484 mAh g^(-1)at the 100th cycle with an average Coulombic efficiency of near 100%.Moreover,it provides(electro)chemically stable Li resources to offset Li consumption over charge-discharge cycles.As a result the as-fabricated anode-free cell shows a superior cycling stability with 90%retention of the initial capacity over 45 cycles.This study provides a novel approach for fabricating high-energy and stable Li-SPAN cells.展开更多
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 kine...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.展开更多
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 o...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.展开更多
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 pr...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.展开更多
The macroscopic flow behavior and rheological properties of cemented paste backfill(CPB)are highly impacted by the inherent structure of the paste matrix.In this study,the effects of shear-induced forces and proportio...The macroscopic flow behavior and rheological properties of cemented paste backfill(CPB)are highly impacted by the inherent structure of the paste matrix.In this study,the effects of shear-induced forces and proportioning parameters on the microstructure of fresh CPB were studied.The size evolution and distribution of floc/agglomerate/particles of paste were monitored by focused beam reflection measuring(FBRM)technique,and the influencing factors of aggregation and breakage kinetics of CPB were discussed.The results indicate that influenced by both internal and external factors,the paste kinetics evolution covers the dynamic phase and the stable phase.Increasing the mass content or the cement-tailings ratio can accelerate aggregation kinetics,which is advantageous for the rise of average floc size.Besides,the admixture and high shear can improve breaking kinetics,which is beneficial to reduce the average floc size.The chord length resembles a normal distribution somewhat,with a peak value of approximate 20μm.The particle disaggregation con-stant(k_(2))is positively correlated with the agitation rate,and k_(2) is five orders of magnitude greater than the particle aggregation constant(k1).The kinetics model depicts the evolution law of particles over time quantitatively and provides a theoretical foundation for the micromechanics of complicated rheological behavior of paste.展开更多
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...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.展开更多
Doped two-dimensional(2D)materials hold significant promise for advancing many technologies,such as microelectronics,optoelectronics,and energy storage.Herein,n-type 2D oxidized Si nanosheets,namely n-type siloxene(n-...Doped two-dimensional(2D)materials hold significant promise for advancing many technologies,such as microelectronics,optoelectronics,and energy storage.Herein,n-type 2D oxidized Si nanosheets,namely n-type siloxene(n-SX),are employed as Li-ion battery anodes.Via thermal evaporation of sodium hypophosphite at 275℃,P atoms are effectively incorporated into siloxene(SX)without compromising its 2D layered morphology and unique Kautsky-type crystal structure.Further,selective nucleophilic substitution occurs,with only Si atoms being replaced by P atoms in the O_(3)≡Si-H tetrahedra.The resulting n-SX possesses two delocalized electrons arising from the presence of two electron donor types:(i)P atoms residing in Si sites and(ii)H vacancies.The doping concentrations are varied by controlling the amount of precursors or their mean free paths.Even at 2000 mA g^(-1),the n-SX electrode with the optimized doping concentration(6.7×10^(19) atoms cm^(-3))delivers a capacity of 594 mAh g^(-1) with a 73%capacity retention after 500 cycles.These improvements originate from the enhanced kinetics of charge transport processes,including electronic conduction,charge transfer,and solid-state diffusion.The approach proposed herein offers an unprecedented route for engineering SX anodes to boost Li-ion storage.展开更多
In the cooling crystallization process of thiourea,a significant issue is the excessively wide crystal size distribution(CSD)and the abundance of fine crystals.This investigation delves into the growth kinetics and me...In the cooling crystallization process of thiourea,a significant issue is the excessively wide crystal size distribution(CSD)and the abundance of fine crystals.This investigation delves into the growth kinetics and mechanisms governing thiourea crystals during the cooling crystallization process.The fitting results indicate that the crystal growth rate coefficient,falls within the range of 10^(-7)to 10^(-8)m·s^(-1).Moreover,with decreasing crystallization temperature,the growth process undergoes a transition from diffusion-controlled to surface reaction-controlled,with temperature primarily influencing the surface reaction process and having a limited impact on the diffusion process.Comparing the crystal growth rate,and the diffusion-limited growth rate,at different temperatures,it is observed that the crystal growth process can be broadly divided into two stages.At temperatures above 25℃,1/qd(qd is diffusion control index)approaches 1,indicating the predominance of diffusion control.Conversely,at temperatures below 25℃,1/qd increases rapidly,signifying the dominance of surface reaction control.To address these findings,process optimization was conducted.During the high-temperature phase(35-25℃),agitation was increased to reduce the limitations posed by bulk-phase diffusion in the crystallization process.In the low-temperature phase(25-15℃),agitation was reduced to minimize crystal breakage.The optimized process resulted in a thiourea crystal product with a particle size distribution predominantly ranging from 0.7 to 0.9 mm,accounting for 84%of the total.This study provides valuable insights into resolving the issue of excessive fine crystals in the thiourea crystallization process.展开更多
This study explored the synergistic interaction of sewage sludge(SS)and distillation residue(DR)during co-pyrolysis for the optimized treatment of sewage sludge in cement kiln systems,utilizing thermogravimetric analy...This study explored the synergistic interaction of sewage sludge(SS)and distillation residue(DR)during co-pyrolysis for the optimized treatment of sewage sludge in cement kiln systems,utilizing thermogravimetric analysis(TGA)and thermogravimetric analysis with mass spectrometry(TGA-MS).The results reveal the coexisting synergistic and antagonistic effects in the co-pyrolysis of SS/DR.The synergistic effect arises from hydrogen free radicals in SS and catalytic components in ash fractions,while the antagonistic effect is mainly due to the melting of DR on the surface of SS particles during pyrolysis and the reaction of SS ash with alkali metals to form inert substances.SS/DR co-pyrolysis reduces the yielding of coke and gas while increasing tar production.This study will promote the reduction,recycling,and harmless treatment of hazardous solid waste.展开更多
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 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.展开更多
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...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.展开更多
Liquid-phase acrylic acid hydration over solid-phase catalysts is a key reaction for the industrial productionof 3-hydroxypropionic acid. However, the relevant literature primarily focuses on the experimental aspects ...Liquid-phase acrylic acid hydration over solid-phase catalysts is a key reaction for the industrial productionof 3-hydroxypropionic acid. However, the relevant literature primarily focuses on the experimental aspects of catalystscreening and exploring reaction conditions, with few accurate descriptions of the reaction kinetics and determination ofthe reaction mechanism. Here, we combined kinetics experiments and theoretical calculations to elucidate the kinetics andmechanism of acrylic acid hydration on a resin catalyst. The pseudo-homogeneous model, and Langmuir-Hinshelwood-Haugen-Watson and Elie-Riedel (ER) heterogeneous models were used to explain the experimental kinetics data. TheER model can explain the experimental data very well, suggesting strong adsorption of acrylic acid on the surface of theresin catalyst. Furthermore, density functional theory calculations show that the hydration follows a stepwise, rather than aconcerted, reaction pathway. The present study provides theoretical insights into the reaction mechanism and kinetics, fillingthe gap in our understanding of the reaction on a fundamental level.展开更多
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 nanocompo...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.展开更多
Controlling the content of athermal martensite and retained austenite is important to improving the mechanical properties of high-strength steels,but a mechanism for the accurate description of martensitic transformat...Controlling the content of athermal martensite and retained austenite is important to improving the mechanical properties of high-strength steels,but a mechanism for the accurate description of martensitic transformation during the cooling process must be addressed.At present,frequently used semi-empirical kinetics models suffer from huge errors at the beginning of transformation,and most of them fail to exhibit the sigmoidal shape characteristic of transformation curves.To describe the martensitic transformation process accurately,based on the Magee model,we introduced the changes in the nucleation activation energy of martensite with temperature,which led to the varying nucleation rates of this model during martensitic transformation.According to the calculation results,the relative error of the modified model for the martensitic transformation kinetics curves of Fe-C-X(X = Ni,Cr,Mn,Si) alloys reached 9.5% compared with those measured via the thermal expansion method.The relative error was approximately reduced by two-thirds compared with that of the Magee model.The incorporation of nucleation activation energy into the kinetics model contributes to the improvement of its precision.展开更多
Bisphenol A,a hazardous endocrine disruptor,poses significant environmental and human health threats,demanding efficient removal approaches.Traditional biological methods struggle to treat BPA wastewater with high chl...Bisphenol A,a hazardous endocrine disruptor,poses significant environmental and human health threats,demanding efficient removal approaches.Traditional biological methods struggle to treat BPA wastewater with high chloride(Cl^(-))levels due to the toxicity of high Cl^(-)to microorganisms.While persulfate-based advanced oxidation processes(PS-AOPs)have shown promise in removing BPA from high Cl^(-)wastewater,their widespread application is always limited by the high energy and chemical usage costs.Here we show that peroxymonosulfate(PMS)degrades BPA in situ under high Cl^(-)concentrations.BPA was completely removed in 30 min with 0.3 mM PMS and 60 mM Cl^(-).Non-radical reactive species,notably free chlorine species,including dissolved Cl2(l),HClO,and ClO−dominate the removal of BPA at temperatures ranging from 15 to 60°C.Besides,free radicals,including•OH and Cl_(2)^(•−),contribute minimally to BPA removal at 60°C.Based on the elementary kinetic models,the production rate constant of Cl2(l)(32.5 M^(−1) s^(−1))is much higher than HClO(6.5×10^(−4) M^(−1) s^(−1)),and its degradation rate with BPA(2×10^(7) M^(−1) s^(−1))is also much faster than HClO(18 M^(−1) s^(−1)).Furthermore,the degradation of BPA by Cl2(l)and HClO were enlarged by 10-and 18-fold at 60°C compared to room temperature,suggesting waste heat utilization can enhance treatment performance.Overall,this research provides valuable insights into the effectiveness of direct PMS introduction for removing organic micropollutants from high Cl^(-)wastewater.It further underscores the critical kinetics and mechanisms within the PMS/Cl⁻system,presenting a cost-effective and environmentally sustainable alternative for wastewater treatment.展开更多
In this paper,two lifting mechanism models with opposing placements,which use the same hydraulic hoist model and have the same angle of 50°,have been developed.The mechanical and hydraulic simulation models are e...In this paper,two lifting mechanism models with opposing placements,which use the same hydraulic hoist model and have the same angle of 50°,have been developed.The mechanical and hydraulic simulation models are established using MATLAB Simscape to analyze their kinetics and dynamics in the lifting and holding stages.The simulation findings are compared to the analytical calculation results in the steady state,and both methods show good agreement.In the early lifting stage,Model 1 produces greater force and discharges goods in the container faster than Model 2.Meanwhile,Model 2 reaches a higher force and ejects goods from the container cleaner than its counterpart at the end lifting stage.The established simulation models can consider the effects of dynamic loads due to inertial moments and forces generated during the system operation.It is crucial in studying,designing,and optimizing the structure of hydraulic-mechanical systems.展开更多
基金We are grateful to National Natural Science Foundation of China(Grant No.22375056,52272163)the Key R&D Program of Hebei(Grant No.216Z1201G)+1 种基金Natural Science Foundation of Hebei Province(Grant No.E2022208066,B2021208014)Key R&D Program of Hebei Technological Innovation Center of Chiral Medicine(Grant No.ZXJJ20220105).
文摘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.
基金supported by the National Natural Science Foundation of China(21972131)。
文摘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.
基金supported by the National Natural Science Foundation of China(22208039)the Basic Scientific Research Project of the Educational Department of Liaoning Province(LJKMZ20220878)+1 种基金and the Dalian Science and Technology Talent Innovation Support Plan(2022RQ036)supported by the Natural Science and Engineering Research Council of Canada(NSERC),the Canada Research Chair Program(CRC),the Canada Foundation for Innovation(CFI),and Western University。
文摘Applications of lithium-sulfur(Li-S)batteries are still limited by the sluggish conversion kinetics from polysulfide to Li_(2)S.Although various single-atom catalysts are available for improving the conversion kinetics,the sulfur redox kinetics for Li-S batteries is still not ultrafast.Herein,in this work,a catalyst with dual-single-atom Pt-Co embedded in N-doped carbon nanotubes(Pt&Co@NCNT)was proposed by the atomic layer deposition method to suppress the shuttle effect and synergistically improve the interconversion kinetics from polysulfides to Li_(2)S.The X-ray absorption near edge curves indicated the reversible conversion of Li_(2)Sx on the S/Pt&Co@NCNT electrode.Meanwhile,density functional theory demonstrated that the Pt&Co@NCNT promoted the free energy of the phase transition of sulfur species and reduced the oxidative decomposition energy of Li_(2)S.As a result,the batteries assembled with S/Pt&Co@NCNT electrodes exhibited a high capacity retention of 80%at 100 cycles at a current density of 1.3 mA cm^(−2)(S loading:2.5 mg cm^(−2)).More importantly,an excellent rate performance was achieved with a high capacity of 822.1 mAh g^(−1) at a high current density of 12.7 mA cm^(−2).This work opens a new direction to boost the sulfur redox kinetics for ultrafast Li-S batteries.
基金supported by National Key Research and Development Program of China(2021YFB4000604)National Natural Science Foundation of China(52271220)111 Project(B12015)and the Fundamental Research Funds for the Central Universities.
文摘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.
基金financial support from The Hong Kong Polytechnic University(ZZLM,YY4V,YY5K)Inner Mongolia Scientific and Technological Achievements Transformation Project(no.CGZH2018132)+6 种基金Inner Mongolia Major Science and Technology Project(no.2020ZD0024)the Alashan League’s Project of Applied Technology Research and Development Fund(no.AMYY2020-01)Local Science and Technology Development Project of the Central Government(no.2021ZY0006,2022ZY0011)National Natural Science Foundation of China(no.52202245)Natural Science Fund for Colleges and Universities in Jiangsu Province(no.22KJB430004)Natural Science Foundation of Jiangsu Province(BE2020759)Jiangsu Outstanding Professors
文摘Organosulfur materials containing sulfur-sulfur bonds are an emerging class of high-capacity cathodes for lithium storage.However,it remains a great challenge to achieve rapid conversion reaction kinetics at practical testing conditions of high cathode mass loading and low electrolyte utilization.In this study,a Li-rich pyrolyzed polyacrylonitrile/selenium disulfide(pPAN/Se_(2)S_(3))composite cathode is synthesized by deep lithiation to address the above challenges.The Li-rich molecular structure significantly boosts the lithium storage kinetics by accelerating lithium diffusivity and improving electronic conductivity.Even under practical test conditions requiring a lean electrolyte(Electrolyte/sulfur ratio of 4.1μL mg^(-1))and high loading(7 mg cm^(-2)of pPAN/Se_(2)S_(3)),DL-pPAN/Se_(2)S_(3)exhibits a specific capacity of 558 mAh g^(-1),maintaining 484 mAh g^(-1)at the 100th cycle with an average Coulombic efficiency of near 100%.Moreover,it provides(electro)chemically stable Li resources to offset Li consumption over charge-discharge cycles.As a result the as-fabricated anode-free cell shows a superior cycling stability with 90%retention of the initial capacity over 45 cycles.This study provides a novel approach for fabricating high-energy and stable Li-SPAN cells.
基金This work was financially supported by the National Natural Science Foundation of China(No.52171144)the Fundamental Research Special Zone Program of Shanghai Jiao Tong University(No.21TQ1400215).
文摘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.
基金the financial supports from National Natural Science Foundation of China(22378344,22208278)Natural Science Foundation of Shandong Province(ZR2023MB120,ZR2023QB152)Youth Innovation Team Plan of Shandong Province(2022KJ270)。
文摘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.
基金financially supported by the National Key Research and Development Program of China(2022YFA1503504)the National Natural Science Foundation of China(22038003,22178100,22178101,and U22B20141)+3 种基金the Shanghai Pilot Program for Basic Research(22TQ1400100-15)the Innovation Program of Shanghai Municipal Education Commissionthe Program of Shanghai Academic/Technology Research Leader(21XD1421000)the Shanghai Science and Technology Innovation Action Plan(22JC1403800)。
文摘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.
基金financially supported by the National Natural Science Foundation of China(No.52104129)the Shandong Provincial Major Science and Technology Innovation Project,China(No.2019SDZY05)+2 种基金the key Laboratory of Mine Ecological Effects and Systematic Restoration,Ministry of Natural Resources(No.MEER-2022-09)the Double First-class Construction Project in Henan Province,China(No.AQ20230735)the Doctoral Fund of Henan Polytechnic University(No.B2021-59).
文摘The macroscopic flow behavior and rheological properties of cemented paste backfill(CPB)are highly impacted by the inherent structure of the paste matrix.In this study,the effects of shear-induced forces and proportioning parameters on the microstructure of fresh CPB were studied.The size evolution and distribution of floc/agglomerate/particles of paste were monitored by focused beam reflection measuring(FBRM)technique,and the influencing factors of aggregation and breakage kinetics of CPB were discussed.The results indicate that influenced by both internal and external factors,the paste kinetics evolution covers the dynamic phase and the stable phase.Increasing the mass content or the cement-tailings ratio can accelerate aggregation kinetics,which is advantageous for the rise of average floc size.Besides,the admixture and high shear can improve breaking kinetics,which is beneficial to reduce the average floc size.The chord length resembles a normal distribution somewhat,with a peak value of approximate 20μm.The particle disaggregation con-stant(k_(2))is positively correlated with the agitation rate,and k_(2) is five orders of magnitude greater than the particle aggregation constant(k1).The kinetics model depicts the evolution law of particles over time quantitatively and provides a theoretical foundation for the micromechanics of complicated rheological behavior of paste.
基金China Scholarship Council,Grant/Award Number:201806950083Advanced Materials research program of the Zernike National Research CentreFaculty of Science and Engineering(FSE),University of Groningen。
文摘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.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(2020R1A6A1A03045059)+1 种基金by Ministry of Science and ICT(2022R1A2C3003319)by the Institutional Program(2E33221)of the Korea Institute of Science and Technology(KIST).
文摘Doped two-dimensional(2D)materials hold significant promise for advancing many technologies,such as microelectronics,optoelectronics,and energy storage.Herein,n-type 2D oxidized Si nanosheets,namely n-type siloxene(n-SX),are employed as Li-ion battery anodes.Via thermal evaporation of sodium hypophosphite at 275℃,P atoms are effectively incorporated into siloxene(SX)without compromising its 2D layered morphology and unique Kautsky-type crystal structure.Further,selective nucleophilic substitution occurs,with only Si atoms being replaced by P atoms in the O_(3)≡Si-H tetrahedra.The resulting n-SX possesses two delocalized electrons arising from the presence of two electron donor types:(i)P atoms residing in Si sites and(ii)H vacancies.The doping concentrations are varied by controlling the amount of precursors or their mean free paths.Even at 2000 mA g^(-1),the n-SX electrode with the optimized doping concentration(6.7×10^(19) atoms cm^(-3))delivers a capacity of 594 mAh g^(-1) with a 73%capacity retention after 500 cycles.These improvements originate from the enhanced kinetics of charge transport processes,including electronic conduction,charge transfer,and solid-state diffusion.The approach proposed herein offers an unprecedented route for engineering SX anodes to boost Li-ion storage.
基金supported by Priority Academic Program Development of Jiangsu Higher Educatior(PPZY2015A044).
文摘In the cooling crystallization process of thiourea,a significant issue is the excessively wide crystal size distribution(CSD)and the abundance of fine crystals.This investigation delves into the growth kinetics and mechanisms governing thiourea crystals during the cooling crystallization process.The fitting results indicate that the crystal growth rate coefficient,falls within the range of 10^(-7)to 10^(-8)m·s^(-1).Moreover,with decreasing crystallization temperature,the growth process undergoes a transition from diffusion-controlled to surface reaction-controlled,with temperature primarily influencing the surface reaction process and having a limited impact on the diffusion process.Comparing the crystal growth rate,and the diffusion-limited growth rate,at different temperatures,it is observed that the crystal growth process can be broadly divided into two stages.At temperatures above 25℃,1/qd(qd is diffusion control index)approaches 1,indicating the predominance of diffusion control.Conversely,at temperatures below 25℃,1/qd increases rapidly,signifying the dominance of surface reaction control.To address these findings,process optimization was conducted.During the high-temperature phase(35-25℃),agitation was increased to reduce the limitations posed by bulk-phase diffusion in the crystallization process.In the low-temperature phase(25-15℃),agitation was reduced to minimize crystal breakage.The optimized process resulted in a thiourea crystal product with a particle size distribution predominantly ranging from 0.7 to 0.9 mm,accounting for 84%of the total.This study provides valuable insights into resolving the issue of excessive fine crystals in the thiourea crystallization process.
基金Funded by National College Student Innovation and Entrepreneurship Training Program Project(No.CY202036)。
文摘This study explored the synergistic interaction of sewage sludge(SS)and distillation residue(DR)during co-pyrolysis for the optimized treatment of sewage sludge in cement kiln systems,utilizing thermogravimetric analysis(TGA)and thermogravimetric analysis with mass spectrometry(TGA-MS).The results reveal the coexisting synergistic and antagonistic effects in the co-pyrolysis of SS/DR.The synergistic effect arises from hydrogen free radicals in SS and catalytic components in ash fractions,while the antagonistic effect is mainly due to the melting of DR on the surface of SS particles during pyrolysis and the reaction of SS ash with alkali metals to form inert substances.SS/DR co-pyrolysis reduces the yielding of coke and gas while increasing tar production.This study will promote the reduction,recycling,and harmless treatment of hazardous solid waste.
基金supported by the Ministry of Science and Higher Education of the Russian Federation(Agreement with Zelinsky Institute of Organic Chemistry RAS Grant No.075-15-2020-803).
文摘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.
基金supports from National Natural Science Foundation of China(21938009,22308358,22208346,22078332)National Key Research and Development Program(2022YFC3902701)+2 种基金Ningxia Natural Science Foundation(2021AAC01002)the External Cooperation Program of BIC,Chinese Academy of Sciences(122111KYSB20190032)CAS Project for Young Scientists in Basic Research(YSBR-038)are gratefully acknowledged.
文摘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.
文摘Liquid-phase acrylic acid hydration over solid-phase catalysts is a key reaction for the industrial productionof 3-hydroxypropionic acid. However, the relevant literature primarily focuses on the experimental aspects of catalystscreening and exploring reaction conditions, with few accurate descriptions of the reaction kinetics and determination ofthe reaction mechanism. Here, we combined kinetics experiments and theoretical calculations to elucidate the kinetics andmechanism of acrylic acid hydration on a resin catalyst. The pseudo-homogeneous model, and Langmuir-Hinshelwood-Haugen-Watson and Elie-Riedel (ER) heterogeneous models were used to explain the experimental kinetics data. TheER model can explain the experimental data very well, suggesting strong adsorption of acrylic acid on the surface of theresin catalyst. Furthermore, density functional theory calculations show that the hydration follows a stepwise, rather than aconcerted, reaction pathway. The present study provides theoretical insights into the reaction mechanism and kinetics, fillingthe gap in our understanding of the reaction on a fundamental level.
基金the National Natural Science Foundation of China(Nos.51871125,51761032,52001005 and 51731002)Major Science and Technology Innovation Projects in Shandong Province(No.2019JZZY010320)for financial support of the work.
文摘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.
基金financially supported by the National Natural Science Foundation of China(No.U2102212)the Shanghai Rising-Star Program(No.21QA1403200)。
文摘Controlling the content of athermal martensite and retained austenite is important to improving the mechanical properties of high-strength steels,but a mechanism for the accurate description of martensitic transformation during the cooling process must be addressed.At present,frequently used semi-empirical kinetics models suffer from huge errors at the beginning of transformation,and most of them fail to exhibit the sigmoidal shape characteristic of transformation curves.To describe the martensitic transformation process accurately,based on the Magee model,we introduced the changes in the nucleation activation energy of martensite with temperature,which led to the varying nucleation rates of this model during martensitic transformation.According to the calculation results,the relative error of the modified model for the martensitic transformation kinetics curves of Fe-C-X(X = Ni,Cr,Mn,Si) alloys reached 9.5% compared with those measured via the thermal expansion method.The relative error was approximately reduced by two-thirds compared with that of the Magee model.The incorporation of nucleation activation energy into the kinetics model contributes to the improvement of its precision.
基金Key-Area Research and Development Program of Guangdong Province(No.2023B0101200004)Shenzhen Science and Technology Innovation Program(No.RCBS20210706092219047,GXWD20231129122140001,KQTD20190929172630447,2022A1515110698,and RCBS 20221008093229033)+1 种基金National Natural Science Foundation of China(No.52000053)Open Project of State Key Laboratory of Urban Water Resources and Environment(QA202440).
文摘Bisphenol A,a hazardous endocrine disruptor,poses significant environmental and human health threats,demanding efficient removal approaches.Traditional biological methods struggle to treat BPA wastewater with high chloride(Cl^(-))levels due to the toxicity of high Cl^(-)to microorganisms.While persulfate-based advanced oxidation processes(PS-AOPs)have shown promise in removing BPA from high Cl^(-)wastewater,their widespread application is always limited by the high energy and chemical usage costs.Here we show that peroxymonosulfate(PMS)degrades BPA in situ under high Cl^(-)concentrations.BPA was completely removed in 30 min with 0.3 mM PMS and 60 mM Cl^(-).Non-radical reactive species,notably free chlorine species,including dissolved Cl2(l),HClO,and ClO−dominate the removal of BPA at temperatures ranging from 15 to 60°C.Besides,free radicals,including•OH and Cl_(2)^(•−),contribute minimally to BPA removal at 60°C.Based on the elementary kinetic models,the production rate constant of Cl2(l)(32.5 M^(−1) s^(−1))is much higher than HClO(6.5×10^(−4) M^(−1) s^(−1)),and its degradation rate with BPA(2×10^(7) M^(−1) s^(−1))is also much faster than HClO(18 M^(−1) s^(−1)).Furthermore,the degradation of BPA by Cl2(l)and HClO were enlarged by 10-and 18-fold at 60°C compared to room temperature,suggesting waste heat utilization can enhance treatment performance.Overall,this research provides valuable insights into the effectiveness of direct PMS introduction for removing organic micropollutants from high Cl^(-)wastewater.It further underscores the critical kinetics and mechanisms within the PMS/Cl⁻system,presenting a cost-effective and environmentally sustainable alternative for wastewater treatment.
基金Ho Chi Minh City University of Technology(HCMUT)Vietnam National University Ho Chi Minh City(VNU-HCM)for supporting this study。
文摘In this paper,two lifting mechanism models with opposing placements,which use the same hydraulic hoist model and have the same angle of 50°,have been developed.The mechanical and hydraulic simulation models are established using MATLAB Simscape to analyze their kinetics and dynamics in the lifting and holding stages.The simulation findings are compared to the analytical calculation results in the steady state,and both methods show good agreement.In the early lifting stage,Model 1 produces greater force and discharges goods in the container faster than Model 2.Meanwhile,Model 2 reaches a higher force and ejects goods from the container cleaner than its counterpart at the end lifting stage.The established simulation models can consider the effects of dynamic loads due to inertial moments and forces generated during the system operation.It is crucial in studying,designing,and optimizing the structure of hydraulic-mechanical systems.
