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“Buckets effect”in the kinetics of electrocatalytic reactions 被引量:2
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作者 Haowen Cui Yan-Xia Chen 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第2期388-396,I0010,共10页
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
关键词 Oxygen reduction reaction kinetics Zero order Rectangular hyperbolic relationship pH effect
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Dual-single-atoms of Pt-Co boost sulfur redox kinetics for ultrafast Li-S batteries 被引量:1
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作者 Hanyan Wu Xuejie Gao +7 位作者 Xinyang Chen Weihan Li Junjie Li Lei Zhang Yang Zhao Ming Jiang Runcang Sun Xueliang Sun 《Carbon Energy》 SCIE EI CAS CSCD 2024年第3期53-63,共11页
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
关键词 DFT calculation dual-single-atoms of Pt-Co fast Li-sulfur batteries sulfur redox kinetics XANES analysis
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Recent progress in thermodynamic and kinetics modification of magnesium hydride hydrogen storage materials 被引量:1
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作者 Yafei Liu Yusang Guo +3 位作者 Yaru Jiang Lizhuang Feng Yu Sun Yijing Wang 《Materials Reports(Energy)》 EI 2024年第1期3-22,共20页
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
关键词 Magnesium hydride Thermodynamics and kinetics Catalyst doping NANOSTRUCTURES Hydrogenation and dehydrogenation
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Li-Rich Organosulfur Cathode with Boosted Kinetics for High-Energy Lithium-Sulfur Batteries
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作者 Ting Ma Jiaojiao Deng +8 位作者 Yuxiao Lin Qinghua Liang Liang Hu Xiaohu Wang Jun Liu Xinsheng Zhao Yinwei Li Ding Nan Xiaoliang Yu 《Energy & Environmental Materials》 SCIE EI CAS CSCD 2024年第4期118-125,共8页
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
关键词 LITHIUM kinetics ELECTROLYTE
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Continuous synthesis of N,N-dicyanoethylaniline in microreactors:Reaction kinetics and process intensification
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作者 Pengcheng Lu Yaoyao Li +5 位作者 Jianjun Zhang Yuchao Zhao Qingqiang Wang Ying Chen Nan Jin Xiugang Yu 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第8期95-105,共11页
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
关键词 Cyanoethylation MICROREACTOR kinetics N N-dicyanoethylaniline Optimization Safety
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Kinetics insights into size effects of carbon nanotubes'growth and their supported platinum catalysts for 4,6-dinitroresorcinol hydrogenation
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作者 Yan Zhang Xiangxue Zhang +6 位作者 Keng Sang Wenyao Chen Gang Qian Jing Zhang Xuezhi Duan Xinggui Zhou Weikang Yuan 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第8期133-140,共8页
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
关键词 kinetics Size effects Catalytic hydrogenation Active site
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Particle aggregation and breakage kinetics in cemented paste backfill
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作者 Liuhua Yang Hengwei Jia +4 位作者 Aixiang Wu Huazhe Jiao Xinming Chen Yunpeng Kou Mengmeng Dong 《International Journal of Minerals,Metallurgy and Materials》 SCIE EI CAS CSCD 2024年第9期1965-1974,共10页
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
关键词 cemented paste backfill particle kinetics ADMIXTURE rheology
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Tuning the crystallinity of titanium nitride on copper-embedded carbon nanofiber interlayers for accelerated electrochemical kinetics in lithium-sulfur batteries
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作者 Yinyu Xiang Liqiang Lu +4 位作者 Feng Yan Debarun Sengupta Petra Rudolf Ajay Giri Prakash Kottapalli Yutao Pei 《Carbon Energy》 SCIE EI CAS CSCD 2024年第6期40-55,共16页
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
关键词 CRYSTALLINITY electrochemical kinetics INTERLAYER lithium-sulfur batteries titanium nitride
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Boosted Lithium-Ion Transport Kinetics in n-Type Siloxene Anodes Enabled by Selective Nucleophilic Substitution of Phosphorus
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作者 Se In Kim Woong-Ju Kim +1 位作者 Jin Gu Kang Dong-Wan Kim 《Nano-Micro Letters》 SCIE EI CAS CSCD 2024年第10期618-637,共20页
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
关键词 Li-ion battery Two-dimensional N-type siloxene Doping mechanism kinetics
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Thiourea crystal growth kinetics,mechanism and process optimization during cooling crystallization
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作者 Zhongxiang Ding Wei Song +2 位作者 Tong Zhou Weihua Cui Changsong Wang 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第9期62-69,共8页
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
关键词 THIOUREA CRYSTALLIZATION Growth kinetics Process optimization DIFFUSION Surface reaction
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Co-pyrolysis of Sewage Sludge with Distillation Residue: Kinetics Analysis via Iso-conversional Methods
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作者 ZHOU Shangqun ZHAO Qinglin +1 位作者 YU Tian YAO Xiaojie 《Journal of Wuhan University of Technology(Materials Science)》 SCIE EI CAS CSCD 2024年第5期1188-1198,共11页
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
关键词 sewage sludge CO-PYROLYSIS distillation residue kinetics evolved gas analysis
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Kinetics and mechanism of the low-energy β-a phase transition of the second kind in 2,4-dinitroanisole
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作者 Aleksandr V.Stankevich Nikolay A.Rasputin +3 位作者 Anisa KhRudina Gennady L.Rusinov Vera I.Filyakova Valery N.Charushin 《Defence Technology(防务技术)》 SCIE EI CAS CSCD 2024年第10期210-224,共15页
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
关键词 Energetic materials Melt-castable 2 4-Dinitroanisole Polymorphic transition kinetics Mechanism Homodiffusion SUBLIMATION
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Synthesis of NaY zeolite from a submolten depolymerized perlite:Alkalinity effect and crystallization kinetics
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作者 Yanli Qu Peng Dong +4 位作者 Li Yang Yuanyuan Yue Haoliang Wang Jingcai Cheng Chao Yang 《Chinese Journal of Chemical Engineering》 SCIE EI CAS CSCD 2024年第6期130-138,共9页
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
关键词 NaY zeolite Submolten salt depolymerized perlite ALKALINITY Crystallization kinetics
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Kinetics and Mechanism of Hydration of Acrylic Acid over Ion-exchanged Resin:Experimental Exploration and DFT Calculation
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作者 Yang Fengjing Luo Nianjun +11 位作者 Chen Yuxiang Liu Chuanlei Wang Hao Gao Weikang Guo Guanchu Jiang Hao Zhao Qiyue Zhou Yousheng Wang Yifan Li Peicheng Shen Benxian Sun Hui 《China Petroleum Processing & Petrochemical Technology》 SCIE CAS CSCD 2024年第3期109-121,共13页
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
关键词 acrylic acid kinetics resin catalyst DFT method
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Improving hydrogen storage thermodynamics and kinetics of Ce-Mg-Ni-based alloy by mechanical milling with TiF_(3)
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作者 Hongwei Shang Wei Zhang +4 位作者 Xin Wei Yaqin Li Zeming Yuan Jun Li Yanghuan Zhang 《Journal of Magnesium and Alloys》 SCIE EI CAS CSCD 2024年第4期1593-1607,共15页
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
关键词 Mg-based hydrides TiF_(3) Ball milling THERMODYNAMICS kinetics
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Description of martensitic transformation kinetics in Fe-C-X(X = Ni,Cr,Mn,Si) system by a modified model
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作者 Xiyuan Geng Hongcan Chen +3 位作者 Jingjing Wang Yu Zhang Qun Luo Qian Li 《International Journal of Minerals,Metallurgy and Materials》 SCIE EI CAS CSCD 2024年第5期1026-1036,共11页
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
关键词 Fe-C-X system martensitic transformation kinetics curve semi-empirical model nucleation activation energy
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Alleviating the sluggish kinetics of all-solid-state batteries via cathode single-crystallization and multi-functional interface modification
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作者 Wen-Zhe Liu Xin-Hai Meng +4 位作者 Zi-Yi Zhou Qiang Zheng Ji-Lei Shi Yue Gong Yu-Guo Guo 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第11期123-133,共11页
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 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. 展开更多
关键词 All-solid-state Li-ion batteries Li-rich Mn-based cathode materials kinetics Interface Anion redox
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Geochemical modeling to aid experimental design for multiple isotope tracer studies of coupled dissolution and precipitation reaction kinetics
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作者 Mingkun Chen Peng Lu +1 位作者 Yongchen Song Chen Zhu 《Acta Geochimica》 EI CAS CSCD 2024年第1期1-15,共15页
It is a challenge to make thorough but efficient experimental designs for the coupled mineral dissolution and precipitation studies in a multi-mineral system, because it is difficult to speculate the best experimental... It is a challenge to make thorough but efficient experimental designs for the coupled mineral dissolution and precipitation studies in a multi-mineral system, because it is difficult to speculate the best experimental duration, optimal sampling schedule, effects of different experimental conditions, and how to maximize the experimental outputs prior to the actual experiments. Geochemical modeling is an efficient and effective tool to assist the experimental design by virtually running all scenarios of interest for the studied system and predicting the experimental outcomes. Here we demonstrated an example of geochemical modeling assisted experimental design of coupled labradorite dissolution and calcite and clayey mineral precipitation using multiple isotope tracers. In this study, labradorite(plagioclase) was chosen as the reactant because it is both a major component and one of the most reactive minerals in basalt. Following our isotope doping studies of single minerals in the last ten years, initial solutions in the simulations were doped withmultiple isotopes(e.g., Ca and Si). Geochemical modeling results show that the use of isotope tracers gives us orders of magnitude more sensitivity than the conventional method based on concentrations and allows us to decouple dissolution and precipitation reactions at near-equilibrium condition. The simulations suggest that the precise unidirectional dissolution rates can inform us which rate laws plagioclase dissolution has followed. Calcite precipitation occurred at near-equilibrium and the multiple isotope tracer experiments would provide near-equilibrium precipitation rates, which was a challenge for the conventional concentration-based experiments. In addition, whether the precipitation of clayey phases is the rate-limiting step in some multi-mineral systems will be revealed. Overall, the modeling results of multimineral reaction kinetics will improve the understanding of the coupled dissolution–precipitation in the multi-mineral systems and the quality of geochemical modeling prediction of CO_(2) removal and storage efficacy in the basalt systems. 展开更多
关键词 kinetics FELDSPAR Isotope doping Near-equilibrium CO_(2)sequestration BASALT
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Mitigated reaction kinetics between lithium metal anodes and electrolytes by alloying lithium metal with low-content magnesium
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作者 Yang-Yang Wang Ya-Nan Wang +9 位作者 Nan Yao Shu-Yu Sun Xiao-Qing Ding Chen-Xi Bi Qian-Kui Zhang Zhao Zheng Cheng-Bin Jin Bo-Quan Li Xue-Qiang Zhang Jia-Qi Huang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第8期644-650,I0014,共8页
Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reserv... Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes. 展开更多
关键词 Lithium metal anodes ALLOYING Anode/electrolyte interface Reaction kinetics Pouch cell
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Catalytic Reaction Kinetics of Propylene Dimerization to 4-Methyl-1-Pentene Using Cu-K/K_(2)CO_(3) Solid Base Catalyst
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作者 Jin Haibo Chai Jing +3 位作者 Yang Suohe He Guangxiang Ma Lei Guo Xiaoyan 《China Petroleum Processing & Petrochemical Technology》 SCIE CAS CSCD 2024年第1期78-87,共10页
The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of ... The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of propylene dimerization were studied in a fixed-bed continuous reactor.Internal and external diffusion during the dimerization reaction experiments were eliminated by adjusting the flow rate of the carrier gas and the particle size of the catalyst support.Then,the concentration changes of each substance at the outlet of the catalyst bed under different residence times were investigated.Moreover,the suitable reaction kinetics equations was derived using the Langmuir Hinshelwood-Hougen-Watson kinetic model.Finally,the activation energy for each reaction involved in the dimerization reaction was calculated.The activation energies of 4MP1,branched by-products,and 1-hexene were 115.0,150.8,and 177.4 kJ/mol,respectively.The effect of process conditions on propylene dimerization with solid base catalysts was studied through kinetic model simulation.By comparing the theoretical values obtained from the simulation with the experimental results,the applicability and accuracy of the kinetic model were verified. 展开更多
关键词 propylene dimerization 4-methyl-1-pentene intrinsic kinetics surface reaction
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