Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key hal...Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key half-reaction of performance-limiting in water splitting.Given the complicated reaction process and surface reconstruction of the involved catalysts under actual working conditions,unraveling the real active sites,probing multiple reaction intermediates and clarifying catalytic pathways through in-situ characterization techniques and theoretical calculations are essential.In this review,we summarize the recent advancements in understanding the catalytic process,unlocking the water oxidation active phase and elucidating catalytic mechanism of water oxidation by various in-situ characterization techniques.Firstly,we introduce conventionally proposed traditional catalytic mechanisms and novel evolutionary mechanisms of OER,and highlight the significance of optimal catalytic pathways and intrinsic stability.Next,we provide a comprehensive overview of the fundamental working principles,different detection modes,applicable scenarios,and limitations associated with the in-situ characterization techniques.Further,we exemplified the in-situ studies and discussed phase transition detection,visualization of speciation evolution,electronic structure tracking,observation of reaction active intermediates,and monitoring of catalytic products,as well as establishing catalytic structure-activity relationships and catalytic mechanism.Finally,the key challenges and future perspectives for demystifying the water oxidation process are briefly proposed.展开更多
NbC ceramic surface-reinforced steel matrix composites were prepared by an in-situ reaction method at different temperatures(1,050℃,1,100℃and 1,150℃)for different times(1 h,2 h and 3 h).The phase constitution,micro...NbC ceramic surface-reinforced steel matrix composites were prepared by an in-situ reaction method at different temperatures(1,050℃,1,100℃and 1,150℃)for different times(1 h,2 h and 3 h).The phase constitution,microstructure and fracture morphology of NbC ceramic surface-reinforced steel matrix composites were analyzed by XRD,SEM and EDS,and the effects of the in-situ reaction temperature and time on the mechanical properties were systematically studied.The results indicate that the NbC reinforcement layer is formed through the reaction between Nb atoms and carbon atoms diffused from the steel matrix to the Nb plate.The thickness of this reinforcement layer increases as the reaction time prolongs.Additionally,an increase in reaction temperature results in a thicker reinforcement layer,although the rate of increase gradually decreases.The relationship among the thickness of the Nb C reinforcement layer,the reaction time and temperature was established by data fitting.The optimal tensile performance is achieved at 1,100℃for 1 h,with a tensile strength of 228 MPa.It is also found that the defects between the reinforcement layer and the steel matrix are related to reaction temperature.At 1,100℃,these defects are minimal.Fracture mostly occurs in the NbC reinforced layer of the composites,and the fracture mode is characterized by typical intergranular brittle fracture.展开更多
Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic am...Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic amine catalyst hamper its application in in-situ batteries.Herein,a nitrogen-containing eutectic solution is designed as both the catalyst of the thiol-ene reaction and the plasticizer to in-situ synthesize the gel polymer electrolytes,realizing a mild in-situ gelation process and the preparation of high-performance gel electrolytes.The obtained gel polymer electrolytes exhibit a high ionic conductivity of 4×10^(−4)S cm^(−1)and lithium-ion transference number(t_(Li)^(+))of 0.51 at 60°C.The as-assembled Li/LiFePO_(4)(LFP)cell delivers a high initial discharge capacity of 155.9 mAh g^(-1),and a favorable cycling stability with the capacity retention of 82%after 800 cycles at 1 C is also obtained.In addition,this eutectic solution significantly improves the rate performance of the LFP cell with high specific capacity of 141.5 and 126.8 mAh g^(-1)at 5 C and 10 C,respectively,and the cell can steadily work at various charge–discharge rate for 200 cycles.This powerful and efficient strategy may provide a novel way for in-situ preparing gel polymer electrolytes with desirable comprehensive performances.展开更多
Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this s...Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.展开更多
For the rational manipulation of the production quality of high-temperature metallurgical engineering,there are many challenges in understanding the processes involved because of the black box chemical/electrochemical...For the rational manipulation of the production quality of high-temperature metallurgical engineering,there are many challenges in understanding the processes involved because of the black box chemical/electrochemical reactors.To overcome this issue,various in-situ characterization methods have been recently developed to analyze the interactions between the composition,microstructure,and solid-liquid interface of high-temperature electrochemical electrodes and molten salts.In this review,recent progress of in-situ hightemperature characterization techniques is discussed to summarize the advances in understanding the processes in metallurgical engineering.In-situ high-temperature technologies and analytical methods mainly include synchrotron X-ray diffraction(s-XRD),laser scanning confocal microscopy,and X-ray computed microtomography(X-rayμ-CT),which are important platforms for analyzing the structure and morphology of the electrodes to reveal the complexity and variability of their interfaces.In addition,laser-induced breakdown spectroscopy,high-temperature Raman spectroscopy,and ultraviolet-visible absorption spectroscopy provide microscale characterizations of the composition and structure of molten salts.More importantly,the combination of X-rayμ-CT and s-XRD techniques enables the investigation of the chemical reaction mechanisms at the two-phase interface.Therefore,these in-situ methods are essential for analyzing the chemical/electrochemical kinetics of high-temperature reaction processes and establishing the theoretical principles for the efficient and stable operation of chemical/electrochemical metallurgical processes.展开更多
A thorough understanding of the fundamental electrochemical and chemical processes in batteries is crucial to advancing energy density and power density.However,the characterizations of such processes are complex.In-s...A thorough understanding of the fundamental electrochemical and chemical processes in batteries is crucial to advancing energy density and power density.However,the characterizations of such processes are complex.In-situ electrochemical nuclear magnetic resonance(EC-NMR)offers the capability to collect real-time data during battery operation,furnishing insights into the local structures and ionic dynamics of materials by monitoring changes in the chemical environment around the nuclei.EC-NMR also has the advantages of being both quantitative and non-destructive.This paper systematically reviews the design of EC-NMR approach,and delves into the applications and progress of EC-NMR concerning battery reaction mechanisms,failure mechanisms,and overall battery systems.The review culminates in a comprehensive summary of the perspective and challenges associated with EC-NMR.展开更多
TiB2/Al-30Si composites were fabricated via in-situ melt reaction under high-energy ultrasonic field. The microstructure and wear properties of the composite were investigated by XRD, SEM and dry sliding testing. The ...TiB2/Al-30Si composites were fabricated via in-situ melt reaction under high-energy ultrasonic field. The microstructure and wear properties of the composite were investigated by XRD, SEM and dry sliding testing. The results indicate that TiB2 reinforcement particles are uniformly distributed in the aluminum matrix under high-energy ultrasonic field. The morphology of the TiB2 particles is in circle-shape or quadrangle-shape, and the size of the particles is 0.1-1.5μm. The primary silicon particles are in quadrangle-shape and the average size of them is about 10μm. Hardness values of the Al-30Si matrix alloy and the TiB2/Al-30Si composites considerably increase as the high energy ultrasonic power increases. In particular, the maximum hardness value of the in-situ composites is about 1.3 times as high as that of the matrix alloy when the ultrasonic power is 1.2 kW, reaching 412 MPa. Meanwhile, the wear resistance of the in-situ TiB2/Al-30Si composites prepared under high-energy ultrasonic field is obviously improved and is insensitive to the applied loads of the dry sliding testing.展开更多
Fabrication of Gd2O2S：Pr scintillation ceramics by 2Gd2O3.（Gd,Pr）2（SO4）3.mH2O precursor was made Gd2O3, Pr6O11 and H2SO4 as the starting materials pressureless reaction sintering was investigated. The by hydrothe...Fabrication of Gd2O2S：Pr scintillation ceramics by 2Gd2O3.（Gd,Pr）2（SO4）3.mH2O precursor was made Gd2O3, Pr6O11 and H2SO4 as the starting materials pressureless reaction sintering was investigated. The by hydrothermal reaction using commercially available Then single phase Gd2O2SO4：Pr powder was obtained by calcining the precursor at 750℃ for 2 h. The Gd2O2SO4：Pr powder compacts can be sintered to single phase Gd2O2S：Pr ceramics with a relative density of 99% and mean grain size of 30um at 1750℃ for 2 h in flowing hydrogen atmosphere. Densification and microstructural development of the Gd2O2S：Pr ceramics were examined. Luminescence spectra of the Gd2O2S：Pr ceramic under 309 nm UV excitation and X-ray excitation show a green emission at 511 nm as the most prominent peak, which corresponds to the ^3p0-3H4 transition of Pr^3＋ ions.展开更多
Transition metal compound(TMC)/carbon hybrids,as prospering electrocatalyst,have attracted great attention in the field of oxygen reduction reaction(ORR).Their morphology,structure and composition often play a crucial...Transition metal compound(TMC)/carbon hybrids,as prospering electrocatalyst,have attracted great attention in the field of oxygen reduction reaction(ORR).Their morphology,structure and composition often play a crucial role in determining the ORR performance.In this work,we for the first time report the successful fabrication of porous core-shell Fe_(1-x)S@N,S co-doped carbon(Fe_(1-x)S@NSC-t,t represents etching time)by a novel in-situ self-template induced strategy using Fe3O4 nanospheres and pyrrole as sacrificial self-template.The post-polymerization of pyrrole can be accomplished by the Fe^(3+)released through the etching of Fe_(3)O_(4) by HCl acid.Thus,the etching time has a significant effect on the morphology,structure,composition a nd ORR performance of Fe_(1-x)S@NSC-t.Based on the cha racterizations,we find Fe_(1-x)S@NSC-24 can realize effective and balanced combination of Fe_(1-x)S and NSC,possessing porous core-shell architecture,optimized structure defect,specific surface area and doped heteroatoms configurations(especially for pyridinic N,graphitic N and Fe-N structure).These features thus lead to outstanding catalytic activity and cycling stability towards ORR.Our work provides a good guidance on the design of TMC/carbon-based electrodes with unique stable morphology and optimized structure and composition.展开更多
Semiconductor photocatalysis, as a key part of solar energy utilization, has far-reaching implications for industrial, agricultural, and commercial development. Lack of understanding of the catalyst evolution and the ...Semiconductor photocatalysis, as a key part of solar energy utilization, has far-reaching implications for industrial, agricultural, and commercial development. Lack of understanding of the catalyst evolution and the reaction mechanism is a critical obstacle for designing efficient and stable photocatalysts. This review summarizes the recent progress of in-situ exploring the dynamic behavior of catalyst materials and reaction intermediates. Semiconductor photocatalytic processes and two major classes of in-situ techniques that include microscopic imaging and spectroscopic characterization are presented. Finally, problems and challenges in in-situ characterization are proposed, geared toward developing more advanced in-situ techniques and monitoring more accurate and realistic reaction processes, to guide designing advanced photocatalysts.展开更多
Copper azide with high density was successfully synthesized by in-situ reaction of nanoporous copper(NPC)precursor with HN_(3) gaseous.NPC with pore size of about 529 nm has been prepared by electroless plating using ...Copper azide with high density was successfully synthesized by in-situ reaction of nanoporous copper(NPC)precursor with HN_(3) gaseous.NPC with pore size of about 529 nm has been prepared by electroless plating using polystyrene(PS)as templates.The copper shells thickness of NPC was controlled by adjusting the PS loading amount.The effects of copper shell on the morphology,structure and density of copper azide were investigated.The conversion increased from 87.12%to 95.31%when copper shell thickness decrease from 100 to 50 nm.Meanwhile,the density of copper azide prepared by 529 nm NPC for 24 h was up to 2.38 g/cm^(3).The hollow structure of this NPC was filled by swelling of copper azide which guaranteed enough filling volume for keeping the same shape as well as improving the charge density.Moreover,HNS-IV explosive was successfully initiated by copper azide with minimum charge thickness of 0.55 mm,showing that copper azide prepared has excellent initiation performance,which has more advantages in the application of miniaturized explosive systems.展开更多
Electrocatalytic oxygen reduction reaction(ORR)is one of the most important reactions in electrochemical energy technologies such as fuel cells and metal–O2/air batteries,etc.However,the essential catalysts to overco...Electrocatalytic oxygen reduction reaction(ORR)is one of the most important reactions in electrochemical energy technologies such as fuel cells and metal–O2/air batteries,etc.However,the essential catalysts to overcome its slow reaction kinetic always undergo a complex dynamic evolution in the actual catalytic process,and the concomitant intermediates and catalytic products also occur continuous conversion and reconstruction.This makes them difficult to be accurately captured,making the identification of ORR active sites and the elucidation of ORR mechanisms difficult.Thus,it is necessary to use extensive in-situ characterization techniques to proceed the real-time monitoring of the catalyst structure and the evolution state of intermediates and products during ORR.This work reviews the major advances in the use of various in-situ techniques to characterize the catalytic processes of various catalysts.Specifically,the catalyst structure evolutions revealed directly by in-situ techniques are systematically summarized,such as phase,valence,electronic transfer,coordination,and spin states varies.In-situ revelation of intermediate adsorption/desorption behavior,and the real-time monitoring of the product nucleation,growth,and reconstruction evolution are equally emphasized in the discussion.Other interference factors,as well as in-situ signal assignment with the aid of theoretical calculations,are also covered.Finally,some major challenges and prospects of in-situ techniques for future catalysts research in the ORR process are proposed.展开更多
Reaction dynamics in gases at operating temperatures at the atomic level are the basis of heterogeneous gas-solid catalyst reactions and are crucial to the catalyst function.Supported noble metal nanocatalysts such as...Reaction dynamics in gases at operating temperatures at the atomic level are the basis of heterogeneous gas-solid catalyst reactions and are crucial to the catalyst function.Supported noble metal nanocatalysts such as platinum are of interest in fuel cells and as diesel oxidation catalysts for pollution control,and practical ruthenium nanocatalysts are explored for ammonia synthesis.Graphite and graphitic carbons are of interest as supports for the nanocatalysts.Despite considerable literature on the catalytic processes on graphite and graphitic supports,reaction dynamics of the nanocatalysts on the supports in different reactive gas environments and operating temperatures at the single atom level are not well understood.Here we present real time in-situ observations and analyses of reaction dynamics of Pt in oxidation,and practical Ru nanocatalysts in ammonia synthesis,on graphite and related supports under controlled reaction environments using a novel in-situ environmental(scanning) transmission electron microscope with single atom resolution.By recording snapshots of the reaction dynamics,the behaviour of the catalysts is imaged.The images reveal single metal atoms,clusters of a few atoms on the graphitic supports and the support function.These all play key roles in the mobility,sintering and growth of the catalysts.The experimental findings provide new structural insights into atomic scale reaction dynamics,morphology and stability of the nanocatalysts.展开更多
Field-assisted electrocatalytic reactions are demonstrated to be sufficient strategies in enhancing the electrocatalyst activities for oxygen evolution reaction(OER).Here,we report the in-situ magnetic field enhanced ...Field-assisted electrocatalytic reactions are demonstrated to be sufficient strategies in enhancing the electrocatalyst activities for oxygen evolution reaction(OER).Here,we report the in-situ magnetic field enhanced electrocatalytic activity in ferromagnetic FeCo_(2)O_(4)nanofibers.Our results demonstrate that the overpotential of FeCo_(2)O_(4)nanofibers at 10 mA cm^(-2)shows a left-shift of 40 mV for the OER by applying an external magnetic field,and no obvious change has been observed in the non-ferromagnetic-order Co3O4nanofibers.Calculation results indicate that there are more overlaps between the density of states for Co3d and O 2p by applying an external magnetic field.Accordingly,the spin hybridization of 3d-2p and the kinetics of spin charge transfer are optimized in ferromagnetic FeCo_(2)O_(4),which can promote the adsorption of oxygen-intermediates and electron transfer,significantly improving its electrocatalytic efficiency.What’s more,the maximum power density of the FeCo_(2)O_(4)nanofibers based Zn-air battery(ZAB)increases from 97.3 mW cm^(-2)to 108.2 mW cm^(-2)by applying an external magnetic field,providing a new idea for the application of magnetic cathode electrocatalysts in ZABs.展开更多
A novel method was used to fabricate AlN coating on graphite substrate. This approach included two steps： firstly, the emulsion composed of BN and anhydrous ethanol was sprayed on the surface of the graphite substrat...A novel method was used to fabricate AlN coating on graphite substrate. This approach included two steps： firstly, the emulsion composed of BN and anhydrous ethanol was sprayed on the surface of the graphite substrate; secondly, AlN coating was formed through the in-situ reaction of Al with the sprayed BN. The reaction was investigated by thermogravimetric-differential thermal analysis （TG-DTA）, and the phase composition in the synthetic process was characterized by X-ray diffraction （XRD）. Scanning electronic microscopy （SEM） was used to observe the morphology, and electron probe microanalysis （EPMA） was used to observe the distribution of the elements. The experimental results show that the AlN coating is dense and bonded with graphite tightly.展开更多
ZL202 matrix composite reinforced by Al2O3 particles was prepared by combining in-situ reaction and casting techniques. Particles' size in the composites was from 1 to 5 microns in diameter. X-ray diffraction anal...ZL202 matrix composite reinforced by Al2O3 particles was prepared by combining in-situ reaction and casting techniques. Particles' size in the composites was from 1 to 5 microns in diameter. X-ray diffraction analysis verified that the reinforcing particleswere δ-Al2O3 which belong to γ-Al2O3 series. The wetting angle between matrix andreinforcement was less than 90°. Energy spectrum analysis indicated that the reactionin bell cover pressing process took place not so completely as in flouring stir process. When the reaction was finished, the matrix was still ZL202 alloy in both.processes.展开更多
The(TiNbTaZrHf)C high entropy carbide(HEC)was successfully synthesized by complete commercial transition metal powders,obtained fine sintered bulks without additives by in-situ reaction element synthesis method.(TiNbT...The(TiNbTaZrHf)C high entropy carbide(HEC)was successfully synthesized by complete commercial transition metal powders,obtained fine sintered bulks without additives by in-situ reaction element synthesis method.(TiNbTaZrHf)C bulk shows a face centered cubic rock salt structure with homogeneous single-phase FCC structure in composition and structure.The optimum sintering temperature is about 1900℃at which the best mechanical properties are obtained.The mechanical properties of(TiNbTaZrHf)C ceramic block are better than those of binary transition metal carbides,and it has obvious high entropy effect.Adding a small amount of Al as sintering additive,the mechanical properties of(TiNbTaZrHf)C ceramics continue to improve,the bending strength of the samples at each temperature is increased by at least 38%,and the highest is 486 MPa.The elastic modulus and hardness of the sample at 1900℃are also slightly increased by 4%and 14%,respectively.The above conclusions illustrate that the properties of high entropy ceramics are greatly improved by in-situ reaction sintering.展开更多
TiAl3 particle reinforced pure Al composite has been made by direct reaction among molten Al, TiO2 and a flux. The composite exhibits high Synthetically properties. The strength and hardness are higher than those of p...TiAl3 particle reinforced pure Al composite has been made by direct reaction among molten Al, TiO2 and a flux. The composite exhibits high Synthetically properties. The strength and hardness are higher than those of pure Al matrix by 71.5% and 134% respectively However, the elongation is 20.36%, slightly lower than that of the Al matrix.展开更多
The electrochemical performance of lithium-ion batteries,i.e.specific capacity and cyclability,is primarily determined by chemical reversibility and structural stability of the electrodes in cycling.Here we have inves...The electrochemical performance of lithium-ion batteries,i.e.specific capacity and cyclability,is primarily determined by chemical reversibility and structural stability of the electrodes in cycling.Here we have investigated the fundamental reaction behaviors of nickel sulfide(NixSy)as lithium-ion battery anodes by in-situ TEM.We find that Ni_(3)S_(2)is the electrochemically stable phase,which appears in the first cycle of the NixSyanode.From the second cycle,conversion between Ni_(3)S_(2)and Li_(2)S/Ni is the dominant electrochemical reaction.In lithiation,the NixSynanoparticles evolve into a mixture of Ni nanocrystals embedded in Li_(2)S matrix,which form a porous structure upon full lithiation,and with the recrystallization of the Ni_(3)S_(2)phase in delithiation,a compact and interconnected network is built.Structural stability in cycles is susceptible to particle size and substrate restraint.Carbon substrate can certainly improve the tolerance for size-dependent pulverization of NixSynanoparticles.When NixSynanoparticle exceeds the critical size value,the morphology of the particle is no longer well maintained even under the constraints of the carbon substrate.This work deepens the understanding of electrochemical reaction behavior of conversiontype materials and helps to rational design of high-energy density battery anodes.展开更多
Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) throu...Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) through a mild sulfuration and/or selenylation process of Ni(OH)_(2) supported on carbon cloth(CC).Through careful in-situ Raman spectroscopy and ex-situ X-ray photoelectron spectroscopy,surface reconstruction of NiS_(2),NiSe_(2),and Se-NiS_(2) during the OER process has been revealed.A potentialdependent study shows that Se-NiS_(2) undergoes surface evolution at lower potentials and requires the lowest potential for conversion to NiOOH as a highly OER-active species,accompanied by the leaching of SO_(4)^(2-) and SeO_(4)^(2-) that can again be adsorbed on the catalyst surface to enhance the catalytic activity.Density functional theory(DFT) calculations confirm that Se-NiS_(2) is more susceptible to surface oxidation through the OER process.Therefore,Se-NiS_(2) exhibits outstanding OER activity and stability in alkaline conditions,requiring an overpotential of 343 mV at a current density of 50 mA cm^(-2).A novel insight is provided by our work in understanding the surface reconstruction and electrocatalytic mechanism of Ni-based chalcogenides.展开更多
基金support from National Natural Science Foundation of China(Grant Nos.22125903,22209174)the National Key R&D Program of China(Grants 2022YFA1504100)+2 种基金Dalian Innovation Support Plan for High Level Talents(2019RT09)Dalian National Laboratory For Clean Energy(DNL),CAS,DNL Cooperation Fund,CAS(DNL202016,DNL202019)DICP(DICP I2020032).
文摘Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key half-reaction of performance-limiting in water splitting.Given the complicated reaction process and surface reconstruction of the involved catalysts under actual working conditions,unraveling the real active sites,probing multiple reaction intermediates and clarifying catalytic pathways through in-situ characterization techniques and theoretical calculations are essential.In this review,we summarize the recent advancements in understanding the catalytic process,unlocking the water oxidation active phase and elucidating catalytic mechanism of water oxidation by various in-situ characterization techniques.Firstly,we introduce conventionally proposed traditional catalytic mechanisms and novel evolutionary mechanisms of OER,and highlight the significance of optimal catalytic pathways and intrinsic stability.Next,we provide a comprehensive overview of the fundamental working principles,different detection modes,applicable scenarios,and limitations associated with the in-situ characterization techniques.Further,we exemplified the in-situ studies and discussed phase transition detection,visualization of speciation evolution,electronic structure tracking,observation of reaction active intermediates,and monitoring of catalytic products,as well as establishing catalytic structure-activity relationships and catalytic mechanism.Finally,the key challenges and future perspectives for demystifying the water oxidation process are briefly proposed.
基金financially supported by the National Natural Science Foundation of China(Nos.U20A20235,52171127)Guangdong East Northwest New R&D Institution Construction(No.2019B090905009)+2 种基金Guangdong Aluminum Strip and Foil Processing Enterprise Research Institute(No.2014B090903012)Development and Electrochemical Performance of Magnesium Alloy Anode Material for Battery(No.2020GDASYL-20200103137)Qingyuan Science and Technology Plan Project(No.2021SJXM030)。
文摘NbC ceramic surface-reinforced steel matrix composites were prepared by an in-situ reaction method at different temperatures(1,050℃,1,100℃and 1,150℃)for different times(1 h,2 h and 3 h).The phase constitution,microstructure and fracture morphology of NbC ceramic surface-reinforced steel matrix composites were analyzed by XRD,SEM and EDS,and the effects of the in-situ reaction temperature and time on the mechanical properties were systematically studied.The results indicate that the NbC reinforcement layer is formed through the reaction between Nb atoms and carbon atoms diffused from the steel matrix to the Nb plate.The thickness of this reinforcement layer increases as the reaction time prolongs.Additionally,an increase in reaction temperature results in a thicker reinforcement layer,although the rate of increase gradually decreases.The relationship among the thickness of the Nb C reinforcement layer,the reaction time and temperature was established by data fitting.The optimal tensile performance is achieved at 1,100℃for 1 h,with a tensile strength of 228 MPa.It is also found that the defects between the reinforcement layer and the steel matrix are related to reaction temperature.At 1,100℃,these defects are minimal.Fracture mostly occurs in the NbC reinforced layer of the composites,and the fracture mode is characterized by typical intergranular brittle fracture.
基金the National Natural Science Foundation of China(Grant no.51973073)the Fel owship of China Postdoctoral Science Foundation(2021M701303)the analytical and testing assistance from the Analysis and Testing Center of HUST for support of this work
文摘Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic amine catalyst hamper its application in in-situ batteries.Herein,a nitrogen-containing eutectic solution is designed as both the catalyst of the thiol-ene reaction and the plasticizer to in-situ synthesize the gel polymer electrolytes,realizing a mild in-situ gelation process and the preparation of high-performance gel electrolytes.The obtained gel polymer electrolytes exhibit a high ionic conductivity of 4×10^(−4)S cm^(−1)and lithium-ion transference number(t_(Li)^(+))of 0.51 at 60°C.The as-assembled Li/LiFePO_(4)(LFP)cell delivers a high initial discharge capacity of 155.9 mAh g^(-1),and a favorable cycling stability with the capacity retention of 82%after 800 cycles at 1 C is also obtained.In addition,this eutectic solution significantly improves the rate performance of the LFP cell with high specific capacity of 141.5 and 126.8 mAh g^(-1)at 5 C and 10 C,respectively,and the cell can steadily work at various charge–discharge rate for 200 cycles.This powerful and efficient strategy may provide a novel way for in-situ preparing gel polymer electrolytes with desirable comprehensive performances.
基金financially supported by the National Natural Science Foundation of China(No.5217042069)the Young Elite Scientist Sponsorship Program by China Association for Science and Technology(CAST)(No.YESS20200103)the Fundamental Research Funds for the Central Universities(No.265QZ2022004)。
文摘Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.
基金financially supported by the National Key R&D Program of China(No.2022YFC2906100).
文摘For the rational manipulation of the production quality of high-temperature metallurgical engineering,there are many challenges in understanding the processes involved because of the black box chemical/electrochemical reactors.To overcome this issue,various in-situ characterization methods have been recently developed to analyze the interactions between the composition,microstructure,and solid-liquid interface of high-temperature electrochemical electrodes and molten salts.In this review,recent progress of in-situ hightemperature characterization techniques is discussed to summarize the advances in understanding the processes in metallurgical engineering.In-situ high-temperature technologies and analytical methods mainly include synchrotron X-ray diffraction(s-XRD),laser scanning confocal microscopy,and X-ray computed microtomography(X-rayμ-CT),which are important platforms for analyzing the structure and morphology of the electrodes to reveal the complexity and variability of their interfaces.In addition,laser-induced breakdown spectroscopy,high-temperature Raman spectroscopy,and ultraviolet-visible absorption spectroscopy provide microscale characterizations of the composition and structure of molten salts.More importantly,the combination of X-rayμ-CT and s-XRD techniques enables the investigation of the chemical reaction mechanisms at the two-phase interface.Therefore,these in-situ methods are essential for analyzing the chemical/electrochemical kinetics of high-temperature reaction processes and establishing the theoretical principles for the efficient and stable operation of chemical/electrochemical metallurgical processes.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences,Grant No:XDB0600300National Natural Science Foundation of China(22272175,22232005,21825202)+4 种基金National Key R&D Programof China(2022YFA1504002)“Scientist Studio Funding”from Tianmu Lake Institute of Advanced Energy Storage Technologies Co.,Ltd.,Dalian supports high-level talent innovation and entrepreneurship projects(2021RD14)Dalian Institute of Chemical Physics(DICP I202213)Magnetic Resonance Union of Chinese Academy of Sciences(MRU-CAS)(2022GZL001)21C Innovation Laboratory,Contemporary Amperex Technology Ltd by project No.21C-OP-202208.
文摘A thorough understanding of the fundamental electrochemical and chemical processes in batteries is crucial to advancing energy density and power density.However,the characterizations of such processes are complex.In-situ electrochemical nuclear magnetic resonance(EC-NMR)offers the capability to collect real-time data during battery operation,furnishing insights into the local structures and ionic dynamics of materials by monitoring changes in the chemical environment around the nuclei.EC-NMR also has the advantages of being both quantitative and non-destructive.This paper systematically reviews the design of EC-NMR approach,and delves into the applications and progress of EC-NMR concerning battery reaction mechanisms,failure mechanisms,and overall battery systems.The review culminates in a comprehensive summary of the perspective and challenges associated with EC-NMR.
基金Project(51174098)supported by the National Natural Science Foundation of ChinaProject(kjsmcx0903)supported by the Foundation of the Jiangsu Province Key Laboratory of Materials Tribology,China+2 种基金Project(1202015B)supported by the Postdoctoral Science Foundation of Jiangsu Province,ChinaProject(03)supported by the Undergraduate Practice-Innovation Training Foundation of Jiangsu University,ChinaProjects(GY2012020,GY2013032)supported by the Science and Technology Support Plan Project Foundation of Zhenjiang City,China
文摘TiB2/Al-30Si composites were fabricated via in-situ melt reaction under high-energy ultrasonic field. The microstructure and wear properties of the composite were investigated by XRD, SEM and dry sliding testing. The results indicate that TiB2 reinforcement particles are uniformly distributed in the aluminum matrix under high-energy ultrasonic field. The morphology of the TiB2 particles is in circle-shape or quadrangle-shape, and the size of the particles is 0.1-1.5μm. The primary silicon particles are in quadrangle-shape and the average size of them is about 10μm. Hardness values of the Al-30Si matrix alloy and the TiB2/Al-30Si composites considerably increase as the high energy ultrasonic power increases. In particular, the maximum hardness value of the in-situ composites is about 1.3 times as high as that of the matrix alloy when the ultrasonic power is 1.2 kW, reaching 412 MPa. Meanwhile, the wear resistance of the in-situ TiB2/Al-30Si composites prepared under high-energy ultrasonic field is obviously improved and is insensitive to the applied loads of the dry sliding testing.
基金supported by the National Natural Sci-ence Foundation of China (Grant. No. 50672014)the National Science Fund for Distinguished Young Scholars,China (Grant No. 50425413)
文摘Fabrication of Gd2O2S：Pr scintillation ceramics by 2Gd2O3.（Gd,Pr）2（SO4）3.mH2O precursor was made Gd2O3, Pr6O11 and H2SO4 as the starting materials pressureless reaction sintering was investigated. The by hydrothermal reaction using commercially available Then single phase Gd2O2SO4：Pr powder was obtained by calcining the precursor at 750℃ for 2 h. The Gd2O2SO4：Pr powder compacts can be sintered to single phase Gd2O2S：Pr ceramics with a relative density of 99% and mean grain size of 30um at 1750℃ for 2 h in flowing hydrogen atmosphere. Densification and microstructural development of the Gd2O2S：Pr ceramics were examined. Luminescence spectra of the Gd2O2S：Pr ceramic under 309 nm UV excitation and X-ray excitation show a green emission at 511 nm as the most prominent peak, which corresponds to the ^3p0-3H4 transition of Pr^3＋ ions.
基金financially supported by the National Natural Science Foundation of China(Nos.51804116,51772092,51972109)Hunan Provincial Natural Science Foundation of China(Nos.2018JJ3207,2017JJ2103,2019JJ40102,2019JJ50205,2018JJ2149)+1 种基金China Scholarship Councilthe Scientific Research Fund of Hunan Provincial Education Department,China(Nos.18B346,18A315,18B347,19A205)。
文摘Transition metal compound(TMC)/carbon hybrids,as prospering electrocatalyst,have attracted great attention in the field of oxygen reduction reaction(ORR).Their morphology,structure and composition often play a crucial role in determining the ORR performance.In this work,we for the first time report the successful fabrication of porous core-shell Fe_(1-x)S@N,S co-doped carbon(Fe_(1-x)S@NSC-t,t represents etching time)by a novel in-situ self-template induced strategy using Fe3O4 nanospheres and pyrrole as sacrificial self-template.The post-polymerization of pyrrole can be accomplished by the Fe^(3+)released through the etching of Fe_(3)O_(4) by HCl acid.Thus,the etching time has a significant effect on the morphology,structure,composition a nd ORR performance of Fe_(1-x)S@NSC-t.Based on the cha racterizations,we find Fe_(1-x)S@NSC-24 can realize effective and balanced combination of Fe_(1-x)S and NSC,possessing porous core-shell architecture,optimized structure defect,specific surface area and doped heteroatoms configurations(especially for pyridinic N,graphitic N and Fe-N structure).These features thus lead to outstanding catalytic activity and cycling stability towards ORR.Our work provides a good guidance on the design of TMC/carbon-based electrodes with unique stable morphology and optimized structure and composition.
基金supported by the National Science Foundation of China (21875137, 51521004, and 51420105009)Innovation Program of Shanghai Municipal Education Commission (Project No. 2019-01-07-00-02-E00069)+1 种基金the 111 Project (Project No. B16032)the fund from Center of Hydrogen Science and Joint Research Center for Clean Energy Materials at Shanghai Jiao Tong University for financial supports。
文摘Semiconductor photocatalysis, as a key part of solar energy utilization, has far-reaching implications for industrial, agricultural, and commercial development. Lack of understanding of the catalyst evolution and the reaction mechanism is a critical obstacle for designing efficient and stable photocatalysts. This review summarizes the recent progress of in-situ exploring the dynamic behavior of catalyst materials and reaction intermediates. Semiconductor photocatalytic processes and two major classes of in-situ techniques that include microscopic imaging and spectroscopic characterization are presented. Finally, problems and challenges in in-situ characterization are proposed, geared toward developing more advanced in-situ techniques and monitoring more accurate and realistic reaction processes, to guide designing advanced photocatalysts.
基金the financial support provided by the National Natural Science Foundation of China(No.11872013)。
文摘Copper azide with high density was successfully synthesized by in-situ reaction of nanoporous copper(NPC)precursor with HN_(3) gaseous.NPC with pore size of about 529 nm has been prepared by electroless plating using polystyrene(PS)as templates.The copper shells thickness of NPC was controlled by adjusting the PS loading amount.The effects of copper shell on the morphology,structure and density of copper azide were investigated.The conversion increased from 87.12%to 95.31%when copper shell thickness decrease from 100 to 50 nm.Meanwhile,the density of copper azide prepared by 529 nm NPC for 24 h was up to 2.38 g/cm^(3).The hollow structure of this NPC was filled by swelling of copper azide which guaranteed enough filling volume for keeping the same shape as well as improving the charge density.Moreover,HNS-IV explosive was successfully initiated by copper azide with minimum charge thickness of 0.55 mm,showing that copper azide prepared has excellent initiation performance,which has more advantages in the application of miniaturized explosive systems.
基金the National Natural Science Foundation of China(No.52072256)Shanxi Science and Technology Major Project(No.20201101016)+1 种基金Key R&D program of Shanxi Province(No.202102030201006)Research Project Supported by Shanxi Scholarship Council of China(HGKY2019031).
文摘Electrocatalytic oxygen reduction reaction(ORR)is one of the most important reactions in electrochemical energy technologies such as fuel cells and metal–O2/air batteries,etc.However,the essential catalysts to overcome its slow reaction kinetic always undergo a complex dynamic evolution in the actual catalytic process,and the concomitant intermediates and catalytic products also occur continuous conversion and reconstruction.This makes them difficult to be accurately captured,making the identification of ORR active sites and the elucidation of ORR mechanisms difficult.Thus,it is necessary to use extensive in-situ characterization techniques to proceed the real-time monitoring of the catalyst structure and the evolution state of intermediates and products during ORR.This work reviews the major advances in the use of various in-situ techniques to characterize the catalytic processes of various catalysts.Specifically,the catalyst structure evolutions revealed directly by in-situ techniques are systematically summarized,such as phase,valence,electronic transfer,coordination,and spin states varies.In-situ revelation of intermediate adsorption/desorption behavior,and the real-time monitoring of the product nucleation,growth,and reconstruction evolution are equally emphasized in the discussion.Other interference factors,as well as in-situ signal assignment with the aid of theoretical calculations,are also covered.Finally,some major challenges and prospects of in-situ techniques for future catalysts research in the ORR process are proposed.
基金the Engineering and Physical Science Research Council(EPSRC),U.K.for the award of a research grant EP/J0118058/1 and postdoctoral research assistantships(PDRAs) to M.R.W.and R.W.M.from the grant。
文摘Reaction dynamics in gases at operating temperatures at the atomic level are the basis of heterogeneous gas-solid catalyst reactions and are crucial to the catalyst function.Supported noble metal nanocatalysts such as platinum are of interest in fuel cells and as diesel oxidation catalysts for pollution control,and practical ruthenium nanocatalysts are explored for ammonia synthesis.Graphite and graphitic carbons are of interest as supports for the nanocatalysts.Despite considerable literature on the catalytic processes on graphite and graphitic supports,reaction dynamics of the nanocatalysts on the supports in different reactive gas environments and operating temperatures at the single atom level are not well understood.Here we present real time in-situ observations and analyses of reaction dynamics of Pt in oxidation,and practical Ru nanocatalysts in ammonia synthesis,on graphite and related supports under controlled reaction environments using a novel in-situ environmental(scanning) transmission electron microscope with single atom resolution.By recording snapshots of the reaction dynamics,the behaviour of the catalysts is imaged.The images reveal single metal atoms,clusters of a few atoms on the graphitic supports and the support function.These all play key roles in the mobility,sintering and growth of the catalysts.The experimental findings provide new structural insights into atomic scale reaction dynamics,morphology and stability of the nanocatalysts.
基金financially supported by the Natural Science Foundation(NSF) of China(91963201 and 12174163)the Creation of Science and Technology of Northwest Normal University,China(NWNU-LKQN2020-22)。
文摘Field-assisted electrocatalytic reactions are demonstrated to be sufficient strategies in enhancing the electrocatalyst activities for oxygen evolution reaction(OER).Here,we report the in-situ magnetic field enhanced electrocatalytic activity in ferromagnetic FeCo_(2)O_(4)nanofibers.Our results demonstrate that the overpotential of FeCo_(2)O_(4)nanofibers at 10 mA cm^(-2)shows a left-shift of 40 mV for the OER by applying an external magnetic field,and no obvious change has been observed in the non-ferromagnetic-order Co3O4nanofibers.Calculation results indicate that there are more overlaps between the density of states for Co3d and O 2p by applying an external magnetic field.Accordingly,the spin hybridization of 3d-2p and the kinetics of spin charge transfer are optimized in ferromagnetic FeCo_(2)O_(4),which can promote the adsorption of oxygen-intermediates and electron transfer,significantly improving its electrocatalytic efficiency.What’s more,the maximum power density of the FeCo_(2)O_(4)nanofibers based Zn-air battery(ZAB)increases from 97.3 mW cm^(-2)to 108.2 mW cm^(-2)by applying an external magnetic field,providing a new idea for the application of magnetic cathode electrocatalysts in ZABs.
基金the New Century Excellent Youth Fund(NCET-04-0722)
文摘A novel method was used to fabricate AlN coating on graphite substrate. This approach included two steps： firstly, the emulsion composed of BN and anhydrous ethanol was sprayed on the surface of the graphite substrate; secondly, AlN coating was formed through the in-situ reaction of Al with the sprayed BN. The reaction was investigated by thermogravimetric-differential thermal analysis （TG-DTA）, and the phase composition in the synthetic process was characterized by X-ray diffraction （XRD）. Scanning electronic microscopy （SEM） was used to observe the morphology, and electron probe microanalysis （EPMA） was used to observe the distribution of the elements. The experimental results show that the AlN coating is dense and bonded with graphite tightly.
文摘ZL202 matrix composite reinforced by Al2O3 particles was prepared by combining in-situ reaction and casting techniques. Particles' size in the composites was from 1 to 5 microns in diameter. X-ray diffraction analysis verified that the reinforcing particleswere δ-Al2O3 which belong to γ-Al2O3 series. The wetting angle between matrix andreinforcement was less than 90°. Energy spectrum analysis indicated that the reactionin bell cover pressing process took place not so completely as in flouring stir process. When the reaction was finished, the matrix was still ZL202 alloy in both.processes.
基金Funded by the National Natural Science Foundation of China(Nos.43190311,43200301,and 631800611)。
文摘The(TiNbTaZrHf)C high entropy carbide(HEC)was successfully synthesized by complete commercial transition metal powders,obtained fine sintered bulks without additives by in-situ reaction element synthesis method.(TiNbTaZrHf)C bulk shows a face centered cubic rock salt structure with homogeneous single-phase FCC structure in composition and structure.The optimum sintering temperature is about 1900℃at which the best mechanical properties are obtained.The mechanical properties of(TiNbTaZrHf)C ceramic block are better than those of binary transition metal carbides,and it has obvious high entropy effect.Adding a small amount of Al as sintering additive,the mechanical properties of(TiNbTaZrHf)C ceramics continue to improve,the bending strength of the samples at each temperature is increased by at least 38%,and the highest is 486 MPa.The elastic modulus and hardness of the sample at 1900℃are also slightly increased by 4%and 14%,respectively.The above conclusions illustrate that the properties of high entropy ceramics are greatly improved by in-situ reaction sintering.
文摘TiAl3 particle reinforced pure Al composite has been made by direct reaction among molten Al, TiO2 and a flux. The composite exhibits high Synthetically properties. The strength and hardness are higher than those of pure Al matrix by 71.5% and 134% respectively However, the elongation is 20.36%, slightly lower than that of the Al matrix.
基金the support by the National Natural Science Foundation of China(11972219 and 11902185)the support of Shanghai Sailing Program(19YF1415100)+2 种基金the Young Elite Scientist Sponsorship Program by CAST(2019QNRC001)the support of the National Natural Science Foundation of China(52090022)the Natural Science Foundation for Distinguished Young Scholars of Hebei Province(E2020203085)。
文摘The electrochemical performance of lithium-ion batteries,i.e.specific capacity and cyclability,is primarily determined by chemical reversibility and structural stability of the electrodes in cycling.Here we have investigated the fundamental reaction behaviors of nickel sulfide(NixSy)as lithium-ion battery anodes by in-situ TEM.We find that Ni_(3)S_(2)is the electrochemically stable phase,which appears in the first cycle of the NixSyanode.From the second cycle,conversion between Ni_(3)S_(2)and Li_(2)S/Ni is the dominant electrochemical reaction.In lithiation,the NixSynanoparticles evolve into a mixture of Ni nanocrystals embedded in Li_(2)S matrix,which form a porous structure upon full lithiation,and with the recrystallization of the Ni_(3)S_(2)phase in delithiation,a compact and interconnected network is built.Structural stability in cycles is susceptible to particle size and substrate restraint.Carbon substrate can certainly improve the tolerance for size-dependent pulverization of NixSynanoparticles.When NixSynanoparticle exceeds the critical size value,the morphology of the particle is no longer well maintained even under the constraints of the carbon substrate.This work deepens the understanding of electrochemical reaction behavior of conversiontype materials and helps to rational design of high-energy density battery anodes.
基金supported by the financial support from the National Natural Science Foundation of China (21871065, 22071038, 22209129)the Heilongjiang Touyan Team (HITTY20190033)the Interdisciplinary Research Foundation of HIT (IR2021205)。
文摘Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) through a mild sulfuration and/or selenylation process of Ni(OH)_(2) supported on carbon cloth(CC).Through careful in-situ Raman spectroscopy and ex-situ X-ray photoelectron spectroscopy,surface reconstruction of NiS_(2),NiSe_(2),and Se-NiS_(2) during the OER process has been revealed.A potentialdependent study shows that Se-NiS_(2) undergoes surface evolution at lower potentials and requires the lowest potential for conversion to NiOOH as a highly OER-active species,accompanied by the leaching of SO_(4)^(2-) and SeO_(4)^(2-) that can again be adsorbed on the catalyst surface to enhance the catalytic activity.Density functional theory(DFT) calculations confirm that Se-NiS_(2) is more susceptible to surface oxidation through the OER process.Therefore,Se-NiS_(2) exhibits outstanding OER activity and stability in alkaline conditions,requiring an overpotential of 343 mV at a current density of 50 mA cm^(-2).A novel insight is provided by our work in understanding the surface reconstruction and electrocatalytic mechanism of Ni-based chalcogenides.
