The synthetic path of a catalyst determines its morphology,species,and performance,and in-situ monitoring the catalyst formation process is fascinating and challenging.Herein,a newly developed synchrotron radiation sm...The synthetic path of a catalyst determines its morphology,species,and performance,and in-situ monitoring the catalyst formation process is fascinating and challenging.Herein,a newly developed synchrotron radiation smallangle X-ray scattering/X-ray diffraction/X-ray absorption fine structure(SAXS/XRD/XAFS)combined technique was used to in-situ monitor the isothermal-isobaric synthesis process of CO_(2)-assisted(BiO)_(2)CO_(3)(BOC)photocatalyst,and the atomic near-neighbor structure,crystalline structure and nanoscale particle size evolution with reaction time were simultaneously captured.The results show that both polyvinyl pyrrolidone and CO_(2)formed uniformly-distributed nano-sized scatterers in the Bi-based precursor solution,presenting short-range ordered structures to a certain extent.The as-prepared BOC catalytic particles underwent the evolution process of initial Bi(OH)3 precipitate,early-stage formed KBiO_(2)molecules,intermediate amorphous(BiO)4CO3(OH)2 nanoparticles,and finally crystallized flower-like BOC particles self-assembled by nanosheets.The flower-like BOC particles,Bi/BOC composite,and Bi nanospheres were further prepared with different synthesis paths.Flower-like BOC particles showed the best photocatalytic degradation performance of RhB.Scavenger experiment and theoretical calculation revealed the photocatalytic mechanisms of BOC.This work has implications for path-dependent synthesis of other catalysts.展开更多
The atmospheric corrosion behavior of bronze under thin electrolyte layer （TEL） with different thicknesses was monitored using cathodic polarization curves, open circuit potential （OCP） and electrochemical impedan...The atmospheric corrosion behavior of bronze under thin electrolyte layer （TEL） with different thicknesses was monitored using cathodic polarization curves, open circuit potential （OCP） and electrochemical impedance spectroscopy （EIS）. Cathodic polarization result indicates that the cathodic limiting current density increases with decreasing the TEL thickness. EIS result shows that the corrosion rate increases with decreasing the TEL thickness at the initial stage because the corrosion is dominated by the cathodic process, whereas after long immersion time, the corrosion degree with the TEL thickness is in the sequence of 150 μm 〉 310 μm〉 10μm ≈ bulk solution 〉 57 μm. The measurements of OCP and EIS present in-situ electrochemical corrosion information and their results are in good agreement with that of physical characterizations.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
Nowadays,in-situ/operando characterization becomes one of the most powerful as well as available means to monitor intricate reactions and investigate energy-storage mechanisms within advanced batteries.The new applica...Nowadays,in-situ/operando characterization becomes one of the most powerful as well as available means to monitor intricate reactions and investigate energy-storage mechanisms within advanced batteries.The new applications and novel devices constructed in recent years are necessary to be reviewed for inspiring subsequent studies.Hence,we summarize the progress of in-situ/operando techniques employed in rechargeable batteries.The members of this large family are divided into three sections for introduction,including bulk material,electrolyte/electrode interface and gas evolution.In each part,various energy-storage systems are mentioned and the related experimental details as well as data analysis are discussed.The simultaneous strategies of various in-situ methods are highlighted as well.Finally,current challenges and potential solutions are concluded towards the rising influence and enlarged appliance of in-situ/operando techniques in the battery research.展开更多
The catalytic conversion of CO_(2) to fuels or chemicals is considered to be an effective pathway to mitigate the greenhouse effect. To develop new types of efficient and durable catalysts, it is critical to identify ...The catalytic conversion of CO_(2) to fuels or chemicals is considered to be an effective pathway to mitigate the greenhouse effect. To develop new types of efficient and durable catalysts, it is critical to identify the catalytic active sites, surface intermediates, and reaction mechanisms to reveal the relationship between the active sites and catalytic performance. However, the structure of a heterogeneous catalyst usually dynamically changes during reaction, bringing a great challenge for the identification of catalytic active sites and reaction pathways. Therefore, in-situ/operando techniques have been employed to real-time monitor the dynamic evolution of the structure of active sites under actual reaction conditions to precisely build the structure–function relationship. Here, we review the recent progress in the application of various in-situ/operando techniques in identifying active sites for catalytic conversion of CO_(2) over heterogeneous catalysts. We systematically summarize the applications of various optical and X-ray spectroscopy techniques, including Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS), in identifying active sites and determining reaction mechanisms of the CO_(2) thermochemical conversion with hydrogen and light alkanes over heterogeneous catalysts. Finally, we discuss challenges and opportunities for the development of in-situ characterization in the future to further enlarge the capability of these powerful techniques.展开更多
LiMn_(0.5)Fe_(0.5)PO_(4) has attracted great interest due to its good electrochemical performance and higher operating voltages.This has led to a greater than 30 percent higher energy density than for commercial Li Fe...LiMn_(0.5)Fe_(0.5)PO_(4) has attracted great interest due to its good electrochemical performance and higher operating voltages.This has led to a greater than 30 percent higher energy density than for commercial Li Fe PO4 olivine cathodes.Understanding the phase transition behaviors and kinetics of this material will help researchers to design and develop next generation cathodes for Li-ion batteries.In this study,we investigated non-equilibrium phase transition behaviors in a LiMn_(0.5)Fe_(0.5)PO_(4) cathode material during charge–discharge processes by varying current rates(C-rates)using synchrotron in-situ X-ray techniques.These methods included wide angle X-ray scattering(in-situ WAXS)and X-ray absorption spectroscopy(in-situ XAS).The WAXS spectra indicate that the phase transition of LiMn_(0.5)Fe_(0.5)PO_(4) material at slow C-rates is induced by a two-phase reaction.In contrast,at a high C-rate(5 C),the formation of an intermediate phase upon discharge is clearly observed.Concurrently,the oxidation numbers of the redox reactions of Fe^(2+)/Fe^(3+)and Mn^(2+)/Mn^(3+)were evaluated using in-situ XAS.This combination of synchrotron in-situ X-ray techniques gives clear insights into the non-equilibrium phase transition behavior of a LiMn_(0.5)Fe_(0.5)PO_(4) cathode material.This new understanding will be useful for further developments of this highly promising cathode material for practical commercialization.展开更多
Reliable information of in--situ stress state is necessary for the design andconstruction of most important rock projects. As most rock projects are getting deeper and deeper,traditional techniques of in--situ stress ...Reliable information of in--situ stress state is necessary for the design andconstruction of most important rock projects. As most rock projects are getting deeper and deeper,traditional techniques of in--situ stress measurement are not very suitable. The current techniquesof in--situ stress measurement and their insufficiency for use at great depth are analyzed. Somebasic ideas of the development of new techniques and the improvement of current techniques for useat great depth are provided.展开更多
Synchrotron radiation based combined technique can provide multiple structural information simultaneously,which is an important development direction of structural detection.In this study,a novel small-angle X-ray sca...Synchrotron radiation based combined technique can provide multiple structural information simultaneously,which is an important development direction of structural detection.In this study,a novel small-angle X-ray scattering/X-ray diffraction/X-ray absorption fine structure(SAXS/XRD/XAFS)combined setup was constructed,where an area detector,a curved detector,and a point detector are,respectively,used for the measurements of SAXS,XRD,and XAFS signals.A detailed description about the combined setup was given.A minitype diamond detector coupled to a SAXS beamstop was used to record the transmitted X-ray intensity,making the scattering(SAXS and XRD)signal measurement compatible with the absorption(XAFS)signal measurement,avoiding mechanical switching.The two-way sampling strategy was used to acquire XAFS signals,shortening the non-counting time.The two-way and one-way sampling strategies were discussed.High-frequency sampling scheme was used to collect experimental signals,improving the measurement efficiency and signal-to-noise ratio.A detailed description and discussion about the high-frequency scheme were also given in this paper.Except the rotation of monochromator,there is no mechanical movement in measurements,time resolution may reach the level of seconds.Using this SAXS/XRD/XAFS combined setup,SAXS,XRD,and XAFS signals can be acquired simultaneously.With some in-situ sample environment system,the newlydeveloped combined technique can be used to track the structure evolution in complex fluids.During the formation processes of(BiO)2CO3 and ZnAPO-34 particles,the changes of in-situ experimental data with reaction time demonstrate that SAXS/XRD/XAFS combined technique is feasible to track the dynamic process.展开更多
Platinum-palladium nanoparticles are synthesized and characterized with regard to their application in fuel cells due to their high (electro) catalytic activity. Different preparation times are applied leading to diff...Platinum-palladium nanoparticles are synthesized and characterized with regard to their application in fuel cells due to their high (electro) catalytic activity. Different preparation times are applied leading to different structures, from Pd cubic to core-shell PtPd concave, and different chemical compositions. The resulting particles are studied via Transmission Electron Microscopy (TEM) and in-situ X-ray absorption fine structure (XAFS) measurements. The latter allows the investigation of the oxygen reduction reaction following the variations with varying applied potentials by analysis using the Iterative Transformation Factor Analysis (ITFA) and the creation of a two-component system that consists of metallic Pt-Pd and the related oxide. With the used model, the different concentrations of the oxide are linked to the consecutive chemical steps of the oxygen reduction reaction. Finally, the catalytic activity of the particles is determined via linear scanning voltammetry and reveals a dependence on the shape and the composition of the particles.展开更多
Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such...Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such as the traditional Haber-Bosch process,have drawbacks including high energy consumption and significant carbon dioxide emissions.In recent years,the electrocatalytic nitrate reduction reaction(NO_(3)RR)powered by intermittent renewable energy sources has gradually become a multidisciplinary research hotspot,as it allows for the efficient synthesis of NH_(3)under mild conditions.In this review,we focus on the research of electrocatalysts with atomic-level site,which have attracted attention due to their extremely high atomic utilization efficiency and unique structural characteristics in the field of NO_(3)RR.Firstly,we introduce the mechanism of nitrate reduction for ammonia synthesis and discuss the in-situ characterization techniques related to the mechanism study.Secondly,we review the progress of the electrocatalysts with atomic-level site for nitrate reduction and explore the structure-activity relationship to guide the rational design of efficient catalysts.Lastly,the conclusions of this review and the challenges and prospective of this promising field are presented.展开更多
In-situ stress is an essential parameter for design and construction of most engineering projects that involve excavation in rocks. Progress in in-situ stress measurement from the 1950s in China is briefly introduced....In-situ stress is an essential parameter for design and construction of most engineering projects that involve excavation in rocks. Progress in in-situ stress measurement from the 1950s in China is briefly introduced. Stress relief by overcoring technique and hydraulic fracturing： technique are the two main techniques for in-situ stress measurement in China at present. To make them suitable for application at great depth and to increase their measuring reliability and accuracy, a series of techniques have been developed. Applications and achievements of in-situ stress measurement in Chinese rock engineering, including mining, geotechnical and hydropower engineering, and earthquake prediction, are introduced. Suggestions for further development of in-situ stress measurement are also proposed.展开更多
In past decades,the performance of supercapacitors has been greatly improved by rationalizing the electrode materials at the nanoscale.However,there is still a lack of understanding on how the charges are efficiently ...In past decades,the performance of supercapacitors has been greatly improved by rationalizing the electrode materials at the nanoscale.However,there is still a lack of understanding on how the charges are efficiently stored in the electrodes or transported across the electrolyte/electrode interface.As it is very challenging to investigate the ion-involved physical and chemical processes with single experiment or computation,combining advanced analytic techniques with electrochemical measurements,i.e.,developing in-situ characterizations,have shown considerable prospect for the better understanding of behaviors of ions in electrodes for supercapacitors.Herein,we briefly review several typical in-situ techniques and the mechanisms these techniques reveal in charge storage mechanisms specifically in supercapacitors.Possible strategies for designing better electrode materials are also discussed.展开更多
Aluminium alloy AA2219 was reinforced with TiB2 particles introduced in-situ by the saltmetal reaction technique. The microstructural examinations of the composites clearly reveal the formation of TiB2 particles with ...Aluminium alloy AA2219 was reinforced with TiB2 particles introduced in-situ by the saltmetal reaction technique. The microstructural examinations of the composites clearly reveal the formation of TiB2 particles with a hexagonal morphology. The addition of TiB2 particles results in increased mechanical properties, such as 0.2%YS, UTS and hardness. The improvement in mechanical properties is correlated to the microstructure.展开更多
By means of the in-situ Fourier transformation infrared spectroscopy（FTIR）, the properties of BBr3/ benzene solution, which is usually used as the reactant and solution to synthesize BN by benzene-thermal method, ha...By means of the in-situ Fourier transformation infrared spectroscopy（FTIR）, the properties of BBr3/ benzene solution, which is usually used as the reactant and solution to synthesize BN by benzene-thermal method, have been investigated. The results show that there are some side reactions between BBr3 and benzene： （1） BBr3 as an electron-deficient molecule reacts with benzene at room temperature; （2） below 100℃, substitution of Br atom for H atom of benzene（ring-H） dominates in BBr3/benzene solution; （3） cracking of benzene ring occurs at a temperature above 100℃; （4） decomposition of benzene molecules and formation of long-chain aliphatic compounds feature the spectra of BBr3/benzene solution collected at above 160℃, They are unfavor for BN to form when BBr3 is excessive in the synthesis of BN by benzene-thermal route. On the basis of the experimental results, a coordination reaction mechanism via a η^2-C6H6 binding mode in BBr3/benzene solution is suggested.展开更多
Simultaneously realizing improved activity and stability of acidic oxygen evolution reaction(OER) electrocatalysts is highly promising for developing cost-effective sustainable energy in the splitting of water techniq...Simultaneously realizing improved activity and stability of acidic oxygen evolution reaction(OER) electrocatalysts is highly promising for developing cost-effective sustainable energy in the splitting of water technique.Herein,we report iridium nanocrystals embedded into 3D conductive clothes(Ir-NCT/CC) as a low iridium electrocatalyst realizing ultrahigh acidic OER activity and robust stability.The well-designed Ir-NCT/CC requires a low overpotential of 202 mV to reach the current density of 10 mA cm^(-2)with a high mass activity of 1754 A g^(-1).Importantly,in acidic overall water splitting,Ir-NCT/CC merely delivers a cell voltage of 1.469 V at a typical current density of 10 mA cm^(-2)and also maintains robust durability under continuous operation.We identify that a low working voltage drives the formation of a highly stable amorphous IrOxactive phase over the surface of Ir nanocrystals(surface heterojunction IrOx/Ir-NCT) during operating conditions,which contributes to an effective and durable OER process.展开更多
In cooling process of Fe-Cr-Al alloy oxidized at 1 300 ℃, the effect of cooling speed and exposure time on oxide spalled area fraction and successive variety of the spalled region were studied by investigating evolve...In cooling process of Fe-Cr-Al alloy oxidized at 1 300 ℃, the effect of cooling speed and exposure time on oxide spalled area fraction and successive variety of the spalled region were studied by investigating evolvement of the thermally grown oxide using in-situ CCD monitoring technique. The results showed that oxide spallation can be restrained by controlling cooling speed and the critical temperature drop of spallation initiation which is closely related to the oxide thickness or exposure time, and the spallation process of a little region may be described in more detail as two routes： from the oxide/substrate interface micro-decohesion, micro-buckles, buckle spreading, buckle crack to spallation and from the interface micro-decohesion, micro-buckles, buckle crack and spallation to the residual oxide decohesion and spallation.展开更多
The development and utilization of renewable clean energy can effectively solve the two major problems of energy and environment. As an efficient power generation device that converts hydrogen energy into electric ene...The development and utilization of renewable clean energy can effectively solve the two major problems of energy and environment. As an efficient power generation device that converts hydrogen energy into electric energy, fuel cell has attracted more and more attention. For fuel cells, the oxygen reduction reaction(ORR) at the cathode is the core reaction, and the design and development of high-performance ORR catalysts remain quite challenging. Since the microenvironment of the active center of single atom catalysts(SACs) has an important influence on its catalytic performance, it has been a research focus to improve the ORR activity and stability of electrocatalysts by adjusting the structure of the active center through reasonable structural regulation methods. In this review, we reviewed the preparation and structure–activity relationship of SACs for ORR. Then, the structural precision regulation methods for improving the activity and stability of ORR electrocatalysts are discussed. And the advanced in-situ characterization techniques for revealing the changes of active sites in the electrocatalytic ORR process are summarized. Finally, the challenges and future design directions of SACs for ORR are discussed. This work will provide important reference value for the design and synthesis of SACs with high activity and stability for ORR.展开更多
In this paper,the kaolin/urea intercalation composites prepared by direct intercalation method and the catalysis composites containing ZSM-5 molecular sieve synthesized based on the kaolin/urea intercalation composite...In this paper,the kaolin/urea intercalation composites prepared by direct intercalation method and the catalysis composites containing ZSM-5 molecular sieve synthesized based on the kaolin/urea intercalation composites by an in-situ crystallization technique were investigated.The effects of the intercalation ratios and de-intercalation rate and the amounts of added kaolin/urea intercalation composite on the synthesis of the catalysis composites containing the ZSM-5 molecular sieve were studied.The samples were characterized by X-ray diffraction,FT-IR,TG-DTA,N2 adsorption-desorption,and SEM,respectively.The results showed that the structure of the samples prepared by kaolin/urea intercalation composite was pure ZSM-5 molecular sieve.The crystallinity of ZSM-5 molecular sieve increased at first and then decreased with the increase of intercalation ratio of kaolin/urea intercalation composite.When the intercalation ratio was 62%,the crystallinity of ZSM-5 molecular sieve was lower.When the amount of added kaolin/urea intercalation composite with an intercalation ratio of 22%was 3%,the crystallinity of ZSM-5 zeolite was improved to reach 65%.Compared to the crystallization product formed without adding kaolin/urea intercalation composite,the crystallinity of ZSM-5 molecular sieve has increased by 54.8%.The catalytic composites containing ZSM-5 molecular sieve had better thermal stability with a wide pore structure,featuring a particle diameter of about 2.5μm,a BET specific surface area of 236 m^2/g,and a pore size of 10.6 nm.展开更多
基金supported by the National Natural Science Foundation of China(12305372)the National Key R&D Program(2017YFA0403001 and 2022YFA1603802)of China。
文摘The synthetic path of a catalyst determines its morphology,species,and performance,and in-situ monitoring the catalyst formation process is fascinating and challenging.Herein,a newly developed synchrotron radiation smallangle X-ray scattering/X-ray diffraction/X-ray absorption fine structure(SAXS/XRD/XAFS)combined technique was used to in-situ monitor the isothermal-isobaric synthesis process of CO_(2)-assisted(BiO)_(2)CO_(3)(BOC)photocatalyst,and the atomic near-neighbor structure,crystalline structure and nanoscale particle size evolution with reaction time were simultaneously captured.The results show that both polyvinyl pyrrolidone and CO_(2)formed uniformly-distributed nano-sized scatterers in the Bi-based precursor solution,presenting short-range ordered structures to a certain extent.The as-prepared BOC catalytic particles underwent the evolution process of initial Bi(OH)3 precipitate,early-stage formed KBiO_(2)molecules,intermediate amorphous(BiO)4CO3(OH)2 nanoparticles,and finally crystallized flower-like BOC particles self-assembled by nanosheets.The flower-like BOC particles,Bi/BOC composite,and Bi nanospheres were further prepared with different synthesis paths.Flower-like BOC particles showed the best photocatalytic degradation performance of RhB.Scavenger experiment and theoretical calculation revealed the photocatalytic mechanisms of BOC.This work has implications for path-dependent synthesis of other catalysts.
基金Projects (51131005, 51171172, 50801056) supported by the National Natural Science Foundation of ChinaProject (Y4110074) supported by Natural Science Foundation of Zhejiang Province, China
文摘The atmospheric corrosion behavior of bronze under thin electrolyte layer （TEL） with different thicknesses was monitored using cathodic polarization curves, open circuit potential （OCP） and electrochemical impedance spectroscopy （EIS）. Cathodic polarization result indicates that the cathodic limiting current density increases with decreasing the TEL thickness. EIS result shows that the corrosion rate increases with decreasing the TEL thickness at the initial stage because the corrosion is dominated by the cathodic process, whereas after long immersion time, the corrosion degree with the TEL thickness is in the sequence of 150 μm 〉 310 μm〉 10μm ≈ bulk solution 〉 57 μm. The measurements of OCP and EIS present in-situ electrochemical corrosion information and their results are in good agreement with that of physical characterizations.
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supported by the Natural Science Foundation of Jiangsu Province,China(BK20170630)the National Natural Science Foundation of China(51802149 and U1801251)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Nanjing University Technology Innovation Fund Project。
文摘Nowadays,in-situ/operando characterization becomes one of the most powerful as well as available means to monitor intricate reactions and investigate energy-storage mechanisms within advanced batteries.The new applications and novel devices constructed in recent years are necessary to be reviewed for inspiring subsequent studies.Hence,we summarize the progress of in-situ/operando techniques employed in rechargeable batteries.The members of this large family are divided into three sections for introduction,including bulk material,electrolyte/electrode interface and gas evolution.In each part,various energy-storage systems are mentioned and the related experimental details as well as data analysis are discussed.The simultaneous strategies of various in-situ methods are highlighted as well.Finally,current challenges and potential solutions are concluded towards the rising influence and enlarged appliance of in-situ/operando techniques in the battery research.
基金Authors acknowledge the financial support from the National Natural Science Foundation of China(NSFC)under Grant No.21978148 and 21808120.
文摘The catalytic conversion of CO_(2) to fuels or chemicals is considered to be an effective pathway to mitigate the greenhouse effect. To develop new types of efficient and durable catalysts, it is critical to identify the catalytic active sites, surface intermediates, and reaction mechanisms to reveal the relationship between the active sites and catalytic performance. However, the structure of a heterogeneous catalyst usually dynamically changes during reaction, bringing a great challenge for the identification of catalytic active sites and reaction pathways. Therefore, in-situ/operando techniques have been employed to real-time monitor the dynamic evolution of the structure of active sites under actual reaction conditions to precisely build the structure–function relationship. Here, we review the recent progress in the application of various in-situ/operando techniques in identifying active sites for catalytic conversion of CO_(2) over heterogeneous catalysts. We systematically summarize the applications of various optical and X-ray spectroscopy techniques, including Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS), in identifying active sites and determining reaction mechanisms of the CO_(2) thermochemical conversion with hydrogen and light alkanes over heterogeneous catalysts. Finally, we discuss challenges and opportunities for the development of in-situ characterization in the future to further enlarge the capability of these powerful techniques.
基金the Science Achievement Scholarship of Thailand(SAST)for financial supportpartially supported by the Institute of Nanomaterials Research and Innovation for Energy(IN-RIE)+1 种基金the Research and Graduate Studies,Khon Kaen University(KKU)Synchrotron Light Research Institute(SLRI),Thailand。
文摘LiMn_(0.5)Fe_(0.5)PO_(4) has attracted great interest due to its good electrochemical performance and higher operating voltages.This has led to a greater than 30 percent higher energy density than for commercial Li Fe PO4 olivine cathodes.Understanding the phase transition behaviors and kinetics of this material will help researchers to design and develop next generation cathodes for Li-ion batteries.In this study,we investigated non-equilibrium phase transition behaviors in a LiMn_(0.5)Fe_(0.5)PO_(4) cathode material during charge–discharge processes by varying current rates(C-rates)using synchrotron in-situ X-ray techniques.These methods included wide angle X-ray scattering(in-situ WAXS)and X-ray absorption spectroscopy(in-situ XAS).The WAXS spectra indicate that the phase transition of LiMn_(0.5)Fe_(0.5)PO_(4) material at slow C-rates is induced by a two-phase reaction.In contrast,at a high C-rate(5 C),the formation of an intermediate phase upon discharge is clearly observed.Concurrently,the oxidation numbers of the redox reactions of Fe^(2+)/Fe^(3+)and Mn^(2+)/Mn^(3+)were evaluated using in-situ XAS.This combination of synchrotron in-situ X-ray techniques gives clear insights into the non-equilibrium phase transition behavior of a LiMn_(0.5)Fe_(0.5)PO_(4) cathode material.This new understanding will be useful for further developments of this highly promising cathode material for practical commercialization.
文摘Reliable information of in--situ stress state is necessary for the design andconstruction of most important rock projects. As most rock projects are getting deeper and deeper,traditional techniques of in--situ stress measurement are not very suitable. The current techniquesof in--situ stress measurement and their insufficiency for use at great depth are analyzed. Somebasic ideas of the development of new techniques and the improvement of current techniques for useat great depth are provided.
基金This work was supported by the National Key Research and Development Program of China(Nos.2017YFA0403000 and 2017YFA0403100).
文摘Synchrotron radiation based combined technique can provide multiple structural information simultaneously,which is an important development direction of structural detection.In this study,a novel small-angle X-ray scattering/X-ray diffraction/X-ray absorption fine structure(SAXS/XRD/XAFS)combined setup was constructed,where an area detector,a curved detector,and a point detector are,respectively,used for the measurements of SAXS,XRD,and XAFS signals.A detailed description about the combined setup was given.A minitype diamond detector coupled to a SAXS beamstop was used to record the transmitted X-ray intensity,making the scattering(SAXS and XRD)signal measurement compatible with the absorption(XAFS)signal measurement,avoiding mechanical switching.The two-way sampling strategy was used to acquire XAFS signals,shortening the non-counting time.The two-way and one-way sampling strategies were discussed.High-frequency sampling scheme was used to collect experimental signals,improving the measurement efficiency and signal-to-noise ratio.A detailed description and discussion about the high-frequency scheme were also given in this paper.Except the rotation of monochromator,there is no mechanical movement in measurements,time resolution may reach the level of seconds.Using this SAXS/XRD/XAFS combined setup,SAXS,XRD,and XAFS signals can be acquired simultaneously.With some in-situ sample environment system,the newlydeveloped combined technique can be used to track the structure evolution in complex fluids.During the formation processes of(BiO)2CO3 and ZnAPO-34 particles,the changes of in-situ experimental data with reaction time demonstrate that SAXS/XRD/XAFS combined technique is feasible to track the dynamic process.
文摘Platinum-palladium nanoparticles are synthesized and characterized with regard to their application in fuel cells due to their high (electro) catalytic activity. Different preparation times are applied leading to different structures, from Pd cubic to core-shell PtPd concave, and different chemical compositions. The resulting particles are studied via Transmission Electron Microscopy (TEM) and in-situ X-ray absorption fine structure (XAFS) measurements. The latter allows the investigation of the oxygen reduction reaction following the variations with varying applied potentials by analysis using the Iterative Transformation Factor Analysis (ITFA) and the creation of a two-component system that consists of metallic Pt-Pd and the related oxide. With the used model, the different concentrations of the oxide are linked to the consecutive chemical steps of the oxygen reduction reaction. Finally, the catalytic activity of the particles is determined via linear scanning voltammetry and reveals a dependence on the shape and the composition of the particles.
基金financial support from the Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX24_0690)financial support from the National Natural Science Foundation of China (Project No. 22275088, 52101260)+4 种基金the Project of Shuangchuang Scholar of Jiangsu Province (Project No. JSSCBS20210212)the Fundamental Research Funds for the Central Universities (Project No. 30921011203)the Start-Up Grant (Project No. AE89991/340) from Nanjing University of Science and Technologyfinancial support from the Foundation of Jiangsu Educational Committee (22KJB310008)the Senior Talent Program of Jiangsu University (20JDG073)
文摘Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such as the traditional Haber-Bosch process,have drawbacks including high energy consumption and significant carbon dioxide emissions.In recent years,the electrocatalytic nitrate reduction reaction(NO_(3)RR)powered by intermittent renewable energy sources has gradually become a multidisciplinary research hotspot,as it allows for the efficient synthesis of NH_(3)under mild conditions.In this review,we focus on the research of electrocatalysts with atomic-level site,which have attracted attention due to their extremely high atomic utilization efficiency and unique structural characteristics in the field of NO_(3)RR.Firstly,we introduce the mechanism of nitrate reduction for ammonia synthesis and discuss the in-situ characterization techniques related to the mechanism study.Secondly,we review the progress of the electrocatalysts with atomic-level site for nitrate reduction and explore the structure-activity relationship to guide the rational design of efficient catalysts.Lastly,the conclusions of this review and the challenges and prospective of this promising field are presented.
文摘In-situ stress is an essential parameter for design and construction of most engineering projects that involve excavation in rocks. Progress in in-situ stress measurement from the 1950s in China is briefly introduced. Stress relief by overcoring technique and hydraulic fracturing： technique are the two main techniques for in-situ stress measurement in China at present. To make them suitable for application at great depth and to increase their measuring reliability and accuracy, a series of techniques have been developed. Applications and achievements of in-situ stress measurement in Chinese rock engineering, including mining, geotechnical and hydropower engineering, and earthquake prediction, are introduced. Suggestions for further development of in-situ stress measurement are also proposed.
基金supported by the National Natural Science Foundation of China(grant Nos.51322204 and 51772282)。
文摘In past decades,the performance of supercapacitors has been greatly improved by rationalizing the electrode materials at the nanoscale.However,there is still a lack of understanding on how the charges are efficiently stored in the electrodes or transported across the electrolyte/electrode interface.As it is very challenging to investigate the ion-involved physical and chemical processes with single experiment or computation,combining advanced analytic techniques with electrochemical measurements,i.e.,developing in-situ characterizations,have shown considerable prospect for the better understanding of behaviors of ions in electrodes for supercapacitors.Herein,we briefly review several typical in-situ techniques and the mechanisms these techniques reveal in charge storage mechanisms specifically in supercapacitors.Possible strategies for designing better electrode materials are also discussed.
文摘Aluminium alloy AA2219 was reinforced with TiB2 particles introduced in-situ by the saltmetal reaction technique. The microstructural examinations of the composites clearly reveal the formation of TiB2 particles with a hexagonal morphology. The addition of TiB2 particles results in increased mechanical properties, such as 0.2%YS, UTS and hardness. The improvement in mechanical properties is correlated to the microstructure.
基金Supported by the National Natural Science Foundation of China(No.50672048)the Program of Shandong Science & Technology Council,China(No.2006GG2202039)
文摘By means of the in-situ Fourier transformation infrared spectroscopy（FTIR）, the properties of BBr3/ benzene solution, which is usually used as the reactant and solution to synthesize BN by benzene-thermal method, have been investigated. The results show that there are some side reactions between BBr3 and benzene： （1） BBr3 as an electron-deficient molecule reacts with benzene at room temperature; （2） below 100℃, substitution of Br atom for H atom of benzene（ring-H） dominates in BBr3/benzene solution; （3） cracking of benzene ring occurs at a temperature above 100℃; （4） decomposition of benzene molecules and formation of long-chain aliphatic compounds feature the spectra of BBr3/benzene solution collected at above 160℃, They are unfavor for BN to form when BBr3 is excessive in the synthesis of BN by benzene-thermal route. On the basis of the experimental results, a coordination reaction mechanism via a η^2-C6H6 binding mode in BBr3/benzene solution is suggested.
基金supported by the National Natural Science Foundation of China(12205300 and 12135012)the Natural Science Foundation of Anhui Province(2208085QA28 and 2208085J01)。
文摘Simultaneously realizing improved activity and stability of acidic oxygen evolution reaction(OER) electrocatalysts is highly promising for developing cost-effective sustainable energy in the splitting of water technique.Herein,we report iridium nanocrystals embedded into 3D conductive clothes(Ir-NCT/CC) as a low iridium electrocatalyst realizing ultrahigh acidic OER activity and robust stability.The well-designed Ir-NCT/CC requires a low overpotential of 202 mV to reach the current density of 10 mA cm^(-2)with a high mass activity of 1754 A g^(-1).Importantly,in acidic overall water splitting,Ir-NCT/CC merely delivers a cell voltage of 1.469 V at a typical current density of 10 mA cm^(-2)and also maintains robust durability under continuous operation.We identify that a low working voltage drives the formation of a highly stable amorphous IrOxactive phase over the surface of Ir nanocrystals(surface heterojunction IrOx/Ir-NCT) during operating conditions,which contributes to an effective and durable OER process.
基金Item Sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars
文摘In cooling process of Fe-Cr-Al alloy oxidized at 1 300 ℃, the effect of cooling speed and exposure time on oxide spalled area fraction and successive variety of the spalled region were studied by investigating evolvement of the thermally grown oxide using in-situ CCD monitoring technique. The results showed that oxide spallation can be restrained by controlling cooling speed and the critical temperature drop of spallation initiation which is closely related to the oxide thickness or exposure time, and the spallation process of a little region may be described in more detail as two routes： from the oxide/substrate interface micro-decohesion, micro-buckles, buckle spreading, buckle crack to spallation and from the interface micro-decohesion, micro-buckles, buckle crack and spallation to the residual oxide decohesion and spallation.
基金supported by the National Natural Science Foundation of China(Grant No.22108306)the Taishan Scholars Program of Shandong Province(Grant No.tsqn201909065)the Shandong Provincial Natural Science Foundation(Grant Nos.ZR2021YQ15,ZR2020QB174)。
文摘The development and utilization of renewable clean energy can effectively solve the two major problems of energy and environment. As an efficient power generation device that converts hydrogen energy into electric energy, fuel cell has attracted more and more attention. For fuel cells, the oxygen reduction reaction(ORR) at the cathode is the core reaction, and the design and development of high-performance ORR catalysts remain quite challenging. Since the microenvironment of the active center of single atom catalysts(SACs) has an important influence on its catalytic performance, it has been a research focus to improve the ORR activity and stability of electrocatalysts by adjusting the structure of the active center through reasonable structural regulation methods. In this review, we reviewed the preparation and structure–activity relationship of SACs for ORR. Then, the structural precision regulation methods for improving the activity and stability of ORR electrocatalysts are discussed. And the advanced in-situ characterization techniques for revealing the changes of active sites in the electrocatalytic ORR process are summarized. Finally, the challenges and future design directions of SACs for ORR are discussed. This work will provide important reference value for the design and synthesis of SACs with high activity and stability for ORR.
基金This work was financially supported by the National Natural Science Foundation of China(No.21371055)the Key Project of Scientific Research Project of Hunan Education Department(No.18A313).
文摘In this paper,the kaolin/urea intercalation composites prepared by direct intercalation method and the catalysis composites containing ZSM-5 molecular sieve synthesized based on the kaolin/urea intercalation composites by an in-situ crystallization technique were investigated.The effects of the intercalation ratios and de-intercalation rate and the amounts of added kaolin/urea intercalation composite on the synthesis of the catalysis composites containing the ZSM-5 molecular sieve were studied.The samples were characterized by X-ray diffraction,FT-IR,TG-DTA,N2 adsorption-desorption,and SEM,respectively.The results showed that the structure of the samples prepared by kaolin/urea intercalation composite was pure ZSM-5 molecular sieve.The crystallinity of ZSM-5 molecular sieve increased at first and then decreased with the increase of intercalation ratio of kaolin/urea intercalation composite.When the intercalation ratio was 62%,the crystallinity of ZSM-5 molecular sieve was lower.When the amount of added kaolin/urea intercalation composite with an intercalation ratio of 22%was 3%,the crystallinity of ZSM-5 zeolite was improved to reach 65%.Compared to the crystallization product formed without adding kaolin/urea intercalation composite,the crystallinity of ZSM-5 molecular sieve has increased by 54.8%.The catalytic composites containing ZSM-5 molecular sieve had better thermal stability with a wide pore structure,featuring a particle diameter of about 2.5μm,a BET specific surface area of 236 m^2/g,and a pore size of 10.6 nm.
