The escalating global energy crisis,coupled with growing environmental concerns,has necessitated urgent advances in clean and efficient energy conversion technologies.Among the emerging approaches,electrocatalytic wat...The escalating global energy crisis,coupled with growing environmental concerns,has necessitated urgent advances in clean and efficient energy conversion technologies.Among the emerging approaches,electrocatalytic water splitting has garnered substantial interest as a carbonneutral strategy for hydrogen production,positioning hydrogen as a potential replacement for non-renewable fossil fuels[1].This process primarily involves two coupled half-reactions:the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER).In particular,the OER at the anode is hindered by intrinsically slow kinetics due to multi-electron transfer steps,electron-proton coupling,and adsorption/desorption processes.As a result,highly efficient electrocatalysts are required to reduce the overpotential.In this context,deciphering the actual catalytic sites and concomitant evolution of their electronic structure during OER under operando conditions have become a critical imperative.Such mechanistic insights establish structureproperty correlations that underpin the rational engineering of high-performance electrocatalysts.展开更多
The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur(Li/S)cells.A comprehensive understanding of the shuttle-related sulfur speciation and diffusi...The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur(Li/S)cells.A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue.Herein,we employed in situ/operando X-ray absorption spectroscopy(XAS)to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces,respectively,in a real-time condition.After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix(BSOC),we found the Li/S cell showed greatly improved sulfur utilization and longer life span.The operando S Kedge XAS results revealed that the BSOC modification was bi-functional:trapping polysulfides and catalyzing conversion of sulfur species simultaneously.We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection.Our results could offer potential stratagem for designing more advanced Li/S cells.展开更多
The lightweight,rechargeable lithium-ion battery is one of the dominant energy storage devices globally in portable electronics due to its high energy density,no memory effect,wide operating voltage,lightweight,and go...The lightweight,rechargeable lithium-ion battery is one of the dominant energy storage devices globally in portable electronics due to its high energy density,no memory effect,wide operating voltage,lightweight,and good charge efficiency.However,due to safety concerns,the depletion of lithium reserves,and the corresponding increase of cost,an alternative battery system becomes more and more desirable.To develop alternative battery systems with low cost and high material abundance,for example,sodium,magnesium,zinc,and calcium,it is important to understand the chemical and electronic structure of materials.Soft X-ray spectroscopy,for example,X-ray absorption spectroscopy(XAS),X-ray emission spectroscopy(XES),and resonant inelastic soft X-ray scattering(RIXS),is an element-specific technique with sensitivity to the local chemical environment and structural order of the element of interest.Modern soft X-ray systems enable operando experiments that can be applied to amorphous and crystalline samples,making it a powerful tool for studying the electronic and structural changes in electrode and electrolyte species.In this article,the application of in situ/operando(soft)X-ray spectroscopy in beyond lithium-ion batteries is reviewed to demonstrate how such spectroscopic characterizations could facilitate the interpretation of interfacial phenomena under in situ/operando condition and subsequent development of the beyond lithium-ion batteries.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 increasing demands of multifunctional organic electronics require advanced organic semiconducting materials to be developed and significant improvements to be made to device performance. Thus, it is necessary to g...The increasing demands of multifunctional organic electronics require advanced organic semiconducting materials to be developed and significant improvements to be made to device performance. Thus, it is necessary to gain an in-depth understanding of the film growth process, electronic states, and dynamic structure-property relationship under realistic operation conditions, which can be obtained by in-situ/operando characterization techniques for organic devices. Here, the up-todate developments in the in-situ/operando optical, scanning probe microscopy, and spectroscopy techniques that are employed for studies of film morphological evolution, crystal structures, semiconductor-electrolyte interface properties, and charge carrier dynamics are described and summarized. These advanced technologies leverage the traditional static characterizations into an in-situ and interactive manipulation of organic semiconducting films and devices without sacrificing the resolution, which facilitates the exploration of the intrinsic structure-property relationship of organic materials and the optimization of organic devices for advanced applications.展开更多
Catalysts can significantly promote the reaction dynamics and are therefore considered crucial components for achieving high electrochemical energy conversion efficiency.However,the active sites of the catalysts,parti...Catalysts can significantly promote the reaction dynamics and are therefore considered crucial components for achieving high electrochemical energy conversion efficiency.However,the active sites of the catalysts,particularly for nano-level and atomic-level catalysts commonly undergo reconstruction under practical applications.Therefore,obtaining an in-depth and systematic understanding on the real active sites through in situ/operando characterization techniques is a prerequisite for establishing the structureperformance relationship and guiding the future design of more efficient electrocatalysts.Herein,we summarize the recent progress of in situ/operando characterization techniques for identifying the nature of active sites of electrocatalysts when used in electrocatalytic energy conversion reaction.Specifically,our focus lies in the fundamental principles of various in situ/operando characterization techniques,with particular emphasis on their applications for electrocatalytic reactions.Beyond that,the challenges and perspective insights are also added in the final section to highlight the future direction of this important field.展开更多
Accelerating the redox conversion of lithium polysulfides(Li PSs)with electrocatalysts has been regarded as an effective avenue to surmount the shuttle effect and realize high-performance lithium-sulfur(Li-S)batteries...Accelerating the redox conversion of lithium polysulfides(Li PSs)with electrocatalysts has been regarded as an effective avenue to surmount the shuttle effect and realize high-performance lithium-sulfur(Li-S)batteries.However,the complicated reaction process,especially the real-time evolution of sulfur-containing species and electrocatalysts under working conditions,has brought great difficulties in the explicit understanding of reaction mechanism of Li-S batteries,thereby severely hampering the design of highly efficient electrocatalysts.Therefore,a crucial prerequisite for correctly identifying the reaction mechanism is an in-depth analysis of the dynamic evolution of reaction intermediates and their structure-performance relationships.In this review,we comprehensively summarized the most recent progress in the dynamic behaviors of Li PSs and electrocatalysts of Li-S batteries under working conditions in conjunction with closely related in-situ/operando characterizations to recognize the realtime evolution of phase,composition,and atomic/electronic structure,thereby unraveling the corresponding catalytic mechanism.In addition,the major challenges and unexplored issues of catalytic conversion of Li PSs were summarized and discussed,aiming to provide perspectives into the development of highly efficient electrocatalysts in Li-S chemistry.Based on this review,we believe that reasonable regulation of reconstruction behaviors can achieve satisfactory electrocatalysts with high catalytic activity,accelerating the development of green energy.展开更多
Optimizing the microchannel design of the next generation of chips requires an understanding of the in situ property evolution of the chip-based materials under fast cooling.This work overcomes the conventional relian...Optimizing the microchannel design of the next generation of chips requires an understanding of the in situ property evolution of the chip-based materials under fast cooling.This work overcomes the conventional reliance on reheating data of melt-quenched glasses by demonstrating direct observations of glass transition on cooling curves utilizing the most advanced fast differential scanning calorimetry.By leveraging an MEMS chip sensor that allows for rapid heat extraction from microgram-sized samples to a purged gas coolant,the device is able to reach ultra-fast cooling rates of up to 40,000 K·s^(−1).Four thermal regions are identified by examining the cooling behaviors of two metallic glasses.This is because the actual rate of the specimen can differ from the programmed rate,especially at high set rate when the actual rate decreases before the glass transition is completed.We define the operational window for reliable cooling curve analysis,build models with empirical and theoretical analyses to determine the maximum feasible cooling rate,and demonstrate how optimizing sample mass and environment temperature broaden this window.The method avoids deceptive structural relaxation effects verified by fictivetemperature analysis and permits the capture of full glass transition during cooling.展开更多
Aqueous zinc metal batteries(AZMBs)face significant challenges in achieving reversibility and cycling stability,primarily due to hydrogen evolution reactions(HER)and zinc dendrite growth.In this study,by employing car...Aqueous zinc metal batteries(AZMBs)face significant challenges in achieving reversibility and cycling stability,primarily due to hydrogen evolution reactions(HER)and zinc dendrite growth.In this study,by employing carefully designed cells that approximate the structural characteristics of practical batteries,we revisit this widely held view through in-operando X-ray radiography to examine zinc dendrite formation and HER under nearpractical operating conditions.While conventional understanding emphasizes the severity of these processes,our findings suggest that zinc dendrites and HER are noticeably less pronounced in dense,real-operation configurations compared to modified cells,possibly due to a more uniform electric field and the suppression of triple-phase boundaries.This study indicates that other components,such as degradation at the cathode current collector interface and configuration mismatches within the full cell,may also represent important barriers to the practical application of AZMBs,particularly during the early stages of electrodeposition.展开更多
Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-...Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-scale preparation of the“integrated”phosphorus-based precatalyst(FeP-NiP)on nickel foam(NF),which is in situ reconstructed into a highly active and corrosion-resistant(Fe)NiOOH phase for OER.The interaction between phosphate anions(PO_(x)^(y-))and iron ions(Fe^(3+))tunes the electronic structure of the catalytic phase to further enhance OER kinetics.The integrated FeP-NiP@NF electrode exhibits low overpotentials for OER in alkaline water/seawater,requiring only 275/289,320/336,and 349/358 mV to reach 0.1,0.5,and 1.0 A cm^(−2),respectively.The in situ reconstructed PO_(x)^(y-)anion electrostatically repels Cl−in seawater electrolytes,allowing stable operation for over 7 days at 1.0 A cm^(−2) in extreme electrolytes(1.0 M KOH+seawater and 6.0 M KOH+seawater),demonstrating industrial-level stability.This study overcomes the complex synthesis limitations of P-based materials through innovative material design,opening new avenues for electrochemical energy conversion.展开更多
Utilizing CO_(2)as a carbon feedstock for producing fuels and useful chemicals is attractive due to the advantages of being abundant,nontoxic,and economical.Electrochemical CO_(2)reduction(CO_(2)RR)provides an avenue ...Utilizing CO_(2)as a carbon feedstock for producing fuels and useful chemicals is attractive due to the advantages of being abundant,nontoxic,and economical.Electrochemical CO_(2)reduction(CO_(2)RR)provides an avenue to close the anthropogenic carbon cycle.However,the reaction process of multi-electronic products of CO_(2)RR is quite complex.It is hard to yield a target product with high selectivity,high current density,low overpotential,and good stability simultaneously.In recent years,in situ/operando characterization techniques have played important roles in the catalysis field via establishing the structure-reactivity/selectivity relationships of catalysts and thereby obtaining information about mechanisms.As a result,it is necessary to apply in situ/operando characterization technologies to clarify the reaction pathway of CO_(2)RR.In this mini-review,we discuss recent progress on the in situ/operando characterizations for electrochemical CO_(2)RR,including microscopies,infrared spectroscopy,Raman spectroscopy,X-ray photoelectron spectroscopy,and X-ray absorption fine spectroscopy.Moreover,the capabilities of these in situ/operando characterizations and the remaining challenges are also discussed.展开更多
The key to achieving the breakthrough of hydrogen energy from marginal energy sources in large scale applications lies in the development and design of efficient electrocatalysts for the electrochemical oxidation and ...The key to achieving the breakthrough of hydrogen energy from marginal energy sources in large scale applications lies in the development and design of efficient electrocatalysts for the electrochemical oxidation and reduction of water.The unique heterostructure endows the catalyst with a mass of functional interfaces that are decisive for the enhancement of catalyst activity,stability,and reaction kinetics.Although some cutting-edge reviews have focused on the synthesis strategies,constitution,and applications of heterostructure catalysts,the field still lacks a detailed discussion of the actual reaction processes occurring at the interface,which is detrimental to the understanding of the true catalytic mechanism.Relying on advanced in situ/operando characterization techniques to understand the working mechanism of heterostructure catalysts is essential for rational design of advanced catalysts.In this review,we first present the advantages of heterostructure catalysts applied to electrolyzing water.Subsequently,the application of in situ/operando techniques in probing three aspects of heterostructure catalyst surface reconstruction,reaction mechanism,and the role of each component is highlighted with classical case studies.Finally,the current challenges and prospects for the design of heterostructure electrocatalysts are discussed in detail.展开更多
Catalysis research has witnessed remarkable progress with the advent of in situ and operando techniques.These methods enable the study of catalysts under actual operating conditions,providing unprecedented insights in...Catalysis research has witnessed remarkable progress with the advent of in situ and operando techniques.These methods enable the study of catalysts under actual operating conditions,providing unprecedented insights into catalytic mechanisms and dynamic catalyst behavior.This review discusses key in situ techniques and their applications in catalysis research.Advances in in situ electron microscopy allow direct visualization of catalysts at the atomic scale under reaction conditions.In situ spectroscopy techniques like X-ray absorption spectroscopy and nuclear magnetic resonance spectroscopy can track chemical states and reveal transient intermediates.Synchrotron-based techniques offer enhanced capabilities for in situ studies.The integration of in situ methods with machine learning and computational modeling provides a powerful approach to accelerate catalyst optimization.However,challenges remain regarding radiation damage,instrumentation limitations,and data interpretation.Overall,continued development of multi-modal in situ techniques is pivotal for addressing emerging challenges and opportunities in catalysis research and technology.展开更多
In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for met...In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for methanol synthesis. In this work, the catalyst, whose activity increases with the reaction temperature and pressure, was studied at calcined, reduced, and reacted conditions. TEM and EDX images for the calcined and reduced catalysts showed that copper was distributed uniformly at both conditions. TPR profile revealed two reduction peaks at 165 and 195 °C for copper species in the calcined catalyst. QXAFS results demonstrated that the calcined form consisted mainly of a mixed Cu O and Zn O, and it was progressively transformed into Cu metal particles and dispersed Zn O species as the reduction treatment. It was demonstrated that activation of the catalyst precursor occurred via a Cu^+intermediate, and the active catalyst predominantly consisted of metallic Cu and Zn O evenunder higher pressures. Structure of the active catalyst did not change with the temperature or pressure, indicating that the role of the Zn was mainly to improve Cu dispersion.This indicates the potential of QXAFS method in studying the structure evolutions of catalysts in methanol synthesis.展开更多
In situ and operando infrared spectroscopies are powerful techniques to support the design of novel materials for batteries and the development of new battery systems.These techniques can support the study of batterie...In situ and operando infrared spectroscopies are powerful techniques to support the design of novel materials for batteries and the development of new battery systems.These techniques can support the study of batteries by identifying the formation of new species and monitoring electrochemical energy stability.However,few works have employed these techniques,which can be used to investigate various materials,including systems beyond lithium-ion technology,in the research of batteries.Therefore,this review presents a comprehensive overview focusing on the main contributions of in situ and operando infrared spectroscopy for lithium-ion batteries(LIBs)and other battery systems.These techniques can successfully identify the formation of species during the electrolyte reduction,electrode degradation,and the formation of the solid-electrolyte interphase(SEI)layer.From these outcomes,it is possible to conclude that this characterization approach should be employed as a protocol to overcome remaining issues in batteries,consequently supporting battery research.This review aims to be a guide on how infrared spectroscopy can contribute to monitoring battery systems and to lead researchers interested in applying this technique.展开更多
Electrochemical water splitting has attracted considerable attention for the production of hydrogen fuel by using renewable energy resources.However,the sluggish reaction kinetics make it essential to explore precious...Electrochemical water splitting has attracted considerable attention for the production of hydrogen fuel by using renewable energy resources.However,the sluggish reaction kinetics make it essential to explore precious-metal-free electrocatalysts with superior activity and long-term stability.Tremendous efforts have been made in exploring electrocatalysts to reduce the energy barriers and improve catalytic efficiency.This review summarizes different categories of precious-metal-free electrocatalysts developed in the past 5 years for alkaline water splitting.The design strategies for optimizing the electronic and geometric structures of electrocatalysts with enhanced catalytic performance are discussed,including composition modulation,defect engineering,and structural engineering.Particularly,the advancement of operando/in situ characterization techniques toward the understanding of structural evolution,reaction intermediates,and active sites during the water splitting process are summarized.Finally,current challenges and future perspectives toward achieving efficient catalyst systems for industrial applications are proposed.This review will provide insights and strategies to the design of precious-metalfree electrocatalysts and inspire future research in alkaline water splitting.展开更多
In this work,silicon-carbon hybrid materials were adopted as an example to illustrate the novel strategy to in situ construct heterostructure with adjustable microstructure.Based on the temperature-dependent thermodyn...In this work,silicon-carbon hybrid materials were adopted as an example to illustrate the novel strategy to in situ construct heterostructure with adjustable microstructure.Based on the temperature-dependent thermodynamics and kinetics of reaction between Si and C,the processes for Si nanocrystals growth and C decoration were coupled at different zones of plasma flame according to its temperature and velocity fields by theoretical modeling,aiming to intentionally suppress the formation of undesirable carbide,and enable adjusting the microstructure of each counterpart separately in transient process.As a result,well-controlled Si/C nanocomposites,including nanospheres and nanowires with core-shell structures,were achieved,and this continuous and in-flight route is also potential for large-scale production.Further investigation on the electrochemical properties highlights the advantage of as proposed strategy to efficiently construct heterostructures with superior performance for various applications.展开更多
The clinical application of tumor vaccines is hindered by challenges such as timeconsuming and costly production processes.In this context,in situ cancer vaccines represent a promising strategy by leveraging endogenou...The clinical application of tumor vaccines is hindered by challenges such as timeconsuming and costly production processes.In this context,in situ cancer vaccines represent a promising strategy by leveraging endogenous tumor antigens to elicit robust antitumor T cell responses.Herein,a photoactivatable tumor-targeting in situ nanovaccine,Lipo-D8-6,was constructed using cRGD-functionalized liposomes that co-encapsulated the photosensitizer chlorin e6 and a cleavable immunoadjuvant conjugate D8,allowing light-triggered synchronous activation of three therapeutic modules.Upon near-infrared light irradiation,Lipo-D8-6 generates reactive oxygen species that exert direct cytotoxicity on tumor cells and induce immunogenic cell death,while concurrently cleaving the responsive linker within D8 to achieve the controlled release of R848.In vivo biodistribution analysis confirmed the superior intratumoral accumulation of Lipo-D8-6,facilitating precise treatment.In a large-volume tumor model,the nanovaccine exhibited pronounced antitumor efficacy,accompanied by enhanced tumor infiltration of CD8t T cells.Overall,this work provides a simplified and effective approach for developing in situ nanovaccines that enable synergistic photodynamic immunotherapy with precise spatiotemporal control over immune activation.展开更多
The global demand for effective skin injury treatments has prompted the exploration of tissue engineering solutions.While three-dimensional(3D)bioprinting has shown promise,challenges persist with respect to achieving...The global demand for effective skin injury treatments has prompted the exploration of tissue engineering solutions.While three-dimensional(3D)bioprinting has shown promise,challenges persist with respect to achieving timely and compatible solutions to treat diverse skin injuries.In situ bioprinting has emerged as a key new technology,since it reduces risks during the implantation of printed scaffolds and demonstrates superior therapeutic effects.However,maintaining printing fidelity during in situ bioprinting remains a critical challenge,particularly with respect to model layering and path planning.This study proposes a novel optimization-based conformal path planning strategy for in situ bioprinting-based repair of complex skin injuries.This strategy employs constrained optimization to identify optimal waypoints on a point cloud-approximated curved surface,thereby ensuring a high degree of similarity between predesigned planar and surface-mapped 3D paths.Furthermore,this method is applicable for skin wound treatments,since it generates 3D-equidistant zigzag curves along surface tangents and enables multi-layer conformal path planning to facilitate the treatment of volumetric injuries.Furthermore,the proposed algorithm was found to be a feasible and effective treatment in a murine back injury model as well as in other complex models,thereby showcasing its potential to guide in situ bioprinting,enhance bioprinting fidelity,and facilitate improvement of clinical outcomes.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22368020)the Research Foundation for Talented Scholars of Hainan University,China(No.RZ2300002666).
文摘The escalating global energy crisis,coupled with growing environmental concerns,has necessitated urgent advances in clean and efficient energy conversion technologies.Among the emerging approaches,electrocatalytic water splitting has garnered substantial interest as a carbonneutral strategy for hydrogen production,positioning hydrogen as a potential replacement for non-renewable fossil fuels[1].This process primarily involves two coupled half-reactions:the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER).In particular,the OER at the anode is hindered by intrinsically slow kinetics due to multi-electron transfer steps,electron-proton coupling,and adsorption/desorption processes.As a result,highly efficient electrocatalysts are required to reduce the overpotential.In this context,deciphering the actual catalytic sites and concomitant evolution of their electronic structure during OER under operando conditions have become a critical imperative.Such mechanistic insights establish structureproperty correlations that underpin the rational engineering of high-performance electrocatalysts.
基金financially supported by the National Key R&D Program of China(2016YFB0100100)the National Natural Science Foundation of China(Nos.21433013,U1832218)the support from China Scholarship Council
文摘The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur(Li/S)cells.A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue.Herein,we employed in situ/operando X-ray absorption spectroscopy(XAS)to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces,respectively,in a real-time condition.After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix(BSOC),we found the Li/S cell showed greatly improved sulfur utilization and longer life span.The operando S Kedge XAS results revealed that the BSOC modification was bi-functional:trapping polysulfides and catalyzing conversion of sulfur species simultaneously.We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection.Our results could offer potential stratagem for designing more advanced Li/S cells.
基金supported as part of the Joint Center for Energy Storage Research(JCESR)an Energy Innovation Hub funded by the U.S.Department of Energy(DOE),Office of Science,Basic Energy Sciences
文摘The lightweight,rechargeable lithium-ion battery is one of the dominant energy storage devices globally in portable electronics due to its high energy density,no memory effect,wide operating voltage,lightweight,and good charge efficiency.However,due to safety concerns,the depletion of lithium reserves,and the corresponding increase of cost,an alternative battery system becomes more and more desirable.To develop alternative battery systems with low cost and high material abundance,for example,sodium,magnesium,zinc,and calcium,it is important to understand the chemical and electronic structure of materials.Soft X-ray spectroscopy,for example,X-ray absorption spectroscopy(XAS),X-ray emission spectroscopy(XES),and resonant inelastic soft X-ray scattering(RIXS),is an element-specific technique with sensitivity to the local chemical environment and structural order of the element of interest.Modern soft X-ray systems enable operando experiments that can be applied to amorphous and crystalline samples,making it a powerful tool for studying the electronic and structural changes in electrode and electrolyte species.In this article,the application of in situ/operando(soft)X-ray spectroscopy in beyond lithium-ion batteries is reviewed to demonstrate how such spectroscopic characterizations could facilitate the interpretation of interfacial phenomena under in situ/operando condition and subsequent development of the beyond lithium-ion batteries.
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support from Natural Science Foundation of Jiangsu Province (grant number BK20211507)National Natural Science Foundation of China (grant number 61774080)the start-up funds from Changzhou University。
文摘The increasing demands of multifunctional organic electronics require advanced organic semiconducting materials to be developed and significant improvements to be made to device performance. Thus, it is necessary to gain an in-depth understanding of the film growth process, electronic states, and dynamic structure-property relationship under realistic operation conditions, which can be obtained by in-situ/operando characterization techniques for organic devices. Here, the up-todate developments in the in-situ/operando optical, scanning probe microscopy, and spectroscopy techniques that are employed for studies of film morphological evolution, crystal structures, semiconductor-electrolyte interface properties, and charge carrier dynamics are described and summarized. These advanced technologies leverage the traditional static characterizations into an in-situ and interactive manipulation of organic semiconducting films and devices without sacrificing the resolution, which facilitates the exploration of the intrinsic structure-property relationship of organic materials and the optimization of organic devices for advanced applications.
基金financed by the National Natural Science Foundation of China(No.22202169)Xuzhou Science and Technology Plan Project of China(No.KC21294)。
文摘Catalysts can significantly promote the reaction dynamics and are therefore considered crucial components for achieving high electrochemical energy conversion efficiency.However,the active sites of the catalysts,particularly for nano-level and atomic-level catalysts commonly undergo reconstruction under practical applications.Therefore,obtaining an in-depth and systematic understanding on the real active sites through in situ/operando characterization techniques is a prerequisite for establishing the structureperformance relationship and guiding the future design of more efficient electrocatalysts.Herein,we summarize the recent progress of in situ/operando characterization techniques for identifying the nature of active sites of electrocatalysts when used in electrocatalytic energy conversion reaction.Specifically,our focus lies in the fundamental principles of various in situ/operando characterization techniques,with particular emphasis on their applications for electrocatalytic reactions.Beyond that,the challenges and perspective insights are also added in the final section to highlight the future direction of this important field.
基金supported by the National Natural Science Foundation of China(22309019,12275189,22472111,and 11832007)the Natural Science Foundation of Sichuan Province(2023NSFSC1130)+1 种基金the Sichuan Province Support Tianfu Distinguished Scientist Program(126608533369)the Suzhou Science and Technology Project Prospective Application Research Program(SYG202109)。
文摘Accelerating the redox conversion of lithium polysulfides(Li PSs)with electrocatalysts has been regarded as an effective avenue to surmount the shuttle effect and realize high-performance lithium-sulfur(Li-S)batteries.However,the complicated reaction process,especially the real-time evolution of sulfur-containing species and electrocatalysts under working conditions,has brought great difficulties in the explicit understanding of reaction mechanism of Li-S batteries,thereby severely hampering the design of highly efficient electrocatalysts.Therefore,a crucial prerequisite for correctly identifying the reaction mechanism is an in-depth analysis of the dynamic evolution of reaction intermediates and their structure-performance relationships.In this review,we comprehensively summarized the most recent progress in the dynamic behaviors of Li PSs and electrocatalysts of Li-S batteries under working conditions in conjunction with closely related in-situ/operando characterizations to recognize the realtime evolution of phase,composition,and atomic/electronic structure,thereby unraveling the corresponding catalytic mechanism.In addition,the major challenges and unexplored issues of catalytic conversion of Li PSs were summarized and discussed,aiming to provide perspectives into the development of highly efficient electrocatalysts in Li-S chemistry.Based on this review,we believe that reasonable regulation of reconstruction behaviors can achieve satisfactory electrocatalysts with high catalytic activity,accelerating the development of green energy.
基金supported by the National Natural Science Foundation of China (Grant Nos.92580120 and 52471188)。
文摘Optimizing the microchannel design of the next generation of chips requires an understanding of the in situ property evolution of the chip-based materials under fast cooling.This work overcomes the conventional reliance on reheating data of melt-quenched glasses by demonstrating direct observations of glass transition on cooling curves utilizing the most advanced fast differential scanning calorimetry.By leveraging an MEMS chip sensor that allows for rapid heat extraction from microgram-sized samples to a purged gas coolant,the device is able to reach ultra-fast cooling rates of up to 40,000 K·s^(−1).Four thermal regions are identified by examining the cooling behaviors of two metallic glasses.This is because the actual rate of the specimen can differ from the programmed rate,especially at high set rate when the actual rate decreases before the glass transition is completed.We define the operational window for reliable cooling curve analysis,build models with empirical and theoretical analyses to determine the maximum feasible cooling rate,and demonstrate how optimizing sample mass and environment temperature broaden this window.The method avoids deceptive structural relaxation effects verified by fictivetemperature analysis and permits the capture of full glass transition during cooling.
基金the fundamental Research Funds for the central Universities(x2wjD2240360)for the funding supportMeanwhile,Engineering and Physical Sciences Research Council(EPSRC,EP/V027433/3)+2 种基金UK Research and Innovation(UKRI)under the UK government’s Horizon Europe funding(101077226,EP/Y008707/1)Faraday Institution(EP/S003053/1)Degradation project(FIRG001),Royal Society(IEC\NSFC\233361),QUB Agility Fund and Wright Technology and Research Centre(W-Tech,R5240MEE)Funding from UK aid from the UK Government through the Faraday Institution and the Transforming Energy Access Programme(Grant number FIRG050-Device engineering of Zn-based hybrid micro-flow batteries and by-product H2 collection for Emerging Economies)。
文摘Aqueous zinc metal batteries(AZMBs)face significant challenges in achieving reversibility and cycling stability,primarily due to hydrogen evolution reactions(HER)and zinc dendrite growth.In this study,by employing carefully designed cells that approximate the structural characteristics of practical batteries,we revisit this widely held view through in-operando X-ray radiography to examine zinc dendrite formation and HER under nearpractical operating conditions.While conventional understanding emphasizes the severity of these processes,our findings suggest that zinc dendrites and HER are noticeably less pronounced in dense,real-operation configurations compared to modified cells,possibly due to a more uniform electric field and the suppression of triple-phase boundaries.This study indicates that other components,such as degradation at the cathode current collector interface and configuration mismatches within the full cell,may also represent important barriers to the practical application of AZMBs,particularly during the early stages of electrodeposition.
基金funding support from Natural Science Foundation of Shanghai(Grant No.23ZR1443900)the National Natural Science Foundation of China(Grant Nos.22178309,22476131 and 22176127)。
文摘Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-scale preparation of the“integrated”phosphorus-based precatalyst(FeP-NiP)on nickel foam(NF),which is in situ reconstructed into a highly active and corrosion-resistant(Fe)NiOOH phase for OER.The interaction between phosphate anions(PO_(x)^(y-))and iron ions(Fe^(3+))tunes the electronic structure of the catalytic phase to further enhance OER kinetics.The integrated FeP-NiP@NF electrode exhibits low overpotentials for OER in alkaline water/seawater,requiring only 275/289,320/336,and 349/358 mV to reach 0.1,0.5,and 1.0 A cm^(−2),respectively.The in situ reconstructed PO_(x)^(y-)anion electrostatically repels Cl−in seawater electrolytes,allowing stable operation for over 7 days at 1.0 A cm^(−2) in extreme electrolytes(1.0 M KOH+seawater and 6.0 M KOH+seawater),demonstrating industrial-level stability.This study overcomes the complex synthesis limitations of P-based materials through innovative material design,opening new avenues for electrochemical energy conversion.
基金supported by National Natural Science Foundation of China(22002172,22121002)Beijing Natural Science Foundation(J210020)+2 种基金National Key Research and Development Program of China(2020YFA0710203)Chinese Academy of Sciences(QYZDYSSW-SLH013)Photon Science Center for Carbon Neutrality。
文摘Utilizing CO_(2)as a carbon feedstock for producing fuels and useful chemicals is attractive due to the advantages of being abundant,nontoxic,and economical.Electrochemical CO_(2)reduction(CO_(2)RR)provides an avenue to close the anthropogenic carbon cycle.However,the reaction process of multi-electronic products of CO_(2)RR is quite complex.It is hard to yield a target product with high selectivity,high current density,low overpotential,and good stability simultaneously.In recent years,in situ/operando characterization techniques have played important roles in the catalysis field via establishing the structure-reactivity/selectivity relationships of catalysts and thereby obtaining information about mechanisms.As a result,it is necessary to apply in situ/operando characterization technologies to clarify the reaction pathway of CO_(2)RR.In this mini-review,we discuss recent progress on the in situ/operando characterizations for electrochemical CO_(2)RR,including microscopies,infrared spectroscopy,Raman spectroscopy,X-ray photoelectron spectroscopy,and X-ray absorption fine spectroscopy.Moreover,the capabilities of these in situ/operando characterizations and the remaining challenges are also discussed.
基金supported by the Fundamental Research Funds for the Central Universities(Nos.2682022ZTPY049 and 2682020CX57).
文摘The key to achieving the breakthrough of hydrogen energy from marginal energy sources in large scale applications lies in the development and design of efficient electrocatalysts for the electrochemical oxidation and reduction of water.The unique heterostructure endows the catalyst with a mass of functional interfaces that are decisive for the enhancement of catalyst activity,stability,and reaction kinetics.Although some cutting-edge reviews have focused on the synthesis strategies,constitution,and applications of heterostructure catalysts,the field still lacks a detailed discussion of the actual reaction processes occurring at the interface,which is detrimental to the understanding of the true catalytic mechanism.Relying on advanced in situ/operando characterization techniques to understand the working mechanism of heterostructure catalysts is essential for rational design of advanced catalysts.In this review,we first present the advantages of heterostructure catalysts applied to electrolyzing water.Subsequently,the application of in situ/operando techniques in probing three aspects of heterostructure catalyst surface reconstruction,reaction mechanism,and the role of each component is highlighted with classical case studies.Finally,the current challenges and prospects for the design of heterostructure electrocatalysts are discussed in detail.
基金financially supported by the Office of Science,Office of Basic Energy Sciences,of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231.
文摘Catalysis research has witnessed remarkable progress with the advent of in situ and operando techniques.These methods enable the study of catalysts under actual operating conditions,providing unprecedented insights into catalytic mechanisms and dynamic catalyst behavior.This review discusses key in situ techniques and their applications in catalysis research.Advances in in situ electron microscopy allow direct visualization of catalysts at the atomic scale under reaction conditions.In situ spectroscopy techniques like X-ray absorption spectroscopy and nuclear magnetic resonance spectroscopy can track chemical states and reveal transient intermediates.Synchrotron-based techniques offer enhanced capabilities for in situ studies.The integration of in situ methods with machine learning and computational modeling provides a powerful approach to accelerate catalyst optimization.However,challenges remain regarding radiation damage,instrumentation limitations,and data interpretation.Overall,continued development of multi-modal in situ techniques is pivotal for addressing emerging challenges and opportunities in catalysis research and technology.
基金supported by the National Basic Research Program of China(973 Program,2013CB933104)the National Natural Science Foundation of China(Nos.11275258 and 11135008)
文摘In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for methanol synthesis. In this work, the catalyst, whose activity increases with the reaction temperature and pressure, was studied at calcined, reduced, and reacted conditions. TEM and EDX images for the calcined and reduced catalysts showed that copper was distributed uniformly at both conditions. TPR profile revealed two reduction peaks at 165 and 195 °C for copper species in the calcined catalyst. QXAFS results demonstrated that the calcined form consisted mainly of a mixed Cu O and Zn O, and it was progressively transformed into Cu metal particles and dispersed Zn O species as the reduction treatment. It was demonstrated that activation of the catalyst precursor occurred via a Cu^+intermediate, and the active catalyst predominantly consisted of metallic Cu and Zn O evenunder higher pressures. Structure of the active catalyst did not change with the temperature or pressure, indicating that the role of the Zn was mainly to improve Cu dispersion.This indicates the potential of QXAFS method in studying the structure evolutions of catalysts in methanol synthesis.
基金the financial support received from Kansas State University and the UNICAMP Development Foundation (FUNCAMP)the Brazilian Coordination for the Improvement of Higher Education Personnel–CAPES (Pr Int 88887.572651/2020-00+8 种基金88887.374731/2019-00)the financial support from the Brazilian National Council for Scientific and Technological Development–CNPq (310544/2019-0-PQ-2 grant)the S?o Paulo Research Foundation–FAPESP (2020/04431-02017/11958-12014/02163-7)the UNICAMP Development Foundation–FUNCAMP,Shellthe strategic importance of the support given by Brazil’s National Oil,Natural Gas,and Biofuels Agency–ANP via the R&D levy regulationNational Science Foundation Grant (1743701)CMMI NSF CAREER Grant (1454151)。
文摘In situ and operando infrared spectroscopies are powerful techniques to support the design of novel materials for batteries and the development of new battery systems.These techniques can support the study of batteries by identifying the formation of new species and monitoring electrochemical energy stability.However,few works have employed these techniques,which can be used to investigate various materials,including systems beyond lithium-ion technology,in the research of batteries.Therefore,this review presents a comprehensive overview focusing on the main contributions of in situ and operando infrared spectroscopy for lithium-ion batteries(LIBs)and other battery systems.These techniques can successfully identify the formation of species during the electrolyte reduction,electrode degradation,and the formation of the solid-electrolyte interphase(SEI)layer.From these outcomes,it is possible to conclude that this characterization approach should be employed as a protocol to overcome remaining issues in batteries,consequently supporting battery research.This review aims to be a guide on how infrared spectroscopy can contribute to monitoring battery systems and to lead researchers interested in applying this technique.
基金This study was funded by the Australian Research Council(FT170100224)the Australian Renewable Energy Agency+1 种基金National Natural Science Foundation of China(21825501)the Tsinghua University Initiative Scientific Research Program.
文摘Electrochemical water splitting has attracted considerable attention for the production of hydrogen fuel by using renewable energy resources.However,the sluggish reaction kinetics make it essential to explore precious-metal-free electrocatalysts with superior activity and long-term stability.Tremendous efforts have been made in exploring electrocatalysts to reduce the energy barriers and improve catalytic efficiency.This review summarizes different categories of precious-metal-free electrocatalysts developed in the past 5 years for alkaline water splitting.The design strategies for optimizing the electronic and geometric structures of electrocatalysts with enhanced catalytic performance are discussed,including composition modulation,defect engineering,and structural engineering.Particularly,the advancement of operando/in situ characterization techniques toward the understanding of structural evolution,reaction intermediates,and active sites during the water splitting process are summarized.Finally,current challenges and future perspectives toward achieving efficient catalyst systems for industrial applications are proposed.This review will provide insights and strategies to the design of precious-metalfree electrocatalysts and inspire future research in alkaline water splitting.
基金financially supported by the National Natural Science Foundation of China(No.52174342)Beijing Natural Sci-ence Foundation(No.2232044)Beijing Municipal Education Commission Research Plan General Project(No.KM202410005009).
文摘In this work,silicon-carbon hybrid materials were adopted as an example to illustrate the novel strategy to in situ construct heterostructure with adjustable microstructure.Based on the temperature-dependent thermodynamics and kinetics of reaction between Si and C,the processes for Si nanocrystals growth and C decoration were coupled at different zones of plasma flame according to its temperature and velocity fields by theoretical modeling,aiming to intentionally suppress the formation of undesirable carbide,and enable adjusting the microstructure of each counterpart separately in transient process.As a result,well-controlled Si/C nanocomposites,including nanospheres and nanowires with core-shell structures,were achieved,and this continuous and in-flight route is also potential for large-scale production.Further investigation on the electrochemical properties highlights the advantage of as proposed strategy to efficiently construct heterostructures with superior performance for various applications.
基金supported by National Natural Science Foundation of China(22090011)Liaoning Binhai Laboratory(LBLB-2023-03)Fundamental Research Funds for the Central Universities(DUT22LAB608).
文摘The clinical application of tumor vaccines is hindered by challenges such as timeconsuming and costly production processes.In this context,in situ cancer vaccines represent a promising strategy by leveraging endogenous tumor antigens to elicit robust antitumor T cell responses.Herein,a photoactivatable tumor-targeting in situ nanovaccine,Lipo-D8-6,was constructed using cRGD-functionalized liposomes that co-encapsulated the photosensitizer chlorin e6 and a cleavable immunoadjuvant conjugate D8,allowing light-triggered synchronous activation of three therapeutic modules.Upon near-infrared light irradiation,Lipo-D8-6 generates reactive oxygen species that exert direct cytotoxicity on tumor cells and induce immunogenic cell death,while concurrently cleaving the responsive linker within D8 to achieve the controlled release of R848.In vivo biodistribution analysis confirmed the superior intratumoral accumulation of Lipo-D8-6,facilitating precise treatment.In a large-volume tumor model,the nanovaccine exhibited pronounced antitumor efficacy,accompanied by enhanced tumor infiltration of CD8t T cells.Overall,this work provides a simplified and effective approach for developing in situ nanovaccines that enable synergistic photodynamic immunotherapy with precise spatiotemporal control over immune activation.
基金supported in part by the National Natural Science Foundation of China(Nos.52205532 and 624B2077)the National Key Research and Development Program of China(No.2023YFB4302003).
文摘The global demand for effective skin injury treatments has prompted the exploration of tissue engineering solutions.While three-dimensional(3D)bioprinting has shown promise,challenges persist with respect to achieving timely and compatible solutions to treat diverse skin injuries.In situ bioprinting has emerged as a key new technology,since it reduces risks during the implantation of printed scaffolds and demonstrates superior therapeutic effects.However,maintaining printing fidelity during in situ bioprinting remains a critical challenge,particularly with respect to model layering and path planning.This study proposes a novel optimization-based conformal path planning strategy for in situ bioprinting-based repair of complex skin injuries.This strategy employs constrained optimization to identify optimal waypoints on a point cloud-approximated curved surface,thereby ensuring a high degree of similarity between predesigned planar and surface-mapped 3D paths.Furthermore,this method is applicable for skin wound treatments,since it generates 3D-equidistant zigzag curves along surface tangents and enables multi-layer conformal path planning to facilitate the treatment of volumetric injuries.Furthermore,the proposed algorithm was found to be a feasible and effective treatment in a murine back injury model as well as in other complex models,thereby showcasing its potential to guide in situ bioprinting,enhance bioprinting fidelity,and facilitate improvement of clinical outcomes.
