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
Exploring cost-effective and efficient catalysts for oxygen reduction reaction(ORR)poses a significant challenge,espe-cially in the pursuit of alternatives to precious metals like platinum.Significant advancements hav...Exploring cost-effective and efficient catalysts for oxygen reduction reaction(ORR)poses a significant challenge,espe-cially in the pursuit of alternatives to precious metals like platinum.Significant advancements have driven electrochem-ists to develop efficient ORR catalysts using abundant materials,particularly iron(Fe)-based,known for their exceptional performance in ORR.While the crucial function of Fe in boosting ORR catalytic activity is recognized,the connection between material attributes and catalytic performance remains enigmatic.Understanding the dynamic processes involved in oxygen electrocatalysis is paramount for designing precious-metals-free ORR electrocatalysts.Mössbauer spectroscopy stands out as a powerful technique for deciphering the structural characteristics of Fe species in catalysis,facilitating the identification of active sites and the clarification of catalytic mechanisms.By showcasing noteworthy case studies within this review,we demonstrate the application of in-situ/operando 57Fe Mössbauer spectroscopy across diverse Fe-involved materials in ORR catalysis.This sheds light on various aspects of ORR catalysis,such as identifying active sites,assessing stability,and understanding the reaction mechanism.Our inquiry drives towards the opportunities and hurdles associ-ated with Mössbauer spectroscopy,unveiling potential breakthroughs and avenues for enhancement within this pivotal research realm.展开更多
Water electrolysis is pivotal for converting renewable energy into clean hydrogen fuel,addressing global energy demand sustainably.However,the development of highly efficient and cost-effective catalysts for the oxyge...Water electrolysis is pivotal for converting renewable energy into clean hydrogen fuel,addressing global energy demand sustainably.However,the development of highly efficient and cost-effective catalysts for the oxygen evolution reaction(OER)remains a significant challenge,particularly at the industrial scale.This report explores a newly discovered pathway,the oxide path mechanism(OPM) for OER-mechanism involving the oxide formation and evolution during the reaction,emphasizing its potential to overcome existing limitations.OPM enables direct O-O coupling without oxygen vacancies,offering superior stability.We detail both classical and innovative in-situ characterization techniques that are central to unraveling the OER mechanism.The advanced in-situ electrochemical techniques,such as inductively coupled plasma mass spectroscopy,X-ray photoelectron spectroscopy,and Mössbauer spectroscopy,coupled with in-situ structural analyses,provide crucial insights into the catalyst surface,the electrode-electrolyte interface and the kinetics of OER.This review provides a systematic analysis integrating classical electrochemical methods with advanced in-situ/operando techniques,specifically focusing on understanding OPM.While numerous studies have examined individual characterization methods,this study systematically integrates traditional electrochemical approaches with in-situ and operando techniques,offering critical insights into their complementary roles in elucidating reaction pathways.The integration of these methodologies provides unprecedented understanding of catalyst behavior under operational conditions,guiding the rational design of next-generation OER catalysts.Furthermore,we discuss essential standardized test toolkits and protocols,such as those for rotating disk electrode and membrane electrode assembly,which are vital for ensuring reproducibility and scalability in OER catalyst research.展开更多
Despite significant progress in fuel cell technology,its large-scale industrial application is still challenged by the frequently encountered performance failure during long-term operation.Clarifying the failure mecha...Despite significant progress in fuel cell technology,its large-scale industrial application is still challenged by the frequently encountered performance failure during long-term operation.Clarifying the failure mechanism is the key to extending the lifecycle and enhancing stability.Herein,we have developed a time and space resolved multi-field characterization,including electrochemical impedance spectroscopy,to unveil its underlying mechanism.With this operando and non-destructive characterization,the dynamic evolution of the internal mass transport,heat,and electricity field distribution is fully depicted within an industrial-scale fuel cell in operation.Thus,it is revealed that hydrogen starvation occurs in the outlet region due to the excessive hydrogen consumption during the loading-down process.This can induce local low current density and carbon corrosion,which may subsequently cause severe damage to the structure of the catalyst layer and membrane,ultimately leading to performance failure.With this understanding,we further identify a descriptor for early diagnosis to prevent any potential degradation.The methodology is of significance,which can bring fuel cell technology a step further towards industrial applications.展开更多
Lithium metal batteries(LMBs)represent a promising solution for next-generation energy storage due to their high energy density,but the growth of lithium dendrites presents significant challenges to their performance ...Lithium metal batteries(LMBs)represent a promising solution for next-generation energy storage due to their high energy density,but the growth of lithium dendrites presents significant challenges to their performance and safety.This review provides a comprehensive overview of the mechanisms behind lithium dendrite formation and the role of in situ/operando observation and phase field simulation in understanding and mitigating this issue,The key driving factors of dendrite growth,such as lithium-ion flux heterogeneity,surface defects,and localized stress,are explored through advanced experimental techniques,which enable real-time visualization of dendrite nucleation and growth dynamics.Complementarily,phase field simulations provide insights into subsurface and temporal evolution of dendrites by modeling thermodynamic and kinetic processes,while machine learning techniques optimize simulation accuracy through data-driven parameter refinement.The integration of experimental observations with simulation models holds great potential in improving understanding and predictive capabilities.Despite ongoing progress,challenges remain in resolving technical limitations in observation techniques,improving computational efficiency,and fostering interdisciplinary collaboration.This review highlights the synergy between experimental and computational strategies in advancing the development of LMBs and calls for continued research to overcome existing hurdles and unlock the full potential of lithium metal anodes.展开更多
Understanding the charge/discharge mechanism of batteries plays an important role in the development of high-performance systems,but extremely complicated reactions are involved.Because these complex phenomena are als...Understanding the charge/discharge mechanism of batteries plays an important role in the development of high-performance systems,but extremely complicated reactions are involved.Because these complex phenomena are also bottlenecks for the establishment of all-sol id-state batteries(ASSB),we conducted multi-scale analysis using combined multi-measurement techniques,to directly observe charge/discharge reactions at hierarchical scales for the oxide-type ASSB using Na as the carrier cation.In particular,all of measurement techniques are applied to cross-section ASSB in the same cell,to complementarily evaluate the elemental distributions and structural changes.From Operando scanning electron microscopy-energy-dispersive X-ray spectroscopy,the Na concentration in the electrode layers changes on the micrometer scale under charge/discharge reactions in the first cycle.Furthermore,Operando Raman spectroscopy reveal changes in the bonding states at the atomic scale in the active material,including changes in reversible structural changes.After cycling the ASSB,the elemental distributions are clearly observed along with the particle shapes and can reveal the Na migration mechanism at the nanometer scale,by time-of-flight secondary ion mass spectrometry.Therefore,this study can provide a fundamental and comprehensive understanding of the charge/discharge mechanism by observing reaction processes at multiple scales.展开更多
The photocatalytic production of hydrogen peroxide(H_(2)O_(2))via the oxygen reduction reaction(ORR)holds great significance in chemical engineering,agriculture,and national defense.However,the underlying influence of...The photocatalytic production of hydrogen peroxide(H_(2)O_(2))via the oxygen reduction reaction(ORR)holds great significance in chemical engineering,agriculture,and national defense.However,the underlying influence of interfacial charge dynamics on catalytic performance remains poorly understood due to limitations in conventional characterization techniques.In this study,we employ thiolate-protected gold-silver metal nanoclusters(MNCs)and nitrogen-doped carbon dot-modified nanoclusters(MNCs/N-CDs)as model systems to investigate ORR selectivity and charge dynamics under light irradiation.This catalyst design leverages the self-oxidation behavior of thiolate ligands and the intrinsic ORR selectivity of nanoclusters to establish a clean and well-defined photocatalytic system.By integrating time-resolved transient photovoltage(TPV)spectroscopy and operando transient potential scanning(TPS)test,we demonstrate that N-CDs promote the separation and storage of photoinduced charge carriers,as well as enhance oxygen adsorption and activation on the catalyst surface,thereby significantly improving H_(2)O_(2)production efficiency.These findings offer new mechanistic insights into the interplay between interfacial charge dynamics and photocatalytic performance,providing guidance for the rational design of advanced ORR catalysts.展开更多
Battery safety has emerged as a critical challenge for achieving carbon neutrality,driven by the increasing frequency of thermal runaway incidents in electric vehicles(EVs)and stationary energy storage systems(ESSs).C...Battery safety has emerged as a critical challenge for achieving carbon neutrality,driven by the increasing frequency of thermal runaway incidents in electric vehicles(EVs)and stationary energy storage systems(ESSs).Conventional battery monitoring technologies struggle to track multiple physicochemical parameters in real time,hindering early hazard detection.Embedded optical fiber sensors have gained prominence as a transformative solution for next-generation smart battery sensing,owing to their micrometer size,multiplexing capability,and electromagnetic immunity.However,comprehensive reviews focusing on their advancements in operando multi-parameter monitoring remain scarce,despite their critical importance for ensuring battery safety.To address this gap,this review first introduces a classification and the fundamental principles of advanced battery-oriented optical fiber sensors.Subsequently,it summarizes recent developments in single-parameter battery monitoring using optical fiber sensors.Building on this foundation,this review presents the first comprehensive analysis of multifunctional optical fiber sensing platforms capable of simultaneously tracking temperature,strain,pressure,refractive index,and monitoring battery aging.Targeted strategies are proposed to facilitate the practical development of this technology,including optimization of sensor integration techniques,minimizing sensor invasiveness,resolving the cross-sensitivity of fiber Bragg grating(FBG)through structural innovation,enhancing techno-economics,and combining with artificial intelligence(AI).By aligning academic research with industry requirements,this review provides a methodological roadmap for developing robust optical sensing systems to ensure battery safety in decarbonization-driven applications.展开更多
Rechargeable lithium–sulfur(Li–S)batteries are considered promising next-generation energy storage systems owing to their high theoretical energy density,but their application is hindered by the shuttle effect arisi...Rechargeable lithium–sulfur(Li–S)batteries are considered promising next-generation energy storage systems owing to their high theoretical energy density,but their application is hindered by the shuttle effect arising from dissolved lithium polysulfides(LiPSs).Herein,we design an optimized electrolyte to achieve long-term stability by employing an appropriate low-polarity solvent.A combination of diethyl ether(DEE)and 1,2-dimethoxyethane(DME)was selected to improve Li metal stability even in the presence of LiPSs.The DEE/DME electrolyte not only suppresses parasitic reactions between Li and LiPSs but also promotes uniform Li deposition.Moreover,operando optical microscopy was employed to directly visualize electrolyte stability and dendrite evolution in real time,while quantitative analysis was conducted via normalized hue index and contour image mapping.The enhanced anode stability of the DEE/DME electrolyte enabled excellent cycling performance,retaining 80.14%of its initial capacity after300 cycles at 3 C,while maintaining superior performance under practical conditions with high sulfur loading and a low E/S ratio.These findings highlight that solvent properties critically influence Li metal stabilization in Li–S batteries and underscore the significance of solvent engineering in electrolyte design.展开更多
Heterostructured transition-metal compounds show great potential in the oxygen evolution reaction(OER),but the reaction mechanism induced by the surface reconstruction remains unclear.Herein,we develop a kind of Co-O-...Heterostructured transition-metal compounds show great potential in the oxygen evolution reaction(OER),but the reaction mechanism induced by the surface reconstruction remains unclear.Herein,we develop a kind of Co-O-Mo active center in Co oxyhydroxide(MoCoOOH)via in situ reconstruction,which exhibits an overpotential of 275 m V at 10 mA cm^(-2)in alkaline conditions,as well as negligible deactivation after durability operation driven by a solar cell.The operando tests reveal that Mo accelerates the reconstruction from Co-Se-Mo to Co-O-Mo in MoCoOOH,which triggers the lattice oxygen activation for enhanced intrinsic OER activity.Theoretical calculations demonstrate that the Mo atoms can optimize the d-orbital energy level of Co metal atoms,adsorption-desorption oxygenated intermediates,and the rate-determining step barrier.This work gives deep insights into the oxygen-involved mechanism in the reconstructed phase and inspires the rational design of high-activity electrocatalysts in multielectron reactions.展开更多
The conversion of carbon dioxide(CO_(2))into hydrocarbons through electrochemical CO_(2)reduction reaction(eCO_(2)RR)shows a promising method to reduce CO_(2)levels and decrease reliance on fossil fuels in the years t...The conversion of carbon dioxide(CO_(2))into hydrocarbons through electrochemical CO_(2)reduction reaction(eCO_(2)RR)shows a promising method to reduce CO_(2)levels and decrease reliance on fossil fuels in the years to come.Copper-based electrocatalysts exhibit a pronounced inclination for C-C coupling,drawing considerable interest as a favored metal catalyst for generating C_(2+)products through CO_(2)RR.However,CO_(2)RR still has some obstacles including product selectivity,higher overpotential,low Faradic efficiency(FE),stability,and current density(CD).Therefore,advancement in this field enables us to comprehend the complex multi-proton electron transfer during C-C coupling and engineering strategies to improve FE and CD.Herein,this review presents some key features of Cu-based catalysts as an electrocatalyst for C_(2) product formation while addressing the industrial challenges that hinder commercialization of CO_(2)RR.In addition,recent strategies on Cu-based catalysts,synthesis strategies,advanced characterizations,and mechanistic investigations via theoretical simulations have been presented.Furthermore,recent approaches towards the composition,oxidation states,and active facets have been presented.Thus,the most favorable mechanism and possible pathways to synthesize C_(2+)products have been explained using theoretical calculations.展开更多
Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon di...Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon dioxide reduction.This review article summarizes the research progress on improving the performance of Cu-based material electrocatalysts through doping regulation.The background,fundamental research,evaluation parameters,and methods for catalyst design,along with their influencing factors,are introduced.Emphasis is placed on the impact of doping with different elements(such as noble metals,transition metals,main-group metals,non-metals,etc.)on the performance of Cu-based catalysts,including the mechanisms for enhancing activity,selectivity,and stability.In-situ characterization techniques have revealed the structural evolution and catalytic mechanisms during the doping process.Mechanistic studies,leveraging the ever-advancing computational capabilities and high-throughput methods,have given rise to typical computational descriptors like volcano plots,free-energy diagrams,and machine-learning-based approaches.These descriptors have become key tools for screening high-efficiency catalysts in various application scenarios of the electrochemical carbon dioxide reduction reaction(CO_(2)RR).This article comprehensively summarizes the current research achievements and looks ahead to the future,indicating that strengthening the combination of theory and experiment and exploring industrial applications are the future research directions,aiming to provide a comprehensive reference for the development of highly efficient doped Cu-based electrocatalysts.展开更多
Conventional electrocatalytic urea synthesis via CO_(2)+N_(2) or CO_(2)+NO_(3)^(-)coelectrolysis generally suffers from poor reactants coactivation,low C-N coupling efficiency,and serious competing reactions.To overco...Conventional electrocatalytic urea synthesis via CO_(2)+N_(2) or CO_(2)+NO_(3)^(-)coelectrolysis generally suffers from poor reactants coactivation,low C-N coupling efficiency,and serious competing reactions.To overcome these limitations,we implement HCOOH+NO_(3)^(-)coelectrolysis to urea using a Fe-Pd dual-atom catalyst(Fe_(1)Pd_(1)-DAC).Operando spectroscopic measurements and theoretical computations collectively reveal that Pd_(1) selectively dehydrogenates HCOOH to^(*)COOH,while Fe_(1) selectively activates NO_(3)^(-)to^(*)NH_(2).Specifically,the spatial proximity and electrophilic-nucleophilic synergy of^(*)COOH and^(*)NH_(2) enable the high C-N coupling efficiency and well-suppressed competing reactions.Consequently,Fe_(1)Pd_(1)-DAC assembled in a flow cell delivers the unprecedented urea yield rate up to 448.1 mmol h^(-1) g^(-1) and Faradaic efficiency of 78.3%at an industrial-level current density of-215 mA cm^(-2),far outperforming those obtained from CO_(2)+N_(2) or CO_(2)+NO_(3) coelectrolysis.Further techno-economic analysis demonstrates Fe_(1)Pd_(1)-DAC as a promising catalyst for economically feasible urea production via HCOOH+NO_(3)^(-)coelectrolysis.展开更多
Internal gases caused by side reactions are crucial signals for evaluating health and safety states of Li-ion batteries(LIBs)while it is still a great challenge to timely realize accurate monitoring.To address the iss...Internal gases caused by side reactions are crucial signals for evaluating health and safety states of Li-ion batteries(LIBs)while it is still a great challenge to timely realize accurate monitoring.To address the issues of implanting various gas sensors into commercial batteries,here a novel method is developed to fast operando monitoring gas evolution via equipping non-dispersive infrared multi-gases sensors into a sealed tank,where real commercial batteries with one open end could be settled for operating.The generated CO_(2)concentration is strongly linked with both voltage and temperature,while the concentrations of CH_(4) and C_(2)H_(4) are solely dependent on temperature.As a typical trace gas,evolution behaviors of CO_(2)have been related to 0_(2) generation from LiNi_(o.5)Mn_(0.3)CoO_(2)0_(2) positive electrode,implying stable CO_(2)release below a critical voltage of 4.5 V.By tracking CO_(2)concentration,an increased amount of Li_(2)CO_(3) was monitored on the surface of graphite negative electrode during discharge process at dfferent temperatures and cutoff voltages,which contributes to the component variation of solid electrolyte interfaces.Such operando techniques promise a plaform for well understanding the interaction of side reactions linked with gas evolution between positive and negative electrodes in commercial LIBs.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
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
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 (22350410386,W2412116,22375200,U22A202175,21961142006)。
文摘Exploring cost-effective and efficient catalysts for oxygen reduction reaction(ORR)poses a significant challenge,espe-cially in the pursuit of alternatives to precious metals like platinum.Significant advancements have driven electrochem-ists to develop efficient ORR catalysts using abundant materials,particularly iron(Fe)-based,known for their exceptional performance in ORR.While the crucial function of Fe in boosting ORR catalytic activity is recognized,the connection between material attributes and catalytic performance remains enigmatic.Understanding the dynamic processes involved in oxygen electrocatalysis is paramount for designing precious-metals-free ORR electrocatalysts.Mössbauer spectroscopy stands out as a powerful technique for deciphering the structural characteristics of Fe species in catalysis,facilitating the identification of active sites and the clarification of catalytic mechanisms.By showcasing noteworthy case studies within this review,we demonstrate the application of in-situ/operando 57Fe Mössbauer spectroscopy across diverse Fe-involved materials in ORR catalysis.This sheds light on various aspects of ORR catalysis,such as identifying active sites,assessing stability,and understanding the reaction mechanism.Our inquiry drives towards the opportunities and hurdles associ-ated with Mössbauer spectroscopy,unveiling potential breakthroughs and avenues for enhancement within this pivotal research realm.
基金funded by the EU H2020 Marie Skłodowska-Curie Fellowship (1439425)the National Natural Science Foundation of China (No. 52171199 and 22479011)
文摘Water electrolysis is pivotal for converting renewable energy into clean hydrogen fuel,addressing global energy demand sustainably.However,the development of highly efficient and cost-effective catalysts for the oxygen evolution reaction(OER)remains a significant challenge,particularly at the industrial scale.This report explores a newly discovered pathway,the oxide path mechanism(OPM) for OER-mechanism involving the oxide formation and evolution during the reaction,emphasizing its potential to overcome existing limitations.OPM enables direct O-O coupling without oxygen vacancies,offering superior stability.We detail both classical and innovative in-situ characterization techniques that are central to unraveling the OER mechanism.The advanced in-situ electrochemical techniques,such as inductively coupled plasma mass spectroscopy,X-ray photoelectron spectroscopy,and Mössbauer spectroscopy,coupled with in-situ structural analyses,provide crucial insights into the catalyst surface,the electrode-electrolyte interface and the kinetics of OER.This review provides a systematic analysis integrating classical electrochemical methods with advanced in-situ/operando techniques,specifically focusing on understanding OPM.While numerous studies have examined individual characterization methods,this study systematically integrates traditional electrochemical approaches with in-situ and operando techniques,offering critical insights into their complementary roles in elucidating reaction pathways.The integration of these methodologies provides unprecedented understanding of catalyst behavior under operational conditions,guiding the rational design of next-generation OER catalysts.Furthermore,we discuss essential standardized test toolkits and protocols,such as those for rotating disk electrode and membrane electrode assembly,which are vital for ensuring reproducibility and scalability in OER catalyst research.
基金supported by the National Key R&D Program of China[2023YFB4006100]。
文摘Despite significant progress in fuel cell technology,its large-scale industrial application is still challenged by the frequently encountered performance failure during long-term operation.Clarifying the failure mechanism is the key to extending the lifecycle and enhancing stability.Herein,we have developed a time and space resolved multi-field characterization,including electrochemical impedance spectroscopy,to unveil its underlying mechanism.With this operando and non-destructive characterization,the dynamic evolution of the internal mass transport,heat,and electricity field distribution is fully depicted within an industrial-scale fuel cell in operation.Thus,it is revealed that hydrogen starvation occurs in the outlet region due to the excessive hydrogen consumption during the loading-down process.This can induce local low current density and carbon corrosion,which may subsequently cause severe damage to the structure of the catalyst layer and membrane,ultimately leading to performance failure.With this understanding,we further identify a descriptor for early diagnosis to prevent any potential degradation.The methodology is of significance,which can bring fuel cell technology a step further towards industrial applications.
基金the financial support of the National Natural Science Foundation of China(Nos.12172206 and 11972218)。
文摘Lithium metal batteries(LMBs)represent a promising solution for next-generation energy storage due to their high energy density,but the growth of lithium dendrites presents significant challenges to their performance and safety.This review provides a comprehensive overview of the mechanisms behind lithium dendrite formation and the role of in situ/operando observation and phase field simulation in understanding and mitigating this issue,The key driving factors of dendrite growth,such as lithium-ion flux heterogeneity,surface defects,and localized stress,are explored through advanced experimental techniques,which enable real-time visualization of dendrite nucleation and growth dynamics.Complementarily,phase field simulations provide insights into subsurface and temporal evolution of dendrites by modeling thermodynamic and kinetic processes,while machine learning techniques optimize simulation accuracy through data-driven parameter refinement.The integration of experimental observations with simulation models holds great potential in improving understanding and predictive capabilities.Despite ongoing progress,challenges remain in resolving technical limitations in observation techniques,improving computational efficiency,and fostering interdisciplinary collaboration.This review highlights the synergy between experimental and computational strategies in advancing the development of LMBs and calls for continued research to overcome existing hurdles and unlock the full potential of lithium metal anodes.
基金This article is based on results obtained from a project,Grant JPNP14004,commissioned by the New Energy and Industrial Technology Development Organization(NEDO)。
文摘Understanding the charge/discharge mechanism of batteries plays an important role in the development of high-performance systems,but extremely complicated reactions are involved.Because these complex phenomena are also bottlenecks for the establishment of all-sol id-state batteries(ASSB),we conducted multi-scale analysis using combined multi-measurement techniques,to directly observe charge/discharge reactions at hierarchical scales for the oxide-type ASSB using Na as the carrier cation.In particular,all of measurement techniques are applied to cross-section ASSB in the same cell,to complementarily evaluate the elemental distributions and structural changes.From Operando scanning electron microscopy-energy-dispersive X-ray spectroscopy,the Na concentration in the electrode layers changes on the micrometer scale under charge/discharge reactions in the first cycle.Furthermore,Operando Raman spectroscopy reveal changes in the bonding states at the atomic scale in the active material,including changes in reversible structural changes.After cycling the ASSB,the elemental distributions are clearly observed along with the particle shapes and can reveal the Na migration mechanism at the nanometer scale,by time-of-flight secondary ion mass spectrometry.Therefore,this study can provide a fundamental and comprehensive understanding of the charge/discharge mechanism by observing reaction processes at multiple scales.
基金supported by National Natural Science Foundation of China(42076193,52271223,52472049,52472230,52471234,52202107,52272043)Natural Science Foundation of Jiangsu Province(BK20220028,BK20230065)+5 种基金National Key R&D Program of China(2024YFA1509300)Ministry of Science and Technology of China(2024YFA1509500)State Key Laboratory of Catalysis(2024SKL-A-014)Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 ProjectSuzhou Key Laboratory of Functional Nano&Soft Materials
文摘The photocatalytic production of hydrogen peroxide(H_(2)O_(2))via the oxygen reduction reaction(ORR)holds great significance in chemical engineering,agriculture,and national defense.However,the underlying influence of interfacial charge dynamics on catalytic performance remains poorly understood due to limitations in conventional characterization techniques.In this study,we employ thiolate-protected gold-silver metal nanoclusters(MNCs)and nitrogen-doped carbon dot-modified nanoclusters(MNCs/N-CDs)as model systems to investigate ORR selectivity and charge dynamics under light irradiation.This catalyst design leverages the self-oxidation behavior of thiolate ligands and the intrinsic ORR selectivity of nanoclusters to establish a clean and well-defined photocatalytic system.By integrating time-resolved transient photovoltage(TPV)spectroscopy and operando transient potential scanning(TPS)test,we demonstrate that N-CDs promote the separation and storage of photoinduced charge carriers,as well as enhance oxygen adsorption and activation on the catalyst surface,thereby significantly improving H_(2)O_(2)production efficiency.These findings offer new mechanistic insights into the interplay between interfacial charge dynamics and photocatalytic performance,providing guidance for the rational design of advanced ORR catalysts.
基金the financial supports of the National Natural Science Foundation of China(No.52372200)a project supported by the State Key Laboratory of Mechanics and Control for Aerospace Structures(No.MCAS-S-0324G01)。
文摘Battery safety has emerged as a critical challenge for achieving carbon neutrality,driven by the increasing frequency of thermal runaway incidents in electric vehicles(EVs)and stationary energy storage systems(ESSs).Conventional battery monitoring technologies struggle to track multiple physicochemical parameters in real time,hindering early hazard detection.Embedded optical fiber sensors have gained prominence as a transformative solution for next-generation smart battery sensing,owing to their micrometer size,multiplexing capability,and electromagnetic immunity.However,comprehensive reviews focusing on their advancements in operando multi-parameter monitoring remain scarce,despite their critical importance for ensuring battery safety.To address this gap,this review first introduces a classification and the fundamental principles of advanced battery-oriented optical fiber sensors.Subsequently,it summarizes recent developments in single-parameter battery monitoring using optical fiber sensors.Building on this foundation,this review presents the first comprehensive analysis of multifunctional optical fiber sensing platforms capable of simultaneously tracking temperature,strain,pressure,refractive index,and monitoring battery aging.Targeted strategies are proposed to facilitate the practical development of this technology,including optimization of sensor integration techniques,minimizing sensor invasiveness,resolving the cross-sensitivity of fiber Bragg grating(FBG)through structural innovation,enhancing techno-economics,and combining with artificial intelligence(AI).By aligning academic research with industry requirements,this review provides a methodological roadmap for developing robust optical sensing systems to ensure battery safety in decarbonization-driven applications.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2024-00455177)the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2025-00518953)+2 种基金the National Research Council of Science&Technology(NST)grant by the Korea government(MSIT)(GTL24012-000)the support by the National Natural Science Foundation of China(T2322015)the support by The Ministry of Science and ICT in Korea via KBSI(C524100)。
文摘Rechargeable lithium–sulfur(Li–S)batteries are considered promising next-generation energy storage systems owing to their high theoretical energy density,but their application is hindered by the shuttle effect arising from dissolved lithium polysulfides(LiPSs).Herein,we design an optimized electrolyte to achieve long-term stability by employing an appropriate low-polarity solvent.A combination of diethyl ether(DEE)and 1,2-dimethoxyethane(DME)was selected to improve Li metal stability even in the presence of LiPSs.The DEE/DME electrolyte not only suppresses parasitic reactions between Li and LiPSs but also promotes uniform Li deposition.Moreover,operando optical microscopy was employed to directly visualize electrolyte stability and dendrite evolution in real time,while quantitative analysis was conducted via normalized hue index and contour image mapping.The enhanced anode stability of the DEE/DME electrolyte enabled excellent cycling performance,retaining 80.14%of its initial capacity after300 cycles at 3 C,while maintaining superior performance under practical conditions with high sulfur loading and a low E/S ratio.These findings highlight that solvent properties critically influence Li metal stabilization in Li–S batteries and underscore the significance of solvent engineering in electrolyte design.
基金financially supported in part by the National Key R&D Program of China(2020YFA0405800)the National Natural Science Foundation of China(Grant No.U1932201)the Natural Science Foundation of the Jiangsu Higher Education Institutions(23KJA430001)。
文摘Heterostructured transition-metal compounds show great potential in the oxygen evolution reaction(OER),but the reaction mechanism induced by the surface reconstruction remains unclear.Herein,we develop a kind of Co-O-Mo active center in Co oxyhydroxide(MoCoOOH)via in situ reconstruction,which exhibits an overpotential of 275 m V at 10 mA cm^(-2)in alkaline conditions,as well as negligible deactivation after durability operation driven by a solar cell.The operando tests reveal that Mo accelerates the reconstruction from Co-Se-Mo to Co-O-Mo in MoCoOOH,which triggers the lattice oxygen activation for enhanced intrinsic OER activity.Theoretical calculations demonstrate that the Mo atoms can optimize the d-orbital energy level of Co metal atoms,adsorption-desorption oxygenated intermediates,and the rate-determining step barrier.This work gives deep insights into the oxygen-involved mechanism in the reconstructed phase and inspires the rational design of high-activity electrocatalysts in multielectron reactions.
基金the financial support from International Society of Engineering Science and Technology(ISEST)UK。
文摘The conversion of carbon dioxide(CO_(2))into hydrocarbons through electrochemical CO_(2)reduction reaction(eCO_(2)RR)shows a promising method to reduce CO_(2)levels and decrease reliance on fossil fuels in the years to come.Copper-based electrocatalysts exhibit a pronounced inclination for C-C coupling,drawing considerable interest as a favored metal catalyst for generating C_(2+)products through CO_(2)RR.However,CO_(2)RR still has some obstacles including product selectivity,higher overpotential,low Faradic efficiency(FE),stability,and current density(CD).Therefore,advancement in this field enables us to comprehend the complex multi-proton electron transfer during C-C coupling and engineering strategies to improve FE and CD.Herein,this review presents some key features of Cu-based catalysts as an electrocatalyst for C_(2) product formation while addressing the industrial challenges that hinder commercialization of CO_(2)RR.In addition,recent strategies on Cu-based catalysts,synthesis strategies,advanced characterizations,and mechanistic investigations via theoretical simulations have been presented.Furthermore,recent approaches towards the composition,oxidation states,and active facets have been presented.Thus,the most favorable mechanism and possible pathways to synthesize C_(2+)products have been explained using theoretical calculations.
基金financially supported by the National Natural Science Foundation of China(52271200)Guangdong Basic and Applied Basic Research Foundation(2024A1515010393)USTB MatCom of Beijing Advanced Innovation Center for Materials Genome Engineering。
文摘Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon dioxide reduction.This review article summarizes the research progress on improving the performance of Cu-based material electrocatalysts through doping regulation.The background,fundamental research,evaluation parameters,and methods for catalyst design,along with their influencing factors,are introduced.Emphasis is placed on the impact of doping with different elements(such as noble metals,transition metals,main-group metals,non-metals,etc.)on the performance of Cu-based catalysts,including the mechanisms for enhancing activity,selectivity,and stability.In-situ characterization techniques have revealed the structural evolution and catalytic mechanisms during the doping process.Mechanistic studies,leveraging the ever-advancing computational capabilities and high-throughput methods,have given rise to typical computational descriptors like volcano plots,free-energy diagrams,and machine-learning-based approaches.These descriptors have become key tools for screening high-efficiency catalysts in various application scenarios of the electrochemical carbon dioxide reduction reaction(CO_(2)RR).This article comprehensively summarizes the current research achievements and looks ahead to the future,indicating that strengthening the combination of theory and experiment and exploring industrial applications are the future research directions,aiming to provide a comprehensive reference for the development of highly efficient doped Cu-based electrocatalysts.
基金supported by the National Natural Science Foundation of China(52561042)the Industrial Support Plan Project of Gansu Provincial Education Department(2024CYZC-22)。
文摘Conventional electrocatalytic urea synthesis via CO_(2)+N_(2) or CO_(2)+NO_(3)^(-)coelectrolysis generally suffers from poor reactants coactivation,low C-N coupling efficiency,and serious competing reactions.To overcome these limitations,we implement HCOOH+NO_(3)^(-)coelectrolysis to urea using a Fe-Pd dual-atom catalyst(Fe_(1)Pd_(1)-DAC).Operando spectroscopic measurements and theoretical computations collectively reveal that Pd_(1) selectively dehydrogenates HCOOH to^(*)COOH,while Fe_(1) selectively activates NO_(3)^(-)to^(*)NH_(2).Specifically,the spatial proximity and electrophilic-nucleophilic synergy of^(*)COOH and^(*)NH_(2) enable the high C-N coupling efficiency and well-suppressed competing reactions.Consequently,Fe_(1)Pd_(1)-DAC assembled in a flow cell delivers the unprecedented urea yield rate up to 448.1 mmol h^(-1) g^(-1) and Faradaic efficiency of 78.3%at an industrial-level current density of-215 mA cm^(-2),far outperforming those obtained from CO_(2)+N_(2) or CO_(2)+NO_(3) coelectrolysis.Further techno-economic analysis demonstrates Fe_(1)Pd_(1)-DAC as a promising catalyst for economically feasible urea production via HCOOH+NO_(3)^(-)coelectrolysis.
基金supported by the National Key R&D Program of China(Grant No.2021YFB2401900)the National Natural Science Foundation of China(Grant Nos.11672341,11572002,52074036)+1 种基金the Technology Innovation Program of Beijing Institute of Technology(Grant No.2019CX01021)the BIT Teli Young Fellow。
文摘Internal gases caused by side reactions are crucial signals for evaluating health and safety states of Li-ion batteries(LIBs)while it is still a great challenge to timely realize accurate monitoring.To address the issues of implanting various gas sensors into commercial batteries,here a novel method is developed to fast operando monitoring gas evolution via equipping non-dispersive infrared multi-gases sensors into a sealed tank,where real commercial batteries with one open end could be settled for operating.The generated CO_(2)concentration is strongly linked with both voltage and temperature,while the concentrations of CH_(4) and C_(2)H_(4) are solely dependent on temperature.As a typical trace gas,evolution behaviors of CO_(2)have been related to 0_(2) generation from LiNi_(o.5)Mn_(0.3)CoO_(2)0_(2) positive electrode,implying stable CO_(2)release below a critical voltage of 4.5 V.By tracking CO_(2)concentration,an increased amount of Li_(2)CO_(3) was monitored on the surface of graphite negative electrode during discharge process at dfferent temperatures and cutoff voltages,which contributes to the component variation of solid electrolyte interfaces.Such operando techniques promise a plaform for well understanding the interaction of side reactions linked with gas evolution between positive and negative electrodes in commercial LIBs.
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.
