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
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
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
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
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
As the rapid development of more powerful and safer lithiumion batteries, the mechanism study of gases evolution is attacking more and more attention in recent years. Especially under overcharge/discharge and/or high-...As the rapid development of more powerful and safer lithiumion batteries, the mechanism study of gases evolution is attacking more and more attention in recent years. Especially under overcharge/discharge and/or high-temperature working condition.展开更多
Niobates are promising all-climate Li^(+)-storage anode material due to their fast charge transport,large specific capacities,and resistance to electrolyte reaction.However,their moderate unit-cellvolume expansion(gen...Niobates are promising all-climate Li^(+)-storage anode material due to their fast charge transport,large specific capacities,and resistance to electrolyte reaction.However,their moderate unit-cellvolume expansion(generally 5%–10%)during Li^(+)storage causes unsatisfactory long-term cyclability.Here,“zero-strain”NiNb_(2)O_(6) fibers are explored as a new anode material with comprehensively good electrochemical properties.During Li^(+)storage,the expansion of electrochemical inactive NiO_(6) octahedra almost fully offsets the shrinkage of active NbO_(6) octahedra through reversible O movement.Such superior volume-accommodation capability of the NiO_(6) layers guarantees the“zero-strain”behavior of NiNb_(2)O_(6) in a broad temperature range(0.53%//0.51%//0.74%at 25//−10//60℃),leading to the excellent cyclability of the NiNb_(2)O_(6) fibers(92.8%//99.2%//91.1%capacity retention after 1000//2000//1000 cycles at 10C and 25//−10//60℃).This NiNb_(2)O_(6) material further exhibits a large reversible capacity(300//184//318 mAh g−1 at 0.1C and 25//−10//60℃)and outstanding rate performance(10 to 0.5C capacity percentage of 64.3%//50.0%//65.4%at 25//−10//60℃).Therefore,the NiNb_(2)O_(6) fibers are especially suitable for large-capacity,fast-charging,long-life,and all-climate lithium-ion batteries.展开更多
Excessive nitrogen emission caused by human activities has significantly disrupted the global nitrogen cycle,adversely affecting ecosystems and human health.Electrocatalytic nitrate reduction to valuable ammonia(eNRA)...Excessive nitrogen emission caused by human activities has significantly disrupted the global nitrogen cycle,adversely affecting ecosystems and human health.Electrocatalytic nitrate reduction to valuable ammonia(eNRA)presents an encouraging alternative marked by mild reaction conditions,rapid reaction rates,and minimal byproduct pollution,successfully overcoming the challenges of the energy-intensive Haber-Bosch process.Recent innovations in two-dimensional(2D)electrocatalysts have emerged as a promising approach to enhance the efficiency and selectivity of this transformation.This review systematically examines the latest advancements in2D materials,including metals,metal compounds,nonmetallic elements,and organic frameworks,highlighting their unique electronic properties and high surface area that facilitate the electrocatalytic reactions.We explore strategies to optimize these catalysts,such as doping,heterostructure,and surface functionalization,which have shown significant improvements in catalytic performance.Furthermore,the role of in situ/operando characterization techniques in understanding the reaction mechanisms is highlighted,aiming to provide both theoretical and practical insights for the research and development of 2D nanoelectrocatalysts during eNRA.Additionally,future perspectives and ongoing challenges are discussed to offer insights for transitioning from experimental investigations to real-world applications.展开更多
After the synthesis of two‐dimensional(2D)graphene through mechanical exfoliation in 2004,2D nanomaterials have emerged as efficient catalysts for many types of reactions,including heterogeneous catalysis,due to thei...After the synthesis of two‐dimensional(2D)graphene through mechanical exfoliation in 2004,2D nanomaterials have emerged as efficient catalysts for many types of reactions,including heterogeneous catalysis,due to their distinct physicochemical and electronic properties.This review highlights recent progress in the application of 2D materials for selected heterogeneous thermo‐catalytic reactions,with an emphasis on their role as active catalysts or catalyst supports.The catalytic behavior of 2D materials,either as a catalyst or support,in various heterogeneous catalytic reactions,such as Knoevenagel condensation,Suzuki coupling,oxidative dehydrogenation,hydrogenation of nitroarenes,and oxidative desulfurization,is discussed.Particular attention is given to catalyst design strategies involving 2D materials functionalized with metal‐free active sites,as well as hybrid systems incorporating noble and non‐noble metals,although our primary focus is on metal‐free and structurally tunable 2D catalytic platforms.We conclude our discussion with a perspective on present challenges and future recommendations in this fast‐evolving field based on recent state‐of‐the‐art developments.In addition,we provide a critical perspective on current challenges and suggest future directions for the development of cost‐effective,selective,and durable 2D‐based catalysts.展开更多
Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance ...Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.展开更多
Lithium–sulfur batteries exhibit unparalleled merits in theoretical energy density(2600 W h kg^(-1))among next-generation storage systems.However,the sluggish electrochemical kinetics of sulfur reduction reactions,su...Lithium–sulfur batteries exhibit unparalleled merits in theoretical energy density(2600 W h kg^(-1))among next-generation storage systems.However,the sluggish electrochemical kinetics of sulfur reduction reactions,sulfide oxidation reactions in the sulfur cathode,and the lithium dendrite growth resulted from uncontrollable lithium behaviors in lithium anode have inhibited high-rate conversions and uniform deposition to achieve high performances.Thanks to the“adsorption-catalysis”synergetic effects,the reaction kinetics of sulfur reduction reactions/sulfide oxidation reactions composed of the delithiation of Li_(2)S and the interconversions of sulfur species are propelled by lowering the delithiation/diffusion energy barriers,inhibiting polysulfide shuttling.Meanwhile,the anodic plating kinetic behaviors modulated by the catalysts tend to uniformize without dendrite growth.In this review,the various active catalysts in modulating lithium behaviors are summarized,especially for the defect-rich catalysts and single atomic catalysts.The working mechanisms of these highly active catalysts revealed from theoretical simulation to in situ/operando characterizations are also highlighted.Furthermore,the opportunities of future higher performance enhancement to realize practical applications of lithium–sulfur batteries are prospected,shedding light on the future practical development.展开更多
Interfacial reactions in lithium-ion batteries often involve gaseous reaction products.Mechanistic investigation of material degradation processes requires a technique to identify and quantify these gases in battery c...Interfacial reactions in lithium-ion batteries often involve gaseous reaction products.Mechanistic investigation of material degradation processes requires a technique to identify and quantify these gases in battery cells.Online electrochemical mass spectrometry(OEMS)is an operando gas analysis method that continuously samples the headspace of a custom battery cell.Real-time gas analysis by quantitative OEMS was used to create mechanistic understanding of battery degradation reactions,some of which will be highlight in this article.展开更多
Supported Pd based catalysts are considered as the efficient candidates for low-carbon alkane oxidation for their outstanding capability to break C-H bond. Whereas, the irreversible deactivation of Pd based catalysts ...Supported Pd based catalysts are considered as the efficient candidates for low-carbon alkane oxidation for their outstanding capability to break C-H bond. Whereas, the irreversible deactivation of Pd based catalysts was still frequently observed. Herein, we reinforced the extruded Pd nanoparticles with quantitive Pt to assemble the evenly distributed Pd Pt nanoalloy onto ferrite perovskite(Pd Pt-LCF) matrix with strengthened robustness of metal/oxide support interface. We further co-achieved the enhanced performance, anti-overoxidation as well as resistance of vapor-poisoning in durability measurement. The operando X-ray photoelectron spectroscopy(O-XPS) combined with various morphology characterizations confirms that the accumulation of surface deep-oxidation species of Pd^(4+) is the culprit for fast activity loss in exsolved Pd system, especially at high temperature of 400 ℃. Conversely, it could be completely suppressed by in-situ alloying Pd with equal amount of Pt, which helps maintain the metastable Pd^(2+)/Pd shell and metallic solid-solution core structure. The density function theory(DFT) calculations further buttress that the dissociation of C–H was facilitated on alloy/perovskite interface which is, on the contrary, resistant toward O–H bond cleavage, as compared to Pd/perovskite. Our work suggests that the modification of exsolved metal/oxide catalytic interface could further enrich the toolkit of heterogeneous catalyst design.展开更多
The correlation of electrochemical measurements with materials characterization has advanced our understanding of operation and degradation mechanisms in electrochemical energy storage and many other fields.Yet,often ...The correlation of electrochemical measurements with materials characterization has advanced our understanding of operation and degradation mechanisms in electrochemical energy storage and many other fields.Yet,often these correlations are qualitative,preventing the unambiguous identification of both operational principles and the root causes of performance losses.Here we suggest quantitative approaches to define competing mechanisms and determine their relative contributions.We illustrate the importance of quantitative methodologies over a range of electrochemical systems and highlight the need to consider the effect of the experimental design and measurement itself.These approaches will reveal the most detrimental degradation mechanisms and enable the development of strategies to suppress,stabilize or eliminate them,leading to materials and devices with longer lifetimes,reduced environmental impact,and improved performance.展开更多
Heterogeneous catalysis is fundamental to chemical processes,with gas-solid catalysis extensively employed in chemical production,energy conversion,and environmental protection.Attaining high efficiency in these proce...Heterogeneous catalysis is fundamental to chemical processes,with gas-solid catalysis extensively employed in chemical production,energy conversion,and environmental protection.Attaining high efficiency in these processes necessitates catalysts exhibiting exceptional activity,selectivity,and stability,frequently accomplished using nanostructured metal catalysts.The continuous growth of active sites in heterogeneous metal catalysts presents a considerable obstacle for the precise identification of the genuine active sites.The emergence of in situ and operando characterization techniques has clarified the knowledge of dynamic alterations in active sites,offering substantial scientific information to underpin the rational design of catalysts.This review summarizes recent progress in the development of diverse situ/operando approaches for identifying active regions in catalytic conversion over heterogeneous catalysts.We comprehensively outline the applicability of diverse optical and X-ray spectroscopic techniques,including transmission electron microscopy,Raman spectroscopy,ultraviolet-visible spectroscopy,Fourier transform infrared spectroscopy,X-ray diffraction,X-ray photoelectron spectroscopy,and X-ray absorption spectroscopy,in identifying active sites and elucidating reaction processes in heterogeneous catalysis.The discussion encompasses issues and future views on the identification of active sites evolution during the reaction process,as well as the advancement of in situ and operando characterization approaches.展开更多
In-depth understanding of the electrolyte-dependent intercalation chemistry in batteries through direct operando/in situ characterizations is crucial for the development of the high-performance batteries.Herein,taking...In-depth understanding of the electrolyte-dependent intercalation chemistry in batteries through direct operando/in situ characterizations is crucial for the development of the high-performance batteries.Herein,taking the Al/graphite battery as a model system,the effect of electrolyte coordination structure on the intercalation processes has been investigated over the batteries with either 1-hexyl-3-methylimidazolium chloride(HMICl)-AlCl_(3) or 1-ethyl-3-methylimidazolium chloride(EMICl)-AlCl_(3) ionic liquid electrolyte using operando X-ray photoelectron spectroscopy(XPS)and X-ray diffraction.With a weaker anion-cation interaction in HMI-based electrolyte,the XPS-derived atomic ratio between cointercalated N and intercalated Al is 0.9,which is lower than 1.6 for EMI-based electrolyte.Attributed to the additional de-solvation process,the batteries with the HMI-based electrolyte show a lower ionic diffusion rate,capacity,and cycling performance,which agree with the operando characterization results.Our findings highlight the critical role of the electrolyte coordination structure on the(co-)intercalation chemistry.展开更多
Since the 1980s,single-crystal Pt electrodes with well-defined surface structures have been deemed stable under mild electrochemical conditions(e.g.,in the potential region of electric double layers,underpotential dep...Since the 1980s,single-crystal Pt electrodes with well-defined surface structures have been deemed stable under mild electrochemical conditions(e.g.,in the potential region of electric double layers,underpotential deposition of hydrogen,or mild hydrogen evolution/OH adsorption)and have served as model electrodes for unraveling the structure-performance relation in electrocatalysis.With the advancement of in situ electrochemical microscopy/spectroscopy techniques,subtle surface restructuring under mild electrochemical conditions has been achieved in the last decade.Surface restructuring can considerably modify electrocatalytic properties by generating/destroying highly active sites,thereby interfering with the deduction of the structure-performance relation.In this review,we summarize recent progress in the restructuring of well-defined Pt(-based)electrode surfaces under mild electrochemical conditions.The importance of the meticulous structural characterization of Pt electrodes before,during,and after electrochemical measurements is demonstrated using CO adsorption/oxidation,hydrogen adsorption/evolution,and oxygen reduction as examples.The implications of present findings for correctly identifying the reaction mechanisms and kinetics of other electrocatalytic systems are also briefly discussed.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
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 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partially supported by the National Natural Science Foundation of China (grant no. 22021001, 22179111)the Ministry of Science and Technology of China (grant no. 2021YFA1201900)+3 种基金the Basic Research Program of Tan Kah Kee Innovation Laboratory (grant no. RD2021070401)the Principal Fund from Xiamen University (grant no. 20720210015)the Fundamental Research Funds for the Central Universities (grant no. 20720220010)the National Natural Science Foundation of China (grant no. 22202082)。
文摘As the rapid development of more powerful and safer lithiumion batteries, the mechanism study of gases evolution is attacking more and more attention in recent years. Especially under overcharge/discharge and/or high-temperature working condition.
基金supported by the National Natural Science Foundation of China(51762014,52231007,12327804,T2321003,22088101)in part by the National Key Research Program of China under Grant 2021YFA1200600.
文摘Niobates are promising all-climate Li^(+)-storage anode material due to their fast charge transport,large specific capacities,and resistance to electrolyte reaction.However,their moderate unit-cellvolume expansion(generally 5%–10%)during Li^(+)storage causes unsatisfactory long-term cyclability.Here,“zero-strain”NiNb_(2)O_(6) fibers are explored as a new anode material with comprehensively good electrochemical properties.During Li^(+)storage,the expansion of electrochemical inactive NiO_(6) octahedra almost fully offsets the shrinkage of active NbO_(6) octahedra through reversible O movement.Such superior volume-accommodation capability of the NiO_(6) layers guarantees the“zero-strain”behavior of NiNb_(2)O_(6) in a broad temperature range(0.53%//0.51%//0.74%at 25//−10//60℃),leading to the excellent cyclability of the NiNb_(2)O_(6) fibers(92.8%//99.2%//91.1%capacity retention after 1000//2000//1000 cycles at 10C and 25//−10//60℃).This NiNb_(2)O_(6) material further exhibits a large reversible capacity(300//184//318 mAh g−1 at 0.1C and 25//−10//60℃)and outstanding rate performance(10 to 0.5C capacity percentage of 64.3%//50.0%//65.4%at 25//−10//60℃).Therefore,the NiNb_(2)O_(6) fibers are especially suitable for large-capacity,fast-charging,long-life,and all-climate lithium-ion batteries.
基金supported by the National Natural Science Foundation of China(Nos.52172291,52122312,and 52473294)'Shuguang Program'supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(No.22SG31)the State Key Laboratory for Advanced Fiber Materials,Donghua University
文摘Excessive nitrogen emission caused by human activities has significantly disrupted the global nitrogen cycle,adversely affecting ecosystems and human health.Electrocatalytic nitrate reduction to valuable ammonia(eNRA)presents an encouraging alternative marked by mild reaction conditions,rapid reaction rates,and minimal byproduct pollution,successfully overcoming the challenges of the energy-intensive Haber-Bosch process.Recent innovations in two-dimensional(2D)electrocatalysts have emerged as a promising approach to enhance the efficiency and selectivity of this transformation.This review systematically examines the latest advancements in2D materials,including metals,metal compounds,nonmetallic elements,and organic frameworks,highlighting their unique electronic properties and high surface area that facilitate the electrocatalytic reactions.We explore strategies to optimize these catalysts,such as doping,heterostructure,and surface functionalization,which have shown significant improvements in catalytic performance.Furthermore,the role of in situ/operando characterization techniques in understanding the reaction mechanisms is highlighted,aiming to provide both theoretical and practical insights for the research and development of 2D nanoelectrocatalysts during eNRA.Additionally,future perspectives and ongoing challenges are discussed to offer insights for transitioning from experimental investigations to real-world applications.
基金supported by the Joint Funds of the National Natural Science Foundation of China(U24B20201)the National Natural Science Foundation of China(22372007 and 21972010).
文摘After the synthesis of two‐dimensional(2D)graphene through mechanical exfoliation in 2004,2D nanomaterials have emerged as efficient catalysts for many types of reactions,including heterogeneous catalysis,due to their distinct physicochemical and electronic properties.This review highlights recent progress in the application of 2D materials for selected heterogeneous thermo‐catalytic reactions,with an emphasis on their role as active catalysts or catalyst supports.The catalytic behavior of 2D materials,either as a catalyst or support,in various heterogeneous catalytic reactions,such as Knoevenagel condensation,Suzuki coupling,oxidative dehydrogenation,hydrogenation of nitroarenes,and oxidative desulfurization,is discussed.Particular attention is given to catalyst design strategies involving 2D materials functionalized with metal‐free active sites,as well as hybrid systems incorporating noble and non‐noble metals,although our primary focus is on metal‐free and structurally tunable 2D catalytic platforms.We conclude our discussion with a perspective on present challenges and future recommendations in this fast‐evolving field based on recent state‐of‐the‐art developments.In addition,we provide a critical perspective on current challenges and suggest future directions for the development of cost‐effective,selective,and durable 2D‐based catalysts.
基金supported by the National Natural Science Foundation of China(No.52221004)the Shenzhen Science and Technology Program(No.RCJC20221008092758099)+1 种基金the Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(No.SZPR2023004)the Guangdong Higher Education Institutions Innovative Research Team of Urban Water Cycle and Ecological Safety(No.2023KCXTD053).
文摘Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.
基金fellowship funding supported by the Alexander von Humboldt Foundationfinancial funding support from the Natural Science Foundation of Jiangsu Province(BK.20210636)Natural Science Foundation of China(21773294 and 21972164)。
文摘Lithium–sulfur batteries exhibit unparalleled merits in theoretical energy density(2600 W h kg^(-1))among next-generation storage systems.However,the sluggish electrochemical kinetics of sulfur reduction reactions,sulfide oxidation reactions in the sulfur cathode,and the lithium dendrite growth resulted from uncontrollable lithium behaviors in lithium anode have inhibited high-rate conversions and uniform deposition to achieve high performances.Thanks to the“adsorption-catalysis”synergetic effects,the reaction kinetics of sulfur reduction reactions/sulfide oxidation reactions composed of the delithiation of Li_(2)S and the interconversions of sulfur species are propelled by lowering the delithiation/diffusion energy barriers,inhibiting polysulfide shuttling.Meanwhile,the anodic plating kinetic behaviors modulated by the catalysts tend to uniformize without dendrite growth.In this review,the various active catalysts in modulating lithium behaviors are summarized,especially for the defect-rich catalysts and single atomic catalysts.The working mechanisms of these highly active catalysts revealed from theoretical simulation to in situ/operando characterizations are also highlighted.Furthermore,the opportunities of future higher performance enhancement to realize practical applications of lithium–sulfur batteries are prospected,shedding light on the future practical development.
基金BASF SE(Germany)for their fundingfunding from the German Federal Ministry of Education and Research(BMBF)within the projects ExZellTUMⅡ(grant number 03XP0081)and ExZellTUMⅢ(grant number 03XP0255)and of BMW AG。
文摘Interfacial reactions in lithium-ion batteries often involve gaseous reaction products.Mechanistic investigation of material degradation processes requires a technique to identify and quantify these gases in battery cells.Online electrochemical mass spectrometry(OEMS)is an operando gas analysis method that continuously samples the headspace of a custom battery cell.Real-time gas analysis by quantitative OEMS was used to create mechanistic understanding of battery degradation reactions,some of which will be highlight in this article.
基金supported by the National Natural Science Foundation of China (Nos.22272136, 22202041, 22102135, 22202163,22172129)the Fundamental Research Funds for the Central Universities (No.20720220119)+3 种基金Science and Technology Project of Fujian Province (No.2022L3077)the financial support from Guangdong Basic and Applied Basic Research Fund (No.2022A1515110239)the funds from Science and Technology Projects of Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM)(No.HRTP-[2022]-3)the Fundamental Research Funds for the Central Universities (No.20720220008)。
文摘Supported Pd based catalysts are considered as the efficient candidates for low-carbon alkane oxidation for their outstanding capability to break C-H bond. Whereas, the irreversible deactivation of Pd based catalysts was still frequently observed. Herein, we reinforced the extruded Pd nanoparticles with quantitive Pt to assemble the evenly distributed Pd Pt nanoalloy onto ferrite perovskite(Pd Pt-LCF) matrix with strengthened robustness of metal/oxide support interface. We further co-achieved the enhanced performance, anti-overoxidation as well as resistance of vapor-poisoning in durability measurement. The operando X-ray photoelectron spectroscopy(O-XPS) combined with various morphology characterizations confirms that the accumulation of surface deep-oxidation species of Pd^(4+) is the culprit for fast activity loss in exsolved Pd system, especially at high temperature of 400 ℃. Conversely, it could be completely suppressed by in-situ alloying Pd with equal amount of Pt, which helps maintain the metastable Pd^(2+)/Pd shell and metallic solid-solution core structure. The density function theory(DFT) calculations further buttress that the dissociation of C–H was facilitated on alloy/perovskite interface which is, on the contrary, resistant toward O–H bond cleavage, as compared to Pd/perovskite. Our work suggests that the modification of exsolved metal/oxide catalytic interface could further enrich the toolkit of heterogeneous catalyst design.
基金supported in full by the Joint Center for Energy Storage Researchan Energy Innovation Hub funded by the U.S.Department of Energy,Office of Science,Basic Energy Sciences.
文摘The correlation of electrochemical measurements with materials characterization has advanced our understanding of operation and degradation mechanisms in electrochemical energy storage and many other fields.Yet,often these correlations are qualitative,preventing the unambiguous identification of both operational principles and the root causes of performance losses.Here we suggest quantitative approaches to define competing mechanisms and determine their relative contributions.We illustrate the importance of quantitative methodologies over a range of electrochemical systems and highlight the need to consider the effect of the experimental design and measurement itself.These approaches will reveal the most detrimental degradation mechanisms and enable the development of strategies to suppress,stabilize or eliminate them,leading to materials and devices with longer lifetimes,reduced environmental impact,and improved performance.
基金supported by the National Natural Science Foundation of China(Grant Nos.22276145,22406146,and 22476157)the China Postdoctoral Science Foundation(Grant No.2023M732783).
文摘Heterogeneous catalysis is fundamental to chemical processes,with gas-solid catalysis extensively employed in chemical production,energy conversion,and environmental protection.Attaining high efficiency in these processes necessitates catalysts exhibiting exceptional activity,selectivity,and stability,frequently accomplished using nanostructured metal catalysts.The continuous growth of active sites in heterogeneous metal catalysts presents a considerable obstacle for the precise identification of the genuine active sites.The emergence of in situ and operando characterization techniques has clarified the knowledge of dynamic alterations in active sites,offering substantial scientific information to underpin the rational design of catalysts.This review summarizes recent progress in the development of diverse situ/operando approaches for identifying active regions in catalytic conversion over heterogeneous catalysts.We comprehensively outline the applicability of diverse optical and X-ray spectroscopic techniques,including transmission electron microscopy,Raman spectroscopy,ultraviolet-visible spectroscopy,Fourier transform infrared spectroscopy,X-ray diffraction,X-ray photoelectron spectroscopy,and X-ray absorption spectroscopy,in identifying active sites and elucidating reaction processes in heterogeneous catalysis.The discussion encompasses issues and future views on the identification of active sites evolution during the reaction process,as well as the advancement of in situ and operando characterization approaches.
基金financially supported by the National Key R&D Program of China (2021YFA1502800)the National Natural Science Foundation of China (21825203,22288201,and 91945302)+1 种基金the Photon Science Center for Carbon Neutrality,Liao Ning Revitalization Talents Program (XLYC1902117)the Youth Innovation Fund of Dalian institute of Chemical Physics (DICP I202125)。
文摘In-depth understanding of the electrolyte-dependent intercalation chemistry in batteries through direct operando/in situ characterizations is crucial for the development of the high-performance batteries.Herein,taking the Al/graphite battery as a model system,the effect of electrolyte coordination structure on the intercalation processes has been investigated over the batteries with either 1-hexyl-3-methylimidazolium chloride(HMICl)-AlCl_(3) or 1-ethyl-3-methylimidazolium chloride(EMICl)-AlCl_(3) ionic liquid electrolyte using operando X-ray photoelectron spectroscopy(XPS)and X-ray diffraction.With a weaker anion-cation interaction in HMI-based electrolyte,the XPS-derived atomic ratio between cointercalated N and intercalated Al is 0.9,which is lower than 1.6 for EMI-based electrolyte.Attributed to the additional de-solvation process,the batteries with the HMI-based electrolyte show a lower ionic diffusion rate,capacity,and cycling performance,which agree with the operando characterization results.Our findings highlight the critical role of the electrolyte coordination structure on the(co-)intercalation chemistry.
文摘Since the 1980s,single-crystal Pt electrodes with well-defined surface structures have been deemed stable under mild electrochemical conditions(e.g.,in the potential region of electric double layers,underpotential deposition of hydrogen,or mild hydrogen evolution/OH adsorption)and have served as model electrodes for unraveling the structure-performance relation in electrocatalysis.With the advancement of in situ electrochemical microscopy/spectroscopy techniques,subtle surface restructuring under mild electrochemical conditions has been achieved in the last decade.Surface restructuring can considerably modify electrocatalytic properties by generating/destroying highly active sites,thereby interfering with the deduction of the structure-performance relation.In this review,we summarize recent progress in the restructuring of well-defined Pt(-based)electrode surfaces under mild electrochemical conditions.The importance of the meticulous structural characterization of Pt electrodes before,during,and after electrochemical measurements is demonstrated using CO adsorption/oxidation,hydrogen adsorption/evolution,and oxygen reduction as examples.The implications of present findings for correctly identifying the reaction mechanisms and kinetics of other electrocatalytic systems are also briefly discussed.
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.
