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
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
Inhalable particle is a harmful air pollutant that causes a significant threat to people's health and ecological environments,which should be removed to purify air,but there exists limited removal efficiency due t...Inhalable particle is a harmful air pollutant that causes a significant threat to people's health and ecological environments,which should be removed to purify air,but there exists limited removal efficiency due to particle re-entrainment.Here,Operando observation system based on microscopic visualization method is developed to make in situ test of particle migration,deposition and re-entrainment characteristics on a lab-on-a-chip to achieve the investigation in micro-level scale.The deposition evolution of charged particles is recorded in electric field region intuitively,which confirms the fracture of particle chain occurs during the growth process of deposited particles.It captures the instantaneous process that a larger particle with micron size due to the coagulation of submicron particles fractures from main body of the particle chain for the first time.The analysis of migration behavior of a single submicron particle near electrode surface demonstrates the direct influence of drag force on the fracture of particle chain.This work is the first-time visualization of dynamic process and mechanism elucidation of particle re-entrainment at the micron level,and the findings will provide the theory support for the particle re-entrainment mechanism and bring inspires of enhancing capture efficiency of inhalable particle.展开更多
Additives in the electrolytes of Li-S batteries aim to increase overall capacity,improve Li ion conductivity,enhance cyclability,and mitigate the shuttle effect,which is one of the major issues of this system.Here,the...Additives in the electrolytes of Li-S batteries aim to increase overall capacity,improve Li ion conductivity,enhance cyclability,and mitigate the shuttle effect,which is one of the major issues of this system.Here,the use of water as an additive in the commonly used electrolyte,1.0 M LiTFSI/1.0%(w/w) LiNO_(3) and a 1:1 mixture of 1,3-dioxolane(DOL) and 1,2-dimethoxyethane(DME) was investigated.We used Co_(2)Mn_(0.5)Al_(0.5)O_(4)(CMA) as an electrocatalyst anchored on an activated carbon(AC) electrode with added sulfur via a melt-diffusion process.The structural analysis of CMA via Rietveld refinement showed interatomic spaces that can promote ionic conductivity,facilitating Li^(+) ion migration.Electrochemical tests determined 1600 ppm as the optimal water concentration,significantly reducing the shuttle effect.Post-mortem XPS analysis focused on the lithium metal anode revealed the formation of Li_(2)O layers in dry samples and LiOH in wet samples.Better capacity was observed in wet samples,which can be attributed to the superior ionic conductivity of LiOH at the electrode/electrolyte interface,surpassing that of Li_(2)O by 12 times.Finally,Operando FTIR experiments provided real-time insights into electrolyte degradation and SEI formation,elucidating the activity mechanisms of water and Li_(2)CO_(3) over the cycles.This work presents results that could aid future advancements in Li-S battery technology,offering possibilities to mitigate its challenges with inexpensive and scalable additives.展开更多
Semiconductor-molecule surface-enhanced Raman scattering(SERS),especially the stronger interfacial charge transfer process(ICTP),represents a frontier in the field of SERS with spectral reproducibility and unparallele...Semiconductor-molecule surface-enhanced Raman scattering(SERS),especially the stronger interfacial charge transfer process(ICTP),represents a frontier in the field of SERS with spectral reproducibility and unparalleled selectivity.Herein,through a laser microfabrication method in situ,the free-standing,super hydrophilic and vacancy-rich TiO_(2-x)/Ti is successfully synthesized.Using blue TiO_(x)/Ti(B-TiO_(x)/Ti)as preconcentrated substrate,a nanomolar-level limit of detection of 12 nmol/L at 1385 cm–1,is confirmed using crystal violet(CV)bacteriostat as a model under 532 nm excitation.Furthermore,the results demonstrate that the SERS enhancement mechanism is via the moderate adulteration of oxygen vacancy,which leads to a narrow value of band gap and increases the ICTP of substrate to molecules.Using a hand-held extractor assembled with B-TiO_(x)/Ti microfiber,the operando analysis of mixtures distributed information excited in different parts of Asian carp is facilely achieved.This work guides the controlled synthesis of vacancy-rich TiO_(2-x)/Ti nanostructure and its application in ultrasensitive extraction-SERS detection.It also provides the direction for the rapid and operando transmission of biological information with temporal and spatial concentration distribution in human tissues by highly sensitized materials.展开更多
The combination of electrochemical measurements with spectroscopic characterizations provides valuable insights into reaction mechanisms.Nuclear magnetic resonance(NMR)spectroscopy,as a powerful technique due to its a...The combination of electrochemical measurements with spectroscopic characterizations provides valuable insights into reaction mechanisms.Nuclear magnetic resonance(NMR)spectroscopy,as a powerful technique due to its atomic specificity and versatility in studying gas,liquid,and solid,allows the study of electrolyte solution,catalyst and catalyst-adsorbate interfaces.When applied in operando,NMR can offer molecular-level insights into various electrochemical processes.Operando NMR has been applied extensively in battery research,but relatively underexplored for electrocatalysis in the past two decades.In this mini review,we first introduce the operando electrochemical NMR setups,categorized by different probe designs.Then we review the applications of operando NMR for monitoring the electrolyte solution and the catalyst-adsorbate interface.Considering the high environmental impact of electrochemical conversion of CO_(2)into value-added products,we zoom in to the use of operando NMR in studying electrochemical CO_(2)reduction.Finally,we provide our perspective on further developing and applying operando NMR methods for understanding the complex reaction network of Cu-catalyzed electrochemical CO_(2)reduction.展开更多
The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation...The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation of CO_(2)to produce marketable carbon-based products like methanol and ethanol is a practical approach that offers great potential to reduce CO_(2)emissions.Although significant volumes of methanol are currently produced from CO_(2),developing highly efficient and stable catalysts is crucial for further enhancing conversion and selectivity,thereby reducing process costs.An in-depth examination of the differences and similarities in the reaction pathways for methanol and ethanol production highlights the key factors that drive C-C coupling.Identifying these factors guides us toward developing more effective catalysts for ethanol synthesis.In this paper,we explore how different catalysts,through the production of various intermediates,can initiate the synthesis of methanol or ethanol.The catalytic mechanisms proposed by spectroscopic techniques and theoretical calculations,including operando X-ray methods,FTIR analysis,and DFT calculations,are summarized and presented.The following discussion explores the structural properties and composition of catalysts that influence C-C coupling and optimize the conversion rate of CO_(2)into ethanol.Lastly,the review examines recent catalysts employed for selective methanol and ethanol production,focusing on single-atom catalysts.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
Extensively explored for their distinctive pseudocapacitance characteristics,MXenes,a distinguished group of 2D materials,have led to remarkable achievements,particularly in the realm of energy storage devices.This wo...Extensively explored for their distinctive pseudocapacitance characteristics,MXenes,a distinguished group of 2D materials,have led to remarkable achievements,particularly in the realm of energy storage devices.This work presents an innovative Pseudocapacitive Sensor.The key lies in switching the energy storage kinetics from pseudocapacitor to electrical double layer capacitor by employing the change of local pH(-log[H^(+)])in MXene-based flexible supercapacitors during bending.Pseudocapacitive sensing is observed in acidic electrolyte but absent in neutral electrolyte.Applied shearing during bending causes liquid-crystalline MXene sheets to increase in their degree of anisotropic alignment.With blocking of H+mobility due to the higher diffusion barrier,local pH increases.The electrochemical energy storage kinetics transits from Faradaic chemical protonation(intercalation)to non-Faradaic physical adsorption.We utilize the phenomenon of capacitance change due to shifting energy storage kinetics for strain sensing purposes.The developed highly sensitive Pseudocapacitive Sensors feature a remarkable gauge factor(GF)of approximately 1200,far surpassing conventional strain sensors(GF:~1 for dielectric-cap sensor).The introduction of the Pseudocapacitive Sensor represents a paradigm shift,expanding the application of pseudocapacitance from being solely confined to energy devices to the realm of multifunctional electronics.This technological leap enriches our understanding of the pseudocapacitance mechanism of MXenes,and will drive innovation in cutting-edge technology areas,including advanced robotics,implantable biomedical devices,and health monitoring systems.展开更多
The lithium(Li)metal anode is regarded as the upcoming generation of battery anodes due to its high theoretical capacity(3860 mAh g^(-1))and low standard reduction potential(-3.04 vs SHE).Addressing challenges related...The lithium(Li)metal anode is regarded as the upcoming generation of battery anodes due to its high theoretical capacity(3860 mAh g^(-1))and low standard reduction potential(-3.04 vs SHE).Addressing challenges related to the formation of Li metal dendrites,such as short circuits and low Coulombic efficiency,is crucial for the practical implementation of Li metal anodes.Previous research on Li metal has primarily focus on the Li plating process for achieving homogeneous growth.However,our study highlights the significance of pit formation variations,which significantly influence Li growth behavior in subsequent cycles.Expanding on this understanding,we formulated electrochemical activation conditions to promote uniform pit formation,thereby doubling the cycle life in a symmetric cell,and increasing the capacity retention of NCM622||Li full-cell from 68.7%to 79.5%after 500 cycles.展开更多
Tuning the metal-oxide interface to achieve optimal catalytic performance represents a classic yet fast-growing area in catalysis research.This work demonstrated that the decoration of CeO_(2) clusters onto Ni particl...Tuning the metal-oxide interface to achieve optimal catalytic performance represents a classic yet fast-growing area in catalysis research.This work demonstrated that the decoration of CeO_(2) clusters onto Ni particles creates electron-enriched Ni sites at the Ni-CeO_(2) interface with highly efficient CO methanation,by kinetics,chemical titration,and a series of in situ/operando spectroscopic characterizations.These electron-enriched Ni atoms facilitate the back-donation of electrons into the orbital of CO and thus reduce the reaction barrier of CH_(4) formation,but do not alter the catalytic steps and their kinetic relevance as well as the evolution of surface intermediates during CO methanation.The amount of electron-enriched Ni atoms increases significantly to a maximum value and then decreases as the content of CeO_(2) increases,leading the formation rates of CH_(4) to increase in a volcano-type relation with CeO_(2) contents in xCeNi/Al_(2)O_(3) catalysts.These insights provide a comprehensive understanding of the nature and the role of the metal-oxide interface and could potentially guide the rational design of highly efficient oxide-supported catalysts for CO methanation.展开更多
Lithium-rich manganese-based oxide(LRMO)cathode has emerged as a particularly promising candidate for achieving high energy densities in lithium-ion batteries due to its capability to access anion redox reactions at h...Lithium-rich manganese-based oxide(LRMO)cathode has emerged as a particularly promising candidate for achieving high energy densities in lithium-ion batteries due to its capability to access anion redox reactions at high voltage.The successful implementation of LRMO in energy storage systems is contingent upon the enhancement of their rate capabilities.However,the underlying relationship between high-rate cycling and electrode degradation for LRMO,particularly concerning structural evolution,still remains unclear.Benefiting from the high time resolution abilities of liquid-metal-jet operando twodimensional X-ray diffraction,it is observed that the Li_(2)MnO_(3)phase in LRMO is gradually activated accompanied by the emergence of oxygen vacancies during cycling at 1 C(1 C=250 mA/g).Consequently,the crystal lattice flexibility of LRMO is systematically enhanced,thereby preventing the collapse of the bulk structure.While,continuous release of oxygen during extended cycling results in deteriorations of the self-adjusting damping effect of the structure,ultimately leading to a decline in capacity.The findings of this study not only contribute to a more profound understanding of the structural changes of LRMOs at high rates,but also provide novel perspectives for the rational design of LRMOs with superior rate performances.展开更多
Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H_(2)O_(2) is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated ...Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H_(2)O_(2) is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated charge efficiency and unfavorable thermodynamics. Herein, by crystal orientation engineering, the WO_(3) photoanode exposing (200) facets achieves both superior WOR activity (15.4 mA cm^(−2) at 1.76 VRHE) and high selectivity to H_(2)O_(2) (∼70%). Comprehensive experimental and theoretical investigations discover that the high PEC-WOR activity of WO_(3)-(200) is attributed to the rapid photogenerated charge separation/transfer both in bulk and at interfaces of WO_(3)-(200) facet, which reduces the charge transfer resistance. This, coupling with the unique defective hydrogen bonding network at the WO_(3)-(200)/electrolyte interface evidenced by operando PEC Fourier transform infrared spectroscopy, facilitating the outward-transfer of the WOR-produced H^(+), lowers the overall reaction barrier for the PEC-WOR. The superior selectivity of PEC-WOR to H_(2)O_(2) is ascribed to the unique defective hydrogen bonding network alleviated adsorption of ∗OH over the WO_(3)-(200) facet, which specially lowers the energy barrier of the 2-electron pathway, as compared to the 4-electron pathway. This work addresses the significant role of crystal orientation engineering on photoelectrocatalytic activity and selectivity, and sheds lights on the underlying PEC mechanism by understanding the water adsorption behaviors under illumination. The knowledge gained is expected to be extended to other photoeletrochemical reactions.展开更多
The electrochemical CO_(2)reduction reaction(CO_(2)RR)is considered a promising technology for converting atmospheric CO_(2)into valuable chemicals.It is a significant way to mitigate the shortage of fossil energy and...The electrochemical CO_(2)reduction reaction(CO_(2)RR)is considered a promising technology for converting atmospheric CO_(2)into valuable chemicals.It is a significant way to mitigate the shortage of fossil energy and store excessive renewable electricity in fuels to maintain carbon neutrality.Considering the substantially reduced cost of clean electricity,C1 molecule unitization has emerged as a competitive strategy for room-temperature electrolysis.However,the practical implementation of CO_(2)RR has been hindered by low desired product selectivity,high overpotential,and undesirable hydrogen evolution reactions(HER).Consequently,it is imperative to execute a timely assessment of advanced strategies in CO_(2)RR,with emphasis on catalytic design strategies,understanding of structure–activity relationships,and deactivation of catalysts.In this context,it is imperative to investigate the intrinsic active sites and reaction mechanisms.This review focuses on the design of novel catalysts and their active sites via operando techniques.The combination of advanced characterization techniques and theoretical calculations provides a high-throughput way to obtain a deeper understanding of the reaction mechanism.Furthermore,optimization of the interplay between the catalyst surface and reaction intermediate disturbs the linear correlation between the adsorption energies of the intermediates,resulting in a convoluted cascade system.The appropriate strategies for CO_(2)RR,challenges,and future approaches are projected in this review to stimulate major innovations.Moreover,the plausible research directions are discussed for producing C_(1)chemicals via electrochemical CO_(2)RR at room temperature.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
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 the National Natural Science Foundation of China (Nos.52200130 and 22176123)Postdoctoral Science Foundation of China (No.2022M722082)the National Key Research&Development Plan (No.2017YFC0211804)。
文摘Inhalable particle is a harmful air pollutant that causes a significant threat to people's health and ecological environments,which should be removed to purify air,but there exists limited removal efficiency due to particle re-entrainment.Here,Operando observation system based on microscopic visualization method is developed to make in situ test of particle migration,deposition and re-entrainment characteristics on a lab-on-a-chip to achieve the investigation in micro-level scale.The deposition evolution of charged particles is recorded in electric field region intuitively,which confirms the fracture of particle chain occurs during the growth process of deposited particles.It captures the instantaneous process that a larger particle with micron size due to the coagulation of submicron particles fractures from main body of the particle chain for the first time.The analysis of migration behavior of a single submicron particle near electrode surface demonstrates the direct influence of drag force on the fracture of particle chain.This work is the first-time visualization of dynamic process and mechanism elucidation of particle re-entrainment at the micron level,and the findings will provide the theory support for the particle re-entrainment mechanism and bring inspires of enhancing capture efficiency of inhalable particle.
基金the financial support from the Brazilian funding agencies FAPESP. (2024/01031-1, 2022/022220, 2020/04281-8, 21/14442-1, 17/11986-5)support from FAPESP through the research project Pi (2022/02901-4)+2 种基金CAPES (1740195)CNPq through the research grant (313672/2021-0)support Shell and the strategic importance of the support given by ANP (Brazil’s National Oil, Natural Gas and Biofuels Agency) through the R & D levy regulation。
文摘Additives in the electrolytes of Li-S batteries aim to increase overall capacity,improve Li ion conductivity,enhance cyclability,and mitigate the shuttle effect,which is one of the major issues of this system.Here,the use of water as an additive in the commonly used electrolyte,1.0 M LiTFSI/1.0%(w/w) LiNO_(3) and a 1:1 mixture of 1,3-dioxolane(DOL) and 1,2-dimethoxyethane(DME) was investigated.We used Co_(2)Mn_(0.5)Al_(0.5)O_(4)(CMA) as an electrocatalyst anchored on an activated carbon(AC) electrode with added sulfur via a melt-diffusion process.The structural analysis of CMA via Rietveld refinement showed interatomic spaces that can promote ionic conductivity,facilitating Li^(+) ion migration.Electrochemical tests determined 1600 ppm as the optimal water concentration,significantly reducing the shuttle effect.Post-mortem XPS analysis focused on the lithium metal anode revealed the formation of Li_(2)O layers in dry samples and LiOH in wet samples.Better capacity was observed in wet samples,which can be attributed to the superior ionic conductivity of LiOH at the electrode/electrolyte interface,surpassing that of Li_(2)O by 12 times.Finally,Operando FTIR experiments provided real-time insights into electrolyte degradation and SEI formation,elucidating the activity mechanisms of water and Li_(2)CO_(3) over the cycles.This work presents results that could aid future advancements in Li-S battery technology,offering possibilities to mitigate its challenges with inexpensive and scalable additives.
基金supported by National Key Research and Development Program of China(No.2023YFB3210400)Major Scientific and Technological Innovation Project of Shandong Province(No.2021CXGC010603)+1 种基金Natural Science Foundation of Shandong Province(Nos.ZR2020QE057,ZR2020QE071,ZR2020LLZ006)Innovative Team Project of Jinan(No.2021GXRC019)。
文摘Semiconductor-molecule surface-enhanced Raman scattering(SERS),especially the stronger interfacial charge transfer process(ICTP),represents a frontier in the field of SERS with spectral reproducibility and unparalleled selectivity.Herein,through a laser microfabrication method in situ,the free-standing,super hydrophilic and vacancy-rich TiO_(2-x)/Ti is successfully synthesized.Using blue TiO_(x)/Ti(B-TiO_(x)/Ti)as preconcentrated substrate,a nanomolar-level limit of detection of 12 nmol/L at 1385 cm–1,is confirmed using crystal violet(CV)bacteriostat as a model under 532 nm excitation.Furthermore,the results demonstrate that the SERS enhancement mechanism is via the moderate adulteration of oxygen vacancy,which leads to a narrow value of band gap and increases the ICTP of substrate to molecules.Using a hand-held extractor assembled with B-TiO_(x)/Ti microfiber,the operando analysis of mixtures distributed information excited in different parts of Asian carp is facilely achieved.This work guides the controlled synthesis of vacancy-rich TiO_(2-x)/Ti nanostructure and its application in ultrasensitive extraction-SERS detection.It also provides the direction for the rapid and operando transmission of biological information with temporal and spatial concentration distribution in human tissues by highly sensitized materials.
基金support from Radboud University Start-up and NWO Open Competition ENW-M grant (OCENW.M.21.308)support from China Scholarship Council
文摘The combination of electrochemical measurements with spectroscopic characterizations provides valuable insights into reaction mechanisms.Nuclear magnetic resonance(NMR)spectroscopy,as a powerful technique due to its atomic specificity and versatility in studying gas,liquid,and solid,allows the study of electrolyte solution,catalyst and catalyst-adsorbate interfaces.When applied in operando,NMR can offer molecular-level insights into various electrochemical processes.Operando NMR has been applied extensively in battery research,but relatively underexplored for electrocatalysis in the past two decades.In this mini review,we first introduce the operando electrochemical NMR setups,categorized by different probe designs.Then we review the applications of operando NMR for monitoring the electrolyte solution and the catalyst-adsorbate interface.Considering the high environmental impact of electrochemical conversion of CO_(2)into value-added products,we zoom in to the use of operando NMR in studying electrochemical CO_(2)reduction.Finally,we provide our perspective on further developing and applying operando NMR methods for understanding the complex reaction network of Cu-catalyzed electrochemical CO_(2)reduction.
基金the Canadian NRCan OERD Energy Innovation Programthe Natural Sciences and Engineering Research Council of Canada,and the Carbon Solution Program for their financial support.
文摘The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation of CO_(2)to produce marketable carbon-based products like methanol and ethanol is a practical approach that offers great potential to reduce CO_(2)emissions.Although significant volumes of methanol are currently produced from CO_(2),developing highly efficient and stable catalysts is crucial for further enhancing conversion and selectivity,thereby reducing process costs.An in-depth examination of the differences and similarities in the reaction pathways for methanol and ethanol production highlights the key factors that drive C-C coupling.Identifying these factors guides us toward developing more effective catalysts for ethanol synthesis.In this paper,we explore how different catalysts,through the production of various intermediates,can initiate the synthesis of methanol or ethanol.The catalytic mechanisms proposed by spectroscopic techniques and theoretical calculations,including operando X-ray methods,FTIR analysis,and DFT calculations,are summarized and presented.The following discussion explores the structural properties and composition of catalysts that influence C-C coupling and optimize the conversion rate of CO_(2)into ethanol.Lastly,the review examines recent catalysts employed for selective methanol and ethanol production,focusing on single-atom catalysts.
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 NRF-2021M3H4A1A03047333 and NRF-2022R1F1A1075084 of the National Research Foundation(NRF)of Korea funded by the Ministry of Science and ICT,Koreasupported by Semiconductor-Secondary Battery Interfacing Platform Technology Development Project of NNFC.
文摘Extensively explored for their distinctive pseudocapacitance characteristics,MXenes,a distinguished group of 2D materials,have led to remarkable achievements,particularly in the realm of energy storage devices.This work presents an innovative Pseudocapacitive Sensor.The key lies in switching the energy storage kinetics from pseudocapacitor to electrical double layer capacitor by employing the change of local pH(-log[H^(+)])in MXene-based flexible supercapacitors during bending.Pseudocapacitive sensing is observed in acidic electrolyte but absent in neutral electrolyte.Applied shearing during bending causes liquid-crystalline MXene sheets to increase in their degree of anisotropic alignment.With blocking of H+mobility due to the higher diffusion barrier,local pH increases.The electrochemical energy storage kinetics transits from Faradaic chemical protonation(intercalation)to non-Faradaic physical adsorption.We utilize the phenomenon of capacitance change due to shifting energy storage kinetics for strain sensing purposes.The developed highly sensitive Pseudocapacitive Sensors feature a remarkable gauge factor(GF)of approximately 1200,far surpassing conventional strain sensors(GF:~1 for dielectric-cap sensor).The introduction of the Pseudocapacitive Sensor represents a paradigm shift,expanding the application of pseudocapacitance from being solely confined to energy devices to the realm of multifunctional electronics.This technological leap enriches our understanding of the pseudocapacitance mechanism of MXenes,and will drive innovation in cutting-edge technology areas,including advanced robotics,implantable biomedical devices,and health monitoring systems.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea Government(MSIT)(RS-202400422387)the National Research Foundation of Korea(NRF)grant funded by the Korea Government(MSIT)(RS-2024-00404414)support by The Ministry of Science and ICT in Korea via KBSI(Grant No.C524100).
文摘The lithium(Li)metal anode is regarded as the upcoming generation of battery anodes due to its high theoretical capacity(3860 mAh g^(-1))and low standard reduction potential(-3.04 vs SHE).Addressing challenges related to the formation of Li metal dendrites,such as short circuits and low Coulombic efficiency,is crucial for the practical implementation of Li metal anodes.Previous research on Li metal has primarily focus on the Li plating process for achieving homogeneous growth.However,our study highlights the significance of pit formation variations,which significantly influence Li growth behavior in subsequent cycles.Expanding on this understanding,we formulated electrochemical activation conditions to promote uniform pit formation,thereby doubling the cycle life in a symmetric cell,and increasing the capacity retention of NCM622||Li full-cell from 68.7%to 79.5%after 500 cycles.
文摘Tuning the metal-oxide interface to achieve optimal catalytic performance represents a classic yet fast-growing area in catalysis research.This work demonstrated that the decoration of CeO_(2) clusters onto Ni particles creates electron-enriched Ni sites at the Ni-CeO_(2) interface with highly efficient CO methanation,by kinetics,chemical titration,and a series of in situ/operando spectroscopic characterizations.These electron-enriched Ni atoms facilitate the back-donation of electrons into the orbital of CO and thus reduce the reaction barrier of CH_(4) formation,but do not alter the catalytic steps and their kinetic relevance as well as the evolution of surface intermediates during CO methanation.The amount of electron-enriched Ni atoms increases significantly to a maximum value and then decreases as the content of CeO_(2) increases,leading the formation rates of CH_(4) to increase in a volcano-type relation with CeO_(2) contents in xCeNi/Al_(2)O_(3) catalysts.These insights provide a comprehensive understanding of the nature and the role of the metal-oxide interface and could potentially guide the rational design of highly efficient oxide-supported catalysts for CO methanation.
基金financial supports from the National Natural Science Foundation of China(52372211,52371225 and 92472115)the Guangdong Province Major Talent Introducing Program(2021QN020687)+1 种基金the Shenzhen Basic Research Foundation(JCYJ20230807112503007)the Guangdong Basic and Applied Basic Research Foundation(Grant No.2020A1515110176)。
文摘Lithium-rich manganese-based oxide(LRMO)cathode has emerged as a particularly promising candidate for achieving high energy densities in lithium-ion batteries due to its capability to access anion redox reactions at high voltage.The successful implementation of LRMO in energy storage systems is contingent upon the enhancement of their rate capabilities.However,the underlying relationship between high-rate cycling and electrode degradation for LRMO,particularly concerning structural evolution,still remains unclear.Benefiting from the high time resolution abilities of liquid-metal-jet operando twodimensional X-ray diffraction,it is observed that the Li_(2)MnO_(3)phase in LRMO is gradually activated accompanied by the emergence of oxygen vacancies during cycling at 1 C(1 C=250 mA/g).Consequently,the crystal lattice flexibility of LRMO is systematically enhanced,thereby preventing the collapse of the bulk structure.While,continuous release of oxygen during extended cycling results in deteriorations of the self-adjusting damping effect of the structure,ultimately leading to a decline in capacity.The findings of this study not only contribute to a more profound understanding of the structural changes of LRMOs at high rates,but also provide novel perspectives for the rational design of LRMOs with superior rate performances.
基金supported by the National Natural Science Foundation of China(22478211,22179067)the Major Fundamental Research Program of Natural Science Foundation of Shandong Province(ZR2022ZD10).
文摘Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H_(2)O_(2) is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated charge efficiency and unfavorable thermodynamics. Herein, by crystal orientation engineering, the WO_(3) photoanode exposing (200) facets achieves both superior WOR activity (15.4 mA cm^(−2) at 1.76 VRHE) and high selectivity to H_(2)O_(2) (∼70%). Comprehensive experimental and theoretical investigations discover that the high PEC-WOR activity of WO_(3)-(200) is attributed to the rapid photogenerated charge separation/transfer both in bulk and at interfaces of WO_(3)-(200) facet, which reduces the charge transfer resistance. This, coupling with the unique defective hydrogen bonding network at the WO_(3)-(200)/electrolyte interface evidenced by operando PEC Fourier transform infrared spectroscopy, facilitating the outward-transfer of the WOR-produced H^(+), lowers the overall reaction barrier for the PEC-WOR. The superior selectivity of PEC-WOR to H_(2)O_(2) is ascribed to the unique defective hydrogen bonding network alleviated adsorption of ∗OH over the WO_(3)-(200) facet, which specially lowers the energy barrier of the 2-electron pathway, as compared to the 4-electron pathway. This work addresses the significant role of crystal orientation engineering on photoelectrocatalytic activity and selectivity, and sheds lights on the underlying PEC mechanism by understanding the water adsorption behaviors under illumination. The knowledge gained is expected to be extended to other photoeletrochemical reactions.
基金funded by a National Research Council of Science&Technology grant from the Ministry of Science and ICT(MSIT),Republic of Korea(No.CAP21012-100)the Korea Institute of Energy Technology Evaluation and Planning(KETEP)under the Ministry of Trade,Industry&Energy(MOTIE),Republic of Korea(No.20224C10300010)。
文摘The electrochemical CO_(2)reduction reaction(CO_(2)RR)is considered a promising technology for converting atmospheric CO_(2)into valuable chemicals.It is a significant way to mitigate the shortage of fossil energy and store excessive renewable electricity in fuels to maintain carbon neutrality.Considering the substantially reduced cost of clean electricity,C1 molecule unitization has emerged as a competitive strategy for room-temperature electrolysis.However,the practical implementation of CO_(2)RR has been hindered by low desired product selectivity,high overpotential,and undesirable hydrogen evolution reactions(HER).Consequently,it is imperative to execute a timely assessment of advanced strategies in CO_(2)RR,with emphasis on catalytic design strategies,understanding of structure–activity relationships,and deactivation of catalysts.In this context,it is imperative to investigate the intrinsic active sites and reaction mechanisms.This review focuses on the design of novel catalysts and their active sites via operando techniques.The combination of advanced characterization techniques and theoretical calculations provides a high-throughput way to obtain a deeper understanding of the reaction mechanism.Furthermore,optimization of the interplay between the catalyst surface and reaction intermediate disturbs the linear correlation between the adsorption energies of the intermediates,resulting in a convoluted cascade system.The appropriate strategies for CO_(2)RR,challenges,and future approaches are projected in this review to stimulate major innovations.Moreover,the plausible research directions are discussed for producing C_(1)chemicals via electrochemical CO_(2)RR at room temperature.
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.
