To date,much efforts have been devoted to the high-efficiency noble metal-free electrocatalysts for hydrogen-and oxygen-involving energy conversion reactions,due to their abundance,low cost and nultifunctionally.Surfa...To date,much efforts have been devoted to the high-efficiency noble metal-free electrocatalysts for hydrogen-and oxygen-involving energy conversion reactions,due to their abundance,low cost and nultifunctionally.Surface/interface engineering is found to be effective in achieving novel physicochemical properties and synergistic effects in nanomaterials for electrocatalysis.Among various engineering strategies,heteroatom-doping has been regarded as a most promising method to improve the electrocatalytic performance via the regulation of electronic structure of catalysts,and numerous works were reported on the synthesis method and mechanism investigation of heteroatom-doping electrocatalysts,though the heteroatom-doping can only provide limited active sites.Engineering of other defects such as vacancies and edge sites and construction of heterostructure have shown to open up a potential avenue for the development of noble metal-free electrocatalysts.In addition,surface functionalization can attach various molecules onto the surface of materials to easily modify their physical or chemical properties,being as a promising complement or substitute for offering materials with catalytic properties.This paper gives the insights into the diverse strategies of surface/interface engineering of the highefficiency noble metal-free electrocatalysts for energy-related electrochemical reactions.The significant advances are summarized.The unique advantages and mechanisms for specific applications are highlighted.The current challenges and outlook of this growing field are also discussed.展开更多
Surface/interface engineering plays an important role in improving the performance and economizing the cost and usage of electrocatalysts.In recent years,substantial progress has been achieved in designing and develop...Surface/interface engineering plays an important role in improving the performance and economizing the cost and usage of electrocatalysts.In recent years,substantial progress has been achieved in designing and developing highly active electrocatalysts with the deepening understanding of surface and interface enhanced mechanism.In this review,recent development about optimizing the surface and interfacial structure in promoting the electrocatalytic activity of noble-metals and transition metal compounds is presented and the chemical enhancements are also described in detail.The relationship between the surface/interface structures(both atomic and electronic configuration)and the electrochemical behaviors has been discussed.Finally,personal perspectives have been proposed,highlighting the challenges and opportunities for future development in tuning the surface/interface active sites of electrocatalysts.We believe that this timely review will be beneficial to the construction of highly active and durable electrode materials through optimizing surface atomic arrangement and interfacial interaction,which can largely promote the development of next-generation clean energy conversion technologies.展开更多
The oxygen evolution reaction(OER)under alkaline conditions is a crucial anodic reaction for the electrolysis of water to produce clean hydrogen.To address the resource scarcity and poor stability of traditional noble...The oxygen evolution reaction(OER)under alkaline conditions is a crucial anodic reaction for the electrolysis of water to produce clean hydrogen.To address the resource scarcity and poor stability of traditional noble metal catalysts(such as RuO_(2)and IrO_(2)),metal-organic frameworks(MOFs)and their derivatives employ surface engineering and interface engineering to modify the electronic structure of reactive active sites,optimize the d-band center,and adjust the adsorption energy of oxygen-containing intermediates.Research has demonstrated that the true active sites for the OER rely on metal oxides/hydroxides regenerated from metal sites.This review will establish the connection between surface engineering and interface engineering strategies and the induced reconstruction of MOFs-based electrocatalysts.It will also reveal how to effectively achieve the rational design of pre-catalysts through in-situ characterization techniques.Additionally,performance comparisons will be provided to demonstrate the superiority of these strategies.Based on this,the challenges in the rational design of pre-catalysts for MOFs to achieve more efficient OER catalysts in the future will be proposed.展开更多
Lithium-carbon dioxide(Li-CO_(2))batteries with high theoretical energy density are regarded as promising energy storage system toward carbon neutrality.However,bidirectional catalysts design for improving the sluggis...Lithium-carbon dioxide(Li-CO_(2))batteries with high theoretical energy density are regarded as promising energy storage system toward carbon neutrality.However,bidirectional catalysts design for improving the sluggish CO_(2)reduction reaction(CO_(2)RR)/CO_(2)evolution reaction(CO_(2)ER)kinetics remains a huge challenge.In this work,an advanced catalyst with fast-interfacial charge transfer was subtly synthesized through element segregation,which significantly improves the electrocatalytic activity for both CO_(2)RR and CO_(2)ER.Theoretical calculations and characterization analysis demonstrate local charge redistribution at the constructed interface,which leads to optimized binding affinity towards reactants and preferred Li_(2)CO_(3)decomposition behavior,enabling excellent catalytic activity during CO_(2)redox.Benefiting from the enhanced charge transfer ability,the designed highly efficient catalyst with dual active centers and large exposed catalytic area can maintain an ultra-small voltage gap of 0.33 V and high energy efficiency of 90.2%.This work provides an attractive strategy to construct robust catalysts by interface engineering,which could inspire further design of superior bidirectional catalysts for Li-CO_(2)batteries.展开更多
The high energy density of green synthetic liquid chemicals and fuels makes them ideal for sustainable energy storage and transportation applications.Electroreduction of carbon dioxide(CO_(2))directly into such high v...The high energy density of green synthetic liquid chemicals and fuels makes them ideal for sustainable energy storage and transportation applications.Electroreduction of carbon dioxide(CO_(2))directly into such high value-added chemicals can help us achieve a renewable C cycle.Such electrochemical reduction typically suffers from low faradaic efficiencies(FEs)and generates a mixture of products due to the complexity of controlling the reaction selectivity.This perspective summarizes recent advances in the mechanistic understanding of CO_(2) reduction reaction pathways toward liquid products and the state-of-the-art catalytic materials for conversion of CO_(2) to liquid C1(e.g.,formic acid,methanol)and C2+products(e.g.,acetic acid,ethanol,n-propanol).Many liquid fuels are being produced with FEs between 80%and 100%.We discuss the use of structure-binding energy relationships,computational screening,and machine learning to identify promising candidates for experimental validation.Finally,we classify strategies for controlling catalyst selectivity and summarize breakthroughs,prospects,and challenges in electrocatalytic CO_(2) reduction to guide future developments.展开更多
High-performance alloys are indispensable in modern engineering because of their exceptional strength,ductility,corrosion resistance,fatigue resistance,and thermal stability,which are all significantly influenced by t...High-performance alloys are indispensable in modern engineering because of their exceptional strength,ductility,corrosion resistance,fatigue resistance,and thermal stability,which are all significantly influenced by the alloy interface structures.Despite substantial efforts,a comprehensive overview of interface engineering of high-performance alloys has not been presented so far.In this study,the interfaces in high-performance alloys,particularly grain and phase boundaries,were systematically examined,with emphasis on their crystallographic characteristics and chemical element segregations.The effects of the interfaces on the electrical conductivity,mechanical strength,toughness,hydrogen embrittlement resistance,and thermal stability of the alloys were elucidated.Moreover,correlations among various types of interfaces and advanced experimental and computational techniques were examined using big data analytics,enabling robust design strategies.Challenges currently faced in the field of interface engineering and emerging opportunities in the field are also discussed.The study results would guide the development of next-generation high-performance alloys.展开更多
The interface between metal nanoparticles(NPs)and support plays a vital role in catalysis because both electron and atom exchanges occur across the metal-support interface.However,the rational design of interfacial st...The interface between metal nanoparticles(NPs)and support plays a vital role in catalysis because both electron and atom exchanges occur across the metal-support interface.However,the rational design of interfacial structure facilitating the charge transfer between the neighboring parts remains a challenge.Herein,a guided nucleation strategy based on redox reaction between noble metal precursor and supportsurface is introduced to construct epitaxial interfaces between Pt NPs and CeO2 support.The Pt/CeO2 catalyst exhibits near room temperature catalytic activity for CO oxidation that is benefited from the well-defined interface structure facilitating charge transfer from CeO2 support to Pt NPs.Meanwhile,this general approach based on support-surface-induced-nucleation was successfully extended to synthesize Pd and Cu nanocatalysts on CeO2,demonstrating its universal and feasible characteristics.This work is an important step towards developing highly active supported metal catalysts by engineering their interfaces.展开更多
Zn-air batteries(ZABs),especially the secondary batteries,have engrossed a great interest because of its high specific energy,economical and high safety.However,due to the insufficient activity and stability of bifunc...Zn-air batteries(ZABs),especially the secondary batteries,have engrossed a great interest because of its high specific energy,economical and high safety.However,due to the insufficient activity and stability of bifunctional electrocatalysts for air-cathode oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)processes,the practical application of rechargeable ZABs is seriously hindered.In the effort of developing high active,stable and cost-effective electrocatalysts,transition metal nitrides(TMNs)have been regarded as the candidates due to their high conductivity,strong corrosion-resistance,and bifunctional catalytic performance.In this paper,the research progress in TMNs-based material as ORR and OER electrocatalysts for ZABs is discussed with respect to their synthesis,chemical/physical characterization,and performance validation/optimization.The surface/interface nanoengineering strategies such as defect engineering,support binding,heteroatom introduction,crystal plane orientation,interface construction and small size effect,the physical and chemical properties of TMNs-based electrocatalysts are emphasized with respect to their structures/morphologies,composition,electrical conductivity,specific surface area,chemical stability and corrosion resistance.The challenges of TMNs-based materials as bifunctional air-cathode electrocatalysts in practical application are evaluated,and numerous research guidelines to solve these problems are put forward for facilitating further research and development.展开更多
Realizing the hydrogen economy by water electrolysis is an attractive approach for hydrogen production,while the efficient and stable bifunctional catalysts under high current densities are the bottleneck that limits ...Realizing the hydrogen economy by water electrolysis is an attractive approach for hydrogen production,while the efficient and stable bifunctional catalysts under high current densities are the bottleneck that limits the half-cell reactions of water splitting.Here,we propose an approach of hydrothermal and thermal annealing methods for robust MoO_(2)/MoNi_(4)@Ru/RuO_(2) heterogeneous cuboid array electrocatalyst with multiplying surface-active sites by depositing a monolayer amount of Ru.Benefiting from abundant MoO_(2)/MoNi_(4)@Ru/RuO_(2)heterointerfaces,MoO_(2)/MoNi_(4)@Ru/RuO_(2) heterogeneous cuboid array electrocatalysts effectively drive the alkaline water splitting with superior hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)performances.The synthesized MoO_(2)/MoNi_(4)@Ru/RuO_(2) has high HER activity,which realizes the working overpotentials of 48 mV at 50 mA·cm^(-2),further achieving overpotentials of 230 mv for industry-level 1000 mA·cm^(-2) in alkaline water electrolysis.Moreover,it also showed an enhanced OER activity than commercial RuO_(2) with a small overpotential of 280 mV at 200 mA·cm^(-2) in alkaline media.When building an electrolyzer with electrodes of(-)MoO_(2)/MoNi_(4)@Ru/RuO_(2)IIMo02/MoNig@Ru/RuO_(2)(+),a cell voltage of 1.63 V and 1.75 V is just required to support the current density of 200 mA·cm^(-2) and 500 mA-cm^(-2) in alkaline water electrolysis,much lower than that of the electrolyzer of(-)Pt/CIIRuO_(2)(+).This work demonstrates that MoO_(2)/MoNig@Ru/RuO_(2) heterogeneous nanosheet arrays are promising candidates for industrial water electrolysis applications,providing a possibility for the exploration of water electrolysis with a large currentdensity.展开更多
Atomically precise metal nanocluster and ultrasmall nanoparticle catalysts have garnered significant interest in electrocatalysis applications due to their unique geometric and electronic structures.As an intermediate...Atomically precise metal nanocluster and ultrasmall nanoparticle catalysts have garnered significant interest in electrocatalysis applications due to their unique geometric and electronic structures.As an intermediate state between single-atom catalysts(SACs)and nanoparticles in size,nanoclusters with specific low nuclearity provide designated metallic states with multiple atoms or surface sites for the adsorption and transformation of reactants/intermediates.The unique catalytic properties of nanoclusters offer a novel platform for designing effective and efficient electrocatalysts,potentially surpassing the SACs in certain catalytic reactions.This review summarizes and discusses the latest progress of nanoclusters and ultrasmall nanoparticles for various electrocatalysis applications,including oxygen reduction reaction(ORR),oxygen evolution reaction(OER),CO_(2) reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR),hydrogen evolution reaction(HER),various chemicals oxidation reaction(COR),etc.Specifically,this review highlights surface/interface chemical modification strategies and structure-properties relationships,drawing from the atomic-level insights to determine electrocatalytic performance.Lastly,we present the challenges and opportunities associated with nanocluster or ultrasmall nanoparticle electrocatalysts.展开更多
As a mathematical analysis method,fractal analysis can be used to quantitatively describe irregular shapes with self-similar or self-affine properties.Fractal analysis has been used to characterize the shapes of metal...As a mathematical analysis method,fractal analysis can be used to quantitatively describe irregular shapes with self-similar or self-affine properties.Fractal analysis has been used to characterize the shapes of metal materials at various scales and dimensions.Conventional methods make it difficult to quantitatively describe the relationship between the regular characteristics and properties of metal material surfaces and interfaces.However,fractal analysis can be used to quantitatively describe the shape characteristics of metal materials and to establish the quantitative relationships between the shape characteristics and various properties of metal materials.From the perspective of two-dimensional planes and three-dimensional curved surfaces,this paper reviews the current research status of the fractal analysis of metal precipitate interfaces,metal grain boundary interfaces,metal-deposited film surfaces,metal fracture surfaces,metal machined surfaces,and metal wear surfaces.The relationship between the fractal dimensions and properties of metal material surfaces and interfaces is summarized.Starting from three perspectives of fractal analysis,namely,research scope,image acquisition methods,and calculation methods,this paper identifies the direction of research on fractal analysis of metal material surfaces and interfaces that need to be developed.It is believed that revealing the deep influence mechanism between the fractal dimensions and properties of metal material surfaces and interfaces will be the key research direction of the fractal analysis of metal materials in the future.展开更多
Solid-state lithium batteries have become a research hotspot in the field of large-scale energy storage due to their excellent safety performance.The development of high-voltage positive electrode materials matched wi...Solid-state lithium batteries have become a research hotspot in the field of large-scale energy storage due to their excellent safety performance.The development of high-voltage positive electrode materials matched with lithium metal anode have advanced the energy density of solid-state lithium batteries close to or even exceeding that of lithium batteries based on a liquid electrolyte,which is expected to be commercialized in the future.However,in high voltage conditions(>4.3 V),the decomposition of electrolyte components,structural degradation,and interface side reactions significantly reduce battery performance and hinder its further development.This review summarizes the latest research progress of inorganic electrolytes,polymer electrolytes,and composite electrolytes in high-voltage solid-state lithium batteries.At the same time,the designs of high-voltage polymer gel electrolyte and high-voltage quasi solid-state electrolyte are introduced in detail.In addition,interface engineering is crucial for improving the overall performance of high-voltage solid-state batteries.Finally,we highlight the challenges faced by high-voltage solid-state lithium batteries and put forward our own views on future research directions.This review offers instructive insights into the advancement of high-voltage solid-state lithium batteries for large-scale energy storage applications.展开更多
For emerging renewable and sustainable energy technologies,single crystal materials have become key materials to enhance electrocatalytic performance because of their atomic-level ordered structures and tailorable sur...For emerging renewable and sustainable energy technologies,single crystal materials have become key materials to enhance electrocatalytic performance because of their atomic-level ordered structures and tailorable surface and interfacial properties.Various single crystal types,including metals,semiconductors,ceramics,organics,and nanocrystals,exhibit superior catalytic selectivity and stability in reactions such as water splitting and carbon/nitrogen cycles,benefiting from high electrical conductivity,tunable energy bands,and active sites with high surface energy.Through surface modification,interfacial atomic doping,and heterostructure construction,the distribution of active sites,electronic structure,and mass transport can be precisely regulated,significantly optimizing the catalytic kinetics of single crystal materials.In situ characterizations elucidate catalytic mechanisms at the atomic scale,while emerging methods like AI-assisted synthesis and bio-template directed growth offer pathways to overcome bottlenecks in the precision and cost of single crystal preparation.In addressing stability challenges in complex environments,strategies such as organic-inorganic hybridization and gradient interface design effectively mitigate interfacial instability.Future research should focus on cross-scale structural regulation and multidisciplinary integration to facilitate the transition of single crystal electrocatalysts from fundamental research to industrial applications,enabling efficient energy conversion.展开更多
Micron-sized silicon anodes offer significant industrial advantages over nanoscale counterparts due to their cost-effectiveness and scalability.However,their practical applications are significantly hindered by severe...Micron-sized silicon anodes offer significant industrial advantages over nanoscale counterparts due to their cost-effectiveness and scalability.However,their practical applications are significantly hindered by severe stress-induced fragmentation,leading to rapid capacity decay.Addressing this challenge,we introduce a novel dual-conformal encapsulated micron-sized porous Si(μm-pSi)anode by utilizingμm-Si recycled from the photovoltaic industry as the Si precursor.This encapsulation design of the internal conformal SiO_(x)/C layer and external Ti_(3)C_(2)Tx MXene layer forms intergranular and intragranular protective skins onμm-pSi,ensuring simultaneous mechanical and electrochemical stability for efficient Li+storage.As a result,the fabricated WpSi@SiO_(x)/C@MXene anode demonstrates an exceptional cycling performance,delivering 535.1 mA h g^(−1)after 1500 cycles at 5 A g^(−1)with a minimal capacity decay of 0.003%per cycle.Chemo-mechanical modeling and SEI analysis reveal that the dual-conformal coating achieves exceptional mechanical and electrochemical stability through robust mechanical confinement and ultra-fast Li+diffusion kinetics during lithiation,coupled with a Li_(2)CO_(3)/LiF-rich hybrid SEI that facilitates Li+transport,collectively enabling rate-insensitive stress evolution,long-term structural durability,and stable cycling under high-rate conditions.This work provides a compelling design strategy for leveraging sustainableμm-Si to achieve high-rate and long-life lithium-ion batteries.展开更多
Surface passivation with organic ammoniums improves perovskite solar cell performance by forming 2D/quasi-2D structures or adsorbing onto surfaces.However,complexity from mixed phases can trigger phase transitions,com...Surface passivation with organic ammoniums improves perovskite solar cell performance by forming 2D/quasi-2D structures or adsorbing onto surfaces.However,complexity from mixed phases can trigger phase transitions,compromising stability.The control of surface dimensionality after organic ammonium passivation presents significant importance to device stability.In this study,we developed a poly-fluorination strategy for surface treatment in perovskite solar cells,which enabled a high and durable interfacial phase purity after surface passivation.The locked surface dimensionality of perovskite was achieved through robust interaction between the poly-fluorinated ammoniums and the perovskite surface,along with the steric hindrance imparted by fluorine atoms,reducing its reactivity and penetration capabilities.The high hydrophobicity of the poly-fluorinated surface also aids in moisture resistance of the perovskite layer.The champion device achieved a power conversion efficiency(PCE)of 25.2% with certified 24.6%,with 90% of its initial PCE retained after approximately 1200 h under continuous 1-sun illumination,and over 14,400 h storage stability and superior stability under high-temperature operation.展开更多
Lithium-rich manganese-based cathode materials(LMCMs)have garnered significant attention in power lithium-ion batteries(LIBs)and energy storage systems due to their superior energy density and costeffectiveness.Howeve...Lithium-rich manganese-based cathode materials(LMCMs)have garnered significant attention in power lithium-ion batteries(LIBs)and energy storage systems due to their superior energy density and costeffectiveness.However,the commercial application of LMCMs is hindered by challenges such as low initial coulombic efficiency,severe voltage decay,and inferior cycling performance.Surface structure degradation has been confirmed as a critical factor contributing to the electrochemical performance deterioration of LMCMs.Herein,we review the recent progress in surface engineering of LMCMs towards next-generation LIBs.Besides classical surface coating,mechanism and functions of surface oxygen vacancies for greatly boosting the electrochemical performance of LMCMs are also summarized in detail.Finally,we discuss the emerging trends and propose future research directions of surface engineering of LMCMs for achieving more efficient improvements.This work underscores the indispensable potential of surface engineering in enhancing the surface structure stability and electrochemical performance of LMCMs as promising candidates for next-generation high-energy LIBs.Synergistic integration of surface engineering and single-crystal technology will be a promising modification strategy for significantly promoting the commercialization of LMCMs,and the corresponding synergistic mechanisms urgently need to be studied for rationally designing high-performance electrodes.More efforts will be devoted to understand the surface engineering of LMCMs for the large-scale application of high-energy LIBs.展开更多
Based on the theoretical representation of piezoelectric quasicrystal,a generalized dynamic model is built to represent the transmission of wave aspects in surface acoustic pulse nano-devices.Surface elasticity,surfac...Based on the theoretical representation of piezoelectric quasicrystal,a generalized dynamic model is built to represent the transmission of wave aspects in surface acoustic pulse nano-devices.Surface elasticity,surface piezoelectricity,and surface permittivity help to include the surface effect,which equals additional thin sheets.It is shown that,under certain assumptions,this generalized dynamic model may be simplified to a few classical examples that are appropriate for both macro and nano-scale applications.In the current work,surface piezoelectricity is used to develop a theoretical model for shear horizontal(SH)waves where it contains the surface piezoelectricity theory and a linear spring model to quantitatively and qualitatively explore SH waves in an orthotropic piezoelectric quasicrystal layer overlying an elastic framework(Model I),a piezoelectric quasi-crystal nano substrate,and an orthotropic piezoelectric quasicrystal half-space(Model II).The theoretical model stimulates the numerical results,which establish the critical thickness.As the piezoelectric layer’s thickness gets closer to nanometres,surface energy must be included when analyzing dispersion properties.Furthermore,the effects of surface elasticity and density on wave velocity are investigated individually.The authors establish a parameter,precisely the ratio of the physical modulus along the width direction to along the direction of wave travel.The surface effect’s impact on the general char-acteristics of piezoelectric structures is seen as a spring force acting on bulk boundaries.Analytical presentation of frequency equations for both symmetric and anti-symmetric waves pertains to the case of an electrical short circuit in Model II.The project aims to analyze SH waves in orthogonal anisotropic,transversely isotropic piezoelectric layered nanostructures,providing a practical mathematical tool for surface effects analysis and adaptability to other wave types,including Rayleigh waves and acoustic surface waves.展开更多
In the past decade,dry reforming of methane(DRM)has garnered increasing interest as it converts CH_(4)and CO_(2),two typical greenhouse gases,into synthesis gas(H_(2)and CO)for the production of high-value-added chemi...In the past decade,dry reforming of methane(DRM)has garnered increasing interest as it converts CH_(4)and CO_(2),two typical greenhouse gases,into synthesis gas(H_(2)and CO)for the production of high-value-added chemicals and fuels.Nickel-based DRM catalysts,renowned for their high activity and low cost,however,encounter challenges such as severe deactivation from sintering and carbon deposition.Herein,a surrounded NiO@NiAlO precursor derived from Ni(OH)_(2)nanosheets was modified at both the core and shell interfaces with MgO via wet impregnation.The obtained 0.8MgO^(WI)/Ni@NiAlO catalyst achieved a high CH_(4)reaction rate of~177 mmol gNi^(-1)min^(-1)and remained stable for 50 h at 600℃without coke formation.In sharp contrast,other Mg-doped catalysts(MgO modified the core or shell interfaces)and the catalyst without Mg-doping deactivated within 10 h due to coking or Ni particle sintering.The Ni/MgNiO_(2)interfaces and abundant oxygen vacancies(O_(v))generated by Mg-doping contributed to the outstanding resistance to sintering&coking as well as the superior activity and stability of the 0.8MgO^(WI)/Ni@NiAlO catalyst.In-situ investigation further unveiled the reaction mechanism:the activation of CO_(2)via adsorption on O_(v)generates active oxygen species(O^(*)),which reacts with CH_(x)^(*)intermediates formed by the dissociation of CH_(4)on Ni sites,yielding CO and H_(2).This work not only fabricates coke-free and high-stability Ni-based DRM catalysts via interface engineering but also provides insights and a new strategy for the design of high-efficiency and stable catalysts for DRM.展开更多
Silicon(Si)anodes,with a theoretical specific capacity of 4200 mAh g^(-1),hold significant promise for the development of high-energy-density lithium-ion batteries(LIBs).However,practical applications are hindered by ...Silicon(Si)anodes,with a theoretical specific capacity of 4200 mAh g^(-1),hold significant promise for the development of high-energy-density lithium-ion batteries(LIBs).However,practical applications are hindered by sluggish charge transfer kinetics,substantial volume expansion,and an unstable solid elec-trolyte interphase during cycling.To address these challenges,we propose a centimeter-scale Si anode design featuring a three-dimensional continuous network structure of Si nanowires(SiNWs)decorated with high-density Ag nanoparticles(Ag-SiNWs-Net)on both the surface and internally.This architecture effectively mitigates mechanical stress from Si volume changes through the high-aspect-ratio wire network.Additionally,the distribution of Ag nanoparticles on the Si induces electronic structure redistribution,generating built-in electric fields that accelerate charge transfer within the Si,significantly enhancing rate performance and cycling stability.The Ag-SiNWs-Net anode achieves a high reversible capacity of 3780.9 mAh g^(-1)at 0.1 A g^(-1),with an initial coulombic efficiency of 85.1%.Moreover,the energy density of full cells assembled with Ag-SiNWs-Net anodes and LiFePO4 cathodes can be pushed further up to 395.8 Wh kg^(-1).This study offers valuable insights and methodologies for the development of high-capacity and practical Si anodes-.展开更多
Precise control of luminescence in carbon quantum dots(CQDs),from single-color to full-color emission,is crucial for advancing their applications in biomedical imaging and display technologies.While CQDs luminescence ...Precise control of luminescence in carbon quantum dots(CQDs),from single-color to full-color emission,is crucial for advancing their applications in biomedical imaging and display technologies.While CQDs luminescence is primarily influenced by conjugated domains and surface states,the underlying interaction mechanisms remain poorly understood.This study explores a graded nitro-engineering approach to simultaneously regulate surface states and sp^(2)conjugated domains through nitro(-NO_(2))modulation,enabling comprehensive color tuning.Using o-phenylenediamine(o-PD)as the carbon source and adjusting nitric acid(HNO_(3))concentrations,we synthesized tricolor-emitting nitro-functionalized CQDs(NO_(2)-CQDs).At lower-NO_(2) concentrations,luminescence is mainly influenced by surface states,where the electron-withdrawing effect of-NO_(2) enhancesπ-electron delocalization and stabilizes sp^(2)conjugation.With increasing-NO_(2) content,the lowest unoccupied molecular orbital(LUMO)energy level decreases(-2.12 eV to-3.39 eV),resulting in a red-shift in fluorescence.At higher-NO_(2) concentrations,luminescence is primarily affected by the sp^(2)conjugated domain,where steric hindrance reduces molecular planarity and conjugation,leading to a blue-shift in fluorescence as the sp^(2)domain size decreases(4.03 nm to 2.83 nm).Combining experimental results with density functional theory(DFT)calculations,we reveal the dual role of-NO2in modulating CQDs luminescence,an approach rarely achieved through surface functionalization.This work presents a novel strategy for precise tuning of CQDs luminescence across the visible spectrum.展开更多
基金supported by the Natural Science Foundation of Shandong Province(ZR2019PB013)the Natural Science Foundation of Tianjin(19JCZDJC37700)the National Natural Science Foundation of China(21421001 and 21875118)。
文摘To date,much efforts have been devoted to the high-efficiency noble metal-free electrocatalysts for hydrogen-and oxygen-involving energy conversion reactions,due to their abundance,low cost and nultifunctionally.Surface/interface engineering is found to be effective in achieving novel physicochemical properties and synergistic effects in nanomaterials for electrocatalysis.Among various engineering strategies,heteroatom-doping has been regarded as a most promising method to improve the electrocatalytic performance via the regulation of electronic structure of catalysts,and numerous works were reported on the synthesis method and mechanism investigation of heteroatom-doping electrocatalysts,though the heteroatom-doping can only provide limited active sites.Engineering of other defects such as vacancies and edge sites and construction of heterostructure have shown to open up a potential avenue for the development of noble metal-free electrocatalysts.In addition,surface functionalization can attach various molecules onto the surface of materials to easily modify their physical or chemical properties,being as a promising complement or substitute for offering materials with catalytic properties.This paper gives the insights into the diverse strategies of surface/interface engineering of the highefficiency noble metal-free electrocatalysts for energy-related electrochemical reactions.The significant advances are summarized.The unique advantages and mechanisms for specific applications are highlighted.The current challenges and outlook of this growing field are also discussed.
基金supported financially by the Joint Funds of National Natural Science Foundation of China and Guangdong Province(No.U1601216)the National Natural Science Foundation of China(Nos.51602216 and 51472178)+1 种基金Young Elite Scientists Sponsorship Program by CAST(No.2018QNRC001)Tianjin Natural Science Foundation(No.17JCQNJC02100).
文摘Surface/interface engineering plays an important role in improving the performance and economizing the cost and usage of electrocatalysts.In recent years,substantial progress has been achieved in designing and developing highly active electrocatalysts with the deepening understanding of surface and interface enhanced mechanism.In this review,recent development about optimizing the surface and interfacial structure in promoting the electrocatalytic activity of noble-metals and transition metal compounds is presented and the chemical enhancements are also described in detail.The relationship between the surface/interface structures(both atomic and electronic configuration)and the electrochemical behaviors has been discussed.Finally,personal perspectives have been proposed,highlighting the challenges and opportunities for future development in tuning the surface/interface active sites of electrocatalysts.We believe that this timely review will be beneficial to the construction of highly active and durable electrode materials through optimizing surface atomic arrangement and interfacial interaction,which can largely promote the development of next-generation clean energy conversion technologies.
基金the National Natural Science Foundation of China(52371240)Natural Science Foundation of Jiangsu Province(BK20230566)+3 种基金the Priority Academic Program Development of Jiangsu Higher Education InstitutionsNatural Science Research Project of Guangling College,Yangzhou University(ZKZD23005)the Universities’Philosophy and Social Science Researches in Jiangsu Province(2023SJYB2088)the technical support we received at the Testing Center of Yangzhou University。
文摘The oxygen evolution reaction(OER)under alkaline conditions is a crucial anodic reaction for the electrolysis of water to produce clean hydrogen.To address the resource scarcity and poor stability of traditional noble metal catalysts(such as RuO_(2)and IrO_(2)),metal-organic frameworks(MOFs)and their derivatives employ surface engineering and interface engineering to modify the electronic structure of reactive active sites,optimize the d-band center,and adjust the adsorption energy of oxygen-containing intermediates.Research has demonstrated that the true active sites for the OER rely on metal oxides/hydroxides regenerated from metal sites.This review will establish the connection between surface engineering and interface engineering strategies and the induced reconstruction of MOFs-based electrocatalysts.It will also reveal how to effectively achieve the rational design of pre-catalysts through in-situ characterization techniques.Additionally,performance comparisons will be provided to demonstrate the superiority of these strategies.Based on this,the challenges in the rational design of pre-catalysts for MOFs to achieve more efficient OER catalysts in the future will be proposed.
基金supported by the National Key Research and Development Program of China(2019YFA0705700)Guangdong Innovative and Entrepreneurial Research Team Program(2021ZT09L197)+2 种基金Shenzhen Science and Technology Program(KQTD20210811090112002)Interdisciplinary Research and Innovation Fund of Tsinghua Shenzhen International Graduate School,National Natural Science Foundation of China(No.52373233)the SIAT International Joint Lab Project(No.E3G113).
文摘Lithium-carbon dioxide(Li-CO_(2))batteries with high theoretical energy density are regarded as promising energy storage system toward carbon neutrality.However,bidirectional catalysts design for improving the sluggish CO_(2)reduction reaction(CO_(2)RR)/CO_(2)evolution reaction(CO_(2)ER)kinetics remains a huge challenge.In this work,an advanced catalyst with fast-interfacial charge transfer was subtly synthesized through element segregation,which significantly improves the electrocatalytic activity for both CO_(2)RR and CO_(2)ER.Theoretical calculations and characterization analysis demonstrate local charge redistribution at the constructed interface,which leads to optimized binding affinity towards reactants and preferred Li_(2)CO_(3)decomposition behavior,enabling excellent catalytic activity during CO_(2)redox.Benefiting from the enhanced charge transfer ability,the designed highly efficient catalyst with dual active centers and large exposed catalytic area can maintain an ultra-small voltage gap of 0.33 V and high energy efficiency of 90.2%.This work provides an attractive strategy to construct robust catalysts by interface engineering,which could inspire further design of superior bidirectional catalysts for Li-CO_(2)batteries.
基金supported by the Joint Funds of the National Natural Science Foundation of China(U24B20201)National Natural Science Foundation of China(22372007 and 21972010)+1 种基金the Fundamental Research Funds for the Central Universities(JD2427)the SRC Center for Electron Transfer(2021R1A5A1030054)funded by NRF Korea and AI Graduate School Program(RS-2021-II211343).
文摘The high energy density of green synthetic liquid chemicals and fuels makes them ideal for sustainable energy storage and transportation applications.Electroreduction of carbon dioxide(CO_(2))directly into such high value-added chemicals can help us achieve a renewable C cycle.Such electrochemical reduction typically suffers from low faradaic efficiencies(FEs)and generates a mixture of products due to the complexity of controlling the reaction selectivity.This perspective summarizes recent advances in the mechanistic understanding of CO_(2) reduction reaction pathways toward liquid products and the state-of-the-art catalytic materials for conversion of CO_(2) to liquid C1(e.g.,formic acid,methanol)and C2+products(e.g.,acetic acid,ethanol,n-propanol).Many liquid fuels are being produced with FEs between 80%and 100%.We discuss the use of structure-binding energy relationships,computational screening,and machine learning to identify promising candidates for experimental validation.Finally,we classify strategies for controlling catalyst selectivity and summarize breakthroughs,prospects,and challenges in electrocatalytic CO_(2) reduction to guide future developments.
基金supported by the National Natural Science Foundation of China(Nos.52122408 and 52474397)the High-level Talent Research Start-up Project Funding of Henan Academy of Sciences(No.242017127)+1 种基金the financial support from the Fundamental Research Funds for the Central Universities(University of Science and Technology Beijing(USTB),Nos.FRF-TP-2021-04C1 and 06500135)supported by USTB MatCom of Beijing Advanced Innovation Center for Materials Genome Engineering。
文摘High-performance alloys are indispensable in modern engineering because of their exceptional strength,ductility,corrosion resistance,fatigue resistance,and thermal stability,which are all significantly influenced by the alloy interface structures.Despite substantial efforts,a comprehensive overview of interface engineering of high-performance alloys has not been presented so far.In this study,the interfaces in high-performance alloys,particularly grain and phase boundaries,were systematically examined,with emphasis on their crystallographic characteristics and chemical element segregations.The effects of the interfaces on the electrical conductivity,mechanical strength,toughness,hydrogen embrittlement resistance,and thermal stability of the alloys were elucidated.Moreover,correlations among various types of interfaces and advanced experimental and computational techniques were examined using big data analytics,enabling robust design strategies.Challenges currently faced in the field of interface engineering and emerging opportunities in the field are also discussed.The study results would guide the development of next-generation high-performance alloys.
基金supported by the National Natural Science Foundation of China(Nos.51771047,51525101,U1602275,51601119)the Fundamental Research Funds for the Central Universities(N180204014)+1 种基金the Key Lab for ATM of Northeastern University(China)the Natural Science Foundation of Shenzhen University(No.2019006).
文摘The interface between metal nanoparticles(NPs)and support plays a vital role in catalysis because both electron and atom exchanges occur across the metal-support interface.However,the rational design of interfacial structure facilitating the charge transfer between the neighboring parts remains a challenge.Herein,a guided nucleation strategy based on redox reaction between noble metal precursor and supportsurface is introduced to construct epitaxial interfaces between Pt NPs and CeO2 support.The Pt/CeO2 catalyst exhibits near room temperature catalytic activity for CO oxidation that is benefited from the well-defined interface structure facilitating charge transfer from CeO2 support to Pt NPs.Meanwhile,this general approach based on support-surface-induced-nucleation was successfully extended to synthesize Pd and Cu nanocatalysts on CeO2,demonstrating its universal and feasible characteristics.This work is an important step towards developing highly active supported metal catalysts by engineering their interfaces.
基金financial support from the National Key Research and Development Program of China(2017YFB0102900)
文摘Zn-air batteries(ZABs),especially the secondary batteries,have engrossed a great interest because of its high specific energy,economical and high safety.However,due to the insufficient activity and stability of bifunctional electrocatalysts for air-cathode oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)processes,the practical application of rechargeable ZABs is seriously hindered.In the effort of developing high active,stable and cost-effective electrocatalysts,transition metal nitrides(TMNs)have been regarded as the candidates due to their high conductivity,strong corrosion-resistance,and bifunctional catalytic performance.In this paper,the research progress in TMNs-based material as ORR and OER electrocatalysts for ZABs is discussed with respect to their synthesis,chemical/physical characterization,and performance validation/optimization.The surface/interface nanoengineering strategies such as defect engineering,support binding,heteroatom introduction,crystal plane orientation,interface construction and small size effect,the physical and chemical properties of TMNs-based electrocatalysts are emphasized with respect to their structures/morphologies,composition,electrical conductivity,specific surface area,chemical stability and corrosion resistance.The challenges of TMNs-based materials as bifunctional air-cathode electrocatalysts in practical application are evaluated,and numerous research guidelines to solve these problems are put forward for facilitating further research and development.
基金sponsored by the National Natural Science Foundation of China(51772162,52072197)the China Postdoctoral Science Foundation(2023M732132)+4 种基金Youth Innovation Team Development Program of Shandong Higher Education Institutions(2022KJ155)Outstanding Youth Foundation of Shandong Province,China(ZR2019JQ14)Taishan Scholar Young Talent Program(tsqn201909114)Major Scientific and Technological Innovation Project(2019JZZY020405)Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant(ZR2020ZD09).
文摘Realizing the hydrogen economy by water electrolysis is an attractive approach for hydrogen production,while the efficient and stable bifunctional catalysts under high current densities are the bottleneck that limits the half-cell reactions of water splitting.Here,we propose an approach of hydrothermal and thermal annealing methods for robust MoO_(2)/MoNi_(4)@Ru/RuO_(2) heterogeneous cuboid array electrocatalyst with multiplying surface-active sites by depositing a monolayer amount of Ru.Benefiting from abundant MoO_(2)/MoNi_(4)@Ru/RuO_(2)heterointerfaces,MoO_(2)/MoNi_(4)@Ru/RuO_(2) heterogeneous cuboid array electrocatalysts effectively drive the alkaline water splitting with superior hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)performances.The synthesized MoO_(2)/MoNi_(4)@Ru/RuO_(2) has high HER activity,which realizes the working overpotentials of 48 mV at 50 mA·cm^(-2),further achieving overpotentials of 230 mv for industry-level 1000 mA·cm^(-2) in alkaline water electrolysis.Moreover,it also showed an enhanced OER activity than commercial RuO_(2) with a small overpotential of 280 mV at 200 mA·cm^(-2) in alkaline media.When building an electrolyzer with electrodes of(-)MoO_(2)/MoNi_(4)@Ru/RuO_(2)IIMo02/MoNig@Ru/RuO_(2)(+),a cell voltage of 1.63 V and 1.75 V is just required to support the current density of 200 mA·cm^(-2) and 500 mA-cm^(-2) in alkaline water electrolysis,much lower than that of the electrolyzer of(-)Pt/CIIRuO_(2)(+).This work demonstrates that MoO_(2)/MoNig@Ru/RuO_(2) heterogeneous nanosheet arrays are promising candidates for industrial water electrolysis applications,providing a possibility for the exploration of water electrolysis with a large currentdensity.
基金financially supported by the National Natural Science Foundation of China(22208331)the Natural Sciences and Engineering Research Council of Canada(NSERC)+2 种基金the Fonds de Recherche du Québec-Nature et Technologies(FRQNT)McGill University,Institut National de la Recherche Scientifique(INRS)andÉcole de Technologie Supérieure(ÉTS).
文摘Atomically precise metal nanocluster and ultrasmall nanoparticle catalysts have garnered significant interest in electrocatalysis applications due to their unique geometric and electronic structures.As an intermediate state between single-atom catalysts(SACs)and nanoparticles in size,nanoclusters with specific low nuclearity provide designated metallic states with multiple atoms or surface sites for the adsorption and transformation of reactants/intermediates.The unique catalytic properties of nanoclusters offer a novel platform for designing effective and efficient electrocatalysts,potentially surpassing the SACs in certain catalytic reactions.This review summarizes and discusses the latest progress of nanoclusters and ultrasmall nanoparticles for various electrocatalysis applications,including oxygen reduction reaction(ORR),oxygen evolution reaction(OER),CO_(2) reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR),hydrogen evolution reaction(HER),various chemicals oxidation reaction(COR),etc.Specifically,this review highlights surface/interface chemical modification strategies and structure-properties relationships,drawing from the atomic-level insights to determine electrocatalytic performance.Lastly,we present the challenges and opportunities associated with nanocluster or ultrasmall nanoparticle electrocatalysts.
基金financially supported by the National Key R&D Program of China(No.2022YFE0121300)the National Natural Science Foundation of China(No.52374376)the Introduction Plan for High-end Foreign Experts(No.G2023105001L)。
文摘As a mathematical analysis method,fractal analysis can be used to quantitatively describe irregular shapes with self-similar or self-affine properties.Fractal analysis has been used to characterize the shapes of metal materials at various scales and dimensions.Conventional methods make it difficult to quantitatively describe the relationship between the regular characteristics and properties of metal material surfaces and interfaces.However,fractal analysis can be used to quantitatively describe the shape characteristics of metal materials and to establish the quantitative relationships between the shape characteristics and various properties of metal materials.From the perspective of two-dimensional planes and three-dimensional curved surfaces,this paper reviews the current research status of the fractal analysis of metal precipitate interfaces,metal grain boundary interfaces,metal-deposited film surfaces,metal fracture surfaces,metal machined surfaces,and metal wear surfaces.The relationship between the fractal dimensions and properties of metal material surfaces and interfaces is summarized.Starting from three perspectives of fractal analysis,namely,research scope,image acquisition methods,and calculation methods,this paper identifies the direction of research on fractal analysis of metal material surfaces and interfaces that need to be developed.It is believed that revealing the deep influence mechanism between the fractal dimensions and properties of metal material surfaces and interfaces will be the key research direction of the fractal analysis of metal materials in the future.
基金supported by the National Key R&D Program of China(2024YFA1211100)the National Natural Science Foundation of China(52301278,22479080,52202254,92372001,22393900,and 92372203)+2 种基金the Natural Science Foundation of Jiangsu Province(BK20230937,BK20220966)the Science and Technology Plans of Tianjin(23JCYBJC00170,24JCJQJC00220,and 24ZXZSSS00390)the Fundamental Research Funds for the Central Universities(02063253167,30922010708)。
文摘Solid-state lithium batteries have become a research hotspot in the field of large-scale energy storage due to their excellent safety performance.The development of high-voltage positive electrode materials matched with lithium metal anode have advanced the energy density of solid-state lithium batteries close to or even exceeding that of lithium batteries based on a liquid electrolyte,which is expected to be commercialized in the future.However,in high voltage conditions(>4.3 V),the decomposition of electrolyte components,structural degradation,and interface side reactions significantly reduce battery performance and hinder its further development.This review summarizes the latest research progress of inorganic electrolytes,polymer electrolytes,and composite electrolytes in high-voltage solid-state lithium batteries.At the same time,the designs of high-voltage polymer gel electrolyte and high-voltage quasi solid-state electrolyte are introduced in detail.In addition,interface engineering is crucial for improving the overall performance of high-voltage solid-state batteries.Finally,we highlight the challenges faced by high-voltage solid-state lithium batteries and put forward our own views on future research directions.This review offers instructive insights into the advancement of high-voltage solid-state lithium batteries for large-scale energy storage applications.
基金supported by National Natural Science Foundation of China(No.52202366)Taishan Scholar Project of Shandong Province(tstp20240515,tsqn202312217)+1 种基金Natural Science Foundation of Shandong Province(China,No.2025HWYQ-050,ZR2021QE011,ZR2022QH072,ZR2021QE284)the King Abdullah University of Science and Technology,the Center of Excellence for Renewable Energy and Storage Technologies.
文摘For emerging renewable and sustainable energy technologies,single crystal materials have become key materials to enhance electrocatalytic performance because of their atomic-level ordered structures and tailorable surface and interfacial properties.Various single crystal types,including metals,semiconductors,ceramics,organics,and nanocrystals,exhibit superior catalytic selectivity and stability in reactions such as water splitting and carbon/nitrogen cycles,benefiting from high electrical conductivity,tunable energy bands,and active sites with high surface energy.Through surface modification,interfacial atomic doping,and heterostructure construction,the distribution of active sites,electronic structure,and mass transport can be precisely regulated,significantly optimizing the catalytic kinetics of single crystal materials.In situ characterizations elucidate catalytic mechanisms at the atomic scale,while emerging methods like AI-assisted synthesis and bio-template directed growth offer pathways to overcome bottlenecks in the precision and cost of single crystal preparation.In addressing stability challenges in complex environments,strategies such as organic-inorganic hybridization and gradient interface design effectively mitigate interfacial instability.Future research should focus on cross-scale structural regulation and multidisciplinary integration to facilitate the transition of single crystal electrocatalysts from fundamental research to industrial applications,enabling efficient energy conversion.
基金the financial support from the Natural Science Foundation of Shanghai(23ZR1423800)Open Research Fund of Shanghai Key Laboratory of Green Chemistry and Chemical Processes(East China Normal University,202503)+1 种基金State Key Laboratory of Advanced Fiber Materials(Donghua University,KF2406)Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University。
文摘Micron-sized silicon anodes offer significant industrial advantages over nanoscale counterparts due to their cost-effectiveness and scalability.However,their practical applications are significantly hindered by severe stress-induced fragmentation,leading to rapid capacity decay.Addressing this challenge,we introduce a novel dual-conformal encapsulated micron-sized porous Si(μm-pSi)anode by utilizingμm-Si recycled from the photovoltaic industry as the Si precursor.This encapsulation design of the internal conformal SiO_(x)/C layer and external Ti_(3)C_(2)Tx MXene layer forms intergranular and intragranular protective skins onμm-pSi,ensuring simultaneous mechanical and electrochemical stability for efficient Li+storage.As a result,the fabricated WpSi@SiO_(x)/C@MXene anode demonstrates an exceptional cycling performance,delivering 535.1 mA h g^(−1)after 1500 cycles at 5 A g^(−1)with a minimal capacity decay of 0.003%per cycle.Chemo-mechanical modeling and SEI analysis reveal that the dual-conformal coating achieves exceptional mechanical and electrochemical stability through robust mechanical confinement and ultra-fast Li+diffusion kinetics during lithiation,coupled with a Li_(2)CO_(3)/LiF-rich hybrid SEI that facilitates Li+transport,collectively enabling rate-insensitive stress evolution,long-term structural durability,and stable cycling under high-rate conditions.This work provides a compelling design strategy for leveraging sustainableμm-Si to achieve high-rate and long-life lithium-ion batteries.
基金grants(grant numbers LR24F040001,LD24E020001 and LD22E020002)from the Natural Science Foundation of Zhejiang Province of Chinathe National Natural Science Foundation of China(grant number 62274146)+1 种基金the support of Key R&D Program of Zhejiang(2024SSYS0061)supported by the Fundamental Research Funds for the Central Universities(226-2022-00200).
文摘Surface passivation with organic ammoniums improves perovskite solar cell performance by forming 2D/quasi-2D structures or adsorbing onto surfaces.However,complexity from mixed phases can trigger phase transitions,compromising stability.The control of surface dimensionality after organic ammonium passivation presents significant importance to device stability.In this study,we developed a poly-fluorination strategy for surface treatment in perovskite solar cells,which enabled a high and durable interfacial phase purity after surface passivation.The locked surface dimensionality of perovskite was achieved through robust interaction between the poly-fluorinated ammoniums and the perovskite surface,along with the steric hindrance imparted by fluorine atoms,reducing its reactivity and penetration capabilities.The high hydrophobicity of the poly-fluorinated surface also aids in moisture resistance of the perovskite layer.The champion device achieved a power conversion efficiency(PCE)of 25.2% with certified 24.6%,with 90% of its initial PCE retained after approximately 1200 h under continuous 1-sun illumination,and over 14,400 h storage stability and superior stability under high-temperature operation.
基金financially supported by the National Natura Science Foundation of China(51108455,52106264)Civil Aviation Safety Capacity Building Fund(ADSA2022026)+2 种基金Liaoning Revitalization Talents Program(XLYC2018013)Liaoning Province AppliedFoundation Research Program Project(2023JH2/101300215)Unveiled the List of Local Service Projects from Education Department of Liaoning Province(JYTMS20230227)。
文摘Lithium-rich manganese-based cathode materials(LMCMs)have garnered significant attention in power lithium-ion batteries(LIBs)and energy storage systems due to their superior energy density and costeffectiveness.However,the commercial application of LMCMs is hindered by challenges such as low initial coulombic efficiency,severe voltage decay,and inferior cycling performance.Surface structure degradation has been confirmed as a critical factor contributing to the electrochemical performance deterioration of LMCMs.Herein,we review the recent progress in surface engineering of LMCMs towards next-generation LIBs.Besides classical surface coating,mechanism and functions of surface oxygen vacancies for greatly boosting the electrochemical performance of LMCMs are also summarized in detail.Finally,we discuss the emerging trends and propose future research directions of surface engineering of LMCMs for achieving more efficient improvements.This work underscores the indispensable potential of surface engineering in enhancing the surface structure stability and electrochemical performance of LMCMs as promising candidates for next-generation high-energy LIBs.Synergistic integration of surface engineering and single-crystal technology will be a promising modification strategy for significantly promoting the commercialization of LMCMs,and the corresponding synergistic mechanisms urgently need to be studied for rationally designing high-performance electrodes.More efforts will be devoted to understand the surface engineering of LMCMs for the large-scale application of high-energy LIBs.
文摘Based on the theoretical representation of piezoelectric quasicrystal,a generalized dynamic model is built to represent the transmission of wave aspects in surface acoustic pulse nano-devices.Surface elasticity,surface piezoelectricity,and surface permittivity help to include the surface effect,which equals additional thin sheets.It is shown that,under certain assumptions,this generalized dynamic model may be simplified to a few classical examples that are appropriate for both macro and nano-scale applications.In the current work,surface piezoelectricity is used to develop a theoretical model for shear horizontal(SH)waves where it contains the surface piezoelectricity theory and a linear spring model to quantitatively and qualitatively explore SH waves in an orthotropic piezoelectric quasicrystal layer overlying an elastic framework(Model I),a piezoelectric quasi-crystal nano substrate,and an orthotropic piezoelectric quasicrystal half-space(Model II).The theoretical model stimulates the numerical results,which establish the critical thickness.As the piezoelectric layer’s thickness gets closer to nanometres,surface energy must be included when analyzing dispersion properties.Furthermore,the effects of surface elasticity and density on wave velocity are investigated individually.The authors establish a parameter,precisely the ratio of the physical modulus along the width direction to along the direction of wave travel.The surface effect’s impact on the general char-acteristics of piezoelectric structures is seen as a spring force acting on bulk boundaries.Analytical presentation of frequency equations for both symmetric and anti-symmetric waves pertains to the case of an electrical short circuit in Model II.The project aims to analyze SH waves in orthogonal anisotropic,transversely isotropic piezoelectric layered nanostructures,providing a practical mathematical tool for surface effects analysis and adaptability to other wave types,including Rayleigh waves and acoustic surface waves.
文摘In the past decade,dry reforming of methane(DRM)has garnered increasing interest as it converts CH_(4)and CO_(2),two typical greenhouse gases,into synthesis gas(H_(2)and CO)for the production of high-value-added chemicals and fuels.Nickel-based DRM catalysts,renowned for their high activity and low cost,however,encounter challenges such as severe deactivation from sintering and carbon deposition.Herein,a surrounded NiO@NiAlO precursor derived from Ni(OH)_(2)nanosheets was modified at both the core and shell interfaces with MgO via wet impregnation.The obtained 0.8MgO^(WI)/Ni@NiAlO catalyst achieved a high CH_(4)reaction rate of~177 mmol gNi^(-1)min^(-1)and remained stable for 50 h at 600℃without coke formation.In sharp contrast,other Mg-doped catalysts(MgO modified the core or shell interfaces)and the catalyst without Mg-doping deactivated within 10 h due to coking or Ni particle sintering.The Ni/MgNiO_(2)interfaces and abundant oxygen vacancies(O_(v))generated by Mg-doping contributed to the outstanding resistance to sintering&coking as well as the superior activity and stability of the 0.8MgO^(WI)/Ni@NiAlO catalyst.In-situ investigation further unveiled the reaction mechanism:the activation of CO_(2)via adsorption on O_(v)generates active oxygen species(O^(*)),which reacts with CH_(x)^(*)intermediates formed by the dissociation of CH_(4)on Ni sites,yielding CO and H_(2).This work not only fabricates coke-free and high-stability Ni-based DRM catalysts via interface engineering but also provides insights and a new strategy for the design of high-efficiency and stable catalysts for DRM.
基金supported by the National Natural Science Foundation of China(No.61904130)the Key Research and Development Program of Hubei Province(Nos.2023BAB122,2021BAA063,and 2020BAB084)the Key Laboratory of Coal Conversion and New Carbon Materials in Hubei Province(No.WKDM201907)for their invaluable support.
文摘Silicon(Si)anodes,with a theoretical specific capacity of 4200 mAh g^(-1),hold significant promise for the development of high-energy-density lithium-ion batteries(LIBs).However,practical applications are hindered by sluggish charge transfer kinetics,substantial volume expansion,and an unstable solid elec-trolyte interphase during cycling.To address these challenges,we propose a centimeter-scale Si anode design featuring a three-dimensional continuous network structure of Si nanowires(SiNWs)decorated with high-density Ag nanoparticles(Ag-SiNWs-Net)on both the surface and internally.This architecture effectively mitigates mechanical stress from Si volume changes through the high-aspect-ratio wire network.Additionally,the distribution of Ag nanoparticles on the Si induces electronic structure redistribution,generating built-in electric fields that accelerate charge transfer within the Si,significantly enhancing rate performance and cycling stability.The Ag-SiNWs-Net anode achieves a high reversible capacity of 3780.9 mAh g^(-1)at 0.1 A g^(-1),with an initial coulombic efficiency of 85.1%.Moreover,the energy density of full cells assembled with Ag-SiNWs-Net anodes and LiFePO4 cathodes can be pushed further up to 395.8 Wh kg^(-1).This study offers valuable insights and methodologies for the development of high-capacity and practical Si anodes-.
基金supported by National Natural Science Foundation of China(No.51873085)Natural Science Foundation of Liaoning Province-Outstanding Youth Foundation(No.2022-YQ-14)+2 种基金Liaoning Revitalization Talents Program(No.XLYC2007056)China Scholarship Council(CSC Scholarship,No.202006800009)the Shenyang Science and Technology Project(No.RC230707)。
文摘Precise control of luminescence in carbon quantum dots(CQDs),from single-color to full-color emission,is crucial for advancing their applications in biomedical imaging and display technologies.While CQDs luminescence is primarily influenced by conjugated domains and surface states,the underlying interaction mechanisms remain poorly understood.This study explores a graded nitro-engineering approach to simultaneously regulate surface states and sp^(2)conjugated domains through nitro(-NO_(2))modulation,enabling comprehensive color tuning.Using o-phenylenediamine(o-PD)as the carbon source and adjusting nitric acid(HNO_(3))concentrations,we synthesized tricolor-emitting nitro-functionalized CQDs(NO_(2)-CQDs).At lower-NO_(2) concentrations,luminescence is mainly influenced by surface states,where the electron-withdrawing effect of-NO_(2) enhancesπ-electron delocalization and stabilizes sp^(2)conjugation.With increasing-NO_(2) content,the lowest unoccupied molecular orbital(LUMO)energy level decreases(-2.12 eV to-3.39 eV),resulting in a red-shift in fluorescence.At higher-NO_(2) concentrations,luminescence is primarily affected by the sp^(2)conjugated domain,where steric hindrance reduces molecular planarity and conjugation,leading to a blue-shift in fluorescence as the sp^(2)domain size decreases(4.03 nm to 2.83 nm).Combining experimental results with density functional theory(DFT)calculations,we reveal the dual role of-NO2in modulating CQDs luminescence,an approach rarely achieved through surface functionalization.This work presents a novel strategy for precise tuning of CQDs luminescence across the visible spectrum.
