A review of defect engineering in two‐dimensional materials for electrocatalytic hydrogen evolution reaction

The exploration of efficient and earth‐rich electrocatalysts for electrochemical reactions is critical to the implementation of large‐scale green energy conversion and storage techniques.Two‐dimensional(2D)materials with distinctive structural and electrochemical properties provide fertile soil for researchers to harvest basic science and emerging applications,which can be divided into metal‐free materials(such as graphene,carbon nitride and black phosphorus)and transition metal‐based materials(such as halogenides,phosphates,oxides,hydroxides,and MXenes).For faultless 2D materials,they usually exhibit poor electrochemical hydrogen evolution reaction(HER)activity because only edge sites can be available while the base surface is chemically inactive.Defect engineering is an effective strategy to generate active sites in 2D materials for improving electrocatalytic activity.This review presents feasible design strategies for constructing defect sites(including edge defects,vacancy defects and dopant derived defects)in 2D materials to improve their HER performance.The essential relationships between defect structures and electrocatalytic HER performance are discussed in detail,providing valuable guidance for rationally fabricating efficient HER electrocatalysts.The hydrogen adsorption/desorption energy can be optimized by constructing defect sites at different locations and by adjusting the local electronic structure to form unsaturated coordination states for efficient HER.

Stable immobilization of lithium polysulfides using three-dimensional ordered mesoporous Mn_(2)O_(3) as the host material in lithium-sulfur batteries

Lithium-sulfur batteries(LSBs)have drawn significant attention owing to their high theoretical discharge capacity and energy density.However,the dissolution of long-chain polysulfides into the electrolyte during the charge and discharge process(“shuttle effect”)results in fast capacity fading and inferior electrochemical performance.In this study,Mn_(2)O_(3)with an ordered mesoporous structure(OM-Mn_(2)O_(3))was designed as a cathode host for LSBs via KIT-6 hard templating,to effectively inhibit the polysulfide shuttle effect.OM-Mn_(2)O_(3)offers numerous pores to confine sulfur and tightly anchor the dissolved polysulfides through the combined effects of strong polar-polar interactions,polysulfides,and sulfur chain catenation.The OM-Mn_(2)O_(3)/S composite electrode delivered a discharge capacity of 561 mAh g^(-1) after 250 cycles at 0.5 C owing to the excellent performance of OM-Mn_(2)O_(3).Furthermore,it retained a discharge capacity of 628mA h g^(-1) even at a rate of 2 C,which was significantly higher than that of a pristine sulfur electrode(206mA h g^(-1)).These findings provide a prospective strategy for designing cathode materials for high-performance LSBs.

Synthesis and Modulation of Low-Dimensional Transition Metal Chalcogenide Materials via Atomic Substitution

In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.

Emerging two-dimensional Mo-based materials for rechargeable metal-ion batteries:Advances and perspectives

With the rapid development of rechargeable metal-ion batteries(MIBs)with safety,stability and high energy density,significant efforts have been devoted to exploring high-performance electrode materials.In recent years,two-dimensional(2D)molybdenum-based(Mo-based)materials have drawn considerable attention due to their exceptional characteristics,including low cost,unique crystal structure,high theoretical capacity and controllable chemical compositions.However,like other transition metal compounds,Mo-based materials are facing thorny challenges to overcome,such as slow electron/ion transfer kinetics and substantial volume changes during the charge and discharge processes.In this review,we summarize the recent progress in developing emerging 2D Mo-based electrode materials for MIBs,encompassing oxides,sulfides,selenides,carbides.After introducing the crystal structure and common synthesis methods,this review sheds light on the charge storage mechanism of several 2D Mo-based materials by various advanced characterization techniques.The latest achievements in utilizing 2D Mo-based materials as electrode materials for various MIBs(including lithium-ion batteries(LIBs),sodium-ion batteries(SIBs)and zinc-ion batteries(ZIBs))are discussed in detail.Afterwards,the modulation strategies for enhancing the electrochemical performance of 2D Mo-based materials are highlighted,focusing on heteroatom doping,vacancies creation,composite coupling engineering and nanostructure design.Finally,we present the existing challenges and future research directions for 2D Mo-based materials to realize high-performance energy storage systems.

Electrocatalytic stability of two-dimensional materials

In electrocatalysis,two-dimensional(2D)materials have attracted extensive interests due to their unique electronic structure and physical properties.In recent years,many efforts have been devoted to improving the catalytic activity of 2D materials.However,the stability of 2D materials under catalytic conditions,as a critical issue,requires better understanding for any practical applications.This review summarizes recent progress in electrocatalytic stability of 2D materials,including four intrinsic factors that affect the stability of 2D materials:1.Weak interactions between 2D catalyst and substrate;2,delamination of 2D catalyst layers;3.metastable phase of 2D materials;4.chemistry and environmental instability of 2D materials.Meanwhile,some corresponding solutions are summarized for each factor.In addition,this review proposes potential routes for developing 2D catalytic materials with both high activity and stability.

Progress on two-dimensional ferrovalley materials

The electron's charge and spin degrees of freedom are at the core of modern electronic devices. With the in-depth investigation of two-dimensional materials, another degree of freedom, valley, has also attracted tremendous research interest. The intrinsic spontaneous valley polarization in two-dimensional magnetic systems, ferrovalley material, provides convenience for detecting and modulating the valley. In this review, we first introduce the development of valleytronics.Then, the valley polarization forms by the p-, d-, and f-orbit that are discussed. Following, we discuss the investigation progress of modulating the valley polarization of two-dimensional ferrovalley materials by multiple physical fields, such as electric, stacking mode, strain, and interface. Finally, we look forward to the future developments of valleytronics.

Alternating spin splitting of electronic and magnon bands in two-dimensional altermagnetic materials

Unconventional antiferromagnetism dubbed as altermagnetism was first discovered in rutile structured magnets,which is featured by spin splitting even without the spin–orbital coupling effect.This interesting phenomenon has been discovered in more altermagnetic materials.In this work,we explore two-dimensional altermagnetic materials by studying two series of two-dimensional magnets,including MF4 with M covering all 3d and 4d transition metal elements,as well as TS2 with T=V,Cr,Mn,Fe.Through the magnetic symmetry operation of RuF4 and MnS2,it is verified that breaking the time inversion is a necessary condition for spin splitting.Based on symmetry analysis and first-principles calculations,we find that the electronic bands and magnon dispersion experience alternating spin splitting along the same path.This work paves the way for exploring altermagnetism in two-dimensional materials.

Unlocking the potential of ultra-thin two-dimensional antimony materials:Selective growth and carbon coating for efficient potassium-ion storage

Antimony-based anodes have attracted wide attention in potassium-ion batteries due to their high theoretical specific capacities(∼660 mA h g^(-1))and suitable voltage platforms.However,severe capacity fading caused by huge volume change and limited ion transportation hinders their practical applications.Recently,strategies for controlling the morphologies of Sb-based materials to improve the electrochemical performances have been proposed.Among these,the two-dimensional Sb(2D-Sb)materials present excellent properties due to shorted ion immigration paths and enhanced ion diffusion.Nevertheless,the synthetic methods are usually tedious,and even the mechanism of these strategies remains elusive,especially how to obtain large-scale 2D-Sb materials.Herein,a novel strategy to synthesize 2D-Sb material using a straightforward solvothermal method without the requirement of a complex nanostructure design is provided.This method leverages the selective adsorption of aldehyde groups in furfural to induce crystal growth,while concurrently reducing and coating a nitrogen-doped carbon layer.Compared to the reported methods,it is simpler,more efficient,and conducive to the production of composite nanosheets with uniform thickness(3–4 nm).The 2D-Sb@NC nanosheet anode delivers an extremely high capacity of 504.5 mA h g^(-1) at current densities of 100 mA g^(-1) and remains stable for more than 200 cycles.Through characterizations and molecular dynamic simulations,how potassium storage kinetics between 2D Sb-based materials and bulk Sb-based materials are explored,and detailed explanations are provided.These findings offer novel insights into the development of durable 2D alloy-based anodes for next-generation potassium-ion batteries.

Recent progress on valley polarization and valley-polarized topological states in two-dimensional materials

Valleytronics, using valley degree of freedom to encode, process, and store information, may find practical applications in low-power-consumption devices. Recent theoretical and experimental studies have demonstrated that twodimensional(2D) honeycomb lattice systems with inversion symmetry breaking, such as transition-metal dichalcogenides(TMDs), are ideal candidates for realizing valley polarization. In addition to the optical field, lifting the valley degeneracy of TMDs by introducing magnetism is an efficient way to manipulate the valley degree of freedom. In this paper, we first review the recent progress on valley polarization in various TMD-based systems, including magnetically doped TMDs,intrinsic TMDs with both inversion and time-reversal symmetry broken, and magnetic TMD heterostructures. When topologically nontrivial bands are empowered into valley-polarized systems, valley-polarized topological states, namely valleypolarized quantum anomalous Hall effect can be realized. Therefore, we have also reviewed the theoretical proposals for realizing valley-polarized topological states in 2D honeycomb lattices. Our paper can help readers quickly grasp the latest research developments in this field.

Anomalous valley Hall effect in two-dimensional valleytronic materials

The anomalous valley Hall effect(AVHE)can be used to explore and utilize valley degrees of freedom in materials,which has potential applications in fields such as information storage,quantum computing and optoelectronics.AVHE exists in two-dimensional(2D)materials possessing valley polarization(VP),and such 2D materials usually belong to the hexagonal honeycomb lattice.Therefore,it is necessary to achieve valleytronic materials with VP that are more readily to be synthesized and applicated experimentally.In this topical review,we introduce recent developments on realizing VP as well as AVHE through different methods,i.e.,doping transition metal atoms,building ferrovalley heterostructures and searching for ferrovalley materials.Moreover,2D ferrovalley systems under external modulation are also discussed.2D valleytronic materials with AVHE demonstrate excellent performance and potential applications,which offer the possibility of realizing novel low-energy-consuming devices,facilitating further development of device technology,realizing miniaturization and enhancing functionality of them.

Image segmentation of exfoliated two-dimensional materials by generative adversarial network-based data augmentation

Mechanically cleaved two-dimensional materials are random in size and thickness.Recognizing atomically thin flakes by human experts is inefficient and unsuitable for scalable production.Deep learning algorithms have been adopted as an alternative,nevertheless a major challenge is a lack of sufficient actual training images.Here we report the generation of synthetic two-dimensional materials images using StyleGAN3 to complement the dataset.DeepLabv3Plus network is trained with the synthetic images which reduces overfitting and improves recognition accuracy to over 90%.A semi-supervisory technique for labeling images is introduced to reduce manual efforts.The sharper edges recognized by this method facilitate material stacking with precise edge alignment,which benefits exploring novel properties of layered-material devices that crucially depend on the interlayer twist-angle.This feasible and efficient method allows for the rapid and high-quality manufacturing of atomically thin materials and devices.

Two-dimensional MOF-based materials:Preparations and applications as electrodes in Li-ion batteries

Two-dimensional(2D)metal-organic frameworks(MOFs)are rapidly emerging as a unique class of mushrooming family of 2D materials offering distinctive features,such as hierarchical porosity,extensive surface area,easily available active sites,and versatile,adaptable structures.These promising characteristics have positioned them as highly appealing alternatives for a wide range of applications in energy storage technologies,including lithium batteries.Nevertheless,the poor conductivity and limited stability of 2D MOFs have limited their real applications in electrochemical energy storage.These limitations have therefore warranted ongoing research to enhance the performance of 2D MOFs.Given the significance of 2D MOF-based materials as an emerging class of advanced materials,a multitude of strategy has been devised to address these challenges such as synthesizing 2D conductive MOFs and derivatives along with 2D MOF hybridization.One promising approach involves the use of 2D MOF derivatives,including transition metal oxides,which due to their abundant unsatu rated active metal sites and shorter diffusion paths,offer superior electrochemical performance.Additionally,by combining pristine 2D MOFs with other materials,hybrid 2D MOF materials can be created.These hybrids,with their enhanced stability and conductivity,can be directly utilized as active materials in lithium batteries.In the present review,we categorize 2D MOF-based materials into three distinct groups:pristine 2D MOFs,2D MOFderived materials,and 2D MOF hybrid materials.The synthesis methods for each group,along with their specific applications as electrode materials in lithium-ion batteries,are discussed in detail.This comprehensive review provides insights into the potential of 2D MOFs while highlighting the opportunities and challenges that are present in this evolving field.

Two-Dimensional Materials for Highly Efficient and Stable Perovskite Solar Cells

Perovskite solar cells(PSCs)offer low costs and high power conversion efficiency.However,the lack of long-term stability,primarily stemming from the interfacial defects and the sus-ceptible metal electrodes,hinders their practical application.In the past few years,two-dimensional(2D)materials(e.g.,graphene and its derivatives,transitional metal dichalcogenides,MXenes,and black phosphorus)have been identified as a promising solution to solving these problems because of their dangling bond-free surfaces,layer-dependent electronic band structures,tunable functional groups,and inherent compactness.Here,recent progress of 2D material toward efficient and stable PSCs is summarized,including its role as both interface materials and electrodes.We discuss their beneficial effects on perovskite growth,energy level alignment,defect passivation,as well as blocking external stimulus.In particular,the unique properties of 2D materials to form van der Waals heterojunction at the bottom interface are emphasized.Finally,perspectives on the further development of PSCs using 2D materials are provided,such as designing high-quality van der Waals heterojunction,enhancing the uniformity and coverage of 2D nanosheets,and developing new 2D materials-based electrodes.

Control of light-matter interactions in two-dimensional materials with nanoparticle-on-mirror structures

Light–matter interactions in two-dimensional(2D)materials have been the focus of research since the discovery of graphene.The light–matter interaction length in 2D materials is,however,much shorter than that in bulk materials owing to the atomic nature of 2D materials.Plasmonic nanostructures are usually integrated with 2D materials to enhance the light–matter interactions,offering great opportunities for both fundamental research and technological applications.Nanoparticle-on-mirror(NPo M)structures with extremely confined optical fields are highly desired in this aspect.In addition,2D materials provide a good platform for the study of plasmonic fields with subnanometer resolution and quantum plasmonics down to the characteristic length scale of a single atom.A focused and up-to-date review article is highly desired for a timely summary of the progress in this rapidly growing field and to encourage more research efforts in this direction.In this review,we will first introduce the basic concepts of plasmonic modes in NPo M structures.Interactions between plasmons and quasi-particles in 2D materials,e.g.,excitons and phonons,from weak to strong coupling and potential applications will then be described in detail.Related phenomena in subnanometer metallic gaps separated by 2D materials,such as quantum tunneling,will also be touched.We will finally discuss phenomena and physical processes that have not been understood clearly and provide an outlook for future research.We believe that the hybrid systems of2D materials and NPo M structures will be a promising research field in the future.

Two-dimensional layered In_(2)P_(3)S_(9): A novel superior anode material for sodium-ion batteries

Developing reliable and efficient anode materials is essential for the successfully practical application of sodium-ion batteries.Herein,employing a straightforward and rapid chemical vapor deposition technique,two-dimensional layered ternary indium phosphorus sulfide(In_(2)P_(3)S_(9)) nanosheets are prepared.The layered structure and ternary composition of the In_(2)P_(3)S_(9) electrode result in impressive electrochemical performance,including a high reversible capacity of 704 mA h g^(-1) at 0.1 A g^(-1),an outstanding rate capability with 425 mA h g^(-1) at 5 A g^(-1),and an exceptional cycling stability with a capacity retention of88% after 350 cycles at 1 A g^(-1).Furthermore,sodium-ion full cell also affords a high capacity of 308 and114 mA h g^(-1) at 0.1 and 5 A g^(-1).Ex-situ X-ray diffraction and ex-situ high-resolution transmission electron microscopy tests are conducted to investigate the underlying Na-storage mechanism of In_(2)P_(3)S_(9).The results reveal that during the first cycle,the P-S bond is broken to form the elemental P and In_(2)S_(3),collectively contributing to a remarkably high reversible specific capacity.The excellent electrochemical energy storage results corroborate the practical application potential of In_(2)P_(3)S_(9) for sodium-ion batteries.

Chemical vapor deposition for few‐layer two‐dimensional materials

Chemical vapor deposition(CVD)approach offers a controllable strategy for preparing large‐area and high‐quality few‐layer(mainly bilayer or trilayer)twisted or untwisted two‐dimensional(2D)materials,and is predicted to boost the development of 2D materials from laboratory research to industrial applications.

Research status and prospects of the fractal analysis of metal material surfaces and interfaces

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.

High‑Entropy Electrode Materials:Synthesis,Properties and Outlook

High-entropy materials represent a new category of high-performance materials,first proposed in 2004 and extensively investigated by researchers over the past two decades.The definition of high-entropy materials has continuously evolved.In the last ten years,the discovery of an increasing number of high-entropy materials has led to significant advancements in their utilization in energy storage,electrocatalysis,and related domains,accompanied by a rise in techniques for fabricating high-entropy electrode materials.Recently,the research emphasis has shifted from solely improving the performance of high-entropy materials toward exploring their reaction mechanisms and adopting cleaner preparation approaches.However,the current definition of high-entropy materials remains relatively vague,and the preparation method of high-entropy materials is based on the preparation method of single metal/low-or medium-entropy materials.It should be noted that not all methods applicable to single metal/low-or medium-entropy materials can be directly applied to high-entropy materials.In this review,the definition and development of high-entropy materials are briefly reviewed.Subsequently,the classification of high-entropy electrode materials is presented,followed by a discussion of their applications in energy storage and catalysis from the perspective of synthesis methods.Finally,an evaluation of the advantages and disadvantages of various synthesis methods in the production process of different high-entropy materials is provided,along with a proposal for potential future development directions for high-entropy materials.

Recent Advances in Fibrous Materials for Hydroelectricity Generation

Depleting fossil energy sources and conventional polluting power generation pose a threat to sustainable development.Hydroelectricity generation from ubiquitous and spontaneous phase transitions between liquid and gaseous water has been considered a promising strategy for mitigating the energy crisis.Fibrous materials with unique flexibility,processability,multifunctionality,and practicability have been widely applied for fibrous materials-based hydroelectricity generation(FHG).In this review,the power generation mechanisms,design principles,and electricity enhancement factors of FHG are first introduced.Then,the fabrication strategies and characteristics of varied constructions including 1D fiber,1D yarn,2D fabric,2D membrane,3D fibrous framework,and 3D fibrous gel are demonstrated.Afterward,the advanced functions of FHG during water harvesting,proton dissociation,ion separation,and charge accumulation processes are analyzed in detail.Moreover,the potential applications including power supply,energy storage,electrical sensor,and information expression are also discussed.Finally,some existing challenges are considered and prospects for future development are sincerely proposed.

Preparation and applications of calcium ferrite as a functional material:A review

Calcium ferrite(CF)is recognized as a potential green and efficient functional material because of its advantages of magnetism,electrochemistry,catalysis,and biocompatibility in the fields of materials chemistry,environmental engineering,and biomedicine.There-fore,the obtained research results need to be systematically summarized,and new perspectives on CF and its composite materials need to be analyzed.Based on the presented studies of CF and its composite materials,the types and structures of the crystal are summarized.In addition,the current application technologies and theoretical mechanisms with various properties in different fields are elucidated.Moreover,the various preparation methods of CF and its composite materials are elaborated in detail.Most importantly,the advantages and disadvantages of the synthesis methods of CF and its composite materials are discussed,and the existing problems and emerging challenges in practical production are identified.Furthermore,the key future research directions of CF and its composite materials have been prospected from the potential application technologies to provide references for its synthesis and efficient utilization.