Wearable smart sensors are considered to be the new generation of personal portable devices for health monitoring.By attaching to the skin surface,these sensors are closely related to body signals(such as heart rate,b...Wearable smart sensors are considered to be the new generation of personal portable devices for health monitoring.By attaching to the skin surface,these sensors are closely related to body signals(such as heart rate,blood oxygen saturation,breath markers,etc.)and ambient signals(such as ultraviolet radiation,inflammable and explosive,toxic and harmful gases),thus providing new opportunities for human activity monitoring and personal telemedicine care.Here we focus on photodetectors and gas sensors built from metal chalcogenide,which have made great progress in recent years.Firstly,we present an overview of healthcare applications based on photodetectors and gas sensors,and discuss the requirement associated with these applications in detail.We then discuss advantages and properties of solution-processable metal chalcogenides,followed by some recent achievements in health monitoring with photodetectors and gas sensors based on metal chalcogenides.Last we present further research directions and challenges to develop an integrated wearable platform for monitoring human activity and personal healthcare.展开更多
Two-dimensional(2D)transition metal chalcogenides(TMC)and their heterostructures are appealing as building blocks in a wide range of electronic and optoelectronic devices,particularly futuristic memristive and synapti...Two-dimensional(2D)transition metal chalcogenides(TMC)and their heterostructures are appealing as building blocks in a wide range of electronic and optoelectronic devices,particularly futuristic memristive and synaptic devices for brain-inspired neuromorphic computing systems.The distinct properties such as high durability,electrical and optical tunability,clean surface,flexibility,and LEGO-staking capability enable simple fabrication with high integration density,energy-efficient operation,and high scalability.This review provides a thorough examination of high-performance memristors based on 2D TMCs for neuromorphic computing applications,including the promise of 2D TMC materials and heterostructures,as well as the state-of-the-art demonstration of memristive devices.The challenges and future prospects for the development of these emerging materials and devices are also discussed.The purpose of this review is to provide an outlook on the fabrication and characterization of neuromorphic memristors based on 2D TMCs.展开更多
Transition metal chalcogenides(TMCs)and TMCs-based nanocomposites have attracted extensive attention due to their versatile material species,low cost,and rich physical and chemical characteristics.As anode materials o...Transition metal chalcogenides(TMCs)and TMCs-based nanocomposites have attracted extensive attention due to their versatile material species,low cost,and rich physical and chemical characteristics.As anode materials of lithium-ion capacitors(LICs),TMCs have exhibited high theoretical capacities and pseudocapacitance storage mechanism.However,there are many intrinsic challenges,such as low electrical conductivity,repeatedly high-volume changes and sluggish ionic diffusion kinetics.Hence,many traditional and unconventional techniques have been reported to solve these critical problems,and many innovative strategies are also used to prepare high quality anode materials for LICs.In this mini review,a detailed family member list and comparison of TMCs in the field of lithium-ion capacitors have been summarized firstly.Then,many rectification stratagems and recent researches of TMCs have been exhibited and discussed.In the end,as an outcome of these discussions,some further challenges and perspectives are envisioned to promote the application of TMCs materials for lithium-ion c apacitors.展开更多
Ternary transition metal chalcogenides provide a rich platform to search and study intriguing electronic properties. Using angle-resolved photoemission spectroscopy and ab initio calculation, we investigate the electr...Ternary transition metal chalcogenides provide a rich platform to search and study intriguing electronic properties. Using angle-resolved photoemission spectroscopy and ab initio calculation, we investigate the electronic structure of Cu_(2)TlX_(2)(X = Se, Te), ternary transition metal chalcogenides with quasi-two-dimensional crystal structure. The band dispersions near the Fermi level are mainly contributed by the Te/Se p orbitals. According to our ab-initio calculation, the electronic structure changes from a semiconductor with indirect band gap in Cu_(2)TlSe_(2) to a semimetal in Cu_(2)TlTe_(2), suggesting a band-gap tunability with the composition of Se and Te. By comparing ARPES experimental data with the calculated results, we identify strong modulation of the band structure by spin–orbit coupling in the compounds. Our results provide a ternary platform to study and engineer the electronic properties of transition metal chalcogenides related to large spin–orbit coupling.展开更多
Transition-metal chalcogenide nanowires(TMCN) as a viable candidate for nanoscale applications have been attracting much attention for the last few decades. Starting from the rigid building block of M6 octahedra(M = t...Transition-metal chalcogenide nanowires(TMCN) as a viable candidate for nanoscale applications have been attracting much attention for the last few decades. Starting from the rigid building block of M6 octahedra(M = transition metal),depending on the way of connection between M6 and decoration by chalcogenide atoms, multiple types of extended TMCN nanowires can be constructed based on some basic rules of backbone construction proposed here. Note that the well-known Chevrel-phase based M6X6 and M6X9(X = chalcogenide atom) nanowires, which are among our proposed structures, have been successfully synthesized by experiment and well studied. More interestingly, based on the construction principles, we predict three new structural phases(the cap, edge, and C&E phases) of Mo5S4, one of which(the edge phase) has been obtained by top-down electron beam lithography on two-dimensional MoS2, and the C&E phase is yet to be synthesized but appears more stable than the edge phase. The stability of the new phases of Mo5S4 is further substantiated by crystal orbital overlapping population(COOP), phonon dispersion relation, and thermodynamic calculation. The barrier of the structural transition between different phases of Mo5S4 shows that it is very likely to realize an conversion from the experimentally achieved structure to the most stable C&E phase. The calculated electronic structure shows an interesting band nesting between valence and conduction bands of the C&E Mo5S4 phase, suggesting that such a nanowire structure can be well suitable for optoelectronic sensor applications.展开更多
Intense efforts have been devoted to the synthesis of heterogeneous nanocomposites consisting of chalcogenide semiconductors and noble metals,which usually exhibit enhanced properties owing to the synergistic effect b...Intense efforts have been devoted to the synthesis of heterogeneous nanocomposites consisting of chalcogenide semiconductors and noble metals,which usually exhibit enhanced properties owing to the synergistic effect between their different material domains.Tailoring the structure of the metal domains in the nanocomposites may lead to further improvements of its performance for a given application.This review therefore highlights the strategies based on a structural conversion process for the fabrication of nanocomposites consisting of chalcogenide semiconductors and noble metals with various internal structures,e.g.,hollow or cage-bell.This strategy relies on a unique inside-out diffusion phenomenon of Ag in core-shell nanoparticles with Ag residing at core or inner shell region.In the presence of sulfur or selenium precursors,the diffused Ag are converted into Ag2S or Ag2Se,which is connected with the remaining noble metal parts,forming nanocomposites consisting of silver chalcogenide and noble metal nanoparticles with hollow or cage-bell structures.We would focus on the introduction of the fundamentals,principles,electrocatalytic applications as well as perspectives of the chalcogenide semiconductor-noble metal nanocomposites derived from their core-shell precursors so as to provide the readers insights in designing efficient nanocomposites for electrocatalysis.展开更多
Combining with the advantages of two-dimensional(2D)nanomaterials,MXenes have shown great potential in next generation rechargeable batteries.Similar with other 2D materials,MXenes generally suffer severe self-agglome...Combining with the advantages of two-dimensional(2D)nanomaterials,MXenes have shown great potential in next generation rechargeable batteries.Similar with other 2D materials,MXenes generally suffer severe self-agglomeration,low capacity,and unsatisfied durability,particularly for larger sodium/potassium ions,compromising their practical values.In this work,a novel ternary heterostructure self-assembled from transition metal selenides(MSe,M=Cu,Ni,and Co),MXene nanosheets and N-rich carbonaceous nanoribbons(CNRibs)with ultrafast ion transport properties is designed for sluggish sodium-ion(SIB)and potassium-ion(PIB)batteries.Benefiting from the diverse chemical characteristics,the positively charged MSe anchored onto the electronegative hydroxy(-OH)functionalized MXene surfaces through electrostatic adsorption,while the fungal-derived CNRibs bonded with the other side of MXene through amino bridging and hydrogen bonds.This unique MXene-based heterostructure prevents the restacking of 2D materials,increases the intrinsic conductivity,and most importantly,provides ultrafast interfacial ion transport pathways and extra surficial and interfacial storage sites,and thus,boosts the high-rate storage performances in SIB and PIB applications.Both the quantitatively kinetic analysis and the density functional theory(DFT)calculations revealed that the interfacial ion transport is several orders higher than that of the pristine MXenes,which delivered much enhanced Na+(536.3 mAh g^(−1)@0.1 A g^(−1))and K^(+)(305.6 mAh g^(−1)@1.0 A g^(−1))storage capabilities and excel-lent long-term cycling stability.Therefore,this work provides new insights into 2D materials engineering and low-cost,but kinetically sluggish post-Li batteries.展开更多
Layered two-dimensional(2 D)materials have received tremendous attention due to their unique physical and chemical properties when downsized to single or few layers.Several types of layered materials,especially transi...Layered two-dimensional(2 D)materials have received tremendous attention due to their unique physical and chemical properties when downsized to single or few layers.Several types of layered materials,especially transition metal dichalcogenides(TMDs)have been demonstrated to be good electrode materials due to their interesting physical and chemical properties.Apart from TMDs,post-transition metal chalcogenides(PTMCs)recently have emerged as a family of important semiconducting materials for electrochemical studies.PTMCs are layered materials which are composed of post-transition metals raging from main group IIIA to group VA(Ga,In,Ge,Sn,Sb and Bi)and group VI chalcogen atoms(S,selenium(Se)and tellurium(Te)).Although a large number of literatures have reviewed the electrochemical and electrocatalytic applications of TMDs,less attention has been focused on PTMCs.In this review,we focus our attention on PTMCs with the aim to provide a summary to describe their fundamental electrochemical properties and electrocatalytic activity towards hydrogen evolution reaction(HER).The characteristic chemical compositions and crystal structures of PTMCs are firstly discussed,which are different from TMDs.Then,inherent electrochemistry of PTMCs is discussed to unveil the well-defined redox behaviors of PTMCs,which could potentially affect their efficiency when applied as electrode materials.Following,we focus our attention on electrocatalytic activity of PTMCs towards HER including novel synthetic strategies developed for the optimization of their HER activity.This review ends with the perspectives for the future research direction in the field of PTMC based electrocatalysts.展开更多
Photoelectrochemical water splitting(PEC-WS)is a promising technique for transforming solar energy into storable and environmentally friendly chemical energy.Designing semiconductor photoelectrodes with high light abs...Photoelectrochemical water splitting(PEC-WS)is a promising technique for transforming solar energy into storable and environmentally friendly chemical energy.Designing semiconductor photoelectrodes with high light absorption capability,rapid e-/h+separation and transfer,and sufficient chemical stability is vital for developing an efficient PEC-WS system.Metal chalcogenides(MCs)have emerged as promising candidates for light absorbers because of their unique electrical and optical characteristics.In this review,we present recent developments in hydrogen generation via PEC-WS using MC-based photoelectrodes.First,we present a simple illustration of PEC-WS fundamentals.Second,the current performance of various metal(mono-,di-,and tri-)chalcogenide/semiconductor photoelectrodes in PEC-WS is summarized.Then,the charge transfer mechanism at the MC/semiconductor interface and the PEC-WS mechanism is thoroughly explained.Finally,we discuss future research perspectives toward developing efficient and stable MC/semiconductor photoelectrodes.展开更多
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 counterpart...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.展开更多
Non-layered two-dimensional(2D)materials have sparked much interest recently due to their atomic thickness,large surface area,thickness-and facet-dependent properties.Currently,these materials are mainly grown from we...Non-layered two-dimensional(2D)materials have sparked much interest recently due to their atomic thickness,large surface area,thickness-and facet-dependent properties.Currently,these materials are mainly grown from wet-chemistry methods but suffer from small size,low quality,and multi-facets,which is a major challenge hindering their facet-dependent property studies and applications.Here,we report the facet-engineered growth(FEG)of non-layered 2D manganese chalcogenides(MnX,X=S,Se,Te)based on the chemical vapor deposition method.The as-grown samples exhibit large-area surfaces of single facet,high-crystallinity,and ordered domain orientation.As a proof-of-concept,we show the facet-dependent electrocatalytic property of non-layered 2D MnSe,proving they are ideal candidates for fundamental research.Furthermore,we elucidate the underlying mechanism of FEG during the vapor growth process by the interfacial energy derived nucleation models.The method developed in this work provides new opportunities for regulating and designing the structure of 2D materials.展开更多
For more than a decade,the exfoliation of graphene and other layered materials has led to a tremendous amount of research in two-dimensional(2D)materials,among which 2D transition metal chalcogenides(TMCs)nanomaterial...For more than a decade,the exfoliation of graphene and other layered materials has led to a tremendous amount of research in two-dimensional(2D)materials,among which 2D transition metal chalcogenides(TMCs)nanomaterials have attracted much attention in a wide range of applications including photoelectric devices,lithium-ion batteries,catalysis,and energy conversion and storage owing to their unique photoelectric physical properties.With such large specific surface area,strong near-infrared(NIR)absorption and abundant chemical element composition,2D TMCs nanomaterials have become good candidates in biomedical imaging and cancer treatment.This review systematically summarizes recent progress on 2D TMCs nanomaterials,which includes their synthesis methods and applications in cancer treatment.At the end of this review,we also highlight the future prospects and challenges of 2D TMCs nanomaterials.It is expected that this work can provide the readers with a detailed overview of the synthesis of 2D TMCs and inspire more novel functional biomaterials based on 2D TMCs for cancer treatment in the future.展开更多
Photodegradation of aqueous organic pollutants is a very promising strategy to address environmental issues and energy problems.Among all the reported photocatalysts,crystalline metal chalcogenides not only possess di...Photodegradation of aqueous organic pollutants is a very promising strategy to address environmental issues and energy problems.Among all the reported photocatalysts,crystalline metal chalcogenides not only possess diverse architectures that can be enriched by integrating different metal ions and templates,but also have narrower band gaps(visible light adsorption)and suitable band positions that can be tuned through composition regulation.Therefore,the application of crystalline metal chalcogenides as efficient photocatalysts has attracted much attention.However,the limited synthetic methods,low degradation efficiency,and poor chemical stability are the major challenges that impede their practical application.In this review,the recent progress in employing crystalline metal chalcogenides as visible-light-driven catalysts for the photodegradation of organic contaminants is summarized.Besides this,the synthetic methods to prepare crystalline chalcogenides are discussed and the perspectives in regard to the improvement of the degradation efficiency and the chemical stability of metal chalcogenides are proposed.展开更多
Transition metal chalcogenides(TMCs)have been well-established as ideal low-dimensional systems for photocatalytic hydrogen evolution.Strategies toward improving the activity of these TMC photocatalysts by crafting he...Transition metal chalcogenides(TMCs)have been well-established as ideal low-dimensional systems for photocatalytic hydrogen evolution.Strategies toward improving the activity of these TMC photocatalysts by crafting heterostructures have been intensively studied.In this study,a two-dimensional(2D)CoAl layered double hydroxide(CoAl-LDH)has been assembled on 2D TMCs(CdIn_(2)S_(4),In_(2)S_(3),and ZnIn_(2)S_(4))to construct novel 2D/2D heterostructures by a facile electrostatic assembly method.The intimate interaction at the interface of hybrids and the suitable energy level alignment enable an efficient pathway for electron transfer to improve the photoactivity.Experimental results show that the photocatalytic activity of the CdIn_(2)S_(4)@CoAl-LDH hybrids for H_(2)production is about 4.3 times higher than that of CdIn_(2)S_(4)nanosheets under visible-light irradiation.The effect of 2D CoAl-LDH on enhancing the photoactivities of In_(2)S_(3)and ZnIn_(2)S_(4)by similarly constructing 2D heterostructures has also been determined.This work establishes a foundation to construct 2D TMC-based heterostructures using CoAl-LDH nanosheets toward enhanced photoredox activity.展开更多
The large amount of radioactive waste generated by the rapid development of nuclear energy is in urgent need of disposal.Metal chalcogenide ion-exchangers(MCIEs)are newly developed in recent years that show great pote...The large amount of radioactive waste generated by the rapid development of nuclear energy is in urgent need of disposal.Metal chalcogenide ion-exchangers(MCIEs)are newly developed in recent years that show great potential in the field of removing radionuclides.This is a comprehensive review of the latest research progress on the removal of key radioactive ions(e.g.,radioactive Cs^(+),Sr^(2)+,UO_(2)^(2+),lanthanide ions,and actinide ions)by MCIEs.The structure and ion-exchange properties of MCIEs are summarized emphatically.The ion-exchange mechanism of MCIEs is discussed and the structure-function relationship is preliminarily revealed.Easily exchangeable cations in the interlayer/channel,appropriately sized interlayer/channel/window spaces,flexible open framework,and the strong affinity of the Lewis soft base S^(2−)/Se^(2−)sites in the framework for soft or relatively soft metal ions,are the keys to the excellent selectivity and fast adsorption kinetics of MCIEs for radioactive ions.Finally,future research directions of metal chalcogenides for radioactive ions removal are foreseen.It is hoped that the review will provide a reference for the design of new metal chalcogenide ion-exchangers with practical application prospects for radioactive waste treatment and point to new directions for environmental radioactive contamination control.展开更多
Because the structures and properties of crystalline metal chalcogenides are strongly dependent on their synthetic conditions,developing new methods to approach novel chalcogenides is highly desirable.This review will...Because the structures and properties of crystalline metal chalcogenides are strongly dependent on their synthetic conditions,developing new methods to approach novel chalcogenides is highly desirable.This review will summarize the recent progress in growing crystalline chalcogenides through four new strategies:ionothermal,surfactant-thermal,hydrazine-thermal,and metal Zintl phase usage.展开更多
Alkali metal chalcogenides have emerged as a new class of inorganic materials with diverse applications in energy conversion and storage owing to their structural versatility and wide range of properties.Strategies ar...Alkali metal chalcogenides have emerged as a new class of inorganic materials with diverse applications in energy conversion and storage owing to their structural versatility and wide range of properties.Strategies are needed for simple and cost-efficient synthetic approaches that enable the composition and functional properties of these materials to be systematically tuned.Herein,we present a novel wet-chemistry approach to produce ternary Na-based metal chalcogenides with varying compositions.Phase-pure Na3SbCh4(Ch=S,Se)solid-state electrolytes are synthesized in a single-step fashion by reacting an ethanolic solution of Na chalcogenides with appropriately selected metal halides at room temperature.This process simplifies the reaction protocols,improves yield,and decreases the raw material loss incurred in multistep systems by eliminating the need for phase-pure binary metal chalcogenides.The reaction mechanisms and impurity profile of various sodium metal chalcogenides introduced in this work were methodically investigated through characterization techniques such as X-ray diffraction(XRD)and Raman spectroscopy.Among the chalcogenides,synthesis of the sulfide compounds(∼99 wt%purity)was straightforward,achieving a yield of 92-95%whereas the selenides required more control to generate the appropriate mix of precursors,which resulted in a lower yield of 74-79%but with a high purity of 97.5-99.6 wt%.Electrochemical impedance spectroscopy of as-synthesized Na3SbCh4(Ch=S,Se)showed a high ionic conductivity of 0.17-0.38 mS cm^(-1 )and low activation energy of 0.19-0.21 eV comparable with other reports of solution-based synthesis.The one-pot scheme was successfully extended to the NaSbCh2(Ch=S,Se)system,producing phase pure ternary sodium metal chalcogenides with tunable band gaps(1.6-1.8 eV)appropriate for solar energy conversion applications.The“one-pot”approach offers a simple yet economical route for scalable production of bulk sodium ternary chalcogenides at ambient conditions.展开更多
Atomically precise metal-chalcogenide supertetrahedral clusters (MCSCs) are supposed to be more attractive for functionalization than conventional metal-sulfide quantum dots owing to their potential ability to establi...Atomically precise metal-chalcogenide supertetrahedral clusters (MCSCs) are supposed to be more attractive for functionalization than conventional metal-sulfide quantum dots owing to their potential ability to establish precise structure-composition-property relationships.However,the accurate surface functionalization of such cluster-based species remains difficult.In this paper,we present a facile method for synthesizing discrete MCSCs decorated with different functional groups via a one-step solvothermal reaction,which was demonstrated to have better solvent dispersibility compared with ligand-free ones.In addition,the composites were also prepared by combining ligand-free clusters (or ligand-partially protected or amino-modified ones) with two-dimensional MXene nanosheets.The composites derived from amino-modified clusters exhibited optimal performance of photocatalytic hydrogen evolution.Furthermore,the hydrogen bonding interactions between modified amino groups and MXene nanosheets were verified by 1H-NMR spectroscopy.This work provides a facile approach for the surface functionalization of MCSCs,and facilitates the expansion of the functionality of atomically precise nano-species.展开更多
基金supported by National Natural Science Foundation of China (61861136004)the National Key R&D Program of China (2016YFB0402705)+1 种基金the Innovation Fund of WNLOProgram for HUST Academic Frontier Youth Team (2018QYTD06)
文摘Wearable smart sensors are considered to be the new generation of personal portable devices for health monitoring.By attaching to the skin surface,these sensors are closely related to body signals(such as heart rate,blood oxygen saturation,breath markers,etc.)and ambient signals(such as ultraviolet radiation,inflammable and explosive,toxic and harmful gases),thus providing new opportunities for human activity monitoring and personal telemedicine care.Here we focus on photodetectors and gas sensors built from metal chalcogenide,which have made great progress in recent years.Firstly,we present an overview of healthcare applications based on photodetectors and gas sensors,and discuss the requirement associated with these applications in detail.We then discuss advantages and properties of solution-processable metal chalcogenides,followed by some recent achievements in health monitoring with photodetectors and gas sensors based on metal chalcogenides.Last we present further research directions and challenges to develop an integrated wearable platform for monitoring human activity and personal healthcare.
基金supported by the Characterization platform for advanced materials funded by the Korea Research Institute of Standards and Science(KRISS-2021-GP2021-0011)supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government MSIT(2021M3D1A20396541).
文摘Two-dimensional(2D)transition metal chalcogenides(TMC)and their heterostructures are appealing as building blocks in a wide range of electronic and optoelectronic devices,particularly futuristic memristive and synaptic devices for brain-inspired neuromorphic computing systems.The distinct properties such as high durability,electrical and optical tunability,clean surface,flexibility,and LEGO-staking capability enable simple fabrication with high integration density,energy-efficient operation,and high scalability.This review provides a thorough examination of high-performance memristors based on 2D TMCs for neuromorphic computing applications,including the promise of 2D TMC materials and heterostructures,as well as the state-of-the-art demonstration of memristive devices.The challenges and future prospects for the development of these emerging materials and devices are also discussed.The purpose of this review is to provide an outlook on the fabrication and characterization of neuromorphic memristors based on 2D TMCs.
基金financially supported by the National Natural Science Foundation of China(No.51907193)the Key Research Program of Frontier Sciences,CAS(No.ZDBS-LYJSC047)+1 种基金the Youth Innovation Promotion Association CAS(No.2020145)Dalian National Laboratory for Clean Energy Cooperation Fund,the CAS(No.DNL201915)。
文摘Transition metal chalcogenides(TMCs)and TMCs-based nanocomposites have attracted extensive attention due to their versatile material species,low cost,and rich physical and chemical characteristics.As anode materials of lithium-ion capacitors(LICs),TMCs have exhibited high theoretical capacities and pseudocapacitance storage mechanism.However,there are many intrinsic challenges,such as low electrical conductivity,repeatedly high-volume changes and sluggish ionic diffusion kinetics.Hence,many traditional and unconventional techniques have been reported to solve these critical problems,and many innovative strategies are also used to prepare high quality anode materials for LICs.In this mini review,a detailed family member list and comparison of TMCs in the field of lithium-ion capacitors have been summarized firstly.Then,many rectification stratagems and recent researches of TMCs have been exhibited and discussed.In the end,as an outcome of these discussions,some further challenges and perspectives are envisioned to promote the application of TMCs materials for lithium-ion c apacitors.
基金supported by the National Natural Science Foundation of China (Grant No. 11774190)。
文摘Ternary transition metal chalcogenides provide a rich platform to search and study intriguing electronic properties. Using angle-resolved photoemission spectroscopy and ab initio calculation, we investigate the electronic structure of Cu_(2)TlX_(2)(X = Se, Te), ternary transition metal chalcogenides with quasi-two-dimensional crystal structure. The band dispersions near the Fermi level are mainly contributed by the Te/Se p orbitals. According to our ab-initio calculation, the electronic structure changes from a semiconductor with indirect band gap in Cu_(2)TlSe_(2) to a semimetal in Cu_(2)TlTe_(2), suggesting a band-gap tunability with the composition of Se and Te. By comparing ARPES experimental data with the calculated results, we identify strong modulation of the band structure by spin–orbit coupling in the compounds. Our results provide a ternary platform to study and engineer the electronic properties of transition metal chalcogenides related to large spin–orbit coupling.
基金Project supported by the National Natural Science Foundation of China(Grant No.51702146)the College Students’ Innovation and Entrepreneurship Projects,China(Grant No.201710148000072)Liaoning Province Doctor Startup Fund,China(Grant No.201601325)
文摘Transition-metal chalcogenide nanowires(TMCN) as a viable candidate for nanoscale applications have been attracting much attention for the last few decades. Starting from the rigid building block of M6 octahedra(M = transition metal),depending on the way of connection between M6 and decoration by chalcogenide atoms, multiple types of extended TMCN nanowires can be constructed based on some basic rules of backbone construction proposed here. Note that the well-known Chevrel-phase based M6X6 and M6X9(X = chalcogenide atom) nanowires, which are among our proposed structures, have been successfully synthesized by experiment and well studied. More interestingly, based on the construction principles, we predict three new structural phases(the cap, edge, and C&E phases) of Mo5S4, one of which(the edge phase) has been obtained by top-down electron beam lithography on two-dimensional MoS2, and the C&E phase is yet to be synthesized but appears more stable than the edge phase. The stability of the new phases of Mo5S4 is further substantiated by crystal orbital overlapping population(COOP), phonon dispersion relation, and thermodynamic calculation. The barrier of the structural transition between different phases of Mo5S4 shows that it is very likely to realize an conversion from the experimentally achieved structure to the most stable C&E phase. The calculated electronic structure shows an interesting band nesting between valence and conduction bands of the C&E Mo5S4 phase, suggesting that such a nanowire structure can be well suitable for optoelectronic sensor applications.
基金Financial supports from the National Natural Science Foundation of China (Grant No. 21573240)Center for Mesoscience, Institute of Process Engineering, Chinese Academy of Sciences (Grant No. COM2015A001 and MPCS-2017-A-02)
文摘Intense efforts have been devoted to the synthesis of heterogeneous nanocomposites consisting of chalcogenide semiconductors and noble metals,which usually exhibit enhanced properties owing to the synergistic effect between their different material domains.Tailoring the structure of the metal domains in the nanocomposites may lead to further improvements of its performance for a given application.This review therefore highlights the strategies based on a structural conversion process for the fabrication of nanocomposites consisting of chalcogenide semiconductors and noble metals with various internal structures,e.g.,hollow or cage-bell.This strategy relies on a unique inside-out diffusion phenomenon of Ag in core-shell nanoparticles with Ag residing at core or inner shell region.In the presence of sulfur or selenium precursors,the diffused Ag are converted into Ag2S or Ag2Se,which is connected with the remaining noble metal parts,forming nanocomposites consisting of silver chalcogenide and noble metal nanoparticles with hollow or cage-bell structures.We would focus on the introduction of the fundamentals,principles,electrocatalytic applications as well as perspectives of the chalcogenide semiconductor-noble metal nanocomposites derived from their core-shell precursors so as to provide the readers insights in designing efficient nanocomposites for electrocatalysis.
基金the National Natural Science Foundation of China(Grant No.21571080)Ziqi thanks the financial support from Australian Research Council through an ARC Future Fellowship(FT180100387)+1 种基金an ARC Discovery Project(DP200103568)Specially,Junming wants to thank his parents and fiancée for their unconditional love and support in his career as a graduate student.
文摘Combining with the advantages of two-dimensional(2D)nanomaterials,MXenes have shown great potential in next generation rechargeable batteries.Similar with other 2D materials,MXenes generally suffer severe self-agglomeration,low capacity,and unsatisfied durability,particularly for larger sodium/potassium ions,compromising their practical values.In this work,a novel ternary heterostructure self-assembled from transition metal selenides(MSe,M=Cu,Ni,and Co),MXene nanosheets and N-rich carbonaceous nanoribbons(CNRibs)with ultrafast ion transport properties is designed for sluggish sodium-ion(SIB)and potassium-ion(PIB)batteries.Benefiting from the diverse chemical characteristics,the positively charged MSe anchored onto the electronegative hydroxy(-OH)functionalized MXene surfaces through electrostatic adsorption,while the fungal-derived CNRibs bonded with the other side of MXene through amino bridging and hydrogen bonds.This unique MXene-based heterostructure prevents the restacking of 2D materials,increases the intrinsic conductivity,and most importantly,provides ultrafast interfacial ion transport pathways and extra surficial and interfacial storage sites,and thus,boosts the high-rate storage performances in SIB and PIB applications.Both the quantitatively kinetic analysis and the density functional theory(DFT)calculations revealed that the interfacial ion transport is several orders higher than that of the pristine MXenes,which delivered much enhanced Na+(536.3 mAh g^(−1)@0.1 A g^(−1))and K^(+)(305.6 mAh g^(−1)@1.0 A g^(−1))storage capabilities and excel-lent long-term cycling stability.Therefore,this work provides new insights into 2D materials engineering and low-cost,but kinetically sluggish post-Li batteries.
基金financial support from the National Natural Science Foundation of China(Grant No.11774044)。
文摘Layered two-dimensional(2 D)materials have received tremendous attention due to their unique physical and chemical properties when downsized to single or few layers.Several types of layered materials,especially transition metal dichalcogenides(TMDs)have been demonstrated to be good electrode materials due to their interesting physical and chemical properties.Apart from TMDs,post-transition metal chalcogenides(PTMCs)recently have emerged as a family of important semiconducting materials for electrochemical studies.PTMCs are layered materials which are composed of post-transition metals raging from main group IIIA to group VA(Ga,In,Ge,Sn,Sb and Bi)and group VI chalcogen atoms(S,selenium(Se)and tellurium(Te)).Although a large number of literatures have reviewed the electrochemical and electrocatalytic applications of TMDs,less attention has been focused on PTMCs.In this review,we focus our attention on PTMCs with the aim to provide a summary to describe their fundamental electrochemical properties and electrocatalytic activity towards hydrogen evolution reaction(HER).The characteristic chemical compositions and crystal structures of PTMCs are firstly discussed,which are different from TMDs.Then,inherent electrochemistry of PTMCs is discussed to unveil the well-defined redox behaviors of PTMCs,which could potentially affect their efficiency when applied as electrode materials.Following,we focus our attention on electrocatalytic activity of PTMCs towards HER including novel synthetic strategies developed for the optimization of their HER activity.This review ends with the perspectives for the future research direction in the field of PTMC based electrocatalysts.
基金funded by a full scholarship(PD-071)from the Ministry of Higher Education of the Arab Republic of EgyptJSPS KAKENHI(21K18823)+3 种基金the Tatematsu FoundationCasio Science Promotion FoundationENEOS Tonengeneral Research/Development Encouragement&Scholarship FoundationJSPS KAKENHI(18H03841)。
文摘Photoelectrochemical water splitting(PEC-WS)is a promising technique for transforming solar energy into storable and environmentally friendly chemical energy.Designing semiconductor photoelectrodes with high light absorption capability,rapid e-/h+separation and transfer,and sufficient chemical stability is vital for developing an efficient PEC-WS system.Metal chalcogenides(MCs)have emerged as promising candidates for light absorbers because of their unique electrical and optical characteristics.In this review,we present recent developments in hydrogen generation via PEC-WS using MC-based photoelectrodes.First,we present a simple illustration of PEC-WS fundamentals.Second,the current performance of various metal(mono-,di-,and tri-)chalcogenide/semiconductor photoelectrodes in PEC-WS is summarized.Then,the charge transfer mechanism at the MC/semiconductor interface and the PEC-WS mechanism is thoroughly explained.Finally,we discuss future research perspectives toward developing efficient and stable MC/semiconductor photoelectrodes.
基金supported by the Teli Fellowship from Beijing Institute of Technology,the National Natural Science Foundation of China(Nos.52303366,22173109).
文摘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.
基金This work was supported by the National Science Fund for Distinguished Young Scholars(52125309)the National Natural Science Foundation of China(51991343,51920105002,and 52102179)+4 种基金Guangdong Basic and Applied Basic Research Foundation(2023A1515011752)Guangdong Innovative and Entrepreneurial Research Team Program(2017ZT07C341)Shenzhen Basic Research Project(JCYJ20200109144616617,JCYJ20220818101014029)Shuimu Tsinghua Scholar Program(2022SM092)China Postdoctoral Science Foundation(2021M691715)。
文摘Non-layered two-dimensional(2D)materials have sparked much interest recently due to their atomic thickness,large surface area,thickness-and facet-dependent properties.Currently,these materials are mainly grown from wet-chemistry methods but suffer from small size,low quality,and multi-facets,which is a major challenge hindering their facet-dependent property studies and applications.Here,we report the facet-engineered growth(FEG)of non-layered 2D manganese chalcogenides(MnX,X=S,Se,Te)based on the chemical vapor deposition method.The as-grown samples exhibit large-area surfaces of single facet,high-crystallinity,and ordered domain orientation.As a proof-of-concept,we show the facet-dependent electrocatalytic property of non-layered 2D MnSe,proving they are ideal candidates for fundamental research.Furthermore,we elucidate the underlying mechanism of FEG during the vapor growth process by the interfacial energy derived nucleation models.The method developed in this work provides new opportunities for regulating and designing the structure of 2D materials.
基金supported by the National Natural Science Foundationof China(NSFC,Nos.21971007,21521005,51902012)Beijing Natural Science Foundation(No.2212044)the Fundamental Research Funds for the Central Universities(Nos.XK1802-6,XK1803-05)。
文摘For more than a decade,the exfoliation of graphene and other layered materials has led to a tremendous amount of research in two-dimensional(2D)materials,among which 2D transition metal chalcogenides(TMCs)nanomaterials have attracted much attention in a wide range of applications including photoelectric devices,lithium-ion batteries,catalysis,and energy conversion and storage owing to their unique photoelectric physical properties.With such large specific surface area,strong near-infrared(NIR)absorption and abundant chemical element composition,2D TMCs nanomaterials have become good candidates in biomedical imaging and cancer treatment.This review systematically summarizes recent progress on 2D TMCs nanomaterials,which includes their synthesis methods and applications in cancer treatment.At the end of this review,we also highlight the future prospects and challenges of 2D TMCs nanomaterials.It is expected that this work can provide the readers with a detailed overview of the synthesis of 2D TMCs and inspire more novel functional biomaterials based on 2D TMCs for cancer treatment in the future.
基金financial support from AcRF Tier 1(RG 13/15)from MOE,Singapore.
文摘Photodegradation of aqueous organic pollutants is a very promising strategy to address environmental issues and energy problems.Among all the reported photocatalysts,crystalline metal chalcogenides not only possess diverse architectures that can be enriched by integrating different metal ions and templates,but also have narrower band gaps(visible light adsorption)and suitable band positions that can be tuned through composition regulation.Therefore,the application of crystalline metal chalcogenides as efficient photocatalysts has attracted much attention.However,the limited synthetic methods,low degradation efficiency,and poor chemical stability are the major challenges that impede their practical application.In this review,the recent progress in employing crystalline metal chalcogenides as visible-light-driven catalysts for the photodegradation of organic contaminants is summarized.Besides this,the synthetic methods to prepare crystalline chalcogenides are discussed and the perspectives in regard to the improvement of the degradation efficiency and the chemical stability of metal chalcogenides are proposed.
基金supported by the National Natural Science Foundation of China(52071137,51977071,51802040,and 21802020)the Science and Technology Innovation Program of Hunan Province(2021RC3066 and 2021RC3067)+1 种基金the Natural Science Foundation of Hunan Province(2020JJ3004 and 2020JJ4192)N.Zhang and X.Xie also acknowledge the financial support from the Fundamental Research Funds for the Central Universities.
文摘Transition metal chalcogenides(TMCs)have been well-established as ideal low-dimensional systems for photocatalytic hydrogen evolution.Strategies toward improving the activity of these TMC photocatalysts by crafting heterostructures have been intensively studied.In this study,a two-dimensional(2D)CoAl layered double hydroxide(CoAl-LDH)has been assembled on 2D TMCs(CdIn_(2)S_(4),In_(2)S_(3),and ZnIn_(2)S_(4))to construct novel 2D/2D heterostructures by a facile electrostatic assembly method.The intimate interaction at the interface of hybrids and the suitable energy level alignment enable an efficient pathway for electron transfer to improve the photoactivity.Experimental results show that the photocatalytic activity of the CdIn_(2)S_(4)@CoAl-LDH hybrids for H_(2)production is about 4.3 times higher than that of CdIn_(2)S_(4)nanosheets under visible-light irradiation.The effect of 2D CoAl-LDH on enhancing the photoactivities of In_(2)S_(3)and ZnIn_(2)S_(4)by similarly constructing 2D heterostructures has also been determined.This work establishes a foundation to construct 2D TMC-based heterostructures using CoAl-LDH nanosheets toward enhanced photoredox activity.
基金financial supports from the National Natural Science Foundation of China(22325605,U21A20296,22076185 and 21771183)the Natural Science Foundation of Fujian Province(2020J06033).
文摘The large amount of radioactive waste generated by the rapid development of nuclear energy is in urgent need of disposal.Metal chalcogenide ion-exchangers(MCIEs)are newly developed in recent years that show great potential in the field of removing radionuclides.This is a comprehensive review of the latest research progress on the removal of key radioactive ions(e.g.,radioactive Cs^(+),Sr^(2)+,UO_(2)^(2+),lanthanide ions,and actinide ions)by MCIEs.The structure and ion-exchange properties of MCIEs are summarized emphatically.The ion-exchange mechanism of MCIEs is discussed and the structure-function relationship is preliminarily revealed.Easily exchangeable cations in the interlayer/channel,appropriately sized interlayer/channel/window spaces,flexible open framework,and the strong affinity of the Lewis soft base S^(2−)/Se^(2−)sites in the framework for soft or relatively soft metal ions,are the keys to the excellent selectivity and fast adsorption kinetics of MCIEs for radioactive ions.Finally,future research directions of metal chalcogenides for radioactive ions removal are foreseen.It is hoped that the review will provide a reference for the design of new metal chalcogenide ion-exchangers with practical application prospects for radioactive waste treatment and point to new directions for environmental radioactive contamination control.
基金financial support from AcRF Tier 1(RG 16/12)and Tier 2(ARC 20/12 and ARC 2/13)from MOE,and the CREATE program(Nanomaterials for Energy and Water Management)from NRF,Singapore.
文摘Because the structures and properties of crystalline metal chalcogenides are strongly dependent on their synthetic conditions,developing new methods to approach novel chalcogenides is highly desirable.This review will summarize the recent progress in growing crystalline chalcogenides through four new strategies:ionothermal,surfactant-thermal,hydrazine-thermal,and metal Zintl phase usage.
基金supported by the National Science Foundation through award 2219184Some of the work was performed in the following core facility,which is a part of Colorado School of Mines’Shared Instrumentation Facility(X-ray Diffraction&Computed Tomography:RRID:SCR_022053Scanning Probe and Optical Microscopy:RRID:SCR_022048).
文摘Alkali metal chalcogenides have emerged as a new class of inorganic materials with diverse applications in energy conversion and storage owing to their structural versatility and wide range of properties.Strategies are needed for simple and cost-efficient synthetic approaches that enable the composition and functional properties of these materials to be systematically tuned.Herein,we present a novel wet-chemistry approach to produce ternary Na-based metal chalcogenides with varying compositions.Phase-pure Na3SbCh4(Ch=S,Se)solid-state electrolytes are synthesized in a single-step fashion by reacting an ethanolic solution of Na chalcogenides with appropriately selected metal halides at room temperature.This process simplifies the reaction protocols,improves yield,and decreases the raw material loss incurred in multistep systems by eliminating the need for phase-pure binary metal chalcogenides.The reaction mechanisms and impurity profile of various sodium metal chalcogenides introduced in this work were methodically investigated through characterization techniques such as X-ray diffraction(XRD)and Raman spectroscopy.Among the chalcogenides,synthesis of the sulfide compounds(∼99 wt%purity)was straightforward,achieving a yield of 92-95%whereas the selenides required more control to generate the appropriate mix of precursors,which resulted in a lower yield of 74-79%but with a high purity of 97.5-99.6 wt%.Electrochemical impedance spectroscopy of as-synthesized Na3SbCh4(Ch=S,Se)showed a high ionic conductivity of 0.17-0.38 mS cm^(-1 )and low activation energy of 0.19-0.21 eV comparable with other reports of solution-based synthesis.The one-pot scheme was successfully extended to the NaSbCh2(Ch=S,Se)system,producing phase pure ternary sodium metal chalcogenides with tunable band gaps(1.6-1.8 eV)appropriate for solar energy conversion applications.The“one-pot”approach offers a simple yet economical route for scalable production of bulk sodium ternary chalcogenides at ambient conditions.
基金financial support from the National Natural Science Foundation of China(No.22071165 and 21875150)the 111 Project(D20015).
文摘Atomically precise metal-chalcogenide supertetrahedral clusters (MCSCs) are supposed to be more attractive for functionalization than conventional metal-sulfide quantum dots owing to their potential ability to establish precise structure-composition-property relationships.However,the accurate surface functionalization of such cluster-based species remains difficult.In this paper,we present a facile method for synthesizing discrete MCSCs decorated with different functional groups via a one-step solvothermal reaction,which was demonstrated to have better solvent dispersibility compared with ligand-free ones.In addition,the composites were also prepared by combining ligand-free clusters (or ligand-partially protected or amino-modified ones) with two-dimensional MXene nanosheets.The composites derived from amino-modified clusters exhibited optimal performance of photocatalytic hydrogen evolution.Furthermore,the hydrogen bonding interactions between modified amino groups and MXene nanosheets were verified by 1H-NMR spectroscopy.This work provides a facile approach for the surface functionalization of MCSCs,and facilitates the expansion of the functionality of atomically precise nano-species.
