Transition Metal Chalcogenides Research Articles

Syntheses, Crystal Structures, and Electronic Structures of Quaternary Group IV-Selenide Semiconductors.

Early transition-metal chalcogenides have garnered recent attention for their optoelectronic properties for solar energy conversion. Herein, the first Zr-/Hf-chalcogenides with a main group cation, Ba9Hf3Sn2Se19 (1) and Ba8Zr2SnSe13(Se2) (2), have been synthesized. The structure of 1 is formed from isolated SnSe44- tetrahedra and distorted HfSe6 octahedra. The latter condense via face-sharing trimeric motifs that are further vertex-bridged into chains of 1∞[Hf(1)2Hf(2)Se11]10-. The structure of 2 is comprised of SnSe44- tetrahedra, Se22- dimers, and face-sharing dimers of distorted ZrSe6 octahedra. These represent the first reported examples of Hf-/Zr-chalcogenides exhibiting face-sharing octahedra with relatively short Hf-Hf and Zr-Zr distances. Their preparation in high purity is inhibited by their low thermodynamic stability, with calculations showing small calculated ΔUdec values of +7 and +9 meV atom-1 for 1 and 2, respectively. Diffuse reflectance measurements confirm the semiconducting nature of 1 with an indirect band gap of ∼1.4(1) eV. Electronic structure calculations show that the band gap absorptions arise from transitions between predominantly Se-4p valence bands and mixed Hf-5d/Sn-5p or Zr-4d/Sn-5p conduction bands. Optical absorption coefficients were calculated to be more than ∼105 cm-1 at greater than 1.8 eV. Thus, promising optical properties are demonstrated for solar energy conversion within these synthetically challenging chemical systems.

Designed MoSe2 modified multi-layer hollow carbon fiber composite material achieves tunable electromagnetic wave absorption in the X and Ku bands

As a substitute for graphene-based carbon materials, carbon fiber (CF) based absorbing materials have enormous application prospects. Effective improvements have been made in solving the problems of heavy quality and complex preparation processes of ordinary absorbing materials. In order to obtain a flexible thin fiber membrane absorbing material with good stability and excellent performance, we prepared a multi-layer hollow carbon sphere/CF@MoSe2 with carbon fiber as the matrix, and controlled the microstructure through hollow carbon shell and MoSe2, and introduced transition metal chalcogenides to coordinate electromagnetic parameters. As a result, the hollow carbon sphere/CF@MoSe2 flexible composite film achieved a minimum reflection loss (RLmin) of −47.98 dB at a thickness of 2.5 mm, and an effective bandwidth (EAB) of 8.1 GHz at a thickness of 2.7 mm. The RLmin of the hollow carbon ball/CF composite film reached −45 dB at a thickness of 2.6 mm, and the EAB reached 3.2 GHz. The theoretical characterization results jointly prove the reason for the improved performance, and this study provides an experimental basis for a more in-depth exploration of the birth of new absorbing materials.

ReS2/CoS heterostructure catalysts for electrochemical application in hydrogen evolution and supercapacitor

Development of Nano-heterostructures based on transition metal chalcogenides is promising strategy to accelerate the catalytic performance for hydrogen evolution reaction (HER) and supercapacitor application. The design and development of non-noble transition metal based catalysts is required for the low-cost, efficient and earth-abundant electrodes for sustainable energy conversion and storage. ReS2/CoS heterostructures were synthesized by two step methods involving liquid phase exfoliation of ReS2 and hydrothermal decoration of CoS. The prepared ReS2/CoS heterostructures shows high performance supercapacitor applications with specific capacitance of 663.2 F/g at 2 A/g and 643.1 F/g at scan rate 5 mV/s, showing enhanced redox reaction and number of electrochemically active sites due to synergistic effect and modulated electronic structure. Additionally, ReS2/CoS heterostructures shows the superior HER performance in alkaline condition with overpotential of 187 mV at 10 mA/cm2 due to accelerated kinetics, enhanced ECSA and low charge transfer resistance. The ReS2/CoS heterostructures shows the stable electrochemical performance for HER for more than 17 h.

Monolayer V_{2}MX_{4}: A New Family of Quantum Anomalous Hall Insulators.

We theoretically propose that the van der Waals layered ternary transition metal chalcogenide V_{2}MX_{4} (M=W, Mo; X=S, Se) is a new family of quantum anomalous Hall insulators with sizable bulk gap and Chern number C=-1. The large topological gap originates from the deep band inversion between spin-up bands contributed by d_{xz}, d_{yz} orbitals of V and spin-down band from d_{z^{2}} orbital of M at the Fermi level. Remarkably, the Curie temperature of monolayer V_{2}MX_{4} is predicted to be much higher than that of monolayer MnBi_{2}Te_{4}. Furthermore, the thickness dependence of the Chern number for few multilayers shows interesting oscillating behavior. The general physics from the d orbitals here applies to a large class of ternary transition metal chalcogenide such as Ti_{2}WX_{4} with the space group P-42m. These interesting predictions, if realized experimentally, could greatly promote the research and application of topological quantum physics.

Antagonism effect of residual S triggers the dual-path mechanism for water oxidation

Transition metal chalcogenides (TMCs) are recognized as pre-catalysts, and their (oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation. However, understanding the role of the residual chalcogen in the reconstructed layer is lacking in detail, and the corresponding catalytic mechanism remains controversial. Here, taking Cu1−xCoxS as a platform, we explore the regulating effect and existence form of the residual S doped into the reconstructive layer for oxygen evolution reaction (OER), where a dual-path OER mechanism is proposed. First-principles calculations and operando 18O isotopic labeling experiments jointly reveal that the residual S in the reconstructive layer of Cu1−xCoxS can wisely balance the adsorbate evolution mechanism (AEM) and lattice oxygen oxidation mechanism (LOM) by activating lattice oxygen and optimizing the adsorption/desorption behaviors at metal active sites, rather than change the reaction mechanism from AEM to LOM. Following such a dual-path OER mechanism, Cu0.4Co0.6S-derived Cu0.4Co0.6OSH not only overcomes the restriction of linear scaling relationship in AEM, but also avoids the structural collapse caused by lattice oxygen migration in LOM, so as to greatly reduce the OER potential and improved stability.

A DFT study of structural, optical, and elastic properties of the transition metal chalcogenide compounds SrXSe3 (X = Ti or Zr)

A DFT study of structural, optical, and elastic properties of the transition metal chalcogenide compounds SrXSe3 (X = Ti or Zr)

Superconductivity in a van der Waals layered quasicrystal

Van der Waals layered transition-metal chalcogenides are drawing significant attention owing to their intriguing physical properties. This group of materials consists of abundant members with various elements, having a variety of different structures. However, they are all crystalline materials, and the physical properties of van der Waals layered quasicrystals have never been studied to date. Here, we report on the discovery of superconductivity in a van der Waals layered quasicrystal of Ta1.6Te. The electrical resistivity, magnetic susceptibility, and specific heat of the quasicrystal unambiguously validate the occurrence of bulk superconductivity at a transition temperature of ~1 K. This discovery can promote new research on assessing the physical properties of novel van der Waals layered quasicrystals as well as two-dimensional quasicrystals; moreover, it paves the way toward new frontiers of superconductivity in thermodynamically stable quasicrystals.

Controlling Phase in Colloidal Synthesis.

A fundamental precept of chemistry is that properties are manifestations of the elements present and their arrangement in space. Controlling the arrangement of atoms in nanocrystals is not well understood in nanocrystal synthesis, especially in the transition metal chalcogenides and pnictides, which have rich phase spaces. This Perspective will cover some of the recent advances and current challenges. The perspective includes introductions to challenges particular to chalcogenide and pnictide chemistry, the often-convoluted roles of bond dissociation energies and mechanisms by which precursors break down, using very organized methods to map the synthetic phase space, a discussion of polytype control, and challenges in characterization, especially for solving novel structures on the nanoscale and time-resolved studies.

2D Monolayer Catalysts: Towards Efficient Water Splitting and Green Hydrogen Production.

A viable alternative to non-renewable hydrocarbon fuels is hydrogen gas, created using a safe, environmentally friendly process like water splitting. An important role in water-splitting applications is played by the development of two-dimensional (2D) layered transition metal chalcogenides (TMDCs), transition metal carbides (MXenes), graphene-derived 2D layered nanomaterials, phosphorene, and hexagonal boron nitride. Advanced synthesis methods and characterization instruments enabled an effective application for improved electrocatalytic water splitting and sustainable hydrogen production. Enhancing active sites, modifying the phase and electronic structure, adding conductive elements like transition metals, forming heterostructures, altering the defect state, etc., can improve the catalytic activity of 2D stacked hybrid monolayer nanomaterials. The majority of global research and development is focused on finding safer substitutes for petrochemical fuels, and this review summarizes recent advancements in the field of 2D monolayer nanomaterials in water splitting for industrial-scale green hydrogen production and fuel cell applications.

High-Density CoSe2 Sites Embedded within 2D Porous N-Doped Carbon for High-Performance Oxygen Reduction Reaction Electrocatalysis.

Designing and fabricating efficient and stable nonprecious metal-based oxygen reduction reaction (ORR) electrocatalysts is a pressing and challenging task for the pursuit of sustainable new energy devices. Herein, porous P-CoSe2@NC electrocatalysts with high-density carbon-coated CoSe2 sites were successfully fabricated based on a pyridyl-porphyrinic metal-organic framework (Co-TPyP MOF) via a molten salt-assisted synthesis method. The hierarchical pore and N-doping carbon substrate of P-CoSe2@NC promotes mass transfer and electron-transfer efficiency, which is beneficial to maximize CoSe2 site utilization. Well-designed P-CoSe2@NC exhibits efficient ORR catalytic activity with a high half-wave potential of 0.863 V and excellent catalytic stability. Meanwhile, rechargeable aqueous primary/quasi-solid-state ZABs based on a P-CoSe2@NC air cathode show a high peak power density and exceptional operating stability, catering to the demands of practical applications. The qualified performance and structure stability of the electrocatalytic system may be mainly attributed to the protection of the CoSe2 nanoparticle by the coated carbon layer. Given the rational design of the structure and the component of the electrocatalyst with enhanced ORR activity, we believe that this work has provided a reliable pathway to the development of high-performance transition-metal chalcogenides for energy-storage and -conversion devices.

Single Transition-Metal Atom Anchored on a Rhenium Disulfide Monolayer: An Efficient Bifunctional Electrocatalyst for the Oxygen Evolution and Oxygen Reduction Reactions.

Developing efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) bifunctional electrocatalysts is attractive for rechargeable metal-air batteries. Meanwhile, single metal atoms embedded in 2D layered transition metal chalcogenides (TMDs) have become a very promising catalyst. Recently, many attentions have been paid to the 2D ReS2 electrocatalyst due to its unique distorted octahedral 1T' crystal structure and thickness-independent electronic properties. Here, the catalytic activity of different transition metal (TM) atoms embedded in ReS2 using the density functional theory is investigated. The results indicate that TM@ReS2 exhibits outstanding thermal stability, good electrical conductivity, and electron transfer for electrochemical reactions. And the Ir@ReS2 and Pd@ReS2 can be used as OER/ORR bifunctional electrocatalysts with a lower overpotential for OER (ηOER) of 0.44 V and overpotentials for ORR (ηORR) of 0.26 V and 0.27 V, respectively. The excellent catalytic activity is attributed to the optimal adsorption strength for oxygen intermediates coming from the effective modulation of the electronic structure of ReS2 after Ir/Pd doping. The results can help to deeply understand the catalytic activity of TM@ReS2 and develop novel and highly efficient OER/ORR electrocatalysts.

A Hybrid Pulsed Laser Deposition Approach to Grow Thin Films of Chalcogenides.

Vapor-pressure mismatched materials such as transition metal chalcogenides have emerged as electronic, photonic, and quantum materials with scientific and technological importance. However, epitaxial growth of vapor-pressure mismatched materials are challenging due to differences in the reactivity, sticking coefficient, and surface adatom mobility of the mismatched species constituting the material, especially sulfur containing compounds. Here, a novel approach is reported to grow chalcogenides-hybrid pulsed laser deposition-wherein an organosulfur precursor is used as a sulfur source in conjunction with pulsed laser deposition to regulate the stoichiometry of the deposited films. Epitaxial or textured thin films of sulfides with variety of structure and chemistry such as alkaline metal chalcogenides, main group chalcogenides, transition metal chalcogenides, and chalcogenide perovskites are demonstrated, and structural characterization reveal improvement in thin film crystallinity, and surface and interface roughness compared to the state-of-the-art. The growth method can be broadened to other vapor-pressure mismatched chalcogenides such as selenides and tellurides. This work opens up opportunities for broader epitaxial growth of chalcogenides, especially sulfide-based thin film technological applications.

Electrodeposited Copper Tin Sulfide/Reduced Graphene Oxide Nanospikes for a High-Performance Supercapacitor Electrode.

Copper tin sulfide, Cu4SnS4 (CTS), a ternary transition-metal chalcogenide with unique properties, including superior electrical conductivity, distinct crystal structure, and high theoretical capacity, is a potential candidate for supercapacitor (SC) electrode materials. However, there are few studies reporting the application of Cu4SnS4 or its composites as electrode materials for SCs. The reported performance of the Cu4SnS4 electrode is insufficient regarding cycle stability, rate capability, and specific capacity; probably resulting from poor electrical conductivity, restacking, and agglomeration of the active material during continued charge-discharge cycles. Such limitations can be overcome by incorporating graphene as a support material and employing a binder-free, facile, electrodeposition technique. This work reports the fabrication of a copper tin sulfide-reduced graphene oxide/nickel foam composite electrode (CTS-rGO/NF) through stepwise, facile electrodeposition of rGO and CTS on a NF substrate. Electrochemical evaluations confirmed the enhanced supercapacitive performance of the CTS-rGO/NF electrode compared to that of CTS/NF. A remarkably improved specific capacitance of 820.83 F g-1 was achieved for the CTS-rGO/NF composite electrode at a current density of 5 mA cm-2, which is higher than that of CTS/NF (516.67 F g-1). The CTS-rGO/NF composite electrode also exhibited a high-rate capability of 73.1% for galvanostatic charge-discharge (GCD) current densities, ranging from 5 to 12 mA cm-2, and improved cycling stability with over a 92% capacitance retention after 1000 continuous GCD cycles; demonstrating its excellent performance as an electrode material for energy storage applications, encompassing SCs. The enhanced performance of the CTS-rGO/NF electrode could be attributed to the synergetic effect of the enhanced conductivity and surface area introduced by the inclusion of rGO in the composite.

Review of Transition Metal Chalcogenides and Halides as Electrode Materials for Thermal Batteries and Secondary Energy Storage Systems.

Transition metal chalcogenides and halides (TMCs and TMHs) have been extensively used and reported as electrode materials in diverse primary and secondary batteries. This review summarizes the suitability of TMCs and TMHs as electrode materials focusing on thermal batteries (utilized for defense applications) and energy storage systems like mono- and multivalent rechargeable batteries. The report also identifies the specific physicochemical properties that need to be achieved for the same materials to be employed as cathode materials in thermal batteries and anode materials in monovalent rechargeable systems. For example, thermal stability of the materials plays a crucial role in delivering the performance of the thermal battery system, whereas the electrical conductivity and layered structure of similar materials play a vital role in enhancing the electrochemical performance of the mono- and multivalent rechargeable batteries. It can be summarized that nonlayered CoS2, FeS2, NiS2, and WS2 were found to be ideal as cathode materials for thermal batteries primarily due to their better thermal stability, whereas the layered structures of these materials with a coating of carbon allotrope (CNT, graphene, rGO) were found to be suitable as anode materials for monovalent alkali metal ion rechargeable batteries. On the other hand, vanadium, titanium, molybdenum, tin, and antimony based chalcogenides were found to be suitable as cathode materials for multivalent rechargeable batteries due to the high oxidation state of cathode materials which resists the stronger field produced during the interaction of di- and trivalent ions with the cathode material facilitating higher energy density with minimal structural and volume changes at a high rate of discharge.

Se-p Orbitals Induced "Strong d-d Orbitals Interaction" Enable High Reversibility of Se-Rich ZnSe/MnSe@C Electrode as Excellent Host for Sodium-Ion Storage.

The heterostructure of transition-metal chalcogenides is a promising approach to boost alkali ion storage due to fast charge kinetics and reduction of activation energy. However, cycling performance is a paramount challenge that is suffering from poor reversibility. Herein, it is reported that Se-rich particles can chemically interact with local hexagonal ZnSe/MnSe@C heterostructure environment, leading to effective ions insertion/extraction, enabling high reversibility. Enlightened by theoretical understanding, Se-rich particles endow high intrinsic conductivities in term of low energy barriers (1.32eV) compared with those without Se-rich particles (1.50eV) toward the sodiation process. Moreover, p orbitals of Se-rich particles may actively participate and further increase the electronegativity that pushes the Mn d orbitals (dxy and dx2-y2) and donate their electrons to dxz and dyz orbitals, manifesting strong d-d orbitals interaction between ZnSe and MnSe. Such fundamental interaction will adopt a well-stable conducive electronic bridge, eventually, charges are easily transferred from ZnSe to MnSe in the heterostructure during sodiation/desodiation. Therefore, the optimized Se-rich ZnSe/MnSe@C electrode delivered high capacity of 576 mAhg-1 at 0.1 Ag-1 after 100 cycles and 384 mAhg-1 at 1 Ag-1 after 2500 cycles, respectively. In situ and ex situ measurements further indicate the integrity and reversibility of the electrode materials upon charging/discharging.

Synergistically Coupling Atomic-Level Defect-Manipulation and Nanoscopic-Level Interfacial Engineering Enables Fast and Durable Sodium Storage.

Through inducing interlayer anionic ligands and functionally modifying conductive carbon-skeleton on the transition metal chalcogenides (TMCs) parent to achieve atomic-level defect-manipulation and nanoscopic-level architecture design is of great significance, which can broaden interlayer distance, optimize electronic structure, and mitigate structural deformation to endow high-efficiency battery performance of TMCs. Herein, an intriguing 3D biconcave hollow-tyre-like anode constituted by carbon-packaged defective-rich SnSSe nanosheet grafting onto Aspergillus niger spores-derived hollow-carbon (ANDC@SnSSe@C) is reported. Systematically experimental investigations and theoretical analyses forcefully demonstrate the existence of anion Se ligand and outer-carbon all-around encapsulation on the ANDC@SnSSe@C can effectively yield abundant structural defects and Na+-reactivity sites, accelerate rapid ion migration, widen interlayer spacing, as well as relieve volume expansion, thus further resolving the critical issues throughout the charge-discharge processes. As anticipated, as-fabricated ANDC@SnSSe@C anode contributes extraordinary reversible capacity, wonderful cyclic lifespan with 83.4% capacity retention over 2000 cycles at 20.0 A g-1, and exceptional rate capability. A series of correlated kinetic investigations and ex situ characterizations deeply reveal the underlying springheads for the ion-transport kinetics, as well as synthetically elucidate phase-transformation mechanism of the ANDC@SnSSe@C. Furthermore, the ANDC@SnSSe@C-based sodium ion full cell and hybrid capacitor offer high-capacity contribution and remarkable energy-density output, indicative of its great practicability.

Evolution of Microscopic Magnetic Domains in Quasi‐2D Cr0.92Te at Room Temperature

Abstract2D materials with long‐range ferromagnetic order hold promises for the development of compact spintronic devices with unprecedented multifunctionality and tunability. Among various 2D magnets, self‐intercalated transition metal chalcogenides Cr1+δTe2 exhibit unique features, especially excellent ambient stability and intrinsic ferromagnetic ordering above room temperature, which are critical requirements for real‐life device applications. Despite the many investigations of the magnetic properties of the Cr1+δTe2 family on the averaging macroscopic level, the domain evolution on the microscale, which is vital to nanoscale spintronics, is yet to be fully understood. Here, the evolution of magnetic behaviors of Cr0.92Te crystals is presented on both macro‐ and micro‐scales under magnetic field and thermal excitation. The crystal exhibits a high Curie temperature (Tc ≈ 343 K) among the Cr1+δTe2 family with weak magnetic anisotropy and in‐plane magnetic easy axis. Utilizing magnetic force microscopy, a pristine multidomain state and typical domain‐switching behavior are observed. Moreover, the evolution of domain texture under thermal excitation shows statistical power‐law scaling as approaching Tc. The results provide microscopic insight into the ferromagnetic behavior of a room‐temperature quasi‐2D crystal, which can be useful for further engineering of domain texture in low‐dimensional magnetic materials.

First-principles calculations of bulk XTe2 (X = Mo, W) as anode materials for Ca ion battery.

Transition metal chalcogenides are excellent anode materials for calcium ion batteries (CIBs). In this study, the structural stability, electronic structure, and diffusion barrier of bulk XTe2 (X = Mo, W) were studied by first-principles calculations within the framework of density functional theory. The density of states analysis shows the metal behavior of XTe2 (X = Mo, W) during calcification. The voltage ranges of CayMoTe2 and CayWTe2 are 1.53-0.45 V and 1.48-0.41 V (y = 0-5), respectively. The diffusion barrier of Ca+ through XTe2 indicates that the compressive strain promotes the diffusion of calcium through XTe2. XTe2 is considered to be a promising electrode material for CIBs. In this paper, the transition metal chalcogenides model is constructed by Material Studio 8.0, and the first-principles calculation is carried out by CASTEP module.

Chemical/Electrochemical Dual‐Driven Transition Behavior of Copper Element from Current Collector to Chalcogenide Anode in Sodium‐Ion Batteries

AbstractThe transition phenomenon involving copper replacing the transition metal elements within transition metal chalcogenides (TMCs) is a recent and unique observation in the context of sodium ion batteries (SIBs) where TMCs serve as anodes. Fundamental understanding of the driving forces and kinetics governing this transition is crucial for elucidating the sodium storage mechanism in TMCs anodes. Herein, cobalt disulfide (CoS2) has been chosen as a representative anode. It is revealed that the transition behavior of copper replacing cobalt during the cycling originates from chemical/electrochemical dual‐driving forces. The chemical driving force emanates from the interaction between Cu+ dissolved in the electrolyte and the resulting sodium polysulfide products. The reaction extent is intricately linked to the surface roughness of the copper collector. The electrochemistrical driving force is effectively elucidated through the application of the Hard‐Soft‐Acid‐Base theory. Multiple charaterization techniques, such as Solid‐state nuclear magnetic resonance (ssNMR) have been employed to confirm that cobalt exists as cation instead of metal after transition. This research offers a novel perspective understanding the transition behavior exhibited by CoS2, with potential wider implications for understanding analogous behaviors in other metal sulfide anodes.

Single-atom catalysts supported on two-dimensional tetragonal transition metal chalcogenides for hydrogen and oxygen evolution

Single-atom catalysts (SACs) offer maximum metal atom utilization and high catalytic performance. Transition metal atoms on two-dimensional (2D) materials are effective for improving electrocatalytic performance. However, few studies exist on SACs supported on 2D tetragonal transition metal chalcogenides (TMX) for OER and HER. We report a detailed theoretical study using DFT calculations on SACs supported on TMX monolayers, denoted as TMA@TMBX. Our findings demonstrate that seven TMA@TMBX electrocatalysts surpass IrO2 (ηOER= 0.56 V), with four TMA@TMBX exhibiting a reduced OER overpotential compared to RuO2 (ηOER= 0.42 V). Additionally, four TMA@TMBX exhibit higher HER performance than Pt (111) (ηHER= 0.10 V). We ultimately identified three SACs with high bifunctional HER/OER activity: Co@NiSe, Rh@NiTe, and Co@NiS. This study on TMA@TMBX provides insights for enhancing the HER and OER activities of SACs supported on 2D materials, which could have significant implications in clean and renewable energy.