Chalcogenide Research Articles

Non-Enzymatic Electrochemical Glucose Sensors Based on Metal Oxides and Sulfides: Recent Progress and Perspectives

With the sudden advancement of glucose biosensors for monitoring blood glucose levels for the prevention and diagnosis of diabetes, non-enzymatic glucose sensors have aroused great interest owing to their sensitivity, stability, and economy. Recently, researchers have dedicated themselves to developing non-enzymatic electrochemical glucose sensors for the rapid, convenient, and sensitive determination of glucose. However, it is desirable to explore economic and effective nanomaterials with a high non-enzymatic catalysis performance toward glucose to modify electrodes. Metal oxides (MOs) and metal sulfides (MSs) have attracted extensive interest among scholars owing to their excellent catalytic activity, good biocompatibility, low cost, simple synthesis process, and controllable morphology and structure. Nonetheless, the exploitation of MOs and MSs in non-enzymatic electrochemical glucose sensors still suffers from relatively low conductivity and biocompatibility. Therefore, it is of significance to integrate MOs and MSs with metal/carbon/conducive polymers to modify electrodes for compensating the aforementioned deficiency. This review introduces the recent developments in non-enzymatic electrochemical glucose sensors based on MOs and MSs, focusing on their preparation methods and how their structural composition influences sensing performance. Finally, this review discusses the prospects and challenges of non-enzymatic electrochemical glucose sensors.

Preparation and Lithium Storage Properties of MOF‐Derived Bimetallic Sulfide ZnxInyS/MXene Composites

Nanostructured metal sulfides (MSs) are considered promising anode materials for Li‐ion batteries (LIBs) due to their high specific capacity and abundant raw material resources. However, the practical application of these materials faces challenges such as poor conductivity and volume expansion. To address these issues and enhance the performance of LIBs, it is crucial to tackle the structural design problem associated with ZnxInyS anode material. The utilization of metal sulfides derived from metal‐organic frameworks (MOFs) not only improves conductivity but also mitigates the issue of volume expansion in metal sulfides. Furthermore, connecting the metal sulfides derived from MOF to various conductive substrates can further enhance their conductivity. Two‐dimensional transition metal carbides and nitrides (MXenes), a novel type of 2D material with plentiful functional groups and chemical properties, offer great potential. In this study, we have strategically constructed ZnxInyS/MXene heterostructures by combining the advantages of 2D Ti3C2TX nanosheets and bimetallic MOF structures. The results demonstrate that due to the synergistic effect between MXene and heterostructure, a significant number of lattice defects and ample buffer space are provided, resulting in excellent lithium storage performance and fast ion diffusion kinetics for the electrode.

Three dimensional CNTs interweaved layered MnTe nanoparticles as a new cathode for aqueous zinc ion battery.

Currently, the development of suitable transition metal chalcogenides (TMDs) for aqueous zinc ion batteries (AZIBs) is plagued by the terrible conductivity and electrochemical properties. Herein, a one-step ball milling method is applied to enhance the conductivity of commercial MnTe cathode by constructing three dimensional (3D) carbon nanotubes (CNTs) interweaved MnTe nanoparticles (abbreviated as MnTe@CNTs), which can achieve ultrafast ion conduction. The stable electrochemistry properties benefit from the synergistic effects between layered MnTe and 3D CNTs, which can improve the electrons/ions diffusion kinetics as cycling. So MnTe@CNTs achieves a ultra-high capacity of 427.2 mAh g-1 at 0.1 A g-1 and superior capacity retention of 97.6% at 1 A g-1 over 200 cycles. Zinc-storage mechanisms can be revealed with the aid of operando XRD and ex situ XPS spectra. MnTe as a new cathode presents superior Zn-storage ability for high-performance AZIBs.

S, Se-Codoped Dual Carbon Coating and Se Substitution in Co-Alkoxide-Derived CoS2 Through SeS2 Triggered Selenization for High-Performance Sodium-Ion Batteries

The development of metal sulfides as anodes for sodium-ion batteries (SIBs) is significantly obstructed by the slow kinetics of the electrochemical reactions and the substantial volume changes on the cycling. Herein, we introduce a selenium-substituted cobalt disulfide embedded within a dual carbon–graphene framework (Se-CoS2/C@rGO) for high-performance SIBs. The Se-CoS2/C@rGO was prepared via a synchronous sulfurization/selenization strategy using Co-alkoxide as the precursor and SeS2 as the source of selenium and sulfur, during which the EG anions are converted in situ to a S, Se codoped carbon scaffold. The dual carbon–graphene matrix not only improves the electronic conductivity but also stabilizes the electrode material effectively. In addition, the Se substitution within the CoS2 lattice further improves the electrical conductivity and promotes the Na+ reaction kinetics. The enhanced intrinsic electronic/ionic conductivity and reinforced structural stability endow the Se-CoS2/C@rGO anode with a high reversible capacity (558.2 mAh g−1 at 0.2 A g−1), superior rate performance (351 mAh g−1 at 20 A g−1), and long cycle life (93.5% capacity retention after 2100 cycles at 1 A g−1). This work provides new insights into the development of stable and reversible anode materials through Se substitution and dual carbon encapsulation.

S-d Coupling-Induced Dynamic Off-Centering of Cu Drives High Thermoelectric Performance in TlCuS.

Seeking new and efficient thermoelectric materials requires a detailed comprehension of chemical bonding and structure in solids at microscopic levels, which dictates their intriguing physical and chemical properties. Herein, we investigate the influence of local structural distortion on the thermoelectric properties of TlCuS, a layered metal sulfide featuring edge-shared Cu-S tetrahedra within Cu2S2 layers. While powder X-ray diffraction suggests average crystallographic symmetry with no distortion in CuS4 tetrahedra, the synchrotron X-ray pair distribution function experiment exposes concealed local symmetry breaking, with dynamic off-centering distortions of the CuS4 tetrahedra. The Cu off-centering is driven by the on-site coupling of filled 3d and unoccupied 4s orbitals (s-d) of Cu through a second-order Jahn-Teller mechanism. Bond softening by the p-d* (S-3p and Cu-3d) antibonding interaction coupled with dynamic off-centering distortions causes significant anharmonicity in the lattice, which acts as a phonon-blocking mechanism conducive to ultralow lattice thermal conductivity (κlat) (∼0.35-0.23 W m-1 K-1 in the ∼296-573 K temperature range) in TlCuS. The synergy between low κlat and multiband electronic structure leads to thermoelectric figure-of-merits (zT) of ∼1 and ∼1.3 at 573 K for pristine TlCuS and TlCu0.98S, respectively, underscoring the potential of metal sulfides as promising high-performance thermoelectrics.

Advances of immunosensors based on noble metal composite materials for detecting procalcitonin.

Procalcitonin (PCT) is a reliable biomarker for diagnosing and monitoring bacterial infections and sepsis. PCT exhibits good stability both in vivo and in vitro, and its levels drastically increase in response to bacterial infection or inflammatory reactions in the human body, making it a dependable indicator for sepsis diagnosis and monitoring with significant implications for clinical diagnosis and treatment guidance. Currently, immunosensors are widely utilized in PCT detection due to their high sensitivity and low detection limits. Noble metals, because of their excellent electronic conductivity, biocompatibility, and superior physicochemical properties, are extensively combined with other materials to play a pivotal role in the construction of PCT immunosensors. This review summarizes the research progress on PCT antigen immunosensors based on noble metal composite materials, encompassing the classification and principles of immunosensors. Starting from noble metals, which are widely used as electrode materials in sensors, the review categorizes and discusses the carbon materials, metal oxides, metal sulfides, and other composites with noble metals. The reviewalso elaborates on the influence of sensitive materials on the performance of immunosensors. Finally, the review discusses and anticipates the challenges and future opportunities for the research on PCT antigen immunosensors using noble metal-composite nanomaterials, providing new insights and directions for their application in the treatment and clinical management of sepsis and other diseases.

Research on the Performance Optimization of Molybdenum Disulfide for Multifunctional Applications

Molybdenum disulfide (MoS2), as a typical transition metal chalcogenide compound, has emerged as a research hotspot in nanomaterials due to its excellent electrochemical properties and catalytic activity. However, conventional MoS2 exhibits certain limitations in terms of its catalytic performance, electrical conductivity, and cycling stability. To address these issues, this paper aims to explore the improvement of the multifunctional performance of MoS2 via different performance optimisation strategies, such as heteroatom doping, semiconductor composites, as well as metallic and non-metallic loading. By reviewing and analyzing the relevant literature on the performance enhancement of MoS2 in recent years, this paper summarizes the specific applications and effects of these optimization strategies, highlighting that they significantly improve the performance of MoS2 in fields such as optics, electrochemical catalysis, lithium batteries, and supercapacitors, particularly in terms of catalytic activity, electrical conductivity, and cycling stability. The results indicate that the optimisation of MoS2 performance provides an important theoretical basis and practical guidance for its application in energy storage and catalytic hydrogen evolution.

Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters.

Exposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide - CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4-vinylpyridine) thin films result in the 3D-nucleation of clusters consistent with a cubane-type Cd4S4 core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few-atom Cd-based clusters are consistent with electronic and vibrational spectroscopy and grazing-incidence total X-ray scattering measurements of 3D-cluster-arrays synthesized at 80 °C. The direct synthesis of few-atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light-absorbing materials including solar energy harvesting and conversion applications.

Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters

AbstractExposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide – CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4‐vinylpyridine) thin films result in the 3D‐nucleation of clusters consistent with a cubane‐type Cd4S4 core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few‐atom Cd‐based clusters are consistent with electronic and vibrational spectroscopy and grazing‐incidence total X‐ray scattering measurements of 3D‐cluster‐arrays synthesized at 80 °C. The direct synthesis of few‐atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light‐absorbing materials including solar energy harvesting and conversion applications.

HRTEM Study of Desulfurization of Pt- and Pd-Rich Sulfides from New Caledonia Ophiolite

Oxygen-bearing platinum group minerals (O-bearing PGMs) are intergrown with base metal sulfides (BMS, e.g., pentlandite–[NiFe]9S8) within fractures in chromite grains from chromitite bodies on Ouen Island, New Caledonia. These PGMs are hosted in chlorite and serpentine, which formed during serpentinization of olivine and pyroxene. The O-bearing PGM grains are polygonal, show microfracturing (indicating volume loss), and contain Pt-Pd-rich sulfide remnants, suggesting pseudomorphic replacement of primary (magmatic) sulfides. They display chemical zonation, with Pt(-Pd-Ni-Fe) relict sulfide cores replaced by Pt-Fe-Ni oxidized alloy mantles and Pt-Cu-Fe(-Pd) alloy rims (tulameenite), indicating desulfurization. The core and mantle show a nanoporous structure, interpreted as the result of coupled dissolution–reprecipitation reactions between magmatic sulfides and low fO2–fS2 serpentinite-related fluids, probably formed during olivine transformation to serpentine + magnetite (early stages of serpentinization). This fluid infiltrated magmatic sulfides (PGE-rich and BMS), degrading them to secondary products and releasing S and metals that were accommodated in the mantle and rim of O-bearing PGMs. Upon olivine exhaustion, an increase in fO2 might have stabilized Pt-Fe-O compounds (likely Pt0/Pt-Fe + Fe oxyhydroxides) alongside Ni-Fe alloys. Our results show that post-magmatic desulfurization of primary sulfides produces complex nano-scale intergrowths, mainly driven by changes in the fluid’s physicochemical properties during serpentinization.

Layered double hydroxide modified bismuth vanadate as an efficient photoanode for enhancing photoelectrochemical water splitting.

Photoelectrochemical (PEC) water splitting has attracted significant interest as a promising approach for producing clean and sustainable hydrogen fuel. An efficient photoanode is critical for enhancing PEC water splitting. Bismuth vanadate (BiVO4) is a widely recognized photoanode for PEC applications due to its visible light absorption, suitable valence band position for water oxidation, and outstanding potential for modifications. Nevertheless, sluggish water oxidation rates, severe charge recombination, limited hole diffusion length, and inadequate electron transport properties restrict the PEC performance of BiVO4. To surmount these constraints, incorporating layered double hydroxides (LDHs) onto BiVO4 photoanodes has emerged as a promising approach for enhancing the performance. Herein, the latest advancements in employing LDHs to decorate BiVO4 photoanodes for enhancing PEC water splitting have been thoroughly studied and outlined. Initially, the fundamental principles of PEC water splitting and the roles of LDHs are summarized. Secondly, it covers the development of different composite structures, including BiVO4 combined with bimetallic and trimetallic LDHs, as well as other BiVO4-based composites such as BiVO4/metal oxide, metal sulfide, and various charge transport layers integrated with LDHs. Additionally, LDH composites incorporating materials like graphene, carbon dots, quantum dots, single-atom catalysts, and techniques for surface engineering and LDH exfoliation with BiVO4 are discussed. The research analyzes the design principles of these composites, with a specific focus on how LDHs enhance the performance of BiVO4 by increasing the efficiency and stability through synergistic effects. Finally, challenges and perspectives in future research toward developing efficient and stable BiVO4/LDHs photoelectrodes for PEC water splitting are described.

Pressure induced semimetal-to-metal transition and new structure of Ta2NiSe5 above 10GPa.

Previous studies of the transition metal chalcogenide Ta2NiSe5 has identified two phase transitions occurring between 0-10GPa, involving the excitonic insulator-to-semiconductor transition at 1GPa and the semiconductor-to-semimetal transition at 3GPa. However, there is still a lack of in-depth research on the changes in its physical properties changes above 10GPa. In this study, Ta2NiSe5 were investigated under high-pressure conditions using high-pressure X-ray diffraction and high-pressure X-ray absorption experiments. During the experimental process, a novel phase transition from the semimetal to the metal phase was observed between 10-60GPa, specifically between 10-14GPa, and the structure of the new phase was determined to be P21/m through first-principles calculations.Thistransition mechanism is attributed to the sliding of the weakly coupled layers of Ta2NiSe5 within the a-c plane, leading to changes in the crystal lattice constants and symmetry. This research fills a gap in the understanding of Ta2NiSe5's crystal structure under high pressure and contributes to the broader field of transition metal chalcogenides.&#xD.

Helical Assemblies of Colloidal Nanocrystals with Long-Range Order and Their Fusion into Continuous Structures.

Chirality epitomizes the sophistication of chemistry, representing some of its most remarkable achievements. Yet, the precise synthesis of chiral structures from achiral building blocks remains a profound and enduring challenge in synthetic chemistry and materials science. Here, we demonstrate that achiral colloidal nanocrystals, including Au and Ag nanocrystals, can assemble into long-range-ordered helical assemblies with the assistance of chiral molecules. The synchronized aggregation kinetics between colloidal silver or gold nanocrystals and π-conjugated perylene diimide molecules enables the nanocrystals to precisely follow the helical pathways of the molecular assemblies. This results in the formation of helical nanocrystal assemblies extending over tens of micrometers. These helically organized nanocrystals, exhibiting high positional precision, display linear size-dependent chiroptical properties. Furthermore, more intricate helical assemblies, featuring triple, quadruple, and quintuple nanocrystal strands, can be observed in addition to the commonly encountered double helical assemblies. Finally, these helical assemblies, composed of discrete Ag nanocrystals, can fuse into continuous Ag2S helical structures following a sulfidation reaction, ultimately leading to the formation of diverse metal sulfide helices through cation exchange processes.

Inorganic ligand capped quantum dot light-emitting diodes: status and perspective.

Quantum dots (QDs) have shown great application potential in a variety of optoelectronic devices due to their unique optoelectronic properties, especially playing a key role in the development of quantum dot light-emitting diodes (QLEDs). Inorganic ligands, including metal or non-metal chalcogenides, oxoanions, halides, and metal cations, play crucial roles in the synthesis, stabilization, and functionalization of QDs. Compared to long-chain organic ligands, inorganic ligands are shorter and possess higher electron mobility, which facilitates their application in high-performance QLEDs. This review explores the mechanisms of ligand exchange, classifies the types of inorganic ligands, and discusses their impact on the properties of QDs. Special attention is given to the latest research developments in inorganic ligand QDs for LEDs and their prospective applications in optoelectronics. This review highlights the versatility and efficacy of inorganic ligands, showcasing their potential to revolutionize QLED technology for future high-resolution displays and efficient optoelectronic devices.

Impact of Electrolyte Decomposition on Copper Corrosion in Li6PS5Cl‐Based All‐Solid‐State Batteries

AbstractAll‐solid‐state batteries (ASSBs) with sulfide‐based electrolytes, such as argyrodite (Li₆PS₅Cl, LPSCl), offer significant advantages regarding safety and energy density. However, conventional Cu current collectors with LPSCl suffer from corrosion, necessitating a deeper understanding of appropriate mechanisms and strategies to address them. This study investigates the impact of electrolyte decomposition on Cu degradation in sulfide‐based ASSBs. Accelerated experiments reveal that LPSCl decomposition forms an ineffective passive layer on Cu, resulting in significant corrosion above 2 V during delithiation. In addition, the corrosion potential implies that sulfide and chlorine species are involved in the corrosion reaction. Comparative analyses with Ni current collectors, which are known for their resistance to the corrosive species, demonstrate superior stability to Cu. Corrosion‐prevention strategies are proposed based on the elucidated mechanisms, with the Pilling–Bedworth ratio explaining why certain metal sulfide layers formed during electrolyte decomposition may fail to effectively prevent corrosion. These insights support the development of targeted protective strategies and alternative current collector materials to enhance the durability and performance of sulfide‐based ASSBs.

Elemental Reaction Steps between Elemental Sulfur and Metal Carboxylate during the Synthesis of Metal Sulfide Nanocrystals in Hydrocarbon Solvents

Elemental Reaction Steps between Elemental Sulfur and Metal Carboxylate during the Synthesis of Metal Sulfide Nanocrystals in Hydrocarbon Solvents

Heterojunctions of ZnS with Zn vacancies and hexagonal CdS pyramids for photocatalytic hydrogen production

Metal sulfides with suitable morphology typically possess efficient solar light utilization and suitable band structures for photocatalytic hydrogen production.

Hierarchical core-shell transitional metal chalcogenides Co9S8/ CoSe2@C nanocube embedded into porous carbon for tunable and efficient microwave absorption

In the domain of electromagnetic (EM) wave absorbing materials, the selection of suitable components and microstructures is an effective approach for designing the intense coupling of wave impedance and EM dissipation. In this study, we have successfully fabricated a double-carbon modified Co9S8/CoSe2 nanocube, where the core-shell Co9S8/CoSe2@C cube was anchored onto porous carbon (PC). The existence of three-dimensional (3D) porous carbon and the fabrication of Co9S8/CoSe2@C distributed on carbon nanosheets contribute to the improvement of conduction, magnetic losses, and the optimization of impedance matching. Substantial heterogeneous interfaces are generated between Co9S8, CoSe2, carbon shells, and PC, leading to extensive interfacial polarization and facilitating the transformation of EM energy into thermal energy. The abundant defects, S and Se vacancies in carbon component can act as polarization centers, inducing dipolar polarization and thus increasing the electromagnetic wave (EMW) loss. The Co9S8/CoSe2@C@PC exhibits the best microwave absorption properties, with a minimum reflection loss (RLmin) of −64.1 dB at 2.5 mm and an effective absorption bandwidth (EAB) of 6.3 GHz. The High-Frequency Structure Simulator results indicate the RCS values of the samples within the range of -90 °C < θ < 90 °C are lower than -20 dB m2, which can achieve almost full-angle coverage in the actual environment. This research offers inspiration and strategies for the design and synthesis of multi-component magneto-electric composites based on transitional metal chalcogenides.

Sr3Zr2Cu4Q9 (Q = S and Se): two novel layered quaternary mixed transition metal chalcogenides.

Depending on their bandgaps, mixed metal layered chalcogenides are potential candidates for thermoelectric and photovoltaic applications. Herein, we reported the exploratory synthesis of Sr-Zr-Cu-Q (Q = S/Se) systems, resulting in the identification of two novel quaternary chalcogenides: Sr3Zr2Cu4S9 and Sr3Zr2Cu4Se9. These isoelectronic compounds (Sr3Zr2Cu4Q9) crystallized in two different structural types. The Sr3Zr2Cu4S9 structure (space group: P1̄) adopted the Ba3Zr2Cu4S9 structure type with eighteen unique atomic sites: 3 × Sr, 2 × Zr, 4 × Cu, and 9 × S. In contrast, the Sr3Zr2Cu4Se9 structure (P1̄) represented a unique structure type with nineteen unique atomic positions including one additional Cu site compared to the Sr3Zr2Cu4S9 structure. The sulfide structure was stoichiometric, whereas the selenide structure was found to be non-stoichiometric with three partially occupied Cu positions. The Sr3Zr2Cu4Q9 structures consisted of layers with the Sr2+ cations occupying the interstitial spaces. In both structures, the Zr atoms occupied distorted octahedral positions. A striking difference between the two structures resulted from the distinct bonding interactions between the Cu and Q atoms. The optical bandgap of polycrystalline Sr3Zr2Cu4S9 was 1.7(1) eV. Interestingly, resistivity measurements of polycrystalline Sr3Zr2Cu4Se9 revealed metallic/degenerate semiconducting behavior at low temperatures. The photovoltaic performance of semiconducting Sr3Zr2Cu4S9 demonstrated ∼24% increment in power conversion efficiency when incorporated into a TiO2/CdS photoanode due to its narrower bandgap, which increased the light-harvesting ability of the cell. We also explored the theoretical electronic structures, COHP, and Bader charges of the Sr3Zr2Cu4Q9 structures using DFT calculations.

A Greener Solution to Direct Low-Temperature Incorporation of Selenium in Chalcogenide Solar Absorber

Low temperature environment friendly solution processing of metal chalcogenide absorbers is highly desired for low-cost and scalable fabrication of thin-film solar cells. However, the incorporation of selenium (Se) into sulfo-selenide absorber films previously reported devices has required the use of harmful solvents in the precursor solution and/or a high-temperature selenization compatible with the substrate type configuration. In this study, we address these issues by introducing a novel, less toxic thiol-amine-based solvent system designed for the direct incorporation of Se. This approach enables the synthesis of sulfo-selenide absorbers at significantly lower temperatures as demonstrated by the successful fabrication of a selenization free CZTSSe absorber layer within a superstrate-type thin-film solar cell for the first time. Our method not only reduces the environmental footprint of the fabrication process but also has the potential for offering the scalability and cost-effectiveness in producing chalcogenide thin films for energy device applications.