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Effectively managing sewage sludge from Fenton reactions in an eco-friendly way is vital for Fenton technology's viability in pollution treatment. This study focuses on sewage sludge across various treatment stages, including generation, concentration, dehydration, and landfill, and employs chemical composite MoS2 to facilitate green resource utilization of all types of sludge. MoS2, with exposed Mo4+ and low-coordination sulfur, enhances iron cycling and creates an acidic microenvironment on the sludge surface. The MoS2-modified iron sludge exhibits outstanding (>95%) phenol and pollutant degradation in hydrogen peroxide and peroxymonosulfate-based Fenton systems, unlike unmodified sludge. This modified sludge maintains excellent Fenton activity in various water conditions and with multiple anions, allowing extended phenol degradation for over 14 d. Notably, the generated chemical oxygen demand (COD) in sludge modification process can be efficiently eliminated through the Fenton reaction, ensuring effluent COD compliance and enabling eco-friendly sewage sludge resource utilization.
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Considerable efforts have been devoted to Li-S batteries, typically the soluble polysulfides shuttling effect. As a typical transition metal sulfide, MoS2 is a magic bullet for addressing the issues of Li-S batteries, drawing increasing attention. In this study, we introduce amorphous MoS3 as analogous sulfur cathode material and elucidate the dynamic phase evolution in the electrochemical reaction. The metallic 1T phase incorporated 2H phase MoS2 with sulfur vacancies (SVs-1T/2H-MoS2) decomposed from amorphous MoS3 achieves refined mixing with the "newborn" sulfur at the molecular level and supplies continuous conduction pathways and controllable physical confinement. Meanwhile, the in situ-generated SVs-1T/2H-MoS2 allows lithium intercalation in advance at high discharge voltage (≥1.8 V) and enables fast electron transfer. Moreover, aiming at the unbonded sulfur, diphenyl diselenide (PDSe), as a model redox mediator is applied, which can covalently bond sulfur atoms to form conversion-type organoselenosulfides, changing the original redox pathway of "newborn" sulfur in MoS3, and suppressing the polysulfides shuttling effect. It also significantly lowers the activation energy and thus accelerates the sulfur reduction kinetics. Thus, the in situ-formed intercalation-conversion hybrid electrode of SVs-1T/2H-MoS2 and organoselenosulfides realizes enhanced rate capability and superior cycling stability. This work provides a novel concept for designing high-energy-density electrode materials.
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Dimensionality of materials is closely related to their physical properties. For two-dimensional (2D) semiconductors such as monolayer molybdenum disulfide (MoS2), converting them from 2D nanosheets to one-dimensional (1D) nanoscrolls could contribute to remarkable electronic and optoelectronic properties, yet the rolling-up process still lacks sufficient controllability, which limits the development of their device applications. Herein we report a modified solvent evaporation-induced rolling process that halts at intermediate states and achieve MoS2 nanoscrolls with high yield and decent axial uniformity. The accordingly fabricated nanoscroll memories exhibit an on/off ratio of â¼104 and a retention time exceeding 103 s and can realize multilevel storage with pulsed gate voltages. Such open-end, high-curvature, and hollow 1D nanostructures provide new possibilities to manipulate the hysteresis windows and, consequently, the charge storage characteristics of nanoscale field-effect transistors, thereby holding great promise for the development of miniaturized memories.
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The design space of two-dimensional materials is undergoing significant expansion through the stacking of layers in non-equilibrium configurations. However, the lack of quantitative insights into twist dynamics impedes the development of such heterostructures. Herein, we utilize the lateral force sensitivity of an atomic force microscope cantilever and specially designed rotational bearing structures to measure the torque in graphite and MoS2 interfaces. While the extracted torsional energies are virtually zero across all angular misfit configurations, commensurate interfaces of graphite and MoS2 are characterized by values of 0.1533 and 0.6384 N-m/m2, respectively. Furthermore, we measured the adhesion energies of graphite and MoS2 to elucidate the interplay between twist and slide. The adhesion energy dominates over the torsional energy for the graphitic interface, suggesting a tendency to twist prior to superlubric sliding. Conversely, MoS2 displays an increased torsional energy exceeding its adhesion energy. Consequently, our findings demonstrate a fundamental disparity between the sliding-to-twisting dynamics at MoS2 and graphite interfaces.
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Revealing low-dimensional material growth dynamics is critical for crystal growth engineering. However, in a practical high-temperature growth system, the crystal growth process is a black box because of the lack of heat-resistant imaging tools. Here, we develop a heat-resistant optical microscope and embed it in a chemical vapor deposition (CVD) system to investigate two-dimensional (2D) crystal growth dynamics. This in situ optical imaging CVD system can tolerate temperatures of ≤900 °C with a spatial resolution of â¼1 µm. The growth of monolayer MoS2 crystals was studied as a model for 2D crystal growth. The nucleation and growth process have been imaged. Model analysis and simulation have revealed the growth rate, diffusion coefficient, and spatial distribution of the precursor. More importantly, a new vertex-kink-ledge model has been suggested for monolayer crystal growth. This work provides a new technique for in situ microscopic imaging at high temperatures and fundamental insight into 2D crystal growth.
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Motional narrowing implies narrowing induced by motion; for example, in nuclear magnetic resonance, the thermally induced random motion of the nuclei in an inhomogeneous environment leads to a counterintuitive narrowing of the resonance line. Similarly, the excitons in monolayer semiconductors experience magnetic inhomogeneity: the electron-hole spin-exchange interaction manifests as an in-plane pseudomagnetic field with a periodically varying orientation inside the exciton band. The excitons undergo random momentum scattering and pseudospin precession repeatedly in this inhomogeneous magnetic environment, typically resulting in fast exciton depolarization. On the contrary, we show that such magnetic inhomogeneity averages out at high scattering rates due to motional narrowing. Physically, a faster exciton scattering leads to a narrower pseudospin distribution on the Bloch sphere, implying a nontrivial improvement in exciton polarization. The in-plane nature of the pseudomagnetic field enforces a contrasting scattering dependence between the circularly and linearly polarized excitons, providing a spectroscopic way to gauge the sample quality.
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2D transition metal dichalcogenides (TMDs) exhibit exceptional resilience to mechanical deformation. Applied strain can have pronounced effects on properties such as the bandgaps and exciton dynamics of TMDs, via deformation potentials and electromechanical coupling. In this work, we use piezoresponse force microscopy to show that the inhomogeneous strain from nanobubbles produces dramatic, localized enhancements of the electromechanical response of monolayer MoS2. Nanobubbles with diameters under 100 nm consistently produce an increased piezoresponse that follows the features' topography, while larger bubbles exhibit a halo-like profile, with maximum piezoresponse near the periphery. We show that spatial filtering enables these effects to be eliminated in the quantitative determination of effective piezoelectric or flexoelectric coefficients. Numerical strain modeling reveals a correlation between the hydrostatic strain gradient and the effective piezoelectric coefficient in large MoS2 nanobubbles, suggesting a localized variation in electromechanical coupling due to symmetry reduction induced by inhomogeneous strain.
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The rich morphology of 2D materials grown through chemical vapor deposition (CVD), is a distinctive feature. However, understanding the complex growth of 2D crystals under practical CVD conditions remains a challenge due to various intertwined factors. Real-time monitoring is crucial to providing essential data and enabling the use of advanced tools like machine learning for unraveling these complexities. In this study, we present a custom-built miniaturized CVD system capable of observing and recording 2D MoS2 crystal growth in real time. Image processing converts the real-time footage into digital data, and machine learning algorithms (ML) unveil the significant factors influencing growth. The machine learning model successfully predicts CVD growth parameters for synthesizing ultralarge monolayer MoS2 crystals. It also demonstrates the potential to reverse engineer CVD growth parameters by analyzing the as-grown 2D crystal morphology. This interdisciplinary approach can be integrated to enhance our understanding of controlled 2D crystal synthesis through CVD.
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The exceptional semiconducting properties of two-dimensional (2D) transition metal dichalcogenides (TMDs) have made them highly promising for the development of future electronic and optoelectronic devices. Extensive studies of TMDs are partly associated with their ability to generate 2D-confined hot carriers above the conduction band edges, enabling potential applications that rely on such transient excited states. In this work, room-temperature spatiotemporal hot carrier dynamics in monolayer MoS2 is studied by transient absorption microscopy (TAM), featuring an initial ultrafast expansion followed by a rapid negative diffusion, and ultimately a slow long-term expansion of the band edge C-excitons. We provide direct experimental evidence to identify the abnormal negative diffusion process as a spatial contraction of the hot carriers resulting from spatial variation in the hot phonon bottleneck effect due to the Gaussian intensity distribution of the pump laser beam.
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Solar-driven photothermal catalytic H2 production from lignocellulosic biomass was achieved by using 1T-2H MoS2 with tunable Lewis acidic sites as catalysts in an alkaline aqueous solution, in which the number of Lewis acidic sites derived from the exposed Mo edges of MoS2 was successfully regulated by both the formation of an edge-terminated 1T-2H phase structure and tunable layer number. Owing to the abundant Lewis acidic sites for the oxygenolysis of lignocellulosic biomass, the 1T-2H MoS2 catalyst shows high photothermal catalytic lignocellulosic biomass-to-H2 transformation performance in polar wood chips, bamboo, rice straw corncobs, and rice hull aqueous solutions, and the highest H2 generation rate and solar-to-H2 (STH) efficiency respectively achieves 3661 µmol·h-1·g-1 and 0.18% in the polar wood chip system under 300 W Xe lamp illumination. This study provides a sustainable and cost-effective method for the direct transformation of renewable lignocellulosic biomass to H2 fuel driven by solar energy.
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Spins confined to point defects in atomically thin semiconductors constitute well-defined atomic-scale quantum systems that are being explored as single-photon emitters and spin qubits. Here, we investigate the in-gap electronic structure of individual sulfur vacancies in molybdenum disulfide (MoS2) monolayers using resonant tunneling scanning probe spectroscopy in the Coulomb blockade regime. Spectroscopic mapping of defect wave functions reveals an interplay of local symmetry breaking by a charge-state-dependent Jahn-Teller lattice distortion that, when combined with strong (≃100 meV) spin-orbit coupling, leads to a locking of an unpaired spin-1/2 magnetic moment to the lattice at low temperature, susceptible to lattice strain. Our results provide new insights into the spin and electronic structure of vacancy-induced in-gap states toward their application as electrically and optically addressable quantum systems.
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Molybdenum disulfide (MoS2) is one of the most intriguing two-dimensional materials, and moreover, its single atomic defects can significantly alter the properties. These defects can be both imaged and engineered using spherical and chromatic aberration-corrected high-resolution transmission electron microscopy (CC/CS-corrected HRTEM). In a few-layer stack, several atoms are vertically aligned in one atomic column. Therefore, it is challenging to determine the positions of missing atoms and the damage cross-section, particularly in the not directly accessible middle layers. In this study, we introduce a technique for extracting subtle intensity differences in CC/CS-corrected HRTEM images. By exploiting the crystal structure of the material, our method discerns chalcogen vacancies even in the middle layer of trilayer MoS2. We found that in trilayer MoS2 the middle layer's damage cross-section is about ten times lower than that in the monolayer. Our findings could be essential for the application of few-layer MoS2 in nanodevices.
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Despite the weak, van der Waals interlayer coupling, photoinduced charge transfer vertically across atomically thin interfaces can occur within surprisingly fast, sub-50 fs time scales. An early theoretical understanding of charge transfer is based on a noninteracting picture, neglecting excitonic effects that dominate optical properties of such materials. We employ an ab initio many-body perturbation theory approach, which explicitly accounts for the excitons and phonons in the heterostructure. Our large-scale first-principles calculations directly probe the role of exciton-phonon coupling in the charge dynamics of the WS2/MoS2 heterobilayer. We find that the exciton-phonon interaction induced relaxation time of photoexcited excitons at the K valley of MoS2 and WS2 is 67 and 15 fs at 300 K, respectively, which sets a lower bound to the intralayer-to-interlayer exciton transfer time and is consistent with experiment reports. We further show that electron-hole correlations facilitate novel transfer pathways that are otherwise inaccessible to noninteracting electrons and holes.
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1T-MoS2 has become an ideal anode for sodium-ion batteries (SIBs). However, the metastable feature of 1T-MoS2 makes it difficult to directly synthesize under normal conditions. In addition, it easily transforms into 2H phase via restacking, resulting in inferior electrochemical performance. Herein, the electron configuration of Mo 4d orbitals is modulated and the stable 1T-MoS2 is constructed by nickel (Ni) introduction (1T-Ni-MoS2). The original electron configuration of Mo 4d orbitals is changed via the electron injection by Ni, which triggers the phase transition from 2H to 1T phase, thus improving the electrical conductivity and accelerating the redox kinetics of the material. Consequently, 1T-Ni-MoS2 exhibits superior rate capability (266.8 mAh g-1 at 10 A g-1) and excellent cycle life (358.7 mAh g-1 at 1 A g-1 after 350 cycles). In addition, the assembled Na3V2(PO4)3/C||1T-Ni-MoS2 full cells deliver excellent electrochemical properties and show great prospects in energy storage devices.
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Two-dimensional transition metal dichalcogenide (2D TMD) semiconductors allow facile integration of p- and n-type materials without a lattice mismatch. Here, we demonstrate gate-tunable n- and p-type junctions based on vertical heterostructures of MoS2 and WSe2 using van der Waals (vdW) contacts. The p-n junction shows negative differential resistance (NDR) due to Fowler-Nordheim (F-N) tunneling through the triangular barrier formed by applying a global back-gate bias (VGS). We also show that the integration of hexagonal boron nitride (h-BN) as an insulating tunnel barrier between MoS2 and WSe2 leads to the formation of sharp band edges and unintentional inelastic tunnelling current. The devices based on vdW contacts, global VGS, and h-BN tunnel barriers exhibit NDR with a peak current (Ipeak) of 315 µA, suggesting that the approach may be useful for applications.
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Contact-induced electrification, commonly referred to as triboelectrification, is the subject of extensive investigation at liquid-solid interfaces due to its wide range of applications in electrochemistry, energy harvesting, and sensors. This study examines the triboelectric between an ionic liquid and 2D MoS2 under light illumination. Notably, when a liquid droplet slides across the MoS2 surface, an increase in the generated current and voltage is observed in the forward direction, while a decrease is observed in the reverse direction. This suggests a memory-like tribo-phototronic effect between ionic liquid and 2D MoS2 . The underlying mechanism behind this tribo-phototronic synaptic plasticity is proposed to be ion adsorption/desorption processes resulting from pseudocapacitive deionization/ionization at the liquid-MoS2 interface. This explanation is supported by the equivalent electrical circuit modeling, contact angle measurements, and electronic band diagrams. Furthermore, the influence of various factors such as velocity, step size, light wavelength and intensity, ion concentration, and bias voltage is thoroughly investigated. The artificial synaptic plasticity arising from this phenomenon exhibits significant synaptic features, including potentiation/inhibition, paired-pulse facilitation/depression, and short-term memory (STM) to long-term memory (LTM) transition. This research opens up promising avenues for the development of synaptic memory systems and intelligent sensing applications based on liquid-solid interfaces.
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In recent years, there has been a substantial surge in the investigation of transition-metal dichalcogenides such as MoS2 as a promising electrochemical catalyst. Inspired by denitrification enzymes such as nitrate reductase and nitrite reductase, the electrochemical nitrate reduction catalyzed by MoS2 with varying local atomic structures is reported. It is demonstrated that the hydrothermally synthesized MoS2 containing sulfur vacancies behaves as promising catalysts for electrochemical denitrification. With copper doping at less than 9% atomic ratio, the selectivity of denitrification to dinitrogen in the products can be effectively improved. X-ray absorption characterizations suggest that two sulfur vacancies are associated with one copper dopant in the MoS2 skeleton. DFT calculation confirms that copper dopants replace three adjacent Mo atoms to form a trigonal defect-enriched region, introducing an exposed Mo reaction center that coordinates with Cu atom to increase N2 selectivity. Apart from the higher activity and selectivity, the Cu-doped MoS2 also demonstrates remarkably improved tolerance toward oxygen poisoning at high oxygen concentration. Finally, Cu-doped MoS2 based catalysts exhibit very low specific energy consumption during the electrochemical denitrification process, paving the way for potential scale-up operations.
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Transition metal dichalcogenides (TMDs) are promising 2D nanomaterials for diverse applications, but their intrinsic chemical inertness hinders their modification. Herein, a novel approach is presented for the photocatalytic acylation of 2H-MoS2 and 2H-MoSe2, utilizing tetrabutyl ammonium decatungstate ((nBu4N)4W10O32) polyoxometalate complex as a catalyst and a conventional halogen lamp as a source of irradiation. By harnessing the semiconducting properties of TMDs, new avenues emerge for the functionalization of these materials. This novel photocatalytic protocol constitutes the first report on the chemical modification of 2D nanomaterials based on a catalytic protocol and applies to both aliphatic and aromatic substrates. The scope of the decatungstate-photocatalyzed acylation reaction of TMDs is explored by employing an alkyl and an aromatic aldehyde and the success of the methodology is confirmed by diverse spectroscopic, thermal, microscopy imaging, and redox techniques. This catalytic approach on modifying 2D nanomaterials introduces the principles of atom economy in a functionalization protocol for TMDs. It marks a transformative shift toward more sustainable and efficient methodologies in the realm of TMD modification and nanomaterial chemistry.
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The volume collapse and slow kinetics reaction of anode materials are two key issues for sodium ion batteries (SIBs). Herein, an "embryo" strategy is proposed for synthesis of nanorod-embedded MoO2/MoS2/C network nanoarchitecture as anode for SIBs with high-rate performance. Interestingly, L-cysteine which plays triple roles including sulfur source, reductant, and carbon source can be utilized to produce the sulfur vacancy-enriched heterostructure. Specifically, L-cysteine can combine with metastable monoclinic MoO3 nanorods at room temperature to encapsulate the "nutrient" of MoOx analogues (MoO2.5(OH)0.5 and MoO3·0.5H2O) and hydrogen-deficient L-cysteine in the "embryo" precursor affording for subsequent in situ multistep heating treatment. The resultant MoO2/MoS2/C presents a high-rate capability of 875 and 420 mAh g-1 at 0.5 and 10 A g-1, respectively, which are much better than the MoS2-based anode materials reported by far. Finite element simulation and analysis results verify that the volume expansion can be reduced to 42.8% from 88.8% when building nanorod-embedded porous network structure. Theoretical calculations reveal that the sulfur vacancies and heterointerface engineering can promote the adsorption and migration of Na+ leading to highly enhanced thermodynamic and kinetic reaction. The work provides an efficient approach to develop advanced electrode materials for energy storage.
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The large-scale commercialization of the hydrogen evolution reaction (HER) necessitates the development of cost-effective and highly efficient electrocatalysts. Although transition metal sulfides, such as MoS2 and Ni3 S2 , hold great potential in the field of HER, their catalytic performance has been unsatisfactory due to incomplete exposure of active sites and poor electrical conductivity. In this work, via a simple hydrothermal strategy, amorphous MoS2 nanoshells in the form of urchin-like MoS2 -Ni3 S2 core-shell heterogeneous structure is realized and in situ loaded on nickel foam (A-MoS2 -Ni3 S2 -NF). In particular, XPS analysis results show that the coupling of amorphous MoS2 and Ni3 S2 makes the electrode surface exhibit electron-abundant property, which will have a positive impact on HER catalytic activity. In addition, the fully exposed active site of amorphous MoS2 is another crucial factor contributing to its high catalytic performance of A-MoS2 -Ni3 S2 -NF electrode. In particular, at a current density of 10 mA cmâ»2 , the overpotential of electrode is 95 mV (1.0 m KOH) and 145 mV (0.5 m H2 SO4 ). This work highlights the importance of amorphous MoS2 and MoS2 -Ni3 S2 of sea-urchin core-shell structure in optimizing HER performance, which provides an important reference for HER research.