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As a clean and effective approach, the introduction of external magnetic fields to improve the performance of catalysts has attracted extensive attention. Owing to its room-temperature ferromagnetism, chemical stability, and earth abundance, VSe2 is expected to be a promising and cost-effective ferromagnetic electrocatalyst for the accomplishment of high-efficient spin-related OER kinetics. In this work, a facile pulsed laser deposition (PLD) method combined with rapid thermal annealing (RTA) treatment is used to successfully confine monodispersed 1T-VSe2 nanoparticles in amorphous carbon matrix. As expected, with external magnetic fields of 800 mT stimulation, the confined 1T-VSe2 nanoparticles exhibit highly efficient oxygen evolution reaction (OER) catalytic activity with an overpotential of 228 mV for 10 mA cm-2 and remarkable durability without deactivation after >100 h OER operation. The experimental results together with theoretical calculations illustrate that magnetic fields can facilitate the surface charge transfer dynamics of 1T-VSe2 , and modify the adsorption-free energy of *OOH, thus finally improving the intrinsic activity of the catalysts. This work realizes the application of ferromagnetic VSe2 electrocatalyst in highly efficient spin-dependent OER kinetics, which is expected to promote the application of transition metal chalcogenides (TMCs) in external magnetic field-assisted electrocatalysis.
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Vanadium diselenide (VSe2) exhibits versatile electronic and magnetic properties in the trigonal prismatic (H-) and octahedral (T-) phases. Compared to the metallic T-phase, the H-phase with a tunable semiconductor property is predicted to be a ferrovalley material with spontaneous valley polarization. Herein we report an epitaxial growth of the monolayer 2D VSe2 on a mica substrate via the chemical vapor deposition (CVD) method by introducing salt in the precursor. Our first-principles calculations suggest that the monolayer H-phase VSe2 with a large lateral size is thermodynamically favorable. The honeycomb-like structure and the broken symmetry are directly observed by spherical aberration-corrected scanning transmission electron microscopy (STEM) and confirmed by giant second harmonic generation (SHG) intensity. The p-type transport behavior is further evidenced by the temperature-dependent resistance and field-effect device study. The present work introduces a new phase-stable 2D transition metal dichalcogenide, opening the prospect of novel electronic and spintronics device design.
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Defect engineering of transition metal dichalcogenides (TMDCs) is important for improving electrocatalytic hydrogen evolution reaction (HER) performance. Herein, a facile and scalable atomic-level di-defect strategy over thermodynamically stable VSe2 nanoflakes, yielding attractive improvements in the electrocatalytic HER performance over a wide electrolyte pH range is reported. The di-defect configuration with controllable spatial relation between single-atom (SA) V defects and single Se vacancy defects effectively triggers the electrocatalytic HER activity of the inert VSe2 basal plane. When employed as a cathode, this di-defects decorated VSe2 electrocatalyst requires overpotentials of 67.2, 72.3, and 122.3 mV to reach a HER current density of 10 mA cm-2 under acidic, alkaline, and neutral conditions, respectively, which are superior to most previously reported non-noble metal HER electrocatalysts. Theoretical calculations reveal that the reactive microenvironment consists of two adjacent SA Mo atoms with two surrounding symmetric Se vacancies, yielding optimal water dissociation and hydrogen desorption kinetics. This study provides a scalable strategy for improving the electrocatalytic activity of other TMDCs with inert atoms in the basal plane.
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The transition-metal dichalcogenide VSe2 exhibits an increased charge density wave transition temperature and an emerging insulating phase when thinned to a single layer. Here, we investigate the interplay of electronic and lattice degrees of freedom that underpin these phases in single-layer VSe2 using ultrafast pump-probe photoemission spectroscopy. In the insulating state, we observe a light-induced closure of the energy gap, which we disentangle from the ensuing hot carrier dynamics by fitting a model spectral function to the time-dependent photoemission intensity. This procedure leads to an estimated time scale of 480 fs for the closure of the gap, which suggests that the phase transition in single-layer VSe2 is driven by electron-lattice interactions rather than by Mott-like electronic effects. The ultrafast optical switching of these interactions in SL VSe2 demonstrates the potential for controlling phase transitions in 2D materials with light.
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The transition metal disulfides of VB group elements have gradually come into people's field of vision owing to their two-dimensional structure and unique optical properties. Vanadium diselenide (VSe2) as a kind of transition metal diselenides, is competent for the applications of nonlinear saturable absorption. The dispersion of few-layer VSe2is prepared by liquid phase exfoliation method. Clearly, it has an obvious layered structure, and the interlayer spacing is 0.31 nm. The VSe2nanosheets are inserted into the Erbium-doped fiber laser through tapered deposition method and the measured modulation depth is 1.46%. A 1530.5 nm centered 851-fs pulse is observed with the 3.2 nm 3-dB spectral width. The experimental results show that the pulse is persistent under the power of 334 mW, with signal-to-noise ratio of 41 dB. And an up to 552.4 MHz modulation phenomenon is observed around 1560 nm, so is its frequency tunability. This is the first time that VSe2is used to realize high frequency modulation in fiber laser. It is proved that VSe2is expected to be a budding material of ultrafast optical modulation devices and widely used in the field of ultrafast photonics.
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The realizing of high-performance rechargeable aqueous zinc-ion batteries (ZIBs) with high energy density and long cycling life is promising but still challenging due to the lack of suitable layered cathode materials. The work reports the excellent zinc-ion storage performance as-observed in few-layered ultrathin VSe2 nanosheets with a two-step Zn2+ intercalation/de-intercalation mechanism verified by ex situ X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) characterizations. The VSe2 nanosheets exhibit a discharge plateau at 1.0-0.7 V, a specific capacity of 131.8 mAh g-1 (at 0.1 A g-1 ), and a high energy density of 107.3 Wh kg-1 (at a power density of 81.2 W kg-1 ). More importantly, outstanding cycle stability (capacity retention of 80.8% after 500 cycles) without any activation process is achieved. Such a prominent cyclic stability should be attributed to its fast Zn2+ diffusion kinetics (DZn 2+ ≈ 10-8 cm-2 s-1 ) and robust structural/crystalline stability. Density functional theory (DFT) calculation further reveals a strong metallic characteristic and optimal zinc-ion diffusion pathway with a hopping energy barrier of 0.91 eV. The present finding implies that 2D ultrathin VSe2 is a very promising cathode material in ZIBs with remarkable battery performance superior to other layered transitional metal dichalcogenides.
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In this work, the ternary hybrid structure VSe2 /SWCNTs/rGO is reported for supercapacitor applications. The ternary composite exhibits a high specific capacitance of 450â F g-1 in a symmetric cell configuration, with maximum energy density of 131.4â Wh kg-1 and power density of 27.49â kW kg-1 . The ternary hybrid also shows a cyclic stability of 91 % after 5000â cycles. Extensive density functional theory (DFT) simulations on the structure as well as on the electronic properties of the binary hybrid structure VSe2 /SWCNTs and the ternary hybrid structure VSe2 /SWCNTs/rGO have been carried out. Due to a synergic effect, there are enhanced density of states near the Fermi level and higher quantum capacitance for the hybrid ternary structure compared to VSe2 /SWCNTs, leading to higher energy and power density for VSe2 /SWCNTs/rGO, supporting our experimental observation. Computed diffusion energy barrier of electrolyte ions (K+ ) predicts that ions move faster in the ternary structure, providing higher charge storage performance.
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How the interacting electronic states and phases of layered transition-metal dichalcogenides evolve when thinned to the single-layer limit is a key open question in the study of two-dimensional materials. Here, we use angle-resolved photoemission to investigate the electronic structure of monolayer VSe2 grown on bilayer graphene/SiC. While the global electronic structure is similar to that of bulk VSe2, we show that, for the monolayer, pronounced energy gaps develop over the entire Fermi surface with decreasing temperature below Tc = 140 ± 5 K, concomitant with the emergence of charge-order superstructures evident in low-energy electron diffraction. These observations point to a charge-density wave instability in the monolayer that is strongly enhanced over that of the bulk. Moreover, our measurements of both the electronic structure and of X-ray magnetic circular dichroism reveal no signatures of a ferromagnetic ordering, in contrast to the results of a recent experimental study as well as expectations from density functional theory. Our study thus points to a delicate balance that can be realized between competing interacting states and phases in monolayer transition-metal dichalcogenides.
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Transition metal dichalcogenides, such as MoS2 and VSe2 have emerged as promising catalysts for the hydrogen evolution reaction (HER). Substantial work has been devoted to optimizing the catalytic performance by constructing materials with specific phases and morphologies. However, the optimization of adsorption/desorption process in HER is rare. Herein, we concentrate on tuning the dynamics of the adsorption process in HER by applying a back gate voltage to the pristine VSe2 nanosheet. The back gate voltage induces the redistribution of the ions at the electrolyte-VSe2 nanosheet interface, which realizes the enhanced electron transport process and facilitates the rate-limiting step (discharge process) under HER conditions. A considerable low onset overpotential of 70 mV is achieved in VSe2 nanosheets without any chemical treatment. Such unexpected improvement is attributed to the field tuned adsorption-dynamics of VSe2 nanosheet, which is demonstrated by the greatly optimized charge transfer resistance (from 1.03 to 0.15 MΩ) and time constant of the adsorption process (from 2.5 × 10-3 to 5.0 × 10-4 s). Our results demonstrate enhanced catalysis performance in the VSe2 nanosheet by tuning the adsorption dynamics with a back gate, which provides new directions for improving the catalytic activity of non-noble materials.
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Interfacial chemical modification is an effective strategy to adjust the strong Coulombic ion-lattice interactions with high valence cations experienced by electrode materials, facilitating the reaction kinetic. In this paper, a simple and fast surface oxygen implantation strategy was designed to adjust the electronic structure of stainless steel (SS) supported vanadium diselenide (VSe2) nanosheets and form a surface protective film, which effectively accelerates the reaction kinetics of Zn2+ and extends the cycle life of the battery. It is demonstrated that the conductivity, pseudocapacitance and specific capacity can be tuned by selectively introducing oxygen species to the surface, which provides an important reference for the design of electrodes with controlled surface chemistry. Density functional theory (DFT) calculations also confirm that the electronic structure can be adjusted by surface oxygen injection strategy, which not only improves the conductivity, but also adjusts the adsorption energy, thus providing favorable conditions for zinc ion storage. Benefiting from the selenium vacancies and pores generated by the removal of part of selenium, and the oxide film formed on the surfaces, the VSe2-xOx-SS-30 electrode showed higher specific capacity (188.4 mAh/g at 0.5 A g-1 after 50 cycles), better rate performance (107.1 mAh/g at 4 A g-1) and more satisfactory cycling stability (83.1 mAh/g at 5 A g-1 after 1800 cycles) than VSe2-SS electrode. Importantly, the flexible quasi-solid-state VSe2-xOx-SS-30//Zn battery also exhibits high specific capacity and excellent environmental adaptability. Furthermore, the zinc (de)intercalation and transformation reactions mechanism was revealed by some ex-situ/in-situ techniques.
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Among the various non-precious metal catalysts that drive hydrogen evolution reactions (HERs) and dye-sensitized solar cells (DSSCs), transition metal selenides (TMSs) stand out due to their unique electronic properties and tunable morphology. Herein, the multicomponent selenide CuSe-Co3Se4@VSe2 was successfully synthesized by doping with metal element vanadium and selenization on the copper-cobalt carbonate hydroxide (CuCo-CH) template. CuSe-Co3Se4@VSe2 exhibited the dandelion-like cluster structure composed of hollow nanotubes doped with VSe2 nanoparticles. Due to the unique structure and the synergistic effect of various elements, CuSe-Co3Se4@VSe2 showed excellent alkaline HER and DSSC performances. The DSSC based on CuSe-Co3Se4@VSe2 exhibited an impressive power conversion efficiency (PCE) of 9.64 %, which was much higher than that of Pt (8.39 %). Besides, it possessed a low HER overpotential of 76 mV@10 mA cm-2 and a small Tafel slope of 88.9 mV dec-1 in 1.0 M KOH.
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Opportune sensing of ammonia (NH3) gas is industrially important for avoiding hazards. With the advent of nanostructured 2D materials, it is felt vital to miniaturize the detector architecture so as to attain more and more efficacy with simultaneous cost reduction. Adaptation of layered transition metal dichalcogenide as the host may be a potential answer to such challenges. The current study presents a theoretical in-depth analysis regarding improvement in efficient detection of NH3 using layered vanadium di-selenide (VSe2) with the introduction of point defects. The poor affinity between VSe2 and NH3 forbids the use of the former in the nano-sensing device's fabrications. The adsorption and electronic properties of VSe2 nanomaterials can be tuned with defect induction, which would modulate the sensing properties. The introduction of Se vacancy to pristine VSe2 was found to cause about an eight-fold increase (from -012 eV to -0.97 eV) in adsorption energy. A charge transfer from the N 2p orbital of NH3 to the V 3d orbital of VSe2 has been observed to cause appreciable NH3 detection by VSe2. In addition to that, the stability of the best-defected system has been confirmed through molecular dynamics simulation, and the possibility of repeated usability has been analyzed for calculating recovery time. Our theoretical results clearly indicate that Se-vacant layered VSe2 can be an efficient NH3 sensor if practically produced in the future. The presented results will thus potentially be useful for experimentalists in designing and developing VSe2-based NH3 sensors.
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Amônia , Eletrônica , Teoria da Densidade Funcional , Adsorção , EmoçõesRESUMO
Anion vacancy engineering (AVE) is widely used to improve the Li-ion and Na-ion storage of conversion-type anode materials. However, AVE is still an emerging strategy in K-ion batteries, which are promising for large-scale energy storage. In addition, the role of anion vacancies on ion storage is far from clear, despite several proposed explanations. Herein, by employing VSe2 as a model conversion-type anode material, Se vacancies are intentionally introduced (labeled as P-VSe2-x ) to investigate their effect on K+ storage. The P-VSe2-x shows excellent cyclability in half cells (143 mA h g-1 at 3.0 A g-1 after 1000 cycles) and high energy density in coin-type full cells (206.8 Wh kg-1 ). By applying various electrochemical techniques, the effects of Se vacancies on the redox potentials of K-ion insertion/extraction and the K-ion diffusion in electrodes upon cycling are uncovered. In addition, the structural evolution of Se vacancies during potassiation/de-potassiation using various operando and ex characterizations is revealed. Moreover, it is demonstrated that Se vacancies can facilitate the breaking of VSe bonds upon the P-VSe2-x conversion using theoretical calculations. This work comprehensively explains the role of anion vacancies in ion storage for developing high-performance conversion-type anode materials.
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The sluggish redox kinetics and the severe shuttle effect of soluble lithium polysulfides (LiPSs) are the main key issues which would hinder the development of lithium-sulfur (Li-S) batteries. In this work, a nickel-doped vanadium selenide in-situ grows on reduced graphene oxide(rGO) to form a two-dimensional (2D) composite Ni-VSe2/rGO by a simple solvothermal method. When it is used as a modified separator in Li-S batteries, the Ni-VSe2/rGO material with the doped defect and super-thin layered structure can greatly adsorb LiPSs and catalyze the conversion reaction of LiPSs, resulting in effectively reducing LiPSs diffusion and suppressing the shuttle effect. More importantly, the cathode-separator bonding body is first developed as a new strategy of electrode-separator integration in Li-S batteries, which not only could decrease the LiPSs dissolution and improve the catalysis performance of the functional separator as the upper current-collector, but also is good for the high sulfur loading and the low electrolyte/sulfur (E/S) ratio for high energy density Li-S batteries. When the Ni-VSe2/rGO-PP (polypropylene, Celgard 2400) modified separator is applied, the Li-S cell can retain 510.3 mA h g-1 capacity after 1190 cycles at 0.5C. In the electrode-separator integrated system, the Li-S cell can still maintain 552.9 mA h g-1 for 190 cycles at a sulfur loading 6.4 mg cm-2 and 4.9 mA h cm-2 for 100 cycles at a sulfur loading 7.0 mg cm-2. The experimental results indicate that both the doped defect engineering and the super-thin layered structure design might optimally be chosen to fabricate a new modified separator material, and especially, the electrode-separator integration strategy would open a practical way to promote the electrochemical behavior of Li-S batteries with high sulfur loading and low E/S ratio.
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The itinerant ferromagnetism can be induced by a van Hove singularity (VHS) with a divergent density of states at Fermi level. Utilizing the giant magnified dielectric constant εr of SrTiO3(111) substrate with cooling, here we successfully manipulated the VHS in the epitaxial monolayer (ML) 1T-VSe2 film approaching to Fermi level via the large interfacial charge transfer, and thus induced a two-dimensional (2D) itinerant ferromagnetic state below 3.3 K. Combining the direct characterization of the VHS structure via angle-resolved photoemission spectroscopy (ARPES), together with the theoretical analysis, we ascribe the manipulation of VHS to the physical origin of the itinerant ferromagnetic state in ML 1T-VSe2. Therefore, we further demonstrated that the ferromagnetic state in the 2D system can be controlled through manipulating the VHS by engineering the film thickness or replacing the substrate. Our findings clearly evidence that the VHS can serve as an effective manipulating degree of freedom for the itinerant ferromagnetic state, expanding the application potentials of 2D magnets for the next-generation information technology.
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Asma , Doença Pulmonar Obstrutiva Crônica , Humanos , Imãs , Temperatura BaixaRESUMO
Our first-principles evidence shows that the two-dimensional (2D) multiferroic VSe2/In2Se3experiences continuous change of electronic structures, i.e. with the change of the ferroelectric (FE) polarization of In2Se3, the heterostructure can possess type-I, -II, and -III band alignments. When the FE polarization points from In2Se3to VSe2, the heterostructure has a type-III band alignment, and the charge transfer from In2Se3into VSe2induces half-metallicity. With reversal of the FE polarization, the heterostructure enters the type-I band alignment, and the spin-polarized current is turned off. When the In2Se3is depolarized, the heterostructure has a type-II band alignment. In addition, influence of the FE polarization on magnetism and magnetic anisotropy energy of VSe2was also analyzed, through which we reveal the interfacial magnetoelectric coupling effects. Our investigation about VSe2/In2Se3predicts its wide applications in the fields of both 2D spintronics and multiferroics.
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Semimetallic nanomaterials as photothermal agents for bioimaging and cancer therapy have attracted tremendous interest. However, the poor photothermal stability, low biocompatibility, and single component limit their therapeutic efficiency in cancer treatment. Here, manganese-doped VSe2 semimetallic nanosheets were prepared and subsequently modified with chitosan (named VSe2/Mn-CS NSs) for combined enzyme catalytic and photothermal therapy. VSe2/Mn-CS NSs show high photothermal property with a photothermal conversion efficiency of 34.61% upon 808 nm near-infrared laser irradiation. In the tumor microenvironment, VSe2/Mn-CS NSs can convert endogenous H2O2 into lethal hydroxyl radicals (â¢OH) to induce cancer cell apoptosis. The interaction between glutathione (GSH) and Se-Se bonds in VSe2/Mn-CS NSs results in the depletion of GSH level, and the valence states transition of manganese ions is also beneficial for the GSH consumption. This dual depletion of GSH markedly enhances the peroxidase (POD) activity, leading to the high â¢OH production and the improved therapeutic effect. What is more, the T1-weighted magnetic resonance and photoacoustic imaging endow VSe2/Mn-CS NSs with the ability to guide and track the treatment process. Our study provides a research strategy for the application of semimetallic nanomaterials in cancer diagnosis and treatment.
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Hipertermia Induzida , Metaloides , Neoplasias , Humanos , Manganês/uso terapêutico , Peróxido de Hidrogênio , Glutationa , Hipertermia Induzida/métodos , Microambiente Tumoral , Neoplasias/terapia , Neoplasias/tratamento farmacológico , Linhagem Celular TumoralRESUMO
Thinning crystalline materials to two dimensions (2D) creates a rich playground for electronic phases, including charge, spin, superconducting, and topological order. Bulk materials hosting charge density waves (CDWs), when reduced to ultrathin films, have shown CDW enhancement and tunability. However, charge order confined to only 2D remains elusive. Here we report a distinct charge ordered state emerging in the monolayer limit of 1T-VSe2. Systematic scanning tunneling microscopy experiments reveal that bilayer VSe2 largely retains the bulk electronic structure, hosting a tridirectional CDW. However, monolayer VSe2 âconsistently across distinct substratesâexhibits a dimensional crossover, hosting two CDWs with distinct wavelengths and transition temperatures. Electronic structure calculations reveal that while one CDW is bulk-like and arises from the well-known Peierls mechanism, the other is decidedly unconventional. The observed CDW-lattice decoupling and the emergence of a flat band suggest that the second CDW could arise from enhanced electron-electron interactions in the 2D limit. These findings establish monolayer-VSe2 as a host of coexisting charge orders with distinct origins, and enable the tailoring of electronic phenomena via emergent interactions in 2D materials.
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Although transitional metal dichalcogenides have been regarded as appealing electrodes for sodium/potassium-ion batteries (SIBs/PIBs) owing to their high theoretical capacity, it is a key challenge to realize dichalcogenide anodes with long-period cycling performance and high-rate capability because of their poor conductivity and large volumetric change. Herein, polypyrrole-encapsulated VSe2 nanoplates (VSe2@PPy) were prepared by the selenization of VOOH hollow nanospheres and subsequent in situ polymerization and coating by pyrrole. Benefiting from the inherent metallicity of VSe2, the improvement in the conductivity and the structural protection provided by the PPy layer, the VSe2@PPy nanoplates exhibited enhanced sodium/potassium-storage performances, delivering a superior rate capability with a capacity of 260.0 mA h g-1 at 10 A g-1 in SIBs and 148.6 mA h g-1 at 5 A g-1 in PIBs, as well as revealing an ultrastability in cycling of 324.6 mA h g-1 after 2800 cycles at 4 A g-1 in SIBs. Moreover, the insertion and conversion mechanisms of VSe2@PPy in SIBs with intermediates of Na0.6VSe2, NaVSe2, and VSe were elucidated by in situ/ex situ X-ray diffraction combined with ex situ transmission electron microscopy observation and in situ potentio-electrochemical impedance spectroscopy during the sodiation and desodiation processes. Density functional theory calculations show that the strong coupling between VSe2 and PPy not only causes it to have a stronger total density of states and a built-in electric field, leading to an increased electrical conductivity, but also effectively decreases the ion diffusion barrier.
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Tuning the electronic structures of transition metal dichalcogenides (TMD) is essential for their implementation in next-generation energy technologies. In this study, we synthesized composition-tuned WSe2-VSe2 (W1-xVxSe2, x = 0-1) alloyed nanosheets using a colloidal reaction. Alloying the semiconducting WSe2 with VSe2 converts the material into a metallic one, followed by a 2H-to-1T phase transition at x = 0.7. Over a wide composition range, WSe2 and VSe2 are atomically immiscible and form separate ordered domains. The miscible alloy at x = 0.1 displayed enhanced electrocatalytic activity toward the hydrogen evolution reaction (HER) in an acidic electrolyte. This trend was correlated with the d-band center via a volcano-type relationship. Spin-polarized density functional theory calculations consistently predicted the atomic immiscibility, which became more significant at the 2H-1T phase transition composition. The Gibbs free energy of H adsorption on the basal planes (Se or hole sites) and the activation barriers along the Volmer-Heyrovsky reaction pathway supported the enhanced HER performance of the alloy phase, suggesting that the dispersed V-doped structures were responsible for the best HER catalytic activity. Our study demonstrates how the atomic structure of TMD alloy nanosheets plays a crucial role in enhancing catalytic activity.