Over 104-fold amplified upconversion luminescence of lanthanide nanocrystals through optical oscillator-like system

Recently, lanthanide (Ln) luminescent nanocrystals have attracted increasing attention in various fields such as biomedical imaging, lasers, and anticounterfeiting. However, due to the forbidden 4f–4f transition of lanthanide ions, the absorption cross-section and luminescence brightness of lanthanide nanocrystals are limited. To address the challenge, we constructed an optical oscillator-like system to repeatedly simulate lanthanide nanocrystals to enhance the absorption efficiency of lanthanide ions on excitation photons. In this optical system, the upconversion luminescence (UCL) of Tm³⁺ emission of ~450 nm excited by a 980 nm laser can be amplified by a factor beyond 10⁴. The corresponding downshifting luminescence of Tm³⁺ at 1460 nm was enhanced by three orders of magnitude. We also demonstrated that the significant luminescence enhancement in the designed optical oscillator-like system was general for various lanthanide nanocrystals including NaYF₄:Yb³⁺/Ln³⁺, NaErF₄@NaYF₄ and NaYF₄:Yb³⁺/Ln³⁺@NaYF₄:Yb³⁺@NaYF₄ (Ln = Er, Tm, Ho) regardless of the wavelengths of excitation sources (808 and 980 nm). The mechanism study revealed that both elevated laser power in the optical system and multiple excitations on lanthanide nanocrystals were the main reason for the luminescence amplification. Our findings may benefit the future development of low-threshold upconversion and downshifting luminescence of lanthanide nanocrystals and expand their applications.     

Tuneable luminescence properties of EDTA‐assisted ZnS:Mn nanocrystals from a yellow‐orange to a red emission band

Luminescence technology has been improved with the help of semiconductor nanoparticles that possess novel optical and electrical properties compared with their bulk counterpart. The aim of this study was to design semiconductor nanocrystals in their pure (ZnS) or doped form (ZnS:Mn) with different concentrations of Mn²⁺ ions by a wet chemical route stabilized by ethylenediamine tetra‐acetic acid (EDTA) and to evaluate their luminescence properties. The nanocrystals were characterized by physicochemical techniques such as X‐ray diffraction (XRD), High‐resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SEAD), EDS, and ultraviolet (UV)–visible light and photoluminescence (PL) studies. These results showed the presence of cubic phase and spherically shaped nanocrystals. A blue shift with respect to their bulk counterpart was observed. PL emission spectra were observed with a fixed blue peak and the yellow‐orange bands were red shifted towards the red region under the same excitation wavelength. The orange‐red bands were attributed to the radiation transition of electrons in 3d5 unfilled shells of Mn²⁺ ions [⁴T₁(⁴G)‐⁶A₁(⁶S)]; the ZnS matrix varied with Mn²⁺ concentration. Shift and increase in the intensity of the PL and absorption bands were observed with increase in Mn content. The study showed that Mn²⁺‐doped ZnS nanocrystal emission bands can be tuned from the yellow‐orange to the red regions under a controlled synthesis process and could be used as promising luminescent emitters in the biology field upon functionalization with suitable materials. Further studies on construction with various other materials will be useful for practical applications.     

Pyrolytic synthesis and luminescence of porous lanthanide Eu‐MOF

A lanthanide metal coordination polymer [Eu₂(BDC)₃(DMSO)(H₂O)] was synthesized by the reaction of europium oxide with benzene‐1,3‐dicarboxylic acid (H₂BDC) in a mixed solution of dimethyl sulfoxide (DMSO) and water under hydrothermal conditions. The crystal structure of Eu₂(BDC)₃(DMSO)(H₂O) was characterized by X‐ray diffraction (XRD). Thermo‐gravimetric analysis of Eu₂(BDC)₃(DMSO)(H₂O) indicated that coordinated DMSO and H₂O molecules could be removed to create Eu₂(BDC)₃(DMSO)(H₂O)‐py with permanent microporosity, which was also verified by powder XRD (PXRD) and elemental analysis. Both Eu₂(BDC)₃(DMSO)(H₂O) and Eu₂(BDC)₃(DMSO)(H₂O)‐py showed mainly Eu‐based luminescence and had characteristic emissions in the range 550–700 nm. Copyright © 2015 John Wiley & Sons, Ltd.     

Sensitive detection of sulfide ions in red region based on luminescence resonance energy transfer between upconversion nanoparticles and dye‐670

Many sulfides are toxic substances that easily harm the respiratory tract, therefore affecting respiratory function or damaging other organs of the body, leading to its failure. Therefore, there is a pressing need to develop methods for sensitive detection of sulfur ions (S^2?). Based on luminescence resonance energy transfer (LRET) theory, we report the construction of a near‐infrared (NIR) excitation luminescence probe using NaGdF₄:Yb³⁺,Er³⁺@NaYF₄ upconversion nanoparticles (UCNPs) as the donor and dye‐670 as the receptor for detection of S^2?. When UCNPs and dye‐670 molecules were combined using ligand exchange and electrostatic attraction, LRET occurred and UCNP luminescence was quenched. When S^2? was added to the system, sulfide ions were able to destroy the double bond of the dye, inhibiting LRET and restoring UCNP luminescence. Under optimum condition, the linear range of S^2? detection was 0.65–18.2 μM, and the detection limit was 34.2 nM. This method was applied for determination of S^2? in water with satisfactory results.     

Enhancing the luminescence of Eu3+/Eu2+ ion‐doped hydroxyapatite by fluoridation and thermal annealing

This paper reports a novel way for the synthesis of a europium (Eu)‐doped fluor‐hydroxyapatite (FHA) nanostructure to control the luminescence of hydroxyapatite nanophosphor, particularly, by applying optimum fluorine concentrations, annealed temperatures and pH value. The Eu‐doped FHA was made using the co‐precipitation method followed by thermal annealing in air and reducing in a H₂ atmosphere to control the visible light emission center of the nanophosphors. The intensities of the OH^? group decreased with the increasing fluorine concentrations. For the specimens annealed in air, the light emission center of the nanophosphor was 615 nm, which was emission from the Eu³⁺ ion. However, when they were annealed in reduced gas (Ar + 5% H₂), a 448 nm light emission center from the Eu²⁺ ion of FHA was observed. The presence of fluorine in Eu‐doped FHA resulted in a significant enhancement of nanophosphor luminescence, which has potential application in light emission and nanomedicine.     

Synthesis and luminescence properties of lanthanide complexes with a new tripodal ligand featuring N‐thenylsalicylamide arms

To explore the relationship between the structure of the ligands and the luminescent properties of the lanthanide complexes, luminescent lanthanide complexes of a new tripodal ligand, featuring N‐thenylsalicylamide arms, were synthesized and characterized by elemental analysis, IR and TGA measurements. Photophysical properties of the complexes were studied by means of UV ? visible absorption and steady‐state luminescence spectroscopy. The results of UV ? vis spectra indicate that metal binding does not disturb the electronic structure of the ligand. Excited‐state luminescence lifetimes and quantum yields of the complexes were determined. The photoluminescence analysis suggested that there is an efficient ligand ? Ln(III) energy transfer for the Tb(III) complex, and the ligand is an efficient 'antenna' for Tb(III). From a more general perspective, the results demonstrated the potential application of the lanthanide complex as luminescent materials in material chemistry. Copyright © 2012 John Wiley & Sons, Ltd.     

Europium‐activated rare earth fluoride (LnF3:Eu3+–Ln = La,Gd) nanocrystals prepared by using ionic liquid/NH4F as a fluorine source via hydrothermal synthesis

Lanthanide (Ln) fluorides are considered exceptional luminescent rigid host matrices for various optical active Ln³⁺ ions due to their high refractive index, high chemical stability and low phonon energy, leading to the low probability of non‐radiative decay, which results in higher photoluminescence quantum yield (PLQY) (usually higher than oxide hosts). In this study, Eu³⁺‐activated Ln fluorides (LnF₃:Eu³⁺–Ln = La, Gd) are synthesized by the hydrothermal method using 1‐butyl‐3‐methylimidazolium tertrafluoroborate [BMIBF₄] and NH₄F as fluorine precursors. The synthesized nanocrystals (NCs) are structurally and morphologically characterized, and their optical properties investigated using spectrofluorometry. The X‐ray diffraction (XRD) patterns of Eu³⁺‐substituted and ‐unsubstituted LnF₃ (prepared from a different fluorine source) are indexed based on the hexagonal and orthorhombic crystal structure, respectively. Average crystalline sizes are calculated using the Scherrer equation and it is found that the synthesized NCs have an average crystalline size of 12–35 nm. Transmission electron microscopy (TEM) images reveal that the NCs are well dispersed and nearly ellipsoid, with an average size of ~ 5 nm. Eu³⁺‐activated NCs show characteristic excitation and emission spectra. The emission spectra show both magnetic (⁵D₀–⁷F₁) and electric (⁵D₀–⁷F₂) dipole transition with appropriate CIE color coordinates; however, the intensity of the magnetic dipole transition is high, which is in accordance with local site symmetry. Owing to their unique size and excellent optical properties, the synthesized NCs may have potential application in the fields bio‐imaging and solar concentrators. Copyright © 2016 John Wiley & Sons, Ltd.     

Enhancement of near‐infrared up‐conversion and blue down‐conversion luminescence in LuNbO4:Yb3+,Tm3+ with Ga3+ and Ta5+ substitutions

Under a 980‐nm excitation, the up‐conversion (UC) spectra of LuNbO₄:Yb³⁺,Tm³⁺ powders exhibited predominantly near‐infrared bands (~805 nm) of Tm³⁺ through an energy transfer process from Yb³⁺ to Tm³⁺. Regarding the down‐conversion (DC) luminescence of the powders, the photoluminescence excitation spectra consisted of a broad charge transfer band (270 nm) due to [NbO₄]^3? and sharp band (360 nm) of Tm³⁺, while the corresponding emission spectra exhibited a blue emission at 458 nm. Upon substitution of Ga³⁺ and Ta⁵⁺ for Lu³⁺ and Nb⁵⁺, respectively, both UC and DC luminescence properties were significantly enhanced. For the Ga³⁺ substitution, the increased emission intensity could be explained by the crystal field asymmetry surrounding the Tm³⁺ ions induced by the large difference in ionic radius between Ga³⁺ and Lu³⁺. For the Ta⁵⁺ substitution, we believe that an M′‐LuTaO₄ substructure was formed in the host, which led to the formation of a TaO₆ octahedral coordination instead of a NbO₄ tetrahedral coordination. Consequently, the crystal symmetry of the local structure was modified, and thus the UC and DC luminescence properties were enhanced. The dual‐mode (UC and DC) luminescence demonstrates that LuNbO₄:Yb³⁺,Tm³⁺ has a great potential in the fields of temperature sensing probes, anti‐counterfeiting, and bioapplications.     

Size‐tailored synthesis and luminescent properties of three‐dimensional BaMoO4, BaMoO4:Eu3+ micron‐octahedrons and micron‐flowers via sonochemical route

Almost monodisperse three‐dimensional (3D) BaMoO_4, BaMoO₄:Eu³⁺ micron‐octahedrons and micron‐flowers were successfully prepared via a large‐scale and facile sonochemical route without using any catalysts or templates. X‐Ray diffraction (XRD), field emission scanning electron microscopy (FE‐SEM), energy dispersion X‐ray (EDS), Fourier transform infrared (FTIR) and photoluminescence (PL) spectroscopy were employed to characterize the as‐obtained products. It was found that size modulation could be easily realized by changing the concentrations of reactants and the pH value of precursors. The formation mechanism for micron‐octahedrons and micron‐flowers was proposed on the basis of time‐dependent experiments. Using excitation wavelengths of 396 or 466 nm for BaMoO₄:Eu³⁺ phosphors, an intense emission line at 614 nm was observed. These phosphors might be promising components with possible application in the fields of near UV‐ and blue‐excited white light‐emitting diodes. Simultaneously, this novel and efficient pathway could open new opportunities for further investigating the properties of molybdate materials. Copyright © 2014 John Wiley & Sons, Ltd.     

Tunable multicolor and white‐light upconversion luminescence in Yb3+/Tm3+/Ho3+ tri‐doped NaYF4 micro‐crystals

NaYF₄ micro‐crystals with various concentrations of Yb³⁺/Tm³⁺/Ho³⁺ were prepared successfully via a simple and reproducible hydrothermal route using EDTA as the chelating agent. Their phase structure and surface morphology were studied using powder X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD patterns revealed that all the samples were pure hexagonal phase NaYF₄. SEM images showed that Yb³⁺/Tm³⁺/Ho³⁺ tri‐doped NaYF₄ were hexagonal micro‐prisms. Upconversion photoluminescence spectra of Yb³⁺/Tm³⁺/Ho³⁺ tri‐doped NaYF₄ micro‐crystals with various dopant concentrations under 980 nm excitation with a 665 mW pump power were studied. Tunable multicolor (purple, purplish blue, yellowish green, green) and white light were achieved by simply adjusting the Ho³⁺ concentration in 20%Yb³⁺/1%Tm³⁺/xHo³⁺ tri‐doped NaYF₄ micro‐crystals. Furthermore, white‐light emissions could be obtained using different pump powers in 20%Yb³⁺/1%Tm³⁺/1%Ho³⁺ tri‐doped NaYF₄ micro‐crystals at 980 nm excitation. The pump power‐dependent intensity relationship was studied and relevant energy transfer processes were discussed in detail. The results suggest that Yb³⁺/Tm³⁺/Ho³⁺ tri‐doped NaYF₄ micro‐crystals have potential applications in optoelectronic devices such as photovoltaic, plasma display panel and white‐light‐emitting diodes. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis,density functional theory calculations and luminescence of lanthanide complexes with 2,6‐bis[(3‐methoxybenzylidene)hydrazinocarbonyl] pyridine Schiff base ligand

A pyridine‐diacylhydrazone Schiff base ligand, L = 2,6‐bis[(3‐methoxy benzylidene)hydrazinocarbonyl]pyridine was prepared and characterized by single crystal X‐ray diffraction. Lanthanide complexes, Ln–L, {[LnL(NO₃)₂]NO₃.xH₂O (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy and Er)} were prepared and characterized by elemental analysis, molar conductance, thermal analysis (TGA/DTGA), mass spectrometry (MS), Fourier transform infra‐red (FT‐IR) and nuclear magnetic resonance (NMR) spectroscopy. Ln–L complexes are isostructural with four binding sites provided by two nitro groups along with four coordination sites for L. Density functional theory (DFT) calculations on L and its cationic [LnL(NO₃)₂]⁺ complexes were carried out at the B3LYP/6–31G(d) level of theory. The FT‐IR vibrational wavenumbers were computed and compared with the experimentally values. The luminescence investigations of L and Ln–L indicated that Tb–L and Eu–L complexes showed the characteristic luminescence of Tb(III) and Eu(III) ions. Ln–L complexes show higher antioxidant activity than the parent L ligand.     

Effects of slight structural distortion on the luminescence performance in (Ca1‐xEux)WO4 luminescent materials

(Ca_1‐xEu_x)WO₄ (x = 0–21 mol%) phosphors were prepared using the classical solid‐state reaction method. The influence of Eu³⁺ ion doping on lattice structure was observed using powder X‐ray diffraction and Fourier transform infrared spectroscopy. Furthermore, under this influence, the luminescence properties of all samples were analyzed. The results clearly illustrated that the element europium was successfully incorporated into the CaWO₄ lattice with a scheelite structure in the form of a Eu³⁺ ion, which introduced a slight lattice distortion into the CaWO₄ matrix. These lattice distortions had no effect on phase purity, but had regular effects on the intrinsic luminescence of the matrix and the f–f excitation transitions of Eu³⁺ activators. When the Eu³⁺ concentration was increased to 21 mol%, a local luminescence centre of [WO₄]^2? groups was detected in the matrix and manifested as the decay curves of [WO₄]^2? groups and luminescence changed from single exponential to double exponential fitting. Furthermore, the excitation transitions of Eu³⁺ between different energy levels (such as ⁷F₀→⁵L₆, ⁷F₀→⁵D₂) also produced interesting changes. Based on analysis of photoluminescence spectra and the chromaticity coordinates in this study, it could be verified that the nonreversing energy transfer of [WO₄]^2?→Eu³⁺ was efficient and incomplete.     

Studies on luminescence from a cerium‐doped strontium stannate phosphor

The crystal structure and morphology of Ce³⁺‐doped SrSnO₃ materials prepared using the solid‐state reaction method were extensively characterized using experimental techniques. X‐Ray diffraction results show that the cerium substitution of strontium does not change the structure of the strontium stannate. Raman spectroscopy was used to investigate the microstructures and lattice vibrations. Environmental scanning electron microscopy images showed that phosphors aggregate and their particles form irregular shapes. SrSnO₃ exhibits an intense green emission with a broad band originating from the 5d¹ → 4f¹ transition of cerium. It was observed that, after exposure to beta‐irradiation, the glow curve of this material has two broad thermoluminescence peaks, one centered at ~ 127°C and the other at ~ 245°C for a heating rate of 5 K/s. The kinetic parameters, which include the frequency factor and the activation energy of the material, were calculated using Chen's method, after beta‐irradiation. The fading and reusability of the phosphor were also studied and it was found that the phosphor is suitable for radiation dosimetry. Copyright © 2014 John Wiley & Sons, Ltd.     

Redox luminescence switch based on Mn2+‐doped NaYF4:Yb,Er upconversion nanorods

An redox luminescence switch was developed for the sensing of glutathione (GSH), l ‐cysteine (Cys) or l ‐ascorbic acid (AA) based on redox reaction. The Mn²⁺‐doped NaYF₄:Yb,Er upconversion nanorods (UCNRs) with an emission peak located in the red region were synthesized. The luminescence intensity of the UCNRs could be quenched due to the Mn²⁺ could be oxidized to MnO₂ by KMnO₄. Subsequently, when the AA, GSH or Cys was added into the MnO₂ modified upconversion nanosystem, which could reduced MnO₂ to Mn²⁺ and the luminescence intensity was recovered. The concentration ranges of the nanosystem are 0.500–3.375 mM (R² = 0.99) for AA, 0.6250–11.88 mM (R² = 0.99) for GSH and 0.6250–9.375 mM (R² = 0.99) for Cys, respectively.     

Silica‐modified luminescent LaPO4:Eu@LaPO4@SiO2 core/shell nanorods: Synthesis,structural and luminescent properties

Monoclinic‐type tetragonal LaPO₄:Eu (core) and LaPO₄:Eu@LaPO₄ (core/shell) nanorods (NRs) were successfully prepared using a urea‐based co‐precipitation process under ambient conditions. An amorphous silica layer was coated around the luminescent core/shell NRs via the sol–gel process to improve their solubility and colloidal stability in aqueous and non‐aqueous media. The prepared nano‐products were systematically characterized by X‐ray diffraction pattern, transmission electron microscopy, energy dispersive X‐ray analysis, and FTIR, UV/Vis, and photoluminescence spectroscopy to examine their phase purity, crystal phase, surface chemistry, solubility and luminescence characteristics. The length and diameter of the nano‐products were in the range 80–120 nm and 10–15 nm, respectively. High solubility of the silica‐modified core/shell/Si NRs was found for the aqueous medium. The luminescent core NRs exhibited characteristic excitation and emission transitions in the visible region that were greatly affected by surface growth of insulating LaPO₄ and silica layers due to the multiphonon relaxation rate. Our luminescence spectral results clearly show a distinct difference in intensities for core, core/shell, and core/shell/Si NRs. Highly luminescent NRs with good solubility could be useful candidates for a variety of photonic‐based biomedical applications.     

Intense photon emission induced by fracture of γ–irradiated Dy‐, Tm‐, Sm‐ and Mn‐doped CaSO4 single crystals

When an γ‐irradiated Dy‐, Tm‐, Sm‐ or Mn‐doped CaSO₄ crystal is impulsively deformed, two peaks appear in the ML intensity versus time curve, whereby the first ML peak is found in the deformation region and the second in the post‐deformation region of the crystals. In this study, intensities I_m1 and I_m2 corresponding to first and second ML peaks, respectively, increased linearly with an impact velocity v₀ of the piston used to deform the crystals, and times t_m1 and t_m2 corresponding to the first and second ML peaks, respectively, decreased with impact velocity. Total ML intensity initially increased with impact velocity and then reached a saturation value for higher values of impact velocity. ML intensity increased with increasing γ‐doses and size of crystals. Results showed that the electric field produced as a result of charging of newly‐created surfaces caused tunneling of electrons to the valence band of the hole‐trapping centres. The free holes generated moved in the valence band and their subsequent recombination with electron trapping centres released energy, thereby resulting in excitation of luminescent centres. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and spectral investigations of Cu(II) ion‐doped NaCaAlPO4F3 phosphor

Cu(II) ion‐doped NaCaAlPO₄F₃ phosphor has been synthesized using a solid state reaction method. The prepared sample is characterized by powder X‐ray diffraction, scanning electron microscope, optical absorption, electron paramagnetic resonance photoluminescence and Fourier transform infrared spectroscopy techniques. The crystallite size evaluated from x‐ray diffraction data is in nanometers. Scanning electron microscopy micrographs showed the presence of several irregular shaped particles. From optical absorption and electron paramagnetic resonance spectral data the doped Cu(II) ions are ascribed to distorted octahedral site symmetry. The synthesized phosphor exhibits emission bands in ultraviolet, blue and green regions under the excitation wavelength of 335 nm. The CIE chromaticity coordinates (x = 0.159, y = 0.204) also calculated for the prepared sample from the emission spectrum. The Fourier transform infrared spectroscopy spectrum revealed the characteristic vibrational bands of the prepared phosphor material. Copyright © 2014 John Wiley & Sons, Ltd.     

Pure rhombohedral Bi1‐xEuxPO4 nano‐/micro‐structures: fast synthesis,shape evolution and luminescence properties

BiPO₄ and Eu‐doped BiPO₄ crystals were synthesized via a simple precipitation route at room temperature , employing Bi ( NO₃ ) ₃ and ( NH₄ ) ₂HPO₄ as the reactants , Eu₂O₃ as the dopant and citric acid as a template . X‐ray powder diffraction analyses showed that pure rhombohedral BiPO₄ form was obtained , and was the preferential orientation growth of the crystal . Field emission scanning electron microscope observations showed that the concentration of Bi ^{3 +} obviously changed the products ' morphologies from nanosphere , hollow sphere to hexagonal prism . The acidity of the solution and the contents of citric acid and Eu ^{3 +} ion tailored the size of the final crystals . Effects of concentration of Eu ^{3 +} ion on the luminescence emission intensity were also investigated . Copyright © 2015 John Wiley & Sons, Ltd.     

Solid‐state synthesis and luminescent properties of yellow‐emitting phosphor NaY(MoO4)2:Dy3+ for white light‐emitting diodes

A yellow‐emitting phosphor NaY(MoO₄)₂:Dy³⁺ was synthesized using a solid‐state reaction at 550 °C for 4 h, and its luminescent properties were investigated. Its phase formation was studied using X‐ray powder diffraction analysis, and there were no crystalline phases other than NaY(MoO₄)₂. NaY(MoO₄)₂:Dy³⁺ produced yellow emission under 386 or 453 nm excitation, and the prominent luminescence was yellow (575 nm) due to the ⁴ F_9/2→⁶H_13/2 transition of Dy³⁺. For the 575 nm emission, the excitation spectrum had one broad band and some narrow peaks; the peaks were located at 290, 351, 365, 386, 426, 453 and 474 nm. Emission intensities were influenced by the Dy³⁺ doping content and a concentration quenching effect was observed; the phenomenon was also proved by the decay curves. Moreover, the Commission International de I'Eclairage chromaticity coordinates of NaY(MoO₄)₂:Dy³⁺ showed similar values at different Dy³⁺ concentrations, and were located in the yellow region. Copyright © 2015 John Wiley & Sons, Ltd.     

Rational Design of Core@shell Structured CoSx@Cu2MoS4 Hybridized MoS2/N,S‐Codoped Graphene as Advanced Electrocatalyst for Water Splitting and Zn‐Air Battery

A novel hybrid of small core@shell structured CoS_x@Cu₂MoS₄ uniformly hybridizing with a molybdenum dichalcogenide/N,S‐codoped graphene hetero‐network (CoS_x@Cu₂MoS₄‐MoS₂/NSG) is prepared by a facile route. It shows excellent performance toward the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) in alkaline medium. The hybrid exhibits rapid kinetics for ORR with high electron transfer number of ≈3.97 and exciting durability superior to commercial Pt/C. It also demonstrates great potential with remarkable stability for HER and OER, requiring low overpotential of 118.1 and 351.4 mV, respectively, to reach a current density of 10 mA cm^?2. An electrolyzer based on CoS_x@Cu₂MoS₄‐MoS₂/NSG produces low cell voltage of 1.60 V and long‐term stability, surpassing a device of Pt/C + RuO₂/C. In addition, a Zn‐air battery using cathodic CoS_x@Cu₂MoS₄‐MoS₂/NSG catalyst delivers a high cell voltage of ≈1.44 V and a power density of 40 mW cm^?2 at 58 mA cm^?2, better than the state‐of‐the‐art Pt/C catalyst. These achievements are due to the rational combination of highly active core@shell CoS_x@Cu₂MoS₄ with large‐area and high‐porosity MoS₂/NSG to produce unique physicochemical properties with multi‐integrated active centers and synergistic effects. The outperformances of such catalyst suggest an advanced candidate for multielectrocatalysis applications in metal‐air batteries and hydrogen production.