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Colloidal semiconductor nanocrystals are promising candidates for quantum light sources, yet their application has been impeded by photoluminescence instability due to blinking and spectral diffusion. This study introduces a new category of cube-shaped CdSe/CdS core/shell nanocrystals with exceptionally stable photoluminescence characteristics. Under continuous excitation, the emissive quantum state remained consistent without alterations of the charge state for 4000 s, and the average photon energy variation stayed within the bounds of spectral resolution throughout this extended duration. Systematic examination of single-nanocrystal photoluminescence, upon variation of the core and shell dimensions, revealed that a thicker CdS shell and increased core edge length significantly curtail spectral diffusion, considering that the nanocrystals possess well-controlled CdSe-CdS and facet-ligand interfaces. This study advances the optimization of colloidal semiconductor nanocrystals as high-performance quantum light sources.
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Despite its effectiveness in eliminating cancer cells, ferroptosis is hindered by the high natural antioxidant glutathione (GSH) levels in the tumor microenvironment. Herein, we developed a spatially asymmetric nanoparticle, Fe3O4@DMS&PDA@MnO2-SRF, for enhanced ferroptosis. It consists of two subunits: Fe3O4 nanoparticles coated with dendritic mesoporous silica (DMS) and PDA@MnO2 (PDA: polydopamine) loaded with sorafenib (SRF). The spatial isolation of the Fe3O4@DMS and PDA@MnO2-SRF subunits enhances the synergistic effect between the GSH-scavengers and ferroptosis-related components. First, the increased exposure of the Fe3O4 subunit enhances the Fenton reaction, leading to increased production of reactive oxygen species. Furthermore, the PDA@MnO2-SRF subunit effectively depletes GSH, thereby inducing ferroptosis by the inactivation of glutathione-dependent peroxidases 4. Moreover, the SRF blocks Xc- transport in tumor cells, augmenting GSH depletion capabilities. The dual GSH depletion of the Fe3O4@DMS&PDA@MnO2-SRF significantly weakens the antioxidative system, boosting the chemodynamic performance and leading to increased ferroptosis of tumor cells.
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Ferroptose , Nanopartículas , Neoplasias , Humanos , Compostos de Manganês/farmacologia , Óxidos , Antioxidantes , Glutationa , Dióxido de Silício , Linhagem Celular Tumoral , Neoplasias/tratamento farmacológico , Microambiente TumoralRESUMO
Organic transistors based on organic semiconductors together with quantum dots (QDs) are attracting more and more interest because both materials have excellent optoelectronic properties and solution processability. Electronics based on nontoxic QDs are highly desired considering the potential health risks but are limited by elevated surface defects, inadequate stability, and diminished luminescent efficiency. Herein, organic synaptic transistors based on environmentally friendly ZnSe/ZnS core/shell QDs with passivating surface defects are developed, exhibiting optically programmable and electrically erasable characteristics. The synaptic transistors feature linear multibit storage capability and wavelength-selective memory function with a retention time above 6000 s. Various neuromorphic applications, including memory enhancement, optical communication, and memory consolidation behaviors, are simulated. Utilizing an established neuromorphic model, accuracies of 92% and 91% are achieved in pattern recognition and complicated electrocardiogram signal processing, respectively. This research highlights the potential of environmentally friendly QDs in neuromorphic applications and health monitoring.
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CuInS2 (CIS) quantum dots (QDs) represent an important class of colloidal materials with broad application potential, owing to their low toxicity and unique optical properties. Although coating with a ZnS shell has been identified as a crucial method to enhance optical performance, the occurrence of cation exchange has historically resulted in the unintended formation of Cu-In-Zn-S alloyed QDs, causing detrimental blueshifts in both absorption and photoluminescence (PL) spectral profiles. In this study, we present a facile one-pot synthetic strategy aimed at impeding the cation exchange process and promoting ZnS shell growth on CIS core QDs. The suppression of both electron-phonon interaction and Auger recombination by the rigid ZnS shell results in CIS/ZnS core/shell QDs that exhibit a wide near-infrared (NIR) emission coverage and a remarkable PL quantum yield of 92.1%. This effect boosts the fabrication of high-performance, QD-based NIR light-emitting diodes with the best stability of such materials so far.
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We study the molecular beam epitaxy of rock-salt ScN on the wurtzite GaN(11Ì 00) surface. To this end, ScN is grown on freestanding GaN(11Ì 00) substrates and self-assembled GaN nanowires exhibiting (11Ì 00) sidewalls. On both substrates, ScN crystallizes twin-free thanks to a specific epitaxial relationship, namely ScN(110)[001]â¥GaN(11Ì 00)[0001], providing a congruent, low-symmetry interface. The 13.1% uniaxial lattice mismatch occurring in this orientation mostly relaxes within the first few monolayers of growth by forming a near-coincidence site lattice, where 7 GaN planes coincide with 8 ScN planes, leaving the ScN surface nearly free of extended defects. Overgrowth of the ScN with GaN leads to a kinetic stabilization of the zinc blende phase, that rapidly develops wurtzite inclusions nucleating on {111} nanofacets, commonly observed during zinc blende GaN growth. Our ScN/GaN(11Ì 00) platform opens a new route for the epitaxy of twin-free metal-semiconductor heterostructures including closely lattice-matched GaN, ScN, HfN, and ZrN compounds.
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An interplay between Pd and PdO and their spatial distribution inside the particles are relevant for numerous catalytic reactions. Using in situ time-resolved X-ray absorption spectroscopy (XAS) supported by theoretical simulations, a mechanistic picture of the structural evolution of 2.3 nm palladium nanoparticles upon their exposure to molecular oxygen is provided. XAS analysis revealed the restructuring of the fcc-like palladium surface into the 4-coordinated structure of palladium oxide upon absorption of oxygen from the gas phase and formation of core@shell Pd@PdO structures. The reconstruction starts from the low-coordinated sites at the edges of palladium nanoparticles. Formation of the PdO shell does not affect the average PdâPd coordination numbers, since the decrease of the size of the metallic core is compensated by a more spherical shape of the oxidized nanoparticles due to a weaker interaction with the support. The metallic core is preserved below 200 °C even after continuous exposure to oxygen, with its size decreasing insignificantly upon increasing the temperature, while above 200 °C, bulk oxidation proceeds. The PdâPd distances in the metallic phase progressively decrease upon increasing the fraction of the Pd oxide due to the alignment of the cell parameters of the two phases.
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Memristors-based integrated circuits for emerging bio-inspired computing paradigms require an integrated approach utilizing both volatile and nonvolatile memristive devices. Here, an innovative architecture comprising of 1D CVD-grown core-shell heterostructures (CSHSs) of MoO2-MoS2 is employed as memristors manifesting both volatile switching (with high selectivity of 107 and steep slope of 0.6 mV decade-1) and nonvolatile switching phenomena (with Ion/Ioff ≈103 and switching speed of 60 ns). In these CSHSs, the metallic core MoO2 with high current carrying capacity provides a conformal and immaculate interface with semiconducting MoS2 shells and therefore it acts as a bottom electrode for the memristors. The power consumption in volatile devices is as low as 50 pW per set transition and 0.1 fW in standby mode. Voltage-driven current spikes are observed for volatile devices while with nonvolatile memristors, key features of a biological synapse such as short/long-term plasticity and paired pulse facilitation are emulated suggesting their potential for the development of neuromorphic circuits. These CSHSs offer an unprecedented solution for the interfacial issues between metallic electrodes and the layered materials-based switching element with the prospects of developing smaller footprint memristive devices for future integrated circuits.
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Lithium (Li) metal batteries have attracted considerable research attention due to their exceptionally high theoretical capacity. However, the commercialization of Li metal batteries faces challenges, primarily attributed to uncontrolled growth of Li dendrites, which raises safety concerns and lowers coulombic efficiency. To mitigate Li dendrites growth and attain dense Li deposition, the hybrid SiO2-Cu2O lithiophilic film applied to a 3D copper foam current collector is developed to regulate the interfacial properties for achieving even and dense Li deposition. The SiO2-Cu2O possesses strong Li+ trapping capability through strong lithiophilicity from Cu2O. Additionally, the SiO2-Cu2O enables uniform ion diffusion through the domain-limiting effect of the holes in the SiO2 layer, inducing an even and dense Li plating/stripping behavior at a large capacity. Furthermore, the SiO2 layer promotes the formation of an initial high inorganic content Solid Electrolyte Interphase (SEI) through selective preferential binding with anion and solvent molecules. When the SiO2-Cu2O@Li anode is coupled with a LiFePO4 (LFP) cathode, the resulting full cell exhibits superior cycling stability and rate performance. These results provide a facile approach to construct a lithiophilic current collector for practical Li metal anodes.
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Functionalization of quantum dots (QDs) via ligand exchange is prone to debase their photoluminescence quantum yield (PL QY) owing to the unavoidable surface damage by excess reactants, and even worse in aqueous medium. Herein, the oligomeric zinc thiolate as the multidentate hydrophilic ligand featuring facile synthetic protocol is proposed. A simple reaction between ZnCl2 and 3-mercaptopropionic acid produces oligomeric ligands containing 3-6 zinc thiolate units, where the terminal moieties provide multidentate anchoring to the surface as well as hydrophilicity. 2D proton nuclear Overhauser effect spectroscopy (2D 1H NOESY) and X-ray photoelectron spectroscopy (XPS) reveal that the oligomeric zinc thiolate ligands adsorb on the surface via multidentate metal carboxylate bindings without destruction of molecular structure, regardless of partial dissociation of thiolate branches in aqueous phase. Enhanced binding affinity granted by the multidentate nature allows for the effective exchange of original surface ligands without considerable surface deterioration. The zinc thiolate-capped Cd-free aqueous QDs exhibit a high photoluminescence quantum yield of ≈90% and extended stability against long-term storage and photochemical stress.
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Core-shell gallium nitride (GaN)-based nanowires offer noteworthy opportunities for innovation in high-frequency opto- and microelectronics. This work delves deeply into the physical properties of crystalline GaN nanowires with aluminum and hafnium oxide shells. Particular attention is paid to partial coverage of nanowires, resulting with exceptional properties. First, the crystal lattice relaxation is observed by X-ray diffraction, photoluminescence, and Raman spectroscopy measurements. A high potential of partial coverage for optoelectronic applications is revealed with photo- and cathodoluminescence spectra along with an exploration of their temperature dependency. Next, the study focuses on understanding the mechanisms behind the observed enhancement of the luminescence efficiency. It is confirmed that nanowires are effectively protected against photoadsorption using partial coatings. This research advances the frontiers of nanotechnology, investigating the benefits of partial coverage, and shedding light on its complex interaction with cores.
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Exploration of multifunctional integrated catalysts is of great significance for photocatalysis toward practical application. Herein, a 1D confined nanoreactor with a heterogeneous core-shell structure is designed for synergies of efficient catalysis and temperature monitoring by custom encapsulation of Z-scheme heterojunction CuS quantum dots/BiVO4 (CuS QDs/BiVO4) and Y2O2S-Er, Yb. The dispersed active sites created by the QDs with high surface energy improve the mass transfer efficiency, and the efficient electron transport channels at the heterogeneous interface extend the carrier lifetime, which endows the nanoreactor with excellent catalytic performance. Meanwhile, real-time temperature monitoring is realized based on the thermally coupled levels 2H11/2/4S3/2â4I15/2 of Er3+ using fluorescence intensity ratio, which enables the monitorable photocatalysis. Furthermore, the nanoreactor with a multidimensional structure increases effective intermolecular collisions to facilitate the catalytic process by restricting the reaction within distinct enclosed spaces and circumvents potential unknown interaction effects. The design of multi-space nanoconfined reactors opens up a new avenue to modulate catalyst function, providing a unique perspective for photocatalytic applications in the mineralization of organic pollutants, hydrogen production, and nitrogen fixation.
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Constructing composite catalysts with refined geometric control and optimal electronic structure provides a promising route to enhance electrocatalytic performance toward the oxygen evolution reaction (OER). Herein, a composite catalyst is prepared with multiple components using chemical vapour deposition method to transform crystalline NiFe2O4 into crystalline NiFe2O4@amorphous S-NiFe2O4 with core-shell structure (C-NiFe2O4@A-S-NiFe2O4), and Fe-NiOOH nanoparticles are subsequently in situ generated on its surface during the process of electrocatalytic OER. The C-NiFe2O4@A-S-NiFe2O4 catalyst exhibits a low overpotential of 275 mV while possessing an excellent stability for 500 h at 10 mA cm-2. The anion exchange membrane water electrolyzer with C-NiFe2O4@A-S-NiFe2O4 anode catalyst obtains a current density of 4270 mA cm- 2 at 2.0 V. Further, in situ Raman spectroscopy result demonstrates that in situ generated Fe-NiOOH nanoparticles are revealed to act as the catalytic active phase for catalyzing the OER. Besides, introducing A-S-NiFe2O4 in C-NiFe2O4@A-S-NiFe2O4 facilitates the formation of Fe-NiOOH nanoparticles with high-valency Ni, thus increasing the proportion of lattice oxygen-participated OER. This work not only provides an alternative strategy for the design of high-performance catalysts, but also lays a foundation for the exploration of catalytic mechanisms.
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Low-cost and high-efficiency non-precious metal-based oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional catalysts are the key to promoting the commercial application of metal-air batteries. Herein, a highly efficient catalyst of Fe0.18Co0.82 alloy anchoring on the nitrogen-doped porous carbon hollow sphere (FexCo1-x/N-C) is intelligently designed by spray pyrolysis (SP). The zinc in the SP-derived metal oxides and metal-organic framework volatilize at high temperature to construct a hierarchical porous structure with abundant defects and fully exposes the FeCo nanoparticles which uniformly anchor on the carbon substrate. In this structure, the coexistence of Fe0.18Co0.82 alloy and binary metal active sites (Fe-Nx/Co-Nx) guarantees the Fe0.2Co0.8/N-C catalyst exhibiting an excellent half-wave potential (E1/2 â 0.84 V) superior to 20% Pt/C for ORR and a suppressed overpotential (280 mV) than RuO2 for OER. Assembled rechargeable Zn-air battery (RZAB) demonstrates a promising specific capacity of 807.02 mAh g-1, peak power density of 159.08 mW cm-2 and durability without electrolyte circulation (550 h). This work proposes the design concept of utilizing an oxide core to in situ consume the porous carbon shell for anchoring metal active sites and construct defects, which benefits from spray pyrolysis in achieving precise control of the alloy structure and mass preparation.
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Bacteria-induced keratitis is a major cause of corneal blindness in both developed and developing countries. Instillation of antibiotic eyedrops is the most common management of bacterial keratitis but usually suffers from low bioavailability (i.e., <5%) and frequent administration, due to the existence of corneal epithelial barrier that prevents large and hydrophilic drug molecules from entering the cornea, and the tear film on corneal surface that rapidly washes drug away from the cornea. Here, a self-implantable core-shell microneedle (MN) patch with programmed drug release property to facilitate bacterial keratitis treatment is reported. The pH-responsive antimicrobial nanoparticles (NPs), Ag@ZIF-8, which are capable of producing antibacterial metal ions in the infected cornea and generating oxidative stress in bacteria, are loaded in the dissolvable core, while the anti-angiogenic drug, rapamycin (Rapa), is encapsulated in the biodegradable shell, thereby enabling rapid release of Ag@ZIF-8 NPs and sustained release of Rapa after corneal insertion. Owing to the programmed release feature, one single administration of the core-shell MN patch in a rat model of bacterial keratitis, can achieve satisfactory antimicrobial activity and superior anti-angiogenic and anti-inflammation effects as compared to daily topical eyedrops, indicating a great potential for the infectious keratitis therapy in clinics.
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Liberação Controlada de Fármacos , Ceratite , Agulhas , Animais , Ceratite/tratamento farmacológico , Ceratite/microbiologia , Ratos , Sirolimo/administração & dosagem , Antibacterianos/farmacologia , Antibacterianos/administração & dosagem , Antibacterianos/química , Antibacterianos/uso terapêutico , Ratos Sprague-Dawley , Córnea/metabolismo , Córnea/efeitos dos fármacos , Prata/química , Sistemas de Liberação de MedicamentosRESUMO
Due to their anisotropy, 1D semiconductor nanorod-based materials have attracted much attention in the process of hydrogen production by solar energy. Nevertheless, the rational design of 1D heterojunction materials and the modulation of photo-generated electron-hole transfer paths remain a challenge. Herein, a ZnxCd1-xS@ZnS/MoS2 core-shell nanorod heterojunction is precisely constructed via in situ growth of discontinuous ZnS shell and MoS2 NCs on the ZnâCdâS nanorods. Among them, the Zn vacancy in the ZnS shell builds the defect level, and the nanoroelded MoS2 builds the electron transport site. The optimized photocatalyst shows significant photocatalytic activity without Platinum as an auxiliary catalyst, mainly due to the new interfacial charge transfer channel constructed by the shell vacancy level, the vertical separation and the de-accumulation process of photo-generated electrons and photo-generated holes. At the same time, spectral analysis, and density functional theory (DFT) calculations fully prove that shortening difference of speed between the photogenerated electron and hole movement process is another key factor to enhance the photocatalytic performance. This study provides a new path for the kinetic design of enhanced carrier density by shortening the carrier retention time of 1D heterojunction photocatalysts with improved photocatalytic performance.
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Attempts are made to design a system for sustaining the delivery of copper ions into diabetic wounds and induce angiogenesis with minimal dose-dependent cytotoxicity. Here, a dual drug-delivery micro/nanofibrous core-shell system is engineered using polycaprolactone/sodium sulfated alginate-polyvinyl alcohol (PCL/SSA-PVA), as core/shell parts, by emulsion electrospinning technique to optimize sustained delivery of copper oxide nanoparticles (CuO NP). Herein, different concentrations of CuO NP (0.2, 0.4, 0.8, and 1.6%w/w) are loaded into the core part of the core-shell system. The morphological, biomechanical, and biocompatibility properties of the scaffolds are fully determined in vitro and in vivo. The 0.8%w/w CuO NP scaffold reveals the highest level of tube formation in HUVEC cells and also upregulates the pro-angiogenesis genes (VEGFA and bFGF) expression with no cytotoxicity effects. The presence of SSA and its interaction with CuO NP, and also core-shell structure sustain the release of the nanoparticles and provide a non-toxic microenvironment for cell adhesion and tube formation, with no sign of adverse immune response in vivo. The optimized scaffold significantly accelerates diabetic wound healing in a rat model. This study strongly suggests the 0.8%w/w CuO NP-loaded PCL/SSA-PVA as an excellent diabetic wound dressing with significantly improved angiogenesis and wound healing.
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Cobre , Células Endoteliais da Veia Umbilical Humana , Nanofibras , Cicatrização , Cobre/química , Cicatrização/efeitos dos fármacos , Animais , Nanofibras/química , Humanos , Emulsões/química , Neovascularização Fisiológica/efeitos dos fármacos , Diabetes Mellitus Experimental/tratamento farmacológico , Alicerces Teciduais/química , Ratos , Nanopartículas/química , Masculino , Ratos Sprague-Dawley , Poliésteres/química , AngiogêneseRESUMO
Metal thiophosphites have recently emerged as a hot electrode material system for sodium-ion batteries because of their large theoretical capacity. Nevertheless, the sluggish electrochemical reaction kinetics and drastic volume expansion induced by the low conductivity and inherent conversion-alloying reaction mechanism, require urgent resolution. Herein, a distinctive porous core-shell structure, denoted as SnPS3@C, is controllably synthesized by synchronously phosphor-sulfurizing resorcinol-formaldehyde-coated tin metal-organic framework cubes. Thanks to the 3D porous structure, the ion diffusion kinetics are accelerated. In addition, SnPS3@C features a tough protective carbon layer, which improves the electrochemical activity and reduces the polarization. As expected, the as-prepared SnPS3@C electrode exhibits superior electrochemical performance compared to pure SnPS3, including excellent rate capability (1342.4 and 731.1 mAh g-1 at 0.1 and 4 A g-1, respectively), and impressive long-term cycling stability (97.9% capacity retention after 1000 cycles at 1 A g-1). Moreover, the sodium storage mechanism is thoroughly studied by in-situ and ex-situ characterizations. This work offers an innovative approach to enhance the energy storage performance of metal thiophosphite materials through meticulous structural design, including the introduction of porous characteristics and core-shell structures.
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The construction of stable and efficient nanocomposites with low addition and light weight has always been the goal pursued in the field of electromagnetic wave (EMW) absorption. In this study, the Co@CNTs nanocomposites with Co nanoparticles (13 nm) nanoconfined in the carbon nanotube (CNT) are successfully synthesized by a simple hydrothermal method and phenolic assisted pyrolysis method. The degree of graphitization of CNTs and the microstructure of Co nanoparticles can be effectively regulated by controlling the calcination temperature. The sample calcined at 700 °C can obtain excellent absorption performance at a low filling capacity of 10 wt.%: the minimum reflection loss (RL) is -41.2 dB and the effective absorption bandwidth (EAB) reaches a maximum width of 14.2 GHz. When the sample thickness is only 2.2 mm, the EAB of <-20 dB reaches 8.3 GHz, which is the maximum EAB of most current Co-based absorbers. In particular, the polarization and ferromagnetic coupling behaviors are elucidated in depth with the aid of electromagnetic field simulations using the High-Frequency Structure Simulator (HFSS). This work provides a new nanoconfinement strategy for constructing the Co@CNTs nanocomposites as lightweight and ultra-broadband absorbing materials for EMW protection and EMW pollution control.
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1D nanowire networks, sharing similarities of structure, information transfer, and computation with biological neural networks, have emerged as a promising platform for neuromorphic systems. Based on brain-like structures of 1D nanowire networks, neuromorphic synaptic devices can overcome the von Neumann bottleneck, achieving intelligent high-efficient sensing and computing function with high information processing rates and low power consumption. Here, high-temperature neuromorphic synaptic devices based on SiC@NiO core-shell nanowire networks optoelectronic memristors (NNOMs) are developed. Experimental results demonstrate that NNOMs attain synaptic short/long-term plasticity and modulation plasticity under both electrical and optical stimulation, and exhibit advanced functions such as short/long-term memory and "learning-forgetting-relearning" under optical stimulation at both room temperature and 200 °C. Based on the advanced functions under light stimulus, the constructed 5 × 3 optoelectronic synaptic array devices exhibit a stable visual memory function up to 200 °C, which can be utilized to develop artificial visual systems. Additionally, when exposed to multiple electronic or optical stimuli, the NNOMs effectively replicate the principles of Pavlovian classical conditioning, achieving visual heterologous synaptic functionality and refining neural networks. Overall, with abundant synaptic characteristics and high-temperature thermal stability, these neuromorphic synaptic devices offer a promising route for advancing neuromorphic computing and visual systems.
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Designing a reasonable heterojunction is an efficient path to improve the separation of photogenerated charges and enhance photocatalytic activity. In this study, Cu2-xS@NiFe-LDH hollow nanoboxes with core-shell structure are successfully prepared. The results show that Cu2-xS@NiFe-LDH with broad-spectrum response has good photothermal and photocatalytic activity, and the photocatalytic activity and stability of the catalyst are enhanced by the establishment of unique hollow structure and core-shell heterojunction structure. Transient PL spectra (TRPL) indicates that constructing Cu2-xS@NiFe-LDH heterojunction can prolong carrier lifetime obviously. Cu2-xS@NiFe-LDH shows a high photocatalytic hydrogen production efficiency (5176.93 µmol h-1 g-1), and tetracycline degradation efficiency (98.3%), and its hydrogen production rate is ≈10-12 times that of pure Cu2-xS and NiFe-LDH. In situ X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) provide proofs of the S-scheme electron transfer path. The S-scheme heterojunction achieves high spatial charge separation and exhibits strong photoredox ability, thus improving the photocatalytic performance.