Structural and Photoluminescence Investigations of Tb3+/Eu3+ Co-Doped Silicate Sol-Gel Glass-Ceramics Containing CaF2 Nanocrystals

In this work, the series of Tb³⁺/Eu³⁺ co-doped xerogels and derivative glass-ceramics containing CaF₂ nanocrystals were prepared and characterized. The in situ formation of fluoride crystals was verified by an X-ray diffraction technique (XRD) and transmission electron microscopy (TEM). The studies of the Tb³⁺/Eu³⁺ energy transfer (ET) process were performed based on excitation and emission spectra along with luminescence decay analysis. According to emission spectra recorded under near-ultraviolet (NUV) excitation (351 nm, ⁷F₆ → ⁵L₉ transition of Tb³⁺), the mutual coexistence of the ⁵D₄ → ⁷F_J (J = 6–3) (Tb³⁺) and the ⁵D₀ → ⁷F_J (J = 0–4) (Eu³⁺) luminescence bands was clearly observed. The co-doping also resulted in gradual shortening of a lifetime from the ⁵D₄ state of Tb³⁺ ions, and the ET efficiencies were varied from η_ET = 11.9% (Tb³⁺:Eu³⁺ = 1:0.5) to η_ET = 22.9% (Tb³⁺:Eu³⁺ = 1:2) for xerogels, and from η_ET = 25.7% (Tb³⁺:Eu³⁺ = 1:0.5) up to η_ET = 67.4% (Tb³⁺:Eu³⁺ = 1:2) for glass-ceramics. Performed decay analysis from the ⁵D₀ (Eu³⁺) and the ⁵D₄ (Tb³⁺) state revealed a correlation with the change in Tb³⁺–Eu³⁺ and Eu³⁺–Eu³⁺ interionic distances resulting from both the variable Tb³⁺:Eu³⁺ molar ratio and their partial segregation in CaF₂ nanophase.     

Effect of Electroless Cu Plating Ti3AlC2 Particles on Microstructure and Properties of Gd2O3/Cu Composites

Ti₃AlC₂ presents a hexagonal layered crystal structure and bridges the gap between metallic and ceramic properties, and Gadolinia (Gd₂O₃) has excellent thermodynamic stability, which make them potentially attractive as dispersive phases for Cu matrix composites. In this paper, Cu@Ti₃AlC₂-Gd₂O₃/Cu composites, Ti₃AlC₂-Gd₂O₃/Cu composites, and Gd₂O₃/Cu composites were prepared by electroless Cu plating, internal oxidation, and vacuum hot press sintering. The microstructure and the effect of the Cu plating on the properties of the Cu@Ti₃AlC₂-Gd₂O₃/Cu composites were discussed. The results showed that a Cu plating with a thickness of about 0.67 μm was successfully plated onto the surface of Ti₃AlC₂ particles. The ex situ Ti₃AlC₂ particles were distributed at the Cu grain boundary, while the in situ Gd₂O₃ particles with a grain size of 20 nm were dispersed in the Cu grains. The electroless Cu plating onto the surface of the Ti₃AlC₂ particles effectively reduces their surfactivity and improves the surface contacting state between the Cu@Ti₃AlC₂ particles and the Cu matrix, and reduces electron scattering, so that the tensile strength reached 378.9 MPa, meanwhile, the electrical conductivity and elongation of the Cu matrix composites was maintained at 93.6 IACS% and 17.6%.     

Calculation of Thermal Expansion Coefficient of Rare Earth Zirconate System at High Temperature by First Principles

Compounds of rare earth zirconates with pyrochlore structure are candidates for the application of thermal barrier coatings of next generation. In order to modify the mechanic properties and maintain the low thermal conductivity, other trivalent rare-earth element substitution is commonly used. Presently, investigation on the evaluation of the property of thermal expansion is attracting more attention. In this paper, a feature parameter of thermal expansion coefficient at high temperature (α_∞) was proposed by combining Grüneisen’s equation and the Debye heat capacity model. Using α_∞ model, the thermal expansion property of different compounds can be easily figured out by first principles. Firstly, α_∞ of ZrO₂, HfO₂, were calculated, and results are in good agreement with the experimental data from the literature. Moreover, α_∞ of La₂Zr₂O₇, Pr₂Zr₂O₇, Gd₂Zr₂O₇, and Dy₂Zr₂O₇ were calculated, and results demonstrated that the model of α_∞ is a useful tool to predict the thermal expansion coefficient at high temperature. Finally, Gd₂Zr₂O₇ with 4 different Yb dopant concentrations (Gd_1-xYb_x)₂Zr₂O₇ (x = 0, 0.125, 0.3125, 0.5) were calculated. Comparing with the experimental data from the literature, the calculation results showed the same tendency with the increasing of Yb concentration.     

Fabricated Flexible Composite for a UV-LED Color Filter and Anti-Counterfeiting Application of Calcium Molybdate Phosphor Synthesized at Room Temperature

Crystalline CaMoO₄ and rare-earth-doped CaMoO₄:RE³⁺ (RE = Tb, Eu) phosphors were synthesized at room temperature using a co-precipitation method. The crystal structure of the synthesized powder was a tetragonal structure with a main diffraction peak (112) phase. When CaMoO₄ was excited at 295 nm, it showed a central peak of 498 nm and light emission in a wide range of 420 to 700 nm. Rare-earth-ion-doped CaMoO₄:Tb³⁺ was excited at 288 nm and a green light emission was observed at 544 nm, and CaMoO₄:Eu³⁺ was excited at 292 nm and a red light emission was observed at 613 nm. To take advantage of the light-emitting characteristics, a flexible composite was manufactured and a color filter that could be used for UV-LEDs was manufactured. In addition, it was suggested that an ink that could be checked only by UV light could be produced and applied to banknotes so as to prevent counterfeiting.     

Synthesis,Characterization and Biodistribution of GdF3:Tb3+@RB Nanocomposites

Herein we report the development of a nanocomposite for X-ray-induced photodynamic therapy (X-PDT) and computed tomography (CT) based on PEG-capped GdF₃:Tb³⁺ scintillating nanoparticles conjugated with Rose Bengal photosensitizer via electrostatic interactions. Scintillating GdF₃:Tb³⁺ nanoparticles were synthesized by a facile and cost-effective wet chemical precipitation method. All synthesized nanoparticles had an elongated “spindle-like” clustered morphology with an orthorhombic structure. The structure, particle size, and morphology were determined by transmission electron microscopy (TEM), X-ray diffraction (XRD), and dynamic light scattering (DLS) analysis. The presence of a polyethylene glycol (PEG) coating and Rose Bengal conjugates was proved by Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), and ultraviolet–visible (UV-vis) analysis. Upon X-ray irradiation of the colloidal PEG-capped GdF₃:Tb³⁺–Rose Bengal nanocomposite solution, an efficient fluorescent resonant energy transfer between scintillating nanoparticles and Rose Bengal was detected. The biodistribution of the synthesized nanoparticles in mice after intravenous administration was studied by in vivo CT imaging.     

H(2)O(2)-induced left ventricular dysfunction in isolated working rat hearts is independent of calcium accumulation

Reactive oxygen species (ROS) and intracellular Ca²⁺ overload play key roles in myocardial ischemia-reperfusion (IR) injury but the relationships among ROS, Ca²⁺ overload and LV mechanical dysfunction remain unclear. We tested the hypothesis that H₂O₂ impairs LV function by causing Ca²⁺ overload by increasing late sodium current (I_Na), similar to Sea Anemone Toxin II (ATX-II). Diastolic and systolic Ca²⁺ concentrations (d[Ca²⁺]_i and s[Ca²⁺]_i) were measured by indo-1 fluorescence simultaneously with LV work in isolated working rat hearts. H₂O₂ (100 μM, 30 min) increased d[Ca²⁺]_i and s[Ca²⁺]_i. LV work increased transiently then declined to 32% of baseline before recovering to 70%. ATX-II (12 nM, 30 min) caused greater increases in d[Ca²⁺]_i and s[Ca²⁺]_i. LV work increased transiently before declining gradually to 17%. Ouabain (80 μM) exerted similar effects to ATX-II. Late I_Na inhibitors, lidocaine (10 μM) or R56865 (2 μM), reduced effects of ATX-II on [Ca²⁺]_i and LV function, but did not alter effects of H₂O₂. The antioxidant, N-(2-mercaptopropionyl)glycine (MPG, 1 mM) prevented H₂O₂-induced LV dysfunction, but did not alter [Ca²⁺]_i. Paradoxically, further increases in [Ca²⁺]_i by ATX-II or ouabain, given 10 min after H₂O₂, improved function. The failure of late I_Na inhibitors to prevent H₂O₂-induced LV dysfunction, and the ability of MPG to prevent H₂O₂-induced LV dysfunction independent of changes in [Ca²⁺]_i indicate that impaired contractility is not due to Ca²⁺ overload. The ability of further increases in [Ca²⁺]_i to reverse H₂O₂-induced LV dysfunction suggests that Ca²⁺ desensitization is the predominant mechanism of ROS-induced contractile dysfunction.     

New Multicolor Tungstate-Molybdate Microphosphors as an Alternative to LED Components

Due to the ongoing need to create phosphors with the appropriate emission color for the production of light emitting diodes, we decided to synthesize a series of multicolour microphosphors with tunable visible emissions, depending on the composition of dopant ions. In this work, we investigated the structure, morphology, and luminescent properties of new molybdate–tungstate phosphors co-doped with Tb³⁺ and Eu³⁺ ions. The conventional high temperature solid state method was used to prepare a series of CaMo_yW_1−yO₄:Eu³⁺_x/Tb³⁺_1−x materials. In order to obtain phosphors with the most promising luminescent properties, the experiment was planned by taking into account the different composition of the matrix and the concentration of the particular dopant ions (Eu³⁺_x/Tb³⁺_1−x, x = 0.001, 0.003, 0.005, 0.007, 0.009). As a result, luminescent materials were obtained with a pure tetragonal crystal structure, the space group of I4₁/a, confirmed by X-ray diffraction (XRD). The size and shape of the particles obtained from the materials were analyzed based on scanning electron microscopy images. Luminescence spectroscopy (excitation and emission spectra, decay lifetimes) was utilized to characterize the luminescence properties of the as-prepared phosphors. The color change of the emission from green-yellow to orange-red was confirmed using the 1931 Comission Internationale de l’Eclairage (CIE) chromaticity coordinates and color correlated temperature (CCT).     

Wide Concentration Range of Tb3+ Doping Influence on Scintillation Properties of (Ce,Tb, Gd)3Ga2Al3O12 Crystals Grown by the Optical Floating Zone Method

To obtain a deeper understand of the energy transfer mechanism between Ce³⁺ and Tb³⁺ ions in the aluminum garnet hosts, (Ce, Tb, Gd)₃Ga₂Al₃O₁₂ (GGAG:Ce, Tb) single crystals grown by the optical floating zone (OFZ) method were investigated systematically in a wide range of Tb³⁺ doping concentration (1–66 at.%). Among those, crystal with 7 at.% Tb reached a single garnet phase while the crystals with other Tb³⁺ concentrations are mixed phases of garnet and perovskite. Obvious Ce and Ga loss can be observed by an energy dispersive X-ray spectroscope (EDS) technology. The absorption bands belonging to both Ce³⁺ and Tb³⁺ ions can be observed in all crystals. Photoluminescence (PL) spectra show the presence of an efficient energy transfer from the Tb³⁺ to Ce³⁺ and the gradually quenching effect with increasing of Tb³⁺ concentration. GGAG: 1% Ce³⁺, 7% Tb³⁺ crystal was found to possess the highest PL intensity under excitation of 450 nm. The maximum light yield (LY) reaches 18,941 pho/MeV. The improved luminescent and scintillation characteristics indicate that the cation engineering of Tb³⁺ can optimize the photoconversion performance of GGAG:Ce.     

Enhanced Cyclability of Cr8O21 Cathode for PEO-Based All-Solid-State Lithium-Ion Batteries by Atomic Layer Deposition of Al2O3

Cr₈O₂₁ can be used as the cathode material in all-solid-state batteries with high energy density due to its high reversible specific capacity and high potential plateau. However, the strong oxidation of Cr₈O₂₁ leads to poor compatibility with polymer-based solid electrolytes. Herein, to improve the cycle performance of the battery, Al₂O₃ atomic layer deposition (ALD) coating is applied on Cr₈O₂₁ cathodes to modify the interface between the electrode and the electrolyte. X-ray photoelectron spectroscopy, scanning electron microscope, transmission electron microscope, and Fourier transform infrared spectroscopy, etc., are used to estimate the morphology of the ALD coating and the interface reaction mechanism. The electrochemical properties of the Cr₈O₂₁ cathodes are investigated. The results show that the uniform and dense Al₂O₃ layer not only prevents the polyethylene oxide from oxidization but also enhances the lithium-ion transport. The 12-ALD-cycle-coated electrode with approximately 4 nm Al₂O₃ layer displays the optimal cycling performance, which delivers a high capacity of 260 mAh g⁻¹ for the 125th cycle at 0.1C with a discharge-specific energy of 630 Wh kg⁻¹.     

Preparation and Electrochemical Properties of LiNi2/3Co1/6Mn1/6O2 Cathode Material for Lithium-Ion Batteries

The cathode material LiNi_2/3Co_1/6Mn_1/6O₂ with excellent electrochemical performance was prepared successfully by a rheological phase method. The materials obtained were characterized by X-ray diffraction, scanning electron microscopy, electrochemical impedance spectroscopy and charge-discharge tests. The results showed that both calcination temperatures and atmosphere are very important factors affecting the structure and electrochemical performance of LiNi_2/3Co_1/6Mn_1/6O₂ material. The sample calcinated at 800 °C under O₂ atmosphere displayed well-crystallized particle morphology, a highly ordered layered structure with low defects, and excellent electrochemical performance. In the voltage range of 2.8–4.3 V, it delivered capacity of 188.9 mAh g⁻¹ at 0.2 C and 130.4 mAh g⁻¹ at 5 C, respectively. The capacity retention also reached 93.9% after 50 cycles at 0.5 C. All the results suggest that LiNi_2/3Co_1/6Mn_1/6O₂ is a promising cathode material for lithium-ion batteries.     

Ion-Enhanced Etching Characteristics of sp2-Rich Hydrogenated Amorphous Carbons in CF4 Plasmas and O2 Plasmas

The sp²-rich hydrogenated amorphous carbon (a-C:H) is widely adopted as hard masks in semiconductor-device fabrication processes. The ion-enhanced etch characteristics of sp²-rich a-C:H films on ion density and ion energy were investigated in CF₄ plasmas and O₂ plasmas in this work. The etch rate of sp²-rich a-C:H films in O₂ plasmas increased linearly with ion density when no bias power was applied, while the fluorocarbon deposition was observed in CF₄ plasmas instead of etching without bias power. The etch rate was found to be dependent on the half-order curve of ion energy in both CF₄ plasmas and O₂ plasmas when bias power was applied. An ion-enhanced etching model was suggested to fit the etch rates of a-C:H in CF₄ plasmas and O₂ plasmas. Then, the etch yield and the threshold energy for etching were determined based on this model from experimental etch rates in CF₄ plasma and O₂ plasma. The etch yield of 3.45 was observed in CF₄ plasmas, while 12.3 was obtained in O₂ plasmas, owing to the high reactivity of O radicals with carbon atoms. The threshold energy of 12 eV for a-C:H etching was obtained in O₂ plasmas, while the high threshold energy of 156 eV was observed in CF₄ plasmas. This high threshold energy is attributed to the formation of a fluorocarbon layer that protects the a-C:H films from ion-enhanced etching.     

1O2-mediated retrograde signaling during late embryogenesis predetermines plastid differentiation in seedlings by recruiting abscisic acid

Plastid development in seedlings of Arabidopsis thaliana is affected by the transfer of ¹O₂-mediated retrograde signals from the plastid to the nucleus and changes in nuclear gene expression during late embryogenesis. The potential impact of these mechanisms on plastid differentiation is maintained throughout seed dormancy and becomes effective only after seed germination. Inactivation of the 2 nuclear-encoded plastid proteins EXECUTER1 and EXECUTER2 blocks ¹O₂-mediated retrograde signaling before the onset of dormancy and impairs normal plastid formation in germinating seeds. This long-term effect of ¹O₂ retrograde signaling depends on the recruitment of abscisic acid (ABA) during seedling development. Unexpectedly, ABA acts as a positive regulator of plastid formation in etiolated and light-grown seedlings.     

Combustion Synthesis and Photoluminescence Properties of Red-Emitting CaAlSiN3:Eu2+ Phosphor for White-LEDs

A combustion synthesis method has been developed for synthesis of Eu²⁺ doped CaAlSiN₃ phosphor and its photoluminescence properties were investigated. Ca, Al, Si, and Eu₂O₃ powders were used as the Ca, Al, Si and Eu sources. The addition of NaN₃, NH₄Cl and Si₃N₄ powders was found to increase significantly the product yield. These powders were mixed and pressed into a compact, which was then wrapped up with an igniting agent (i.e., Mg+Fe₃O₄). The compact was ignited by electrical heating under a N₂ pressure of ≤1.0 MPa. Effects of these experimental parameters on the product yield were investigated and a reaction mechanism was proposed. The synthesized CaAlSiN₃:Eu²⁺ phosphor absorbs light in the region of 200–600 nm and shows a broad band emission in the region of 500–800 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺. The sample doped with Eu²⁺ at the optimized molar ratio of 0.04 is efficiently excited by the blue light (460 nm) and generates emission peaking at ~650 nm with peak emission intensity ~106% of a commercially available phosphor, YAG:Ce³⁺(P46-Y3).The internal quantum efficiency of the synthesized phosphor was measured to be 71%, compared to 69% of the YAG:Ce³⁺ (P46-Y3).     

Red Y2O3:Eu-Based Electroluminescent Device Prepared by Atomic Layer Deposition for Transparent Display Applications

Y₂O_3:Eu is a promising red-emitting phosphor owing to its high luminance efficiency, chemical stability, and non-toxicity. Although Y₂O₃:Eu thin films can be prepared by various deposition methods, most of them require high processing temperatures in order to obtain a crystalline structure. In this work, we report on the fabrication of red Y₂O₃:Eu thin film phosphors and multilayer structure Y₂O₃:Eu-based electroluminescent devices by atomic layer deposition at 300 °C. The structural and optical properties of the phosphor films were investigated using X-ray diffraction and photoluminescence measurements, respectively, whereas the performance of the fabricated device was evaluated using electroluminescence measurements. X-ray diffraction measurements show a polycrystalline structure of the films whereas photoluminescence shows emission above 570 nm. Red electroluminescent devices with a luminance up to 40 cd/m² at a driving frequency of 1 kHz and an efficiency of 0.28 Lm/W were achieved.     

Study of Construction and Performance on Photoelectric Devices of Cs–Pb–Br Perovskite Quantum Dot

White LEDs were encapsulated using Cs₄PbBr₆ quantum dots and Gd₂O₃:Eu red phosphor as lamp powder. Under the excitation of a GaN chip, the color coordinates of the W-LED were (0.33, 0.34), and the color temperature was 5752 K, which is close to the color coordinate and color temperature range of standard sunlight. The electric current stability was excellent with an increase in the electric current, voltage, and luminescence intensity of the quantum dots and phosphors by more than 10 times. However, the stability of the quantum dots was slightly insufficient over long working periods. The photocatalytic devices were constructed using TiO₂, CsPbBr₃, and NiO as an electron transport layer, light absorption layer, and catalyst, respectively. The Cs–Pb–Br-based perovskite quantum dot photocatalytic devices were constructed using a two-step spin coating method, one-step spin coating method, and full PLD technology. In order to improve the water stability of the device, a hydrophobic carbon paste and carbon film were selected as the hole transport layer. The TiO₂ layer and perovskite layer with different thicknesses and film forming qualities were obtained by changing the spin coating speed. The influence of the spin coating speed on the device’s performance was explored through SEM and a J–V curve to find the best spin coating process. The device constructed by the two-step spin coating method had a higher current density but no obvious increase in the current density under light, while the other two methods could obtain a more obvious light response, but the current density was very low.     

Microstructure Evolution and Properties of an In-Situ Nano-Gd2O3/Cu Composite by Powder Metallurgy

Gadolinia (Gd₂O₃) is potentially attractive as a dispersive phase for copper matrix composites due to its excellent thermodynamic stability. In this paper, a series of 1.5 vol% nano-Gd₂O₃/Cu composites were prepared via an internal oxidation method followed by powder metallurgy in the temperature range of 1123–1223 K with a holding time of 5–60 min. The effects of processing parameters on the microstructure and properties of the composites were analyzed. The results showed that the tensile strength and conductivity of the nano-Gd₂O₃/Cu composite have a strong link with the microporosity and grain size, while the microstructure of the composite was determined by the sintering temperature and holding time. The optimal sintering temperature and holding time for the composite were 1173 K and 30 min, respectively, under which a maximum ultimate tensile strength of 317 MPa was obtained, and the conductivity was 96.8% IACS. Transmission electron microscopy observations indicated that nano-Gd₂O₃ particles with a mean size of 76 nm formed a semi-coherent interface with the copper matrix. In the nano-Gd₂O₃/Cu composite, grain-boundary strengthening, Orowan strengthening, thermal mismatch strengthening, and load transfer strengthening mechanisms occurred simultaneously.     

Photocatalytic Water Splitting for Hydrogen Production with Gd2MSbO7 (M = Fe,In, Y) Photocatalysts under Visible Light Irradiation

Novel photocatalysts Gd₂FeSbO₇, Gd₂InSbO₇ and Gd₂YSbO₇ were synthesized by the solid state reaction method for the first time. A comparative study about the structural and photocatalytic properties of Gd₂MSbO₇ (M = Fe, In, Y) was reported. The results showed that Gd₂FeSbO₇, Gd₂InSbO₇ and Gd₂YSbO₇ crystallized with the pyrochlore-type structure, cubic crystal system and space group Fd3m. The lattice parameter a for Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇ was 10.276026 Å, 10.449546 Å or 10.653651 Å. The band gap of Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇ was estimated to be 2.151 eV, 2.897 eV or 2.396 eV. For the photocatalytic water-splitting reaction, H₂ or O₂ evolution was observed from pure water with Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇ as catalyst under visible light irradiation (wavelength > 420 nm). Moreover, H₂ or O₂ also spilt by using Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇ as catalyst from CH₃OH/H₂O or AgNO₃/H₂O solutions under visible light irradiation (λ > 420 nm). Gd₂FeSbO₇ showed the highest activity compared with Gd₂InSbO₇ or Gd₂YSbO₇. At the same time, Gd₂InSbO₇ showed higher activity compared with Gd₂YSbO₇. The photocatalytic activities were further improved under visible light irradiation with Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇ being loaded by Pt, NiO or RuO₂. The effect of Pt was better than that of NiO or RuO₂ for improving the photocatalytic activity of Gd₂FeSbO₇, Gd₂InSbO₇ or Gd₂YSbO₇.     

Synthesis of Green-Emitting (La,Gd)OBr:Tb3+ Phosphors

Green-emitting phosphors based on lanthanum-gadolinium oxybromide were synthesized in a single phase form by the conventional solid state reaction method, and photoluminescence properties of them were characterized. The excitation peak wavelength of (La_1-xGd_x)OBr:Tb³⁺ shifted to the shorter wavelength side with the increase in the crystal field around the Tb³⁺ ions by doping Gd³⁺ ions into the La³⁺ site, and, as a result, the green emission intensity was successfully enhanced. The maximum emission intensity was obtained for (La_0.95Gd_0.05)OBr:5%Tb³⁺, where the relative emission intensity was 45% of that of a commercial green-emitting LaPO₄:Ce³⁺,Tb³⁺ phosphor.     

Direct Electrochemistry and Electrocatalysis of Horseradish Peroxidase Immobilized in a DNA/Chitosan-Fe3O4 Magnetic Nanoparticle Bio-Complex Film

A DNA/chitosan-Fe₃O₄ magnetic nanoparticle bio-complex film was constructed for the immobilization of horseradish peroxidase (HRP) on a glassy carbon electrode. HRP was simply mixed with DNA, chitosan and Fe₃O₄ nanoparticles, and then applied to the electrode surface to form an enzyme-incorporated polyion complex film. Scanning electron microscopy (SEM) was used to study the surface features of DNA/chitosan/Fe₃O₄/HRP layer. The results of electrochemical impedance spectroscopy (EIS) show that Fe₃O₄ and enzyme were successfully immobilized on the electrode surface by the DNA/chitosan bio-polyion complex membrane. Direct electron transfer (DET) and bioelectrocatalysis of HRP in the DNA/chitosan/Fe₃O₄ film were investigated by cyclic voltammetry (CV) and constant potential amperometry. The HRP-immobilized electrode was found to undergo DET and exhibited a fast electron transfer rate constant of 3.7 s⁻¹. The CV results showed that the modified electrode gave rise to well-defined peaks in phosphate buffer, corresponding to the electrochemical redox reaction between HRP(Fe^(III)) and HRP(Fe^(II)). The obtained electrode also displayed an electrocatalytic reduction behavior towards H₂O₂. The resulting DNA/chitosan/Fe₃O₄/HRP/glassy carbon electrode (GCE) shows a high sensitivity (20.8 A·cm⁻²·M⁻¹) toward H₂O₂. A linear response to H₂O₂ measurement was obtained over the range from 2 μM to 100 μM (R² = 0.99) and an amperometric detection limit of 1 μM (S/N = 3). The apparent Michaelis-Menten constant of HRP immobilized on the electrode was 0.28 mM. Furthermore, the electrode exhibits both good operational stability and storage stability.