30 April 2023, Volume 54 Issue 4

    

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Focuses & Concerns(The Project of Chongqing Press Fund in 2022)
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  Preparation of nano-SiO₂ microspheres/fluoroacrylate coatings and the anti-corrosive properties against snow melting salt

  SONG Lifang, LI Kaiyuan, WEI Yansong, ZHANG Ting, XIA Huiyun, NIU Yanhui

  Jorunal of Functional Materials. 2023, 54(4): 4001-4007. https://doi.org/10.3969/j.issn.1001-9731.2023.04.001

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  Dodecafluoroheptyl methacrylate (DFMA) and other acrylate monomers were used as raw materials to prepare a fluoroacrylate copolymeric emulsion by semi-continuous emulsion polymerization. A certain amount of silane was used to obtain surface modified nano-SiO₂ microspheres. Appropriate amount of filler and additives were added and mechanically stirred to obtain nano-SiO₂ microspheres modified fluoroacrylate coatings. FT-IR and XRD show that the silane was grafted on the surface of nano-SiO₂ microspheres and the crystal form was not changed. The results of the mechanical properties, chemical media corrosion resistance and snow melting salt corrosion resistance of the composite coating show that when the addition amount of nano-SiO₂ microspheres is 3%, the comprehensive performance of the composite coating is the best. The pencil hardness is 5 H, the bond strength is 1.88 MPa, and the impact resistance height is more than 50 cm. The contact angle of the coating can reach 110°, and the water absorption is only 0.72%. The corrosion percentage against H₂SO₄(10%), NaOH(10%) and NaCl(5%) were 17%, 11% and 11%, respectively. Compared with the unmodified fluoroacrylate coating and the commercially available coating, under the setting snow melting salt corrosion conditions, the chromatic aberration, gloss and surface condition of the coating remain stable, and the decrease of compressive strength and carbonization depth of the concrete specimen was slowed down.
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  Near-infrared(NIR)-Ⅱ luminescence properties of CaF₂:20Yb2Er/Na@CaF₂:Ce nanomaterial

  LU Zhao, WEI Huixin, ZHAI Chunpeng

  Jorunal of Functional Materials. 2023, 54(4): 4008-4013. https://doi.org/10.3969/j.issn.1001-9731.2023.04.002

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  In this paper, CaF₂:20Yb2Er/Na@CaF₂:Ce nanoparticles were prepared by thermal decomposition method, its NIR-Ⅱ luminescence performance and fluorescence lifetime were explored. The results show that the NIR-Ⅱ luminescence intensity is about 68 times that of CaF₂:20Yb2Er when excited by 980 nm light source. And the fluorescence lifetime at 1 525 nm is 2.29 ms. In this sample, Yb³⁺ acts as sensitizer, Er³⁺ acts as activator, the local symmetry of the crystal field is destroyed after Na⁺ co-doping, and the fluorescence quenching in the luminescence center can be minimized with the construction of core-shell structure. After the introduction of Ce³⁺ into the shell structure, cross-relaxation effect generated from Er³⁺ and Ce³⁺ exists at the interface. Thus it can be seen that the combination of ion co-doping and core-shell structure construction is more conducive to the improvement of the NIR-Ⅱ luminescence performance. The CaF₂:20Yb2Er/Na@CaF₂:Ce nanoparticles have potential applications in the field of bioimaging.
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  High β phase ionic liquid / polyvinylidene fluoride dielectric material and its fused deposition molding

  MA Anan, ZHANG Huiying, CHEN Ye, WANG Huaping

  Jorunal of Functional Materials. 2023, 54(4): 4014-4019. https://doi.org/10.3969/j.issn.1001-9731.2023.04.003

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  IL/PVDF composites are prepared by melt blending of polyvinylidene fluoride (PVDF) and ionic liquid (IL), and the crystal structure is analyzed. The results indicate that the interaction between the ionic liquid imidazolium cation and the -CF₂ group of PVDF could effectively induce the formation of PVDF polar β phase. The relative content of β phase in the composite is up to 81.83% which is 2.7 times that of pure PVDF. The dielectric constant of IL/PVDF composites can reach 21.0 (100 Hz), which is 4 times higher than that of pure PVDF. In addition, the effect of fused deposition molding (FDM) on IL/PVDF composites is discussed. It is found that FDM molding can further improve the polar β phase content of the composites X_c(β), which has a certain reference value for the preparation of PVDF-based electronic energy storage and sensing equipment by FDM molding.
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  Truncation, filtration and magnetic modification of helical carbon nanowires for magnetic-field driving motion

  BAI Xueyuan, YE Zixing, TONG Hao, WANG Chenzi, LI Yong, PAN Lujun

  Jorunal of Functional Materials. 2023, 54(4): 4020-4026. https://doi.org/10.3969/j.issn.1001-9731.2023.04.004

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  To fabricate a new type of micro-nanorobot of helical carbon nanowires (HCNs), the truncation, filtration, and magnetic modification were studied for realizing the motion actuated by magnetic field. The treating method of nitric acid oxidation, ultrasonic vibration, and filter paper filtration was proposed to disperse and shorten into 2-8 μm in length. Magnetic modification methods on the surface of HCNs including magnetron sputtering, electroless plating, and hydrothermal growth of Fe₃O₄ nanoparticles were experimented and compared. The modification effect was evaluated by scanning electron microscopy and element analysis of energy dispersive X-ray spectroscopy. As a result, the HCNs with good magnetic characteristics were obtained. The magnetic-field driving experiments in a micro-channel showed that HCNs modified by magnetron sputtering realized the fast motion speed (3.35 μm/s) and the controllable trajectory motion accuracy <5 μm.
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  Microstructure and cavitation corrosion properties of CeO₂ modified multiscale WC-CoCr coatings

  YANG Changchun, DING Xiang, TIAN Yinghao, YUAN Chengqing, WANG Shaoyi

  Jorunal of Functional Materials. 2023, 54(4): 4027-4033. https://doi.org/10.3969/j.issn.1001-9731.2023.04.005

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  In this paper, bare and nano-CeO₂ modified multi-scale WC-10Co4Cr powders and coatings were prepared. The powder fabrication process mainly involved ball milling of a mixture of 0.06-0.18 μm nano WC, 0.4-0.6 μm submicron WC, 2.2-2.6 μm micron WC, Co, Cr₃C₂, and nano CeO₂, followed by spray drying and sintering. JP8000 HVOF spray system was used to deposit the WC-10Co4Cr coatings on 316 stainless steel substrates. The impact of nano-CeO₂ on the microstructure of multiscale WC-10Co4Cr coating was analyzed by optical microscope, scanning electron microscope and X-ray diffractometer. The cavitation erosion resistance and cavitation behavior of the coatings were studied in fresh water medium. The cavitation mechanism of the coatings was further explored by comparing the microhardness, porosity and cracking toughness of the coatings. The results show that both the bare and nano CeO₂ modified multiscale WC-10Co4Cr coatings prepared by HVOF are mainly composed of WC phase and amorphous CoCr with no obvious decarburization. The nano CeO₂ modified multiscale WC-10Co4Cr coating has lower porosity of 0.25% compared to the bare multiscale WC-10Co4Cr coating (0.32%). However, the microhardness of the nano CeO₂ modified coating is lower (1 134 HV_0.3), only 83% of that of the multi-scale WC-10Co4Cr coating. Similarly, the cracking toughness (5.27 MPa·m^1/2) of nano CeO₂ modified is 4% lower than that of the multiscale WC-10Co4Cr coating. In the multiscale WC-10Co4Cr coating, the nano CeO₂ leads to the decline of the cavitation erosion resistance of the coating in fresh water, with the cavitation erosion rate reaching 1.64 times the rate of the multiscale WC-10Co4Cr coating in the stable cavitation stage. It is concluded that the addition of nano CeO₂ reduces the porosity of the WC-10Co4Cr coating, while the mechanical properties of the coating decrease, thereby reducing the cavitation resistance of the coating.
Review & Advance
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  Research progress on cation-doping to enhance the performance of Cu₂ZnSn(S,Se)₄ cells

  LI Shuyu, YANG Yanchun, WANG Yiming, HUO Hu, ZHU Chengjun

  Jorunal of Functional Materials. 2023, 54(4): 4034-4044. https://doi.org/10.3969/j.issn.1001-9731.2023.04.006

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  Due to the advantages of abundant earth elements, low toxicity and environment protection, Cu₂ZnSn(S,Se)₄ (CZTSSe) thin-film solar cells are thought to be suitable for the large-scale production in the future. At present, the efficiency of these devices is always limited by the high cation disorder of the absorber layer and the low open-circuit voltage of the device. To solve this problem, the cation doping measure has been proposed by scientists, which is the disorder of cations can be reduced by introducing other cations, improving the photoelectric conversion efficiency of the device. It has also been proved that cation doping is great significant in improving the performance of devices. Based on this, the research progress of cation doping measures in optimizing the performance of CZTSSe devices is discussed in detail, including the additional addition of cations (e g, Na, K, Sb) and cation substitution (e g, substitution of Cu, Zn, and Sn with Li/Ag, Mn/Mg/Ba/Cd, and Ge, respectively). It is concluded that the most promising cations are Cd²⁺ and Ge⁴⁺ ions, considering the toxicity of Cd, Ge should be the most promising element in optimizing the performance of CZTSSe devices.
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  Research progress on preparation, surface modification and application of carbon quantum dots

  HUANG Ligang, LYU Chong, LI Xinxin, TANG Gan, YOU Feng, ZHANG Mengqi, LIU Fangjun, JIANG Xueliang

  Jorunal of Functional Materials. 2023, 54(4): 4045-4053. https://doi.org/10.3969/j.issn.1001-9731.2023.04.007

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  Carbon quantum dots (CDs) are widely used in various fields due to their unique physical or chemical properties. Compared with traditional semiconductor quantum dots, the biggest advantages of CDs are low cytotoxicity, high biocompatibility, and at the same time being environmentally friendly. Obtaining carbon dots that meet the application conditions by selecting a specific synthesis or modification method is an urgent need for researchers. This paper reviews various top-down and bottom-up synthesis methods of CDs and describes their various properties after synthesis, in which the top-down method is biased towards producing a larger amount of Cdots, but the size and Cdots form is difficult to control. The bottom-up method can better control the size and shape of carbon dots, but the process is more complicated and time-consuming. The research progress of surface modification of CDs, including surface passivation and surface functionalization, was further discussed. Moreover, the characteristics of Cdots prepared by different synthesis methods or modification methods are quite different, extending their applications in various aspects, including cell imaging, fluorescence sensing, drug delivery, photocatalysis, ion detection, etc. Finally, we summarize and analyze the aspects of carbon dots that can be further explored, in order to provide references for more in-depth research and wider application of carbon dots.
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  Research progress of piezoelectric polymers and high temperature resistance

  LIU Qiaolin, NIU Jiarong, JIN Xin, ZHU Zhengtao, LIN Tong, WANG Wenyu

  Jorunal of Functional Materials. 2023, 54(4): 4054-4064. https://doi.org/10.3969/j.issn.1001-9731.2023.04.008

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  In recent years, with the rapid development of human society, the global fossil fuel resources have declined significantly, and the existing energy reserves are gradually unable to meet the needs of social development. Therefore, it has become a research hotspot to convert the energy that cannot be used in nature into renewable energy. As an important part of piezoelectric materials, piezoelectric polymer has high strength, high flexibility and high sensitivity to voltage. It can convert mechanical energy, thermal energy, sound energy and vibration energy in nature into electric energy. It has great potential in nanogenerators, sensors, biomedicine and other fields. However, most piezoelectric polymers have the problem of low Curie temperature, so developing new high temperature resistant polymers is an important development direction at present. In this paper, the research progress of several widely used piezoelectric polymers (polyvinylidene fluoride, nylon 11 and polyacrylonitrile) is firstly introduced, and then the development of high temperature resistance of these materials is discussed.
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  Research progress of MOFs/g-C₃N₄ composited photo-catalyst

  LIU Jianmin, SHAN Shaoyun, HU Tianding

  Jorunal of Functional Materials. 2023, 54(4): 4065-4072. https://doi.org/10.3969/j.issn.1001-9731.2023.04.009

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  The pristine metal-organic framework materials (MOFs) and graphite-phase carbon nitride (g-C₃N₄) have shown excellent photocatalytic performance in H₂ production, CO₂ reduction, Cr reduction and organic pollutant degradation. The combination of MOFs and g-C₃N₄ to construct binary or ternary heterojunctions could overcome the shortcomings of the two materials, such as rapid recombination of photogenerated electron-hole pairs, further improving their photocatalytic performance under visible light or sunlight irradiation. In this minireview, the preparation methods, photocatalytic properties of several typical g-C₃N₄/MOFs composites were expatiated. Also, the prospect and challenges of this research field were declared.
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  A review of research on the factors influencing the stability of magnetorheological fluids

  SHEN Zhuoshan, PAN Jisheng, YAN Qiusheng

  Jorunal of Functional Materials. 2023, 54(4): 4073-4086. https://doi.org/10.3969/j.issn.1001-9731.2023.04.010

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  The stability of magnetorheological fluids (MRF) plays a very important role in the realization of magnetorheological fluid functions, while magnetorheological fluids have become the most widely used materials with its flexible, controllable and stable characteristics. The applications of magnetorheological fluids in mechanical transmission, precision machining, medicine, civil engineering and other fields and their principles are reviewed, along with a summary comparison of various methods for testing the settling stability of magnetorheological fluids. Focusing on the influencing factors of the settling stability of magnetorheological fluids, the influence of additives on the settling stability of magnetorheological fluids is compared and analyzed from the perspective of settling rate by summarizing the mechanism of action of different types of additives. It is also pointed out that changing the structure of magnetic particles and forming low-density composites mainly improve the settling performance of magnetorheological fluids by increasing the friction between magnetic particles and base carrier fluid and reducing the density difference between magnetic particles and base carrier fluid. Finally, the future development trend of magnetorheological fluids is pointed out.
Research & Development
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  Preparation of graphene modified concrete and research on mechanical properties and frost resistance

  ZHANG Xuemei, LIU Ronggui, DAI Li, ZHOU Kai

  Jorunal of Functional Materials. 2023, 54(4): 4087-4092. https://doi.org/10.3969/j.issn.1001-9731.2023.04.011

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  Using ordinary Portland cement P.O42.5 as matrix material and graphene as reinforcing material, modified concrete with different graphene doping contents (0, 0.04 wt%, 0.08 wt% and 0.12 wt%) was prepared. The effects of graphene doping on the crystal structure, micro morphology, mechanical properties and frost resistance of modified concrete were studied. The results showed that the doping of graphene didn't produce new hydration products, but accelerated the rate of hydration reaction, and the generated hydration product gel was filled into the cracks of concrete and improved the compactness of concrete. When the content of graphene was 0.08 wt%, the number of pores in the modified concrete was the least, the compactness was the largest, and its morphology was the best. The compressive strength of graphene modified concrete at each curing age first increased and then decreased with the increase of graphene doping amount. At the curing age of 28 d, when the doping amount of graphene was 0.08 wt%, the compressive strength of modified concrete reached the maximum value of 48.62 MPa. After 60 freeze-thaw cycles, when the content of graphene was 0.08 wt%, the minimum mass loss rate of modified concrete was 0.414%, and the maximum relative dynamic elastic modulus was 94.02%. The frost resistance of graphene modified concrete was significantly improved. The comprehensive analysis showed that the optimum doping amount of graphene in modified concrete was 0.08 wt%.
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  Study on preparation and properties of SiO₂ reinforced alumina aerogel composite building thermal insulation materials

  ZHU Guoqing

  Jorunal of Functional Materials. 2023, 54(4): 4093-4098. https://doi.org/10.3969/j.issn.1001-9731.2023.04.012

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  Aerogel materials have broad application prospects in the market of building thermal insulation materials because of their high porosity, strong compression resistance and low thermal conductivity. In this paper, Al₂O₃-SiO₂ aerogel composite thermal insulation materials with different SiO₂ content were prepared by sol-gel method using tetraethyl orthosilicate and sec butanol aluminum as raw materials. The effects of SiO₂ doping amount on the crystal structure, micro morphology, mechanical properties and thermal conductivity of composite aerogels were studied. The results showed that Al₂O₃-SiO₂ aerogel was mainly composed of polycrystalline boehmite. SiO₂ doping inhibited the formation of γ- Al₂O₃ phase and hindered the occurrence of hydroxyl condensation reaction. H in AlO-H group was replaced by Si, forming a more stable Al-O-Si bond. Al₂O₃-SiO₂ aerogel showed an open porous structure, and the doping of SiO₂ improved the pore orientation of the aerogel, reducing the pore size and distributing evenly. With the increase of SiO₂ doping, the compressive strength and specific surface area of Al₂O₃-SiO₂ aerogel first increased and then slightly decreased, and the thermal conductivity first decreased and then increased. When the doping amount of SiO₂ was 9 mol %, the maximum compressive strength of the aerogel was 40.92 MPa, which was 58.97% higher than that of the undoped aerogel. The maximum specific surface area was 257.33 m²/g, the lowest thermal conductivity was 0.022 W/(m·K), and the thermal insulation performance was the best. In summary, the optimal doping amount of SiO₂ was 9 mol%.
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  Preparation and oxygen adsorption properties of Sm doped YbBaCo₄O_7+δ nanopowder

  LIU Shaohui, WANG Jiao, WANG Feifei, HAO Haoshan, WANG Yuan

  Jorunal of Functional Materials. 2023, 54(4): 4099-4103. https://doi.org/10.3969/j.issn.1001-9731.2023.04.013

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  YbBaCo₄O_7+δ oxygen adsorption material doped with different concentrations of Sm was prepared by sol-gel method. The structure, morphology and oxygen adsorption/desorption properties of the Yb_1-xSm_xBaCo₄O_7+δ nanopowder were analyzed by XRD, SEM and differential thermal analyzer. The effects of different concentrations of Sm doping on YbBaCo₄O_7+δ nanopowder were studied. The test results show that the rare earth element Sm completely enters the lattice of Yb_1-xSm_xBaCo₄O_7+δ nanopowder. And Yb_1-xSm_xBaCo₄O_7+δ nanopowder is still a single 114 phase structure. Sm doping has little effect on the morphology of Yb_1-xSm_xBaCo₄O_7+δ nanopowder. A certain amount of rare earth element Sm doping can significantly improve YbBaCo₄O_7+δ. For the oxygen adsorption performance of Yb_1-xSm_xBaCo₄O_7+δ nanopowder, the change of oxygen adsorption of YbBaCo₄O_7+δ is 1.7%, while the change of oxygen adsorption of Yb_0.8Sm_0.2BaCo₄O_7+δ is 4.6%. And Yb_1-xSm_xBaCo₄O_7+δ has good circulation performance. The improvement of its oxygen adsorption/desorption performance is due to the improvement of oxygen storage space in Yb_1-xSm_xBaCo₄O_7+δ by rare earth element Sm doping.
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  Characterization and photocatalytic performance of Ag/TiO₂ composite synthesized at low temperature

  FAN Ding, WANG Liming, LIU Fengqiang, XU Lihui, PAN Hong

  Jorunal of Functional Materials. 2023, 54(4): 4104-4109. https://doi.org/10.3969/j.issn.1001-9731.2023.04.014

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  Ag/TiO₂ photocatalyst was prepared by sol-gel and solvothermal method with tetrabutyl titanate and silver nitrate as raw materials at low temperature (120 ℃). The samples were characterized by SEM, EDS, XRD, XPS and DRS, and the photocatalytic performance of Ag/TiO₂ photocatalyst was tested. The results show that the Ag/TiO₂ (3 wt%) photocatalyst synthesized at low temperature (120 ℃) has the best photocatalytic effect. Under 100 W high pressure mercury lamp irradiation, the degradation rate of 30 mg/L reactive Red 24 dye can reach 100% after 90 min photo reaction. Under the irradiation of 500 W xenon lamp for 150 min, the degradation rate of reactive Red 24 of 30 mg/L can reach 92.6%, and the degradation rate of dyes can reach more than 90% under both ultraviolet and visible light. It has excellent ultraviolet/visible light photocatalytic activity, which can provide an effective idea for the research of low temperature synthesis composite photocatalyst.
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  Study on the synthesis of hollow calcium carbonate microsphere by template method using folic acid and its drug loading performance

  GUO Ziting, LI Wei, CHEN Qiujuan, MO Fuwang

  Jorunal of Functional Materials. 2023, 54(4): 4110-4114. https://doi.org/10.3969/j.issn.1001-9731.2023.04.015

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  Hollow calcium carbonate (precursor) were synthesized via a hydro-thermal method with additive of folic acid in PTFE reactor kettle. Hollow calcium carbonate were obtained upon calcination at temperature of 600 ℃ over two hours. The phase structure, morphology were characterized by X-ray diffraction and scan electron microscopy. The results show that particle size was between 5 and 10 μm and showed a hollow microporous structure. The as-prepared samples were a minylated, carboxylated and polythlenimine coated and modified before drug loaded with doxorubicin hydrochloride(DOX). It was found that the drug load rate of DOX reached 349.81 mg/g. In the prototype glutathione solution, the drug carrier could continuously release slowly within 0-12 h. When the tumor microenvironment concentration was relatively low, the highest release rate reached 1.34%, and the release rate was 0.63% after 12 hours. Generally, the drug release is relatively fast within the first 4 hours, and the slow release can be achieved if the tumor level is not high.
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  Study of the BNNS/PES/EP composites prepared by induced phase separation and their thermal properties

  WANG Shuai, LI Xiang, YANG Xueming, YU Tianfu, HE Bingchen

  Jorunal of Functional Materials. 2023, 54(4): 4115-4119. https://doi.org/10.3969/j.issn.1001-9731.2023.04.016

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  In this paper, boron nitride nanosheets (BNNS) were prepared by liquid phase mechanical stripping method and the double modified boron nitride nanosheets (KDBNNS) were prepared by silane coupling agent covalent modification and dopamine non-covalent modification. The reaction induced phase separation was used to distribute KDBNNS at the interface of epoxy resin (EP) and polyether sulfone (PES) to form a thermal conductive pathway. KDBNNS/PES/EP composites were prepared and characterized by Fourier transform infrared spectroscopy analysis, differential scanning calorimetry analysis (DSC), thermal weight loss analysis (TGA), and confocal scanning microscopy. It is observed that BNNS constructs a three-dimensional thermal conductive path in the ternary composite. Studies have shown that when the mass ratio of BNNS is only 3%, the thermal conductivity of the composite reaches 0.394 W/(m·K), which is 103% higher than pure epoxy 0.194 W/(m·K).
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  Photocatalytic degradation of sulfosalicylic acid on BiOI/Zn-Bi₂WO₆ heterojunction

  LI Xiaojie, CHANG Biao, LI Dongmei, TIAN Zhongzhen

  Jorunal of Functional Materials. 2023, 54(4): 4120-4125. https://doi.org/10.3969/j.issn.1001-9731.2023.04.017

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  BiOI/Zn-Bi₂WO₆ heterojunctions were prepared by hydrothermal method. The phase, morphology and elemental composition of BiOI/Zn-Bi₂WO₆ were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM-EDS), respectively. X-ray photoelectron spectroscopy (XPS) was used to analyze the chemical state of its surface species. UV-Vis absorption spectroscopy (UV-Vis) was used to analyze its utilization of sunlight, and photoluminescence spectroscopy (PL) and electrochemical impedance spectroscopy (EIS) was used to analyze the separation of photogenerated carriers. The results indicated that on the one hand, the absorption edge of BiOI/Zn-Bi₂WO₆ shifted to red and the absorption intensity increased, which improved the utilization of visible spectrum. On the other hand, the efficient separation of photogenerated holes and electrons was realized by the formation of heterojunction. BiOI/Zn-Bi₂WO₆ showed good photocatalytic degradation performance and stability on sulfosalicylic acid, and the degradation rate reached 82% within 120 minutes.
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  Preparation and property of sodium lignosulfonate-based polyurethane foam with synergistic flame retardant

  LI Xu, MA Yue, AN Xinyu, YU Ze, JACKO Feng, LIU Zhiming

  Jorunal of Functional Materials. 2023, 54(4): 4126-4131. https://doi.org/10.3969/j.issn.1001-9731.2023.04.018

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  By adding sodium lignosulfonate in the process of polyurethane foam foaming, and using aluminum hypophite (AHP) and expanded graphite (EG) as synergism flame retardants, the sodium lignosulfonate based polyurethane foam (PUF) with flame retardant properties were prepared by “one-step method”. Firstly, the flame retardation properties of the prepared synergism flame retardant PUF materials were characterized by using the limiting oxygen index (LOI) tester. Thermogravimetric analysis (TGA) and CONE calorimetry (CONE) were used to investigate the thermal stability and combustion behavior of flame-retardant PUF materials. Field emission scanning electron microscope (SEM) was used to analyze the microscopic photos of carbon residue after combustion. The analysis results show that when the SLS addition ratio is 4 wt% of the total mass of raw materials, the synergism ratio of AHP and EG is 1∶4, and the addition of the two synergism flame retardants is 30 wt%, the LOI value of biomass-based flame retardant PUF material increases to 31.6%. The addition of coefficent flame retardants improves the thermal stability and carbonization performance of PUF material. Thus, the flame retardant of the material is greatly enhanced.
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  Microcosmic mechanism and properties of MgCl₂·6H₂O as adsorption heat storage material

  HUO Yingjie, YAN Ting, ZHOU Yuxiang, PAN Weiguo

  Jorunal of Functional Materials. 2023, 54(4): 4132-4140. https://doi.org/10.3969/j.issn.1001-9731.2023.04.019

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  Among the technologies for realizing inter-seasonal heat storage, the thermochemical adsorption heat storage technology using hydrated salts as heat storage materials has gathered the attention of a large number of scholars and occupied a key position in heat storage technology because of its advantages of high heat storage density, low energy loss and almost no heat loss for long-term heat storage. MgCl₂·6H₂O is used as a chemisorption material. The changes in thermal conductivity, mass diffusion coefficient, and adsorption energy are calculated by molecular dynamics simulation to investigate the microscopic forms of action in the whole system thermal storage process at the molecular level. The results show that the crystal density of MgCl₂·6H₂O takes on a tendency to decrease with the increase in temperature. A molecular model of thermal conductivity was established, and the thermal conductivity of the system was calculated to be around 0.95 W/(m·K). The diffusion coefficient of each particle is proportional to the temperature, with H₂O having the largest diffusion coefficient, while the adsorption capacity is inversely proportional to the particle spacing.
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  Graft polymerization of quaternary ammonium compounds on PVC surfaces initiated by atmospheric pressure plasma jet and its antibacterial properties

  LIU Yafeng, SUN Tao, SUN Hongmei, MA Zhongyang, SUI Siyuan, NI Guohua

  Jorunal of Functional Materials. 2023, 54(4): 4141-4149. https://doi.org/10.3969/j.issn.1001-9731.2023.04.020

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  To improve the antibacterial properties of medical polyvinyl chloride (PVC), atmospheric pressure plasma jet (APPJ) technology was used to graft and prepare quaternary ammonium compounds (QAC) coatings on the PVC surface. The flow state and active components of the plasma jet were diagnosed by ripple shadowing and emission spectroscopy, respectively. The hydrophilicity, microscopic morphology and chemical components of the PVC surface before and after plasma treatment were characterized by static water contact angle method, scanning electron microscopy and X-ray photoelectron spectroscopy, respectively. The antibacterial performance of QAC/PVC against Escherichia coli was also tested. The results showed that with the increase of discharge voltage, the plasma jet flow state in the area of contact with PVC changed from laminar to turbulent flow. After plasma modification, the hydrophilicity of the PVC surface was enhanced. The water contact angle of the modified PVC surface could be as low as 26°, and the content of oxygen-containing functional groups was as high as 31.02 at%. The increase of discharge voltage contributes to the enhancement of the amount of oxygen-containing functional groups on the PVC surface and promotes the grafting and polymerization of quaternary amines on the PVC surface to form a dense coating, which improves its antibacterial performance against E. coli.
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  Photocatalytic degradation of Rhoda mine B by nano Fe-TiO₂ under visible light

  WANG Song, XU Lixin, GUO Qing, HUANG Dajian, JIANG Changjun

  Jorunal of Functional Materials. 2023, 54(4): 4150-4156. https://doi.org/10.3969/j.issn.1001-9731.2023.04.021

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  Mercury lamp, xenon lamp and ultraviolet lamp are widely used for photocatalytic treatment of water pollution and research. In order to reduce the use of high energy sources, an iron-doped nano-titanium dioxide photocatalyte which can respond under low-consumption LED lamp was prepared by sol-gel method. The physical phase composition, microscopic morphological structure and optical absorption properties in UV and IR were analyzed. The effects of Fe doping amount, initial concentration of solution and initial pH on the photocatalytic degradation of simulated wastewater rhoda mine B solution were investigated under LED white light irradiation conditions, and the degradation mechanism was analyzed. The results show that the doping of Fe³⁺ accelerates the phase transition from anatase to rutile in TiO₂. Under the scanning electron microscope, the nanoparticles are well distributed and the agglomeration is not obvious. Doping of Fe³⁺ decreases the band gap width of TiO₂ and makes the optical absorption edge red-shift, which decreases significantly from 3.2 eV to 2.7 eV. However, when the amount of Fe³⁺ doped is too high, the optical absorption edge of nano-Fe-TiO₂ shifts blue and its activity in the visible region decreases significantly. Comprehensive analysis shows that the removal rate of Rhoda mine B is 89% when irradiated by LED white light (100W) for 72 hours at molar ratio n(Fe):n(Ti)=0.3% and pH=7. It provides reference for catalytic degradation of organic pollutants by low energy consumption LED lamp.
Process & Technology
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  Preparation of UV-curable fluorescent polyurethane dyes and their printing properties

  SHU Yihu, WANG Yaxuan, FANG Dunjie, WANG Chaoxia, YIN Yunjie

  Jorunal of Functional Materials. 2023, 54(4): 4157-4165. https://doi.org/10.3969/j.issn.1001-9731.2023.04.022

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  A series of UV-curable fluorescent polymer dyes (UFPD-0-UFPD-3) were synthesized from isophorone diisocyanate, polyethylene glycol 1000 (PEG1000), 2,2-dihydroxymethylbutyric acid (DMBA), fluorescent monomer acridine yellow hydrochloride (AH), pentaerythritol triacrylate (PETA) and neutralizer triethyla mine (TEA), then acridine yellow hydrochloride was doped into UFPD-0 and mixed homogeneously to prepare UFPD+3. Different UV-curable coated fabrics were obtained by screen printing and UV-light polymerization. The drying time and light conditions of UV-curable coated fabrics were also investigated. The results showed that the fluorescent monomer acridine yellow hydrochloride was successfully grafted onto the polyurethane molecular chain and the grafted samples showed good thermal stability. Aqueous emulsion of UFPD-3 exhibited a maximum relative fluorescence emission intensity of 1 793, compared with only 505 for UFPD+3. The fabrics obtained with a drying time of 20 min, a light intensity of 100% and a light time of 80 s displayed the highest relative fluorescence emission intensity and bright colors. The UV protection factor (UPF value) of the UV-curable coated fabric obtained after printing with UFPD-3 aqueous emulsion reached 66.89, and the color fastness reached 4-5 grade.
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  Synthesis and properties of glyceryl sulfite as novel electrolyte additives for lithium-ion batteries

  AN Jiayu, LIU Jing, SUN Donglan, KONG Deru, HUO Zhengchun

  Jorunal of Functional Materials. 2023, 54(4): 4166-4175. https://doi.org/10.3969/j.issn.1001-9731.2023.04.023

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  We synthesized two new sulfite-type compounds as the electrolyte additive: (2-oxido-1, 3, 2-dioxathiolan-4-yl) methyl benzene sulfonate (ODMB) and (2-oxido-1, 3, 2-dioxathiolan-4-yl) methyl 4-methyl benzene sulfonate (ODMM). The cells’ electrochemical performances are characterized by C-rate test, charge-discharge test, electrochemical impedance spectroscopy (EIS). TG-FTIR measurements indicate that ODMB and ODMM both have good thermal stability and their decomposition temperature is 256 ℃ and 255 ℃, respectively. The cell with 0.7 wt% ODMB discharge capacity (147.98 mAh/g) remain at 97.51% of its initial discharge capacity (151.76 mAh/g) after 50 cycles. Scanning electron microscope (SEM) results demonstrate that a denser and stable layer is observed. Moreover, the charge transfer impedance of the electrodes significantly decreases. And wettability measurement shows that the 0.7 wt% ODMB electrolyte exhibits superior wettability than the blank electrolyte, which can effectively ameliorate the cells' assembly process.
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  Synthesis of magnetic Zr-based MOFs materials and performance of phosphorus removal from water

  GONG Jiankang, LI Guotao, YE Ping, LI Shengjian, SHI Rui, WANG Bangyan

  Jorunal of Functional Materials. 2023, 54(4): 4176-4188. https://doi.org/10.3969/j.issn.1001-9731.2023.04.024

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  Based on the principle of liquid phase epitaxial growth, the magnetic amino functionalized MOFs material of Fe₃O₄@NH₂-UiO-6(Fe-NUiO(Zr)-005) was synthesized by self-assembly method and characterized by XRD, FT-IR, SEM and BET. The adsorption performance and the mechanism of the material for phosphorus in water was investigated. The results show that the mesoporous nano-magnetic composites of Fe-NUiO (Zr)-005 by self-assembly on Fe₃O₄, and it has large specific surface area and high stability.The adsorption effect keeps at a high level over a wide pH range from 3.0 to 9.0, the adsorption process accords with pseudo second order kinetic model and Langmuir isotherm model, and was controlled by multiple mechanisms. The saturation phosphate adsorption capacity can reach 71.94 mg/g, and achieves adsorption equilibrium within 200 min. In addition, Fe-NUiO(Zr)-005 also exhibited strong anti-interference ability and high phosphate removal efficiency in the actual water environment and in the presence of coexisting anions (Cl^-, SO^2-₄, NO^-₃). Therefore, Fe-NUiO(Zr)-005 shows considerable potential for low concentration phosphorus removal. The magnetic property of Fe-NUiO(Zr)-005 led to a rapid and easy solid-liquid separation from solution of the phosphorus by an external magnetic field. It also has good recycling stability and can be recovered magnetically and reused at least five times. Compared with non-magnetic NUiO(Zr), the recovery rate was increased by 49%. Zata potential, pH effect,and FT-IR analyses before and after uptake of phosphate showed that the main process for the removal of phosphate from water by Fe-NUiO(Zr)-005 was the chemical adsorption reaction of an endothermic spontaneous, and the adsorption mechanisms were attributed to the electrostatic adsorption and ligand exchange. In summary, the results of this experiment have important guiding significance for the synthesis of UiO magnetic materials and phosphorus removal contaminated water by the materials.
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  Effects of highly active MgO expansive agent on the performance of UHPC

  ZHANG Zhanqiang, LI Shunkai, CHEN Ping, MING Yang, CHEN Hongrui, LI Hang, WANG Jingyang, RAN Yao

  Jorunal of Functional Materials. 2023, 54(4): 4189-4195. https://doi.org/10.3969/j.issn.1001-9731.2023.04.025

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  In this paper, a highly active MgO expansive agent (MEA) with an active reaction time of 41 s was incorporated into ultra-high performance concrete (UHPC) and its effects on the workability, mechanical properties and volumetric stability of UHPC were investigated. Characterization of porosity and pore structure by mercury intrusion method, and the microscopic morphology of the hardened mortars were analyzed by SEM and EDS. The results showed that UHPC will reduce its fluidity and mechanical properties by incorporating MEA, but can significantly compensate for the early autogenous shrinkage of UHPC. The maximum doping of MEA should not exceed 12% of the total amount of cementitious materials. MEA decreases the porosity of UHPC, and refines it, especially for ＜ 50 nm pore size, which is an important reason for the ability of MEA to compensate for the autogenous shrinkage of UHPC. The microscopic test results showed that the main reason for the swelling is that the MEA hydrates in situ to form dense Mg(OH)₂, the inhibited crystallization will generate crystallization pressure, which leads to volume expansion. From the EDS results, it can be seen that the boundary between MEA without cementing ability and its hydration products and cement slurry gradually blurs with curing age, and UHPC will tend to be denser.
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  Preparation and thermally enhanced luminescence of Lu₂(MoO₄)₃:Eu³⁺ phosphors

  CHEN Zijun, CAO Chunyan, ZHENG Yifei, ZHANG Min, HUANG Nihui, BAI Bihai, XIE An

  Jorunal of Functional Materials. 2023, 54(4): 4196-4201. https://doi.org/10.3969/j.issn.1001-9731.2023.04.026

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  Lu₂(MoO₄)₃:Eu³⁺ red phosphors were synthesized by a solid-state reaction method. The structure, the morphology, the compositions, and the photoluminescence (PL) properties of the phosphors were characterized and analyzed by X-ray powder diffractometer (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), and fluorescence spectrometer. The experimental results suggest that the Eu³⁺ ions were successfully doped into Lu₂(MoO₄)₃ matrix, samples were pure phase of Lu₂(MoO₄)₃:Eu³⁺, and the particle size of the phosphors were about 2 μm in size. The synthetic temperature dependent samples suggest that the Lu₂(MoO₄)₃:Eu³⁺ synthesized at 1 000 ℃ possessed the most excellent PL performance. The calcining time dependent samples suggest the Lu₂(MoO₄)₃:Eu³⁺ synthesized for 6 h at 1 000^oC had the strongest PL intensity. Abnormal to the thermal quenching luminescence of phosphors, the Lu₂(MoO₄)₃:Eu³⁺ samples exhibited thermal enhancing PL intensity with the measuring temperature increased to about 250 ℃, which had relations to the negative thermal expansion characteristics of Lu₂(MoO₄)₃.
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  Synthesis, structural andphotophysical properties of a novel red Iridium (Ⅲ) complex

  CHEN Zhu'an, WANG Zi'ao, ZHANG Ke, JIANG Jing, YU Juan, LIU Weiping, YAN Caixian, CHANG Qiaowen

  Jorunal of Functional Materials. 2023, 54(4): 4202-4208. https://doi.org/10.3969/j.issn.1001-9731.2023.04.027

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  A new iridium(Ⅲ) complex Ir(fdpt)₂(trifbutd) was synthesized with 5-(4-fluorophenyl)-1,3- dimethyl-1H-1,2,4-triazole (fdpt) as the ring metal ligand and 4,4,4-trifluoro-1-(3-pyridyl)-1,3-butanedione (trifbutd) as the auxiliary ligand. Its chemical composition and crystal structure were characterized by elemental analysis, IR, NMR and single crystal X-ray diffraction. The result showed that chemical composition of the complex is C₂₉H₂₃F₅IrN₇O₂, which belongs to monoclinic system and P2₁/n space group. The unit cell parameter was a=1.17369 (10) nm, b =1.68602(14) nm, c =1.42919(12) nm, β=90.925 (3)°, V=2.8278(4)nm³ and Z=4. The maximum emission wavelength of 620 nm was red.
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  Effect of different biomass addition on structure and properties of hypercoal-based activated carbons

  WANG Xueyu, YU Nalin, JIANG Hongwei, FAN Lihua

  Jorunal of Functional Materials. 2023, 54(4): 4209-4215. https://doi.org/10.3969/j.issn.1001-9731.2023.04.028

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  By adding different biomass (corn cob or pine sawdust) to hypercoal, the activated carbon electrode materials for double electric layer capacitors were prepared. The effect of biomass on the structure and electrochemical performance of hypercoal-based activated carbon was explored. Its structure and composition were characterized by SEM, XRD, FTIR and N₂ desorption. Its electrochemical performance was tested by cyclic voltammetry, constant current charge-discharge and AC impedance. In terms of biomass composition, the addition of biomass with high cellulose content is beneficial to the development of mesopore and the pore structure is more perfect. High cellulose and hemicellulose content can effectively reduce the impedance of carbon materials, and make the ion transport between pore structures more rapid. When corn cob was added to hypercoal, the specific capacitance increased by 45% and the charge transfer resistance decreased by 65%. Adding pine sawdust to hypercoal can increase the specific capacitance by 30% and decrease the charge transfer resistance by 35%. It is proved that adding biomass with high cellulose content is more beneficial to improve the structure and electrochemical performance of activated carbon.
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  Study on preparation and properties of graphite ore conductive concrete

  ZHAO Yanru, GUAN He, HOU Mingliang, LIU Daokuan

  Jorunal of Functional Materials. 2023, 54(4): 4216-4224. https://doi.org/10.3969/j.issn.1001-9731.2023.04.029

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  Graphite, graphite raw ore and graphite tailings were selected as conductive phase materials to prepare conductive concrete. Firstly, the mix ratio of graphite raw ore concrete was designed based on orthogonal test. The test results showed that the primary and secondary factors affecting the compressive strength, flexural strength and resistivity of graphite ore concrete were as follows: graphite ore content>water cement ratio>sand ratio>water reducing agent content. The optimal mix ratio was obtained, which was water cement ratio of 0.52, sand ratio of 0.38 and water reducing agent content of 1.4%. Then, the compressive, flexural and resistivity tests of graphite, graphite ore and graphite tailings concrete with different mix ratios were carried out. The results showed that the compressive, flexural and resistivity of the three kinds of concrete decreased with the increase of the content of graphite materials. The resistivity of the three kinds of concrete meets the requirements of conductive concrete engineering. When the content of graphite ore is 15 %, the resistivity of concrete is 10 950 Ω·m, which can be used as anti-static concrete in industrial anti-static, power equipment grounding and other projects.
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  Preparation and properties of octadecane/expanded
  graphite forming phase change materials

  ZHANG Weili, DU Jiaoli, GAO Ning, CAI Di, QIU Jie, LI Youbing

  Jorunal of Functional Materials. 2023, 54(4): 4225-4229. https://doi.org/10.3969/j.issn.1001-9731.2023.04.030

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  Aiming at the application of energy-saving and energy storage materials for buildings, a series of octadecane/intumescent graphite forming phase change materials with different octadecane content were prepared by vacuum adsorption method, and the optimal content of octadecane adsorption and its properties were explored through microscopic morphological observation, leakage performance test, differential scanning calorimetry analysis and cold-thermal cycle stability analysis. Through the analysis, it is concluded that when the adsorption amount of octadecane is 90 wt%, the comprehensive performance of the octadecane/expanded graphite forming phase change material under the adsorption content is the best, and its enthalpy of molten enthalpy and solidification enthalpy are 188 J/g and 186.9 J/g, which has a higher enthalpy values compared with different composite phase change materials at home and abroad. After heating the oven at 50 ℃ for 2 h, there is no obvious phenomenon of octadecane exudation, and the quality loss rate is less than 1%, indicating that it has good anti-leakage performance and structural stability.
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  Preparation and electromagnetic shielding properties of Fe₃O₄/MXene/WPU composite films

  TAO Meijie, LI Zhiwei, YANG Ke, LI Hengfeng

  Jorunal of Functional Materials. 2023, 54(4): 4230-4236. https://doi.org/10.3969/j.issn.1001-9731.2023.04.031

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  To achieve high electromagnetic shielding performance while reducing reflection is the current pursuit of electromagnetic shielding materials. The Fe₃O₄ nanosheet with the transverse size of 30-40 μm, the thickness of 70-200 nm was synthesized by a one-step hydrothermal method and characterized by infrared spectroscopy, X-ray diffraction and scanning electron microscopy, finding that Fe₃O₄ nanosheet have a good crystallinity. By changing the content of Fe₃O₄ nanosheet, the reflection value of Fe₃O₄/MXene/WPU composite film prepared by spraying was as low as 4.3 dB, the reflection power (R) was reduced from 0.81 to 0.63, and the transmission power (T) was only 10^-3 orders of magnitude. Fe₃O₄ nanospheres with a diameter of 180-200 nm was prepared by using a hydrothermal method and had a good dispersion. The longitudinal comparison under the same Fe₃O₄ content demonstrated that the electromagnetic shielding performance of the composite film containing Fe₃O₄ nanospheres was slightly higher than that of the composite film containing Fe₃O₄ nanospheres.