30 December 2022, Volume 53 Issue 12

    

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Focuses & Concerns( The Projectof Chongqing Press Fund in 2021)
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  Progress of p-type conjugated thermoelectric materials

  DING Xiaoming, YANG Jie, ZHANG Ke, WU Sicheng

  Jorunal of Functional Materials. 2022, 53(12): 12001-12013. https://doi.org/10.3969/j.issn.1001-9731.2022.12.001

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  Thermoelectric materials can realize the mutual conversion between thermal energy and electric energy through the thermoelectric effect, and play an increasingly important role in medical treatment, space, military and daily life. Organic thermoelectric materials have rich sources of raw materials, and their structures can be tailored in a targeted manner. At the same time, they have the characteristics of light, thin, soft, and large-area solution preparation. They have recently entered a stage of rapid development, and their thermoelectric properties have been significantly improved. This paper summarizes the evolution and performance progress of p-type polymer thermoelectric materials since the 1980s, and divides the discussion into four parts, focusing on the targeted structural design of polymers, and the incorporation of polymers with dopants. Finally, a summary and an outlook on the future development direction are given.
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  Effect of waterborne polyurethane structure on colour-change behaviour of furfural-derived dyes

  ZHOU Shenglin, MA Hao, WANG Yazhou, XU Linxi, FAN Haojun, XIANG Jun

  Jorunal of Functional Materials. 2022, 53(12): 12014-12020. https://doi.org/10.3969/j.issn.1001-9731.2022.12.002

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  Revealing the colour-change behaviour of furfural-derived dyes (FDs) in waterborne polyurethane (WPU) is the premise to further promote their practical applications. To this end, two types of WPU, polyether WPU (MWPU) and polyester WPU (ZWPU), with different glass transition temperatures (T_g) are designed and prepared to survey FDs’ colour-change behaviour in them. After adding a small amount of FDs (1.5 wt%), the T_g and thermal decomposition properties of WPU filmsremain unchanged. Compared with the initial colour of the obtained FDs-ZWPU film, that of the FDs-MWPU film is much lighter, due to the higher polarity of the synthesized MWPU. When the temperature is close to the T_g of WPU, the colour recover of WPU films is frozen. Finally, the FDs-MWPU can be used as a vaccine safety indicator, which helps to reduce the risk of discomfort caused by injecting invalid vaccines.
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  Theoretical study on energy bands, density of states and optical properties of ferroelectric crystal Ba_1-xCa_xTiO₃

  JI Bin, HE Chongjun, LI Ziqiang, DENG Chenguang, LI Qian

  Jorunal of Functional Materials. 2022, 53(12): 12021-12027. https://doi.org/10.3969/j.issn.1001-9731.2022.12.003

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  BaTiO₃ crystals have been widely used in the field of dielectric and piezoelectric components, but BaTiO₃ has multiple phase transition temperatures, especially at room temperature, which will seriously damage the crystal quality. In order to improve the properties of BaTiO₃, doping BaTiO₃ crystals is considered. In this paper, based on first-principle calculation, the electronic structure and optical properties of BaTiO₃ doped with different Ca contents, namely Ba_1-xCa_xTiO₃ (x=0, 0.125, 0.25, 0.5), were calculated. It is found that BaTiO₃ is a direct band gap semiconductor in terms of electronic structure, and its band gap width is 1.74 eV. Doping Ca leads to an increase in the band gap of BaTiO₃. The density of states of BaTiO₃ doped with Ca is larger than that of undoped BaTiO₃, but the density of states decreases with the increase of doping content. In terms of optical properties, BaTiO₃ doping with Ca results in a significant shift in the dielectric peak. After BaTiO₃ is doped with Ca, its static dielectric constant becomes smaller. The light absorption of different wavelengths is different after BaTiO₃ is doped with different Ca contents. When Ca is 0.125, the light absorption capacity decreases greatly. The research results of Ba_1-xCa_xTiO₃ (x=0, 0.125, 0.25, 0.5) crystals in this paper show a broad application prospects in the field of optoelectronics and provide a theoretical basis for the growth and properties of this series of crystals as well.
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  Research progress of low frequency magnetic loss absorbing materials

  JIA Xuefei, CHANG Qian, CAO Xuefang, WEI Zhixian

  Jorunal of Functional Materials. 2022, 53(12): 12028-12032. https://doi.org/10.3969/j.issn.1001-9731.2022.12.004

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  With the advent of THE 5G era and the rapid development of electronic products, the radiation hazard of electromagnetic waves in the range of 1~8 GHz, such as digital signal broadcasting, satellite communication and navigation, and bluetooth signals, has increased sharply. Long-term exposure to electromagnetic radiation will cause harm to our bodies. Magnetic loss absorbing materials such as ferrite and carbonyl iron have the advantages of low cost and adjustable, which is an ideal material to achieve the comprehensive requirements of “thin, light, wide and strong” for low-frequency absorbing materials. In this paper, the research progress of low frequency magnetic loss absorbing materials in recent five years is reviewed, and the development direction is forecasted.
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  Research on the microwave dielectric properties of a new ultra-low temperature microwave dielectric ceramic Ca₂V₂O₇-LiF

  HAN Ruyi, ZHENG Yuxin, LI Bo

  Jorunal of Functional Materials. 2022, 53(12): 12033-12038. https://doi.org/10.3969/j.issn.1001-9731.2022.12.005

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  Ca₂V₂O₇-LiF microwave dielectric ceramics were prepared by solid-phase method, and the effect of doping LiF on the sintering temperature and microwave dielectric properties of Ca₂V₂O₇ was studied in details. Research results have shown that doping LiF to Ca₂V₂O₇ could lead to the appearance of liquid phase with very low melting point in the sample, and the mass transfer of the liquid phase greatly reduced the sintering temperature from 920 to 550 ℃. At the optimum sintering temperature of 550 ℃, LiF would not react with Ca₂V₂O₇ to form impurity phase, and nor would it change the triclinic crystal structure of Ca₂V₂O₇. However, above 550 ℃, LiF and Ca₂V₂O₇ formed a small amount of Ca₅F(VO₄)₃. The low melting point liquid phase formed by doping LiF helped to obtain high density at lower sintering temperature and thus obtaining higher Q×f. Ca₂V₂O₇ doped with 3 wt% LiF had the best microwave dielectric properties when sintered at 550 ℃ for 3 h of ε_r=11.83, Q×f=46,476 GHz and τ_f=-116.43×10^-6/℃.
Review & Advanc
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  Research progress of AIE hyperbranched polymers

  JIA Yuan, LIU Xi, YANG Juxiang, LIU Zhen

  Jorunal of Functional Materials. 2022, 53(12): 12039-12046. https://doi.org/10.3969/j.issn.1001-9731.2022.12.006

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  Hyperbranched polymer (HBP) is a kind of three-dimensional macromolecule with a large number of functional groups and highly branched structure. It is characterized by non-entanglement, low viscosity and high reactivity. HBP with aggregation induced luminescence (AIE) properties not only has the characteristics mentioned above, but also can emit bright light in the aggregation state, thus it shows great application potential in luminescent imaging, sensing materials, fluorescent materials and other fields. Based on the discussion of the relationship between the structure of AIE type HBP and their luminescence properties, the development status of different AIE type HBP, including the AIE type HBP containing aromatic ring and the AIE type HBP containing atypical luminescence groups, is reviewed. Meanwhile, the luminescence mechanism of AIE type HBP is discussed, and their future development and application direction are prospected.
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  Research progress on electrode materials with high-performance in the supercapacitors of transition metal selenide

  WANG Shuaida, LIU Xiujun, ZHANG Jing

  Jorunal of Functional Materials. 2022, 53(12): 12047-12052. https://doi.org/10.3969/j.issn.1001-9731.2022.12.007

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  Transition metal selenides have high electrical conductivity, and the low electronegativity of selenium makes the weaker metal-selenium bond, which is more favourable for the occurrence of redox reactions. Transition metal selenides thus are potential electrode materials with high-performance in supercapacitors. In this work, it was firstly introduced that the main preparation methods of transition metal selenides were utilized at present. Next, the optimization strategies to improve their electrochemical performance were elaborated. On the one hand, the preparation methods were optimized, and the morphology and structure of the electrode material were adjusted by changing some factors such as reactant time, reaction temperature, electrolyte composition, and so on, improving the efficiency of ion transport. On the other hand, high-performance electrode materials were fabricated by (1) the preparation of binary transition metal components, (2) compounding with carbon-based materials, and (3) controlling structure to improve their electrochemical performance. Finally, its prospect and the key direction of development were described.
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  Recent progress in preparation and application of cellulose nanocrystalline flexible functional photonic materials

  LI Mengqing, LI Ren'ai, ZHANG Hongzhuang, CHEN Yan, LIU Zhulan, CAO Yunfeng

  Jorunal of Functional Materials. 2022, 53(12): 12053-12064. https://doi.org/10.3969/j.issn.1001-9731.2022.12.008

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  The use of green renewable cellulose nanocrystals (CNCs) with the ability to self-assemble photonic structures to construct flexible functional materials can provide rich visual information, reduce the cost and reduce the harm of non-degradable materials. However, due to the lack of effective soft energy consumption phase in the system, the photonic materials based on CNCs have shortcomings such as mechanical fragility and lack of dynamic optical response, which bring certain challenges to their functional expansion and application. Thus, according to the structural characteristics of CNCs, this paper introduces in detail the preparation methods and influencing factors of the current CNCs photonic membrane, and then summarizes the various synthesis and regulation strategies of the current CNCs photonic membrane from mechanical rigidity to mechanical flexibility and machine color responsiveness. At the same time, the promising application directions and future challenges of CNCs flexible functional photonic materials are emphasized in this paper.
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  Research progress of organic modified montmorillonite for wastewater treatment

  WANG Liyan, YANG Chao, LI Huan, ZHAO Bing, MA Wenhui, KAN Wei, YIN Guangming, GAI Yuanyuan, WU Wenting

  Jorunal of Functional Materials. 2022, 53(12): 12065-12072. https://doi.org/10.3969/j.issn.1001-9731.2022.12.009

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  Montmorillonite has good characteristics such as adjustable layer spacing, hydrophilic expansion, strong adsorption and cation exchangeability, which has attracted considerable attention in wastewater treatment. But natural montmorillonite has some shortcomings, such as strong hydrophilicity, low adsorption efficiency and poor selective adsorption, which severely limits the application range of montmorillonite to water treatment. After organically modified natural montmorillonite, the adsorption of the organic montmorillonite is greatly enhanced. Organic modified montmorillonite can significantly improve its adsorption capacity. Embarking from the organic modifier of surfactant, coupling agent and natural polymer, the research progress of organic montmorillonite for pollutants, including heavy metal ions, dyes, phenolic compounds, polycyclic aromatic hydrocarbons, etc. in waste water treatment at home and abroad in recent years are reviewed. The adsorption mechanism of organic montmorillonite to pollutants in water is analyzed. The future development direction and application prospect of organic montmorillonite materials are prospected.
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  Progress in the preparation of modified biochar and its removal of pollutants in water

  JIANG Jing, WU Yi, SHENG Guangyao

  Jorunal of Functional Materials. 2022, 53(12): 12073-12084. https://doi.org/10.3969/j.issn.1001-9731.2022.12.010

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  Biochar is widely used in pollutant removal, soil improvement, carbon fixation and emission reduction because of its wide range of raw materials, developed pore structure, large specific surface area, rich surface functional groups and low preparation cost. Modification of biochar, including physical modification, chemical modification and biological modification can effectively improve its original physical and chemical properties, and improve the removal effect of target pollutants. This paper systematically summarizes the modification method of biochar and its application in pollutant removal in water, as well as the function mechanism of modified biochar as an effective adsorbent in the removal of heavy metals, organic pollutants and inorganic nutrient element mechanism. It puts forward the main problems and possible development direction in the use of modified biochar in water pollution removal. It provides guidance for the application of modified biochar in wastewater treatment.
Research & Development
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  Preparation of high-performance Fe₂O₃ and its supercapacitive properties

  SONG Zhiting, JIANG Wencheng, HU Hongming, YANG Zize, SHU Ting, LI Yanhong

  Jorunal of Functional Materials. 2022, 53(12): 12085-12091. https://doi.org/10.3969/j.issn.1001-9731.2022.12.011

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  Fe₂O₃ is considered to be a promising negative material for aqueous supercapacitors due to its advantages of low cost, non-toxicity, rich sources and environmental friendliness. However, it also suffers from the disadvantages of low conductivity, unsatisfactory cycling and rate performance. In this paper, N, S codoped-Fe₂O₃ was prepared on carbon fiber paper (CFP) by a hydrothermal method followed calcination process in the presence of thiourea under ambient atmosphere. The results demonstrated that calcination in thiourea didn't change the phase of Fe₂O₃, but changed its morphology from interconnected structure composed of nanowires to a dense film with porous structure. Due to the improved conductivity and the increased reaction active sites, N, S-Fe₂O₃ not only showed high specific capacitance (473.2 mF/cm², 2 mA/cm²), superior rate performance (85.5%, 2-20 mA/cm²) and good cycling stability (96%, 15 mA/cm², 10 000 cycles), but also exhibited higher electrochemical reaction reversibility and coulomb efficiency. Finally, asymmetric supercapacitors were assembled employing N, S-Fe₂O₃ and commercial activated carbon as negative and positive electrode, respectively, and the volume specific capacitance was 2.1 F/cm³(1 mA/cm²). By connecting two assembled supercapacitors in series, a series of LED lights (rated voltage of 3 V) could be successfully lit up, demonstrating its practical applications.
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  Photo-electrocatalytic oxidation of sulfonamides by titanate nanotube electrodes

  CHEN Zihui, QIN Han, YANG Peng, LU Yue, YAO Shuo, XIAO Fei, CHEN Huiying, XIA Jianxin, XING Xuan

  Jorunal of Functional Materials. 2022, 53(12): 12092-12099. https://doi.org/10.3969/j.issn.1001-9731.2022.12.012

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  Titanate nanotubes (TNTs) electrodes were produced by hydrothermal treatment of Ti plates and characterized by XRD, TEM and SEM, systematically. The effects of the applied voltage on the degradation effect were investigated. Results showed that the hydrothermal method was successful in producing disordered TNTs electrodes with an inner diameter of 5 nm. Under the conditions of an initial SD concentration of 80 mg/L and an applied voltage of 5 V, the degradation efficiency of the TNTs electrode under the synergistic effect of photo-electrolysis and electrolysis was improved compared with that of photolysis or electrolysis alone, with a degradation rate of 97.38% in 50 min. The low TOC removal rate in the presence of high SD degradation rate itself indicates that a large number of SD degradation intermediates are present in the solution. The reactive sites in the SD molecule were identified by optimizing the conformation of the SD molecule at the B3LYP/6-31+g(d,p) level using Gaussian software and calculating the Fukui function and electron cloud density in combination with density functional theory (DFT). The two degradation pathways of SD were postulated by combining the results of the intermediates determined by high performance liquid chromatography tandem mass spectrometry (LC-MS), which detected six intermediates with mass-to-charge ratios (m/z) of 96, 187, 117, etc. It was investigated that TNTs have excellent performance in degrading antibiotics and have significant implications for the degradation of antibiotic-like pollution in present-day water bodies.
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  Synthesis of a water-soluble protoporphyrin polymer and its research on photodynamic inactivation of drug-resistant bacteria and cancer cells

  SHI Jiahao, LU Zhengnan, SHENG Yang, SUN Yixin, BRADLEY Mark, ZHANG Rong

  Jorunal of Functional Materials. 2022, 53(12): 12100-12109. https://doi.org/10.3969/j.issn.1001-9731.2022.12.013

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  Protoporphyrin IX (PPIX) is a photosensitizer in the photodynamic therapy. However, its aqueous insolubility is always a challenge for extensive applications. In this work, a water-soluble derivative of PPIX were synthesized by esterification of PPIX and polyethylene glycol (PEG400), and the PPIX derivative was polymerized with hexamethylene diisocyanate to form a water-soluble polyurethane. The PPIX derivatives were characterized and the results showed that the polyurethane had the highest singlet oxygen generation efficiency among PPIX and its derivatives. The photodynamic antibacterial activity of PPIX derivatives were investigated on escherichia coli, staphylococcus aureus and methicillin-resistant staphylococcus aureus respectively. The results indicated that the polyurethane reached about 100% antibacterial rate of 40 μmol/L based on PPIX unit after 405 nm laser irradiation for 5 min. The PPIX derivatives showed high biocompatibility when co-cultured with human adipose-derived stem cells and liver cancer cells (HePG2) in the dark. With exposed to 405 nm or 635 nm laser for 5 min, about 90% and 50% HePG2 cells were killed by polyurethane, which was the best among PPIX and its derivatives. Therefore, the polyurethane has the potential to be used as photodynamic therapy for both antibacterial and anticancer treatment.
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  Variation of compressive properties of calcium carbonate whisker reinforced cement-based compositesexposed to high temperature

  ZHANG Yi, WU Lishan, YU Zhihui, ZHANG Cong

  Jorunal of Functional Materials. 2022, 53(12): 12110-12115. https://doi.org/10.3969/j.issn.1001-9731.2022.12.014

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  Calcium carbonate whiskers can effectively improve the compressive properties of cement-based composites at room temperature, but the effect of calcium carbonate whiskers on the compressive properties of cement-based composites after high temperature is not clear. In this paper, the compressive properties of calcium carbonate whisker reinforced cement-based composites with different volume contents (0%, 0.5%, 1%, 2%) were studied at room temperature and 200 , 400 , 600 and 800 ℃ respectively. The test results show that the compressive strength and compressive toughness of the specimens increase first and then decrease with the increase of whisker content at room temperature, and the compressive performance of the material mixed with 1% calcium carbonate whisker is the best. The compressive strength and compressive toughness of the material at 200 ℃ are significantly higher than those at room temperature. When the target temperature exceeds 200 ℃, the high temperature has an obvious deterioration on the compressive performance of the material, and its compressive strength and compressive toughness continue declining. There is no obvious difference in the compressive performance of each group after 800 ℃, but under each target temperature, calcium carbonate whisker can improve the compressive strength and compressive toughness after high temperature. It shows that the addition of calcium carbonate whisker plays a positive role in improving the compressive properties of the material after high temperature.
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  NiCo-LDH/CNW/CC three-dimensional structure composite electrode and its electrochemical performance

  LONG Junjie, WANG Bing, XIONG Ying

  Jorunal of Functional Materials. 2022, 53(12): 12116-12120. https://doi.org/10.3969/j.issn.1001-9731.2022.12.015

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  NiCo-LDH has excellent electrochemical properties, but is easy to agglomerate and has poor electrical conductivity, so its intrinsic electrochemical properties cannot be reflected when used as an electrode. The standard solution is to disperse and load it on the surface of an inert substrate with good conductivity and a large specific surface area. In this paper, carbon nanowalls (CNW) with a three-dimensional porous structure were prepared for the first time on the surface of carbon cloth (CC) with a large specific surface area, good conductivity, and inertness by microwave plasma chemical vapor deposition technology further to improve its specific surface area and particle loading. NiCo-LDH was dispersed and supported on the CNW surface by electrodeposition to form a NiCo-LDH/CNW/CC three-dimensional composite electrode. The microstructure of the composite electrode was observed by SEM, and the material composition of the composite electrode was analyzed by Raman and XRD techniques. Finally, the electrochemical performance of the composite electrode in the three-electrode system was further studied by electrochemical technology. The results show that CNW coated on CC surface as a carrier can effectively inhibit the agglomeration of NiCo-LDH and increase the dispersion and effective exposure area of NiCo-LDH. The formed NiCo-LDH/CNW/CC three-dimensional composite electrode has a specific capacitance of 1.4 times NiCo-LDH/CC at a scan rate of 2 mV/s. At a current density of 2 mA/cm², the specific capacitance is as high as 3.9 F/cm² while exhibiting excellent rate performance. Moreover, after 10 000 cycles, the capacitance retention rate is still up to 70%, which is far better than the cycling stability of NiCo-LDH/CC, indicating that the prepared NiCo-LDH/CNW/CC composite electrode can give full play to the electrochemical performance of NiCo-LDH. It is a new type of electrode material with excellent application potential due to its excellent electrical properties, good loadability of CNW three-dimensional porous structure, and excellent mechanical and electrical properties of CC.
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  Research on the influence of In content on corrosion behavior of Mg-In binary alloys

  DENG Zhichao, SUN Junli, HOU Lifeng, DU Huayun, WANG Qian, LIU Xiaoda, WEI Yinghui

  Jorunal of Functional Materials. 2022, 53(12): 12121-12127. https://doi.org/10.3969/j.issn.1001-9731.2022.12.016

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  The corrosion behavior of solid solution Mg-xIn(x=1 wt%,2 wt%,4 wt%,6 wt%,10 wt%,14 wt%,18 wt%,35 wt%) alloys in 3.5 wt% NaCl solution was investigated using immersion test, electrochemical test, scanning electron microscope (SEM) and X-ray diffractometer (XRD). The results indicated that the corrosion resistance of Mg-In alloy weakened gradually when the In content rised. An appropriate amount of In element would make its inhibitory effect dominate the corrosion process of magnesium alloys, and the surface tends to form a protective double-layer corrosion layer structure, which blocks the erosion of 3.5 wt% NaCl solution to the substrate. On the contrary, its activities ability dominates at higher content, leading to its negative effect on corrosion protection. Therefore, Mg-xIn (x=1 wt%,2 wt,4 wt,6 wt,10 wt%) alloys with lower content have conspicuous corrosion resistance, and Mg-xIn (x=14 wt,18 wt,35 wt%) alloys with higher In content has more rapid corrosion due to the surface cannot form characteristic double-layer corrosion layer structure.
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  Bactericidal silver slow-release coconut shell activated carbon prepared by AgNO₃ vacuum impregnation

  KONG Xiangxin, FAN Jinyue, ZHANG Kun, HUANG Ju, HUANG Xiaoli, LI Wei, LIU Shouxin

  Jorunal of Functional Materials. 2022, 53(12): 12128-12132. https://doi.org/10.3969/j.issn.1001-9731.2022.12.017

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  The coconut shell activated carbon was impregnated with silver nitrate (AgNO₃) under vacuum conditions to prepare silver slow-release coconut shell activated carbon (Ag/AC) with sterilization effect. The bacteriostatic and bactericidal effect of Ag/AC was investigated by E.coli as an experimental strain. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and specific surface area analyzer were used to characterize the surface morphology, crystal structure, specific surface area and pore structure of the Ag/AC samples. The results show that the silver ions are reduced to elemental silver with a particle size of 200-800 nm on the surface of AC. With the increase of AgNO₃ impregnation concentration, the silver loading and particle size increased, and the BET surface area, total pore volume and average pore diameter of Ag/AC decreased, thus the bactericidal performance and anti silver loss performance improved. When the impregnation concentration of AgNO₃ solution was 8.0 g/L, the silver loading was the largest (0.44%) and the bactericidal performance was the best (99.26%). After 15 days of oscillation in water, the silver loss rate was 30%. Compared with atmospheric pressure impregnation under the same conditions, the loss rate of Ag/AC silver was 94.23%. The silver-loaded coconut shell activated carbon prepared by vacuum impregnation achieved a controlled silver release while maintaining a high sterilization rate.
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  Preparation and properties of lignin-based ordered porous carbon composite phase change materials

  LI Tianyang, PAN Hong, XU Lihui, NI Kai, LI Keting, SHEN Yong

  Jorunal of Functional Materials. 2022, 53(12): 12133-12138. https://doi.org/10.3969/j.issn.1001-9731.2022.12.018

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  Lignin-based ordered porous carbon (MC) was prepared using lignin as the raw material and mesoporous molecular sieve (SBA-15) as the template. The lignin-based ordered porous carbon composite MC/PEG was prepared by vacuum impregnation with polyethylene glycol (PEG). Its structure and properties were characterized by SEM, XRD, FT-IR and DSC methods. The results showed that the maximum loading of MC was up to 75% and the enthalpy of phase change was 89.7 J/g. When the loading was 60%, the thermal conductivity of MC/PEG was up to 0.5029 W/mK, which was 50.3% higher than that of pure PEG. The composite phase change material coated cotton fabric was prepared by the MC/PEG coating method. After infrared thermography analysis, it can be found that the coated cotton fabric had good temperature regulation performance compared with the cotton fabric.
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  Study on the influence of Fe²⁺ on the moisture resistance of manganese activated fluoride red phosphor

  CAI Wenting, HE Shengan, LIU Lili, YE Xinyu

  Jorunal of Functional Materials. 2022, 53(12): 12139-12146. https://doi.org/10.3969/j.issn.1001-9731.2022.12.019

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  This paper presents a green and simple redox strategy based on Fe²⁺, which is used for improving the moisture resistance of fluoride red phosphors. Fluorescent material K₂SiF₆:Mn⁴⁺ were synthesized by coprecipitation method, and the corresponding morphology, crystal component, elemental composition, photoluminescence properties, fluorescence lifetime, water resistance and thermal stability of samples before and after Fe²⁺ treatment were investigated. The scan electron microscope (SEM) test predicted that after Fe²⁺ ion treatment, the aggregation of K₂SiF₆:Mn⁴⁺ (T-KSFM) particles was effectively inhibited. The X-ray photoelectron spectroscopy (XPS) indicated that the diminution of Mn was evident on T-KSFM's particle surface after treatment. Spectral test results show that the strongest excitation peak was at about 468 nm, the second strongest peak was at about 360 nm, and the strongest narrowband emission peak was at 632 nm. After the Fe²⁺ treatment, T-KSFM phosphor was soaked in deionized water for 320 min. Its relative luminescence intensity was 80.3% of the initial luminescence intensity, while that of KSFM was only 63.4%. In addition, the color coordinates of WLEDs made by packaging T-KSFM as the red component, yellow powder YAG and blue chip packaging were (0.4110, 0.3963), which were in the warm white light region. The above results show that this simple redox strategy based on Fe²⁺ can improve the moisture resistance of fluoride red phosphors effectively, which provided novel ideas to obtaining fluoride phosphors that possess excellent moisture resistance.
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  Preparation and properties of carbon fiber modified epoxy resin matrix composites

  ZHENG Tianqi

  Jorunal of Functional Materials. 2022, 53(12): 12147-12151. https://doi.org/10.3969/j.issn.1001-9731.2022.12.020

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  Modified epoxy resin matrix composites with different carbon fiber doping amounts (0, 3 wt%, 6 wt%, 9 wt%) were prepared with epoxy resin E51 as the base material and carbon fiber as the reinforcing material. The effects of carbon fiber doping on the mechanical properties, micro morphology, thermal stability and thermal conductivity of epoxy resin matrix composites were studied. The results showed that the appropriate amount of carbon fiber doping improved the mechanical properties, thermal stability and thermal conductivity of epoxy resin matrix composites. With the increase of carbon fiber doping, the tensile strength, elongation at break, flexural strength and flexural modulus of the modified epoxy resin matrix composites first increased and then decreased. When the doping amount of carbon fiber was 6 wt%, the tensile strength, elongation at break, flexural strength and flexural modulus of the composites reached the maximum, which were 48.5 MPa, 1.86%, 85.6 MPa and 3.09 GPa respectively. With the increase of carbon fiber doping, the decomposition temperature and residue of the composites first increased and then decreased. When the doping content of carbon fiber was 6 wt%, the decomposition temperature and residue of the composite reached the maximum, which were 453.7 ℃ and 4.9% respectively. The thermal conductivity of the composites increased with the increase of carbon fiber doping, and when the doping amount of carbon fiber was less than 6 wt%, the growth rate of thermal conductivity was faster. Comprehensive analysis showed that the optimum doping amount of carbon fiber was 6 wt%.
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  Anisotropic magnetocaloric effect of spin-spinning fast-quenched ErCoSi ribbons

  ZHANG Yan, HU Jifan, ZHAO Tongyun, MO Zhaojun, CAO Boyu, SHANG Yingqi

  Jorunal of Functional Materials. 2022, 53(12): 12152-12156. https://doi.org/10.3969/j.issn.1001-9731.2022.12.021

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  The performance of magnetocaloric effect materials is one of the key factors restricting the development of magnetic refrigeration technology. Materials with anisotropic magnetocaloric effect can be used in rotary magnetic refrigeration technology, which is beneficial to the simplification of refrigeration devices. In this paper, the magnetic properties, magnetocaloric effects and magnetic anisotropy of rapidly quenched ErCoSi compounds are investigated. ErCoSi undergoes a second-order phase transition from ferromagnetic (FM) to paramagnetic (PM) at T_c=5.5 K. XRD shows that ErCoSi has a preferred orientation in(211)direction. In order to obtain a large magnetocaloric effect and to determine the effect of preferred orientation on magnetism and magnetocaloric effect, the isothermal magnetization curves in the directions of H∥and ⊥ cross section around the Curie temperature were analyzed. The corresponding magnetic entropy change (-ΔS_M) and magnetic refrigeration capacity (RC) were calculated. Under the magnetic field changed from 0-5 T, the values of -ΔS_M in the directions of H∥and ⊥ cross section were 17.5 J/kg k and 12 J/Kg K, respectively, and corresponding values of RC were 230 J/kg and 120 J/kg, respectively. The value of -ΔS_M reaches 12 J/kg k even at μ₀H=0-2 T in the directions of H∥cross section. It was obvious that ErCoSi fast quenching belt showed a large low-field magnetocaloric effect and obvious magnetic anisotropy, which was expected to realize the magnetic refrigeration technology of rotating samples.
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  Study on preparation and properties of carbon fiber/epoxy composite thermal insulation materials

  LIU Yanjin, ZHONG Xi

  Jorunal of Functional Materials. 2022, 53(12): 12157-12161. https://doi.org/10.3969/j.issn.1001-9731.2022.12.022

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  The untreated carbon fiber has great inertia. In order to improve the bonding effect between carbon fiber and epoxy resin, carbon fiber/epoxy composite thermal insulation materials were prepared by immersing carbon fiber in concentrated HNO₃ and controlling the immersion time. The effects of concentrated HNO₃ treatment time on the micro morphology, mechanical properties and thermal insulation properties of the composites were studied. The results showed that the surface of carbon fiber was oxidized, the number of grooves increased, and the bonding strength between epoxy resin and carbon fiber increased after treated with concentrated HNO₃. The tensile strength and elongation at break of carbon fiber/epoxy composite thermal insulation materials increased first and then decreased with the increaseof treatment time of concentrated HNO₃. When the treatment time of concentrated HNO₃ was 3 h, the tensile strength and elongation at break of the composite reached the maximum value of 45.9 MPa and 1.75% respectively. At 800 ℃, when the HNO₃ treatment time was 3 h, the maximum residual mass of the composite was 7.73%, and the thermal stability was the best. With the increase of treatment time of concentrated HNO₃, the thermal conductivity of the composite decreased first and then increased slightly. When the HNO₃ treatment time was 3 h, the thermal conductivity of the composite was the lowest 0. 027 W/(m·K), showing good thermal insulation performance.
Process & Technology
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  Ammonium polyphosphate modified by n-dodecyl trimethoxysilane and its application in acrylate sealant

  BI Jianhua, WU Jingxing, HAO Wanjun, WANG Zhong, FAN Min, CHEN Le, XUN Baoluo, FU Lisha

  Jorunal of Functional Materials. 2022, 53(12): 12162-12169. https://doi.org/10.3969/j.issn.1001-9731.2022.12.023

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  By ion exchange reaction, γ-Aminopropyl triethoxysilane (KH550) was grafted on the surface of ammonium polyphosphate (APP), and then hydrolyzed n-dodecyl trimethoxysilane (DTMS) was added to initiate the co-condensation reaction. The modified ammonium polyphosphate (C-APP) was successfully prepared. The APP and C-APP were characterized by FT-IR, XPS and SEM. The results showed that long-chain alkanes and Si-O-Si structures were grafted on the surface of APP, and the hydrophobic angle changed from 20.0°to 146.9°. A series of AS flame retardant sealants were prepared and tested for their water resistance. The results show that C-APP can further improve the flame retardant performance of AS composites. When 20 wt% C-APP is added, the LOI reaches 26 vol% and the UL-94 grade is V-0. The weight loss rate of APP/AS after immersion was 17.5%, while that of C-APP/AS decreased to 9.6%. In addition, the addition of C-APP improves the mechanical properties of AS composites and improves the compatibility between APP and AS.
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  Effect of microcystalline cellulose/gelatin on the properties of starch composite films

  ZHANG Jingxian, LONG Zhu, QIN Chengrong, CHEN Jie, ZHANG Dan

  Jorunal of Functional Materials. 2022, 53(12): 12170-12176. https://doi.org/10.3969/j.issn.1001-9731.2022.12.024

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  The work aims to explore the effects of microcrystalline cellulose/gelatin on heat sealing, mechanics and thermal stability performance of starch composite films with a view to improving the comprehensive properties of starch-based films. In this study, microcrystalline cellulose/gelatin (MCC/GL) was used as enhancement phase to prepare microcrystalline cellulose/gelatin/starch film (MCC/GL/ST) by solution casting method. Scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and thermo gravimetric analysis (TG) were used to analyze the films of apparent morphology and thermal stability, and the mechanical properties and heat sealing properties of starch films were characterized by heat sealing instrument and universal material tension. The result shows that compared with that of microcrystalline cellulose/starch film (MCC/ST), in microcrystalline cellulose/gelatin (2∶8)/starch film (MCC/GL/ST-2), heat sealing strength was increased by 352.9% and tensile strength was increased to 9.12 MPa. Infrared spectroscopy (FTIR) shows that there is a hydrogen bond interaction between MCC and GL, and the film barrier performance improves with the decrease of gelatin addition. The DSC and TG curves show that MCC/GL/ST-2 has good thermal stability, which can meet the heat sealing processability and ensure its stable performance.
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  Modification mechanism and fatigue characteristics of RCA modified asphalt

  LU Jiabao, WANG Guozhong, HU Jiangsan, LIU Zhongning

  Jorunal of Functional Materials. 2022, 53(12): 12177-12183. https://doi.org/10.3969/j.issn.1001-9731.2022.12.025

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  In order to further study the modification mechanism and fatigue characteristics of high modulus RCA modified asphalt, its performance is measured by three indexes, Brockfield viscosity, infrared spectrum, linear amplitude scanning and dielectric constant test. The basic indexes, fatigue properties, functional group changes of asphalt and the changes of asphalt components based on dielectric properties with different modifier contents are discussed, and grey correlation degree between the components and asphalt pavement performance index is analyzed. The results show that the optimum content of RCA modifier is 16.7% of asphalt mass. The modification of asphalt by RCA modifier is physical modification. Under low strain, the fatigue performance of RCA modified asphalt is better than that of base asphalt, and the strain dependence is higher. The fatigue life calculated by the new asphalt fatigue failure criterion has a good correlation with the fatigue life of asphalt mixture, and it is feasible to evaluate the fatigue resistance of RCA modified asphalt.
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  Synthesis and properties of amino acid-modified PASP fluorescent tracerantiscalants

  YU Rong, CHENG Keyao, FU Shaohua, LEI Huan, TIAN Zhigang, FANG Ping

  Jorunal of Functional Materials. 2022, 53(12): 12184-12188. https://doi.org/10.3969/j.issn.1001-9731.2022.12.026

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  The environment-friendly scale inhibitor polyaspartic acid (PASP) was grafted with tyrosine (Tyr) with fluorescent property and glutamic acid (Glu) with scale inhibition group. And a new environment-friendly fluorescent tracer scale inhibitor Tyr-Glu-PASP was prepared, which improved the CaSO₄ inhibition performance of PASP and added the fluorescent tracer effect. The synthesized product was characterized by IR, TGA and fluorescence spectrum. The results show that PASP, where phenolic hydroxyl group, carboxyl group, amide group and other scale inhibition groups were added, had excellent thermal stability. The results of scale inhibition performance research show that the scale inhibition rate of CaSO₄ could reach 96% when the ratio of total amino acid to PSI monomer was 0.6, the dosage concentration was 4 mg/L and the calcium ion concentration was 6 000 mg/L. The crystal changes of calcium sulfate were studied by scanning electron microscope, X-ray powder diffraction analysis and fluorescence spectrometry. The results show that CaSO₄ changed from regular columnar structure to agglomerate structure, and the crystal grains became smaller, which promoted the solubility of calcium scale crystal grains in water.
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  Preparation of carbon dot doped composite hydrogel and its detection and adsorption of Fe³⁺

  MA Peilin, ZHANG Yikun, SONG Yating, ZHANG Tao, LI Xu, LIU Zhiming

  Jorunal of Functional Materials. 2022, 53(12): 12189-12195. https://doi.org/10.3969/j.issn.1001-9731.2022.12.027

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  In this paper, CS-CD_S, GL-CD_S and SA-CD_S were prepared by using chitosan (CS), glucose (GL) and sodium alginate (SA) as the matrix of three biomass materials and melamine. CS-CD_S has the best fluorescence performance by comparison. By introducing CS-CD_S into the hydrogel based on SA, the specific fluorescence quenching effect of Fe³⁺ was obtained, and it had good adsorbability and recycle performance.The results show that (CS-CD_S)-SA-gel hydrogel can be used as an effective visual detection and adsorption of Fe³⁺, and has a good application prospect.
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  Effects of Zn²⁺ doping on properties of LiNiO₂ cathode materials

  ZHANG Qingbo, LI Donglin, GAO Jianhang, LI Tongxin, ZHANG Long

  Jorunal of Functional Materials. 2022, 53(12): 12196-12202. https://doi.org/10.3969/j.issn.1001-9731.2022.12.028

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  The Zn-doped LNO cathode material was synthesized by sol-gel method. The effects of doping different amounts of Zn²⁺ on the properties of LNO were investigated. The results show that the sample doped with 2 mol% Zn (LNO-2Zn) delivers enhanced cycling performance and rate capability. The capacity retention rate for doped sample is 80.0% at 1 C rate after 100 cycles, which is higher than 74.8% for pristine LNO. Pristine LNO delivers a discharge capacity of only 48 mAh/g at 10C, which is much lower than that of 112.1 mAh/g of LNO-2Zn under the same condition. The introduction of Zn²⁺ ion reduces the degree of Li/Ni mixing, accelerates the lithium ion transfer, and slows down the harmful phase transition, thereby enhancing the electrochemical performance of LNO.
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  Preparation and properties of rare earth Ce-modified Mg-Zn alloy

  LI Wei, HU Junmei, JIA Yajuan

  Jorunal of Functional Materials. 2022, 53(12): 12203-12207. https://doi.org/10.3969/j.issn.1001-9731.2022.12.029

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  Rare earth Ce-modified Mg-Zn alloy was prepared by casting method with Mg-Zn alloy as matrix and different content of rare earth element Ce. Scanning electron microscope (SEM), X-ray diffraction (XRD) and electronic universal testing machine were used to study the effect of the amount of rare earth element Ce on the crystal structure, micro morphology and mechanical properties of cast Mg-Zn alloy, in order to prepare rare earth magnesium alloy with high comprehensive properties. The results showed that the addition of rare earth Ce to Mg-Zn alloy formed Al₄Ce, which improved the crystallinity of Mg-Zn alloy, refined the average grain size of the alloy, and presented ductile fracture behavior. When the content of rare earth Ce was 0.8 wt%, the number of dimples on the fracture surface of Mg-Zn alloy was the most, and the grain size was the smallest, about 3.8-4.2 μm. After adding rare earth Ce, the hardness, tensile strength and fracture elongation of Mg-Zn alloy were significantly improved. When the doping amount of rare earth Ce was 0.8 wt%, the tensile strength and fracture elongation of Mg-Zn alloy reached the maximum, which were 192.5 MPa and 8.5% respectively. At this time, the hardness of Mg-Zn alloy basically reached the stable value of 52.8 HB. Comprehensive analysis shows that the optimum doping amount of rare earth Ce is 0.8 wt%.
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  Preparation and performance of flexible energy storage electrode materials with high areal capacitance

  SUN Jiafeng, JIN Zhendong, JIN Zhehai, ZHAO Yaping, CAI Zaisheng

  Jorunal of Functional Materials. 2022, 53(12): 12208-12214. https://doi.org/10.3969/j.issn.1001-9731.2022.12.030

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  A composite electrode material (CF-MCNT/Ni@Ni(OH)₂) with hierarchical structure composed of cotton fabric (CF), multi-walled carbon nanotubes (MCNT) and core-shell structured nickel@nickel hydroxide (Ni@Ni(OH)₂) was prepared by ultrasound-assisted impregnation-drying, chemical deposition and anodic oxidation. The structure and properties were characterized by means of scanning electron microscopy, X-ray diffraction analysis and electrochemical tests. The results show that the area specific capacitance of the electrode can reach 6 300 mF/cm² (4 927 mF/cm² at 3 mA/cm²) at a current density of 0.5 mA/cm² in 2 mol/L KOH solution, which is higher than that of CF-Ni@Ni(OH)₂, and the charge/discharge cycle performance has also been improved. The introduction of MCNT facilitates the formation of rough conductive layers on the surface of CF, which provides a reference for optimizing the electrode structure to prepare devices with high performance energy storage.
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  Preparation and electrochemical properties of graphene/lithium composite

  DU Zhenzhen, YU Fan, WANG Jun, WANG Jing, LI Jiongli, WANG Xudong

  Jorunal of Functional Materials. 2022, 53(12): 12215-12223. https://doi.org/10.3969/j.issn.1001-9731.2022.12.031

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  Safe and stable lithium anode material is the key for high energy density lithium metal battery system. Firstly, three kinds of graphene with different morphologic structures were prepared by microwave reduction, thermal reduction and mechanical exfoliation techniques, and then graphene/lithium composites were successfully prepared by pressing and laminating processes. The morphology, composition and structure of different graphene materials and the morphology of graphene/lithium composites were analyzed by scanning electron microscopy (SEM), Raman, X-ray photoelectron spectroscopy (XPS) and N₂ adsorption/desorption isotherms. At the same time, we evaluated the electrochemical performance of graphene/lithium composites as anodes by assembling Li||Li symmetry cells and all LiFeO₄ full batteries. The results show that graphene/lithium composites have a layered structure. Among microwave reduced graphene (MRGO), thermal reduced graphene (RGO) and mechanical exfoliated graphene (EG), MRGO is the most suitable for modifying lithium metal. The 4MRGO/3Li composite obtained by stacking three times have the best electrochemical properties. The symmetric battery based on 4MRGO/3Li has a stable cycle of 1200 cycles at a polarization voltage of about 9.9 mV. Compared with the symmetric battery using pure lithium metal, the polarization voltage of the symmetric battery using 4MRGO/3Li is reduced by 10.6 mV, indicating the excellent safety and stability for 4MRGO/3Li composite. The discharge capacity of LiFeO₄ full battery with 4MRGO/3Li composite as anode is maintained at 156 mAh/g after 800 cycles.
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  First principle calculation on magnetic and mechanical properties of Fe-Si alloys

  WANG Ting, YANG Jichun, LIU Xiangjun, YANG Changqiao

  Jorunal of Functional Materials. 2022, 53(12): 12224-12229. https://doi.org/10.3969/j.issn.1001-9731.2022.12.032

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  Based on the first-principles method, the effects of Si doping on the stability, magnetic properties and mechanical properties of the α-Fe system were calculated. The calculation results show that Si can exist stably in α-Fe and Fe-Si system is more stable than α-Fe. The total magnetic moment of the Fe-Si system is smaller than that of α-Fe, making the magnetostriction coefficient of the Fe-Si system smaller than that of α-Fe, and Si doping makes the peak value of state density shift to the left. The conductivity of Fe-Si system decreases and the resistivity increases, which increases the soft magnetic properties of the system. The doping of Si increases the hardness, decreases the toughness and reduces the machinability of the system. Moreover, the average bond length of Fe-Si system is smaller than that of pure Fe system, which enhances the bond energy of Fe-Si system. This is the main reason why the hardness of Fe-Si system is larger than that of pure Fe system. The doping of Si causes the charge density around Si to be significantly smaller than that of pure Fe system, which is the reason why the toughness of Fe-Si system is reduced.
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  Preparation of shrimp shells derived solid acid with deep eutectic solvents and its catalytic performance

  WANG Peng, DAI Yadong, ZHANG Jiajia, ZHAO Yupei

  Jorunal of Functional Materials. 2022, 53(12): 12230-12236. https://doi.org/10.3969/j.issn.1001-9731.2022.12.033

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  Phosphotungstic acid (HPW) was immobilized on shrimp shell (SS) powers with a three-component (HCl-choline chloride-ethylene glycol) acid deep eutectic solvent (ADES) as the impregnating solution, and the final product was named as ADES-HPW-SS. It was important that the strong affinity between DES and SS was the main reason for formation of stable HPW@SS composites, which was proved by various characterized technologies to conform the alternation of SS structures. Furthermore, acid components played a key role in decalcification of raw shrimp shells, and the acidity and structure of immobilized HPW was maintained with the aid of protons. The catalyst was tested in the condensation between acetone and glycerol, and it showed high catalytic performance as solid acids. Under mild reaction conditions (50 ℃, molar ratio of acetone to glycerol as 3∶1), the conversion of glycerol reached 97.1% in 2 h with solketal as the main product.