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伯仲胺基团修饰Fe3O4磁性材料的制备和性能表征

周书威 傅红 杨方

周书威, 傅红, 杨方. 伯仲胺基团修饰Fe3O4磁性材料的制备和性能表征[J]. 复合材料学报, 2024, 41(4): 1977-1986. doi: 10.13801/j.cnki.fhclxb.20230831.003
引用本文: 周书威, 傅红, 杨方. 伯仲胺基团修饰Fe3O4磁性材料的制备和性能表征[J]. 复合材料学报, 2024, 41(4): 1977-1986. doi: 10.13801/j.cnki.fhclxb.20230831.003
ZHOU Shuwei, FU Hong, YANG Fang. Preparation and performance characterization of primary secondary amine-modified Fe3O4 magnetic materials[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1977-1986. doi: 10.13801/j.cnki.fhclxb.20230831.003
Citation: ZHOU Shuwei, FU Hong, YANG Fang. Preparation and performance characterization of primary secondary amine-modified Fe3O4 magnetic materials[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1977-1986. doi: 10.13801/j.cnki.fhclxb.20230831.003

伯仲胺基团修饰Fe3O4磁性材料的制备和性能表征

doi: 10.13801/j.cnki.fhclxb.20230831.003
基金项目: 国家重点研发专项(2017YFF0211304);福建省自然基金项目(2020J01098)
详细信息
    通讯作者:

    杨方,博士,主任技师,研究方向为食品安全检测 E-mail: 964890740@qq.com

  • 中图分类号: TB331

Preparation and performance characterization of primary secondary amine-modified Fe3O4 magnetic materials

Funds: National Key Research and Development Special Project (2017YFF0211304); Fujian Provincial Natural Fund Project (2020J01098)
  • 摘要: 食品中的有机酸等内源性物质会干扰其中痕量残留物的检测,为消除此影响,以N-β-(氨乙基)-γ-氨丙基三甲氧基硅烷(KH792)为氨基化试剂,直接修饰酸化后的Fe3O4得到磁性吸附材料。经响应面试验优化得到KH792对酸化Fe3O4的最佳修饰条件为温度 82.5℃、pH=4.9,KH792添加量 1.8 mL,在最佳条件下,KH792直接修饰的酸化Fe3O4对没食子酸吸附量为22.8 mg/g,比市售Fe3O4提高了188%,且具备快速固液分离的能力、良好的稳定性及分散性。通过BET、Zeta电位、FTIR和XPS对直接修饰的产物性能进行了表征,结果表明,KH792与Fe3O4表面羟基通过Fe—O—Si键结合,酸化提高了Fe3O4表面羟基含量,因此也增强了KH792对Fe3O4的修饰效果,本文制备的磁性产物可用于净化复杂样品基质中的有机酸。

     

  • 图  1  不同pH下Fe3O4消耗盐酸量随时间的变化(a)、回收率的变化(b)、不同温度下Fe3O4消耗盐酸量(c)

    Figure  1.  Variation of hydrochloric acid consumption by Fe3O4 with time (a), the recovery at different pH (b), the consumption of hydrochloric acid by Fe3O4 at different temperatures (c)

    V—Consumption of hydrochloric acid by Fe3O4; t—Acidification time

    图  2  自变量和没食子酸吸附量的等高线和响应面图:(a) 温度和pH;(b) pH和KH792添加量;(c) 温度和KH792添加量

    Figure  2.  Contour and response surface plots of the independent variables and gallic acid sorption: (a) Temperature and pH; (b) pH and KH792 addition level; (c) Temperature and KH792 addition level

    Qe—Adsorption capacity of Fe3O4-2NH2 for gallic acid; Volume is KH792 addition level

    图  3  不同材料的没食子酸吸附量

    Figure  3.  Adsorption capacity of different materials for gallic acid

    GCB—Graphitized carbon black; PSA—Primary secondary amine; I—KH792 post-modification product; II—KH792 modified unacidified Fe3O4; III—KH792 modified acidified Fe3O4; IV—KH792 acidified Fe3O4 modified by optimized conditions

    图  4  Fe3O4 (a)和酸化的Fe3O4 (b)的N2吸附-解吸等温线;Fe3O4和酸化的Fe3O4的红外图谱(c)和XPS全谱(d); Fe3O4 (e)和酸化的Fe3O4(f)的O1s图谱

    Figure  4.  N2 adsorption-desorption isotherms of Fe3O4 (a) and acidified Fe3O4 (b); Infrared spectra (c) and XPS wide-scan spectra (d) of Fe3O4 and acidified Fe3O4; O1s XPS spectra of Fe3O4 (e) and acidified Fe3O4 (f)

    图  5  (a) Fe3O4和KH792修饰的未酸化Fe3O4的红外图谱;酸化的Fe3O4和KH792修饰的酸化Fe3O4的红外图谱(b)和XPS全谱(c);KH792修饰的酸化Fe3O4的N1s (d)、Si2p (e)、O1s (f) XPS图谱;(g) 酸化的Fe3O4的O1s XPS图谱

    Figure  5.  (a) Infrared spectra of Fe3O4 and KH792 modified unacidified Fe3O4; Infrared (b) and XPS full spectra (c) of acidified Fe3O4 and KH792 modified acidified Fe3O4; N1s (d), Si2p (e), O1s (f) XPS spectra of KH792 modified acidified Fe3O4; (g) O1 XPS spectra of acidified Fe3O4

    图  6  Fe3O4和KH792修饰的酸化Fe3O4的XRD衍射图(a)和磁滞回线(b)

    Figure  6.  XRD diffraction patterns (a) and magnetic hysteresis loops (b) of Fe3O4 and KH792 modified acidified Fe3O4

    图  7  KH792对酸化Fe3O4的修饰

    Figure  7.  Modification of acidified Fe3O4 by KH792

    图  8  不同时间下乙醇中的KH792修饰Fe3O4产物

    Figure  8.  KH792 modified Fe3O4 products in ethanol at different time

    1—Fe3O4; 2—KH792 modified unacidified Fe3O4; 3—KH792 modified acidified Fe3O4

    表  1  响应面试验设计、结果及方差分析

    Table  1.   Response surface experimental design, result and analysis of variance

    No.A: Temperature/℃B: pHC: KH792 addition level/mLY: Adsorption capacity for
    gallic acid/(mg·g−1)
    170.04.01.516.33
    290.04.01.519.39
    370.06.01.517.04
    490.06.01.515.78
    570.05.00.515.45
    690.05.00.516.01
    770.05.02.518.92
    890.05.02.519.93
    980.04.00.515.21
    1080.06.00.514.68
    1180.04.02.517.56
    1280.06.02.516.45
    1380.05.01.521.54
    1480.05.01.521.35
    1580.05.01.521.56
    1680.05.01.520.11
    1780.05.01.521.66
    EquationY=21.25+0.4204A−0.5677B+1.44C−1.08AB+0.1126AC−0.1437BC−1.25A2−2.86B2−2.41C2
    Note: KH792—N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.
    下载: 导出CSV

    表  2  不同修饰方法制得产物的Zeta电位

    Table  2.   Zeta potential of products made by different modification methods

    Product Zeta potential/mV
    Fe3O4 19.02
    KH792 post-modification product 33.99
    KH792 modified unacidified Fe3O4 30.59
    KH792 modified acidified Fe3O4 42.92
    下载: 导出CSV
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  • 收稿日期:  2023-06-14
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