伯仲胺基团修饰Fe<sub>3</sub>O<sub>4</sub>磁性材料的制备和性能表征

周书威; 傅红; 杨方

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

周书威^{1, 2},
傅红²,
杨方^1, ,

1.
福州海关技术中心，福州 350001
2.
福州大学　生物科学与工程学院，福州 350108

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
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- 文章访问数: 245
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- PDF下载量: 6
- 被引次数: 0
出版历程
- 收稿日期: 2023-06-14
- 修回日期: 2023-08-10
- 录用日期: 2023-08-25
- 网络出版日期: 2023-08-31
- 刊出日期: 2024-04-15

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

ZHOU Shuwei^{1, 2},
FU Hong²,
YANG Fang^{1
, ,}

1.
Fuzhou Customs Technical Center, Fuzhou 350001, China
2.
College of Biological Science and Engineering, Fuzhou University, Fuzhou 350108, China

Funds: National Key Research and Development Special Project (2017YFF0211304); Fujian Provincial Natural Fund Project (2020J01098)

摘要

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。
- N-β-(氨乙基)-γ-氨丙基三甲氧基硅烷 /
- 酸化Fe₃O₄ /
- 直接修饰法 /
- 磁性吸附材料 /
- 修饰机制
Abstract: Endogenous substances, such as organic acids in food, can interfere with the detection of trace residues. To eliminate this effect, the magnetic adsorbent material was obtained by directly modifying acidified Fe₃O₄ with N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane (KH792) as an amination reagent. The optimal modification condition of KH792 for acidified Fe₃O₄ was optimized by response surface methodology, which was 82.5℃, pH=4.9, and KH792 addition of 1.8 mL. Under these optimal conditions, the acidified Fe₃O₄ directly modified by KH792 has an adsorption capacity of 22.8 mg/g and shows a 188% increase in the adsorption capacity of the gallic acid compared to commercially available Fe₃O₄. Additionally, the modified Fe₃O₄ exhibits excellent performances of rapid solid-liquid separation, good stability, and dispersibility. The properties of the directly modified products were characterized by BET, Zeta potential, FTIR, and XPS. The results show that KH792 bonds on Fe₃O₄ surface hydroxyl group's by Fe—O—Si bonding, and acidification improves the number of hydroxyl groups on Fe₃O₄ surface, thus improving the KH792 modification for Fe₃O₄. The magnetic products prepared in this work can be used for the purification of organic acids in complex sample matrices.
- N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane /
- acidified Fe₃O₄ /
- direct modification method /
- magnetic adsorbent materials /
- modification mechanism

HTML全文

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

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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

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

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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

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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)

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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

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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

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图 7 KH792对酸化Fe₃O₄的修饰

Figure 7. Modification of acidified Fe₃O₄ by KH792

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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

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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: pH	C: KH792 addition level/mL	Y: Adsorption capacity for gallic acid/(mg·g⁻¹)
1	70.0	4.0	1.5	16.33
2	90.0	4.0	1.5	19.39
3	70.0	6.0	1.5	17.04
4	90.0	6.0	1.5	15.78
5	70.0	5.0	0.5	15.45
6	90.0	5.0	0.5	16.01
7	70.0	5.0	2.5	18.92
8	90.0	5.0	2.5	19.93
9	80.0	4.0	0.5	15.21
10	80.0	6.0	0.5	14.68
11	80.0	4.0	2.5	17.56
12	80.0	6.0	2.5	16.45
13	80.0	5.0	1.5	21.54
14	80.0	5.0	1.5	21.35
15	80.0	5.0	1.5	21.56
16	80.0	5.0	1.5	20.11
17	80.0	5.0	1.5	21.66
Equation	Y=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.

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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

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