粉煤灰漂珠负载聚苯胺/ZnFe2O4复合材料制备及光催化降解性能研究

doi:10.3969/j.issn.2097-2806.2026.10.005

摘要/Abstract

摘要：

为了解决磺胺类抗生素造成的水污染问题，该研究采用原位聚合法制备了粉煤灰漂珠负载聚苯胺@铁酸锌（PANI@ZnFe₂O₄/FAC）复合材料。通过X射线衍射（XRD）、扫描电镜（SEM）、红外光谱（FT-IR）、紫外可见漫反射光谱（UV-vis DRS）、光致发光光谱（PL）和电化学阻抗谱（EIS）等手段表征分析了复合材料的物相结构、微观形貌和光电化学性质。以磺胺二甲基嘧啶（SMZ）作为降解废水中的目标污染物，评价了复合材料的光催化性能、耐久稳定性能和底物普适性能，并分析提出了光催化机理，通过L₉（3⁴）正交实验优化了制备条件。结果表明：在苯胺和ZnFe₂O₄/FAC质量比为1:1、苯胺和过硫酸铵摩尔比为1:2、盐酸浓度为0.5 mol/L和反应时间为8 h条件下制备的复合材料表现出优异的光催化性能，模拟可见光照射60 min时其对SMZ的最高降解率达到了98.90%。光催化活性的增强得益于PANI和ZnFe₂O₄/FAC之间Ⅱ型异质结的构建，实现了光生载流子的高效分离，降低了电化学阻抗。活性物种猝灭结果表明·O₂^-和h⁺在光催化过程中起到关键作用。

关键词: 粉煤灰漂珠, 聚苯胺, 铁酸锌, 复合材料, 光催化降解, 磺胺二甲基嘧啶

Abstract:

To solve the problem of water pollution caused by sulfonamide antibiotics, in this study, the composites of polyaniline@zinc ferrite loaded on fly-ash cenospheres （PANI@ZnFe₂O₄/FAC） were prepared by in-situ polymerization. The crystal structure, microstructure and photoelectrochemical properties of the composites were characterized by XRD, SEM, FT-IR, UV-vis DRS, PL and EIS. Sulfamethazine （SMZ） was used as the target pollutant in wastewater for degradation. The photocatalytic performance, durability and substrate universality of the composite were evaluated, and the photocatalytic mechanism was analyzed and proposed. The preparation conditions were optimized by L₉（3⁴） orthogonal experiment. The results showed that the composite material prepared under the condition of the mass ratio of aniline:ZnFe₂O₄/FAC of 1:1, the molar ratio of aniline: ammonium persulfate of 1:2, the concentration of hydrochloric acid of 0.5 mol/L and the reaction time of 8 h showed excellent photocatalytic performance. The highest degradation percentage of SMZ reached 98.90% under simulated visible light irradiation for 60 min. The enhanced photocatalytic activity could be ascribed to the construction of type-II heterojunction between PANI and ZnFe₂O₄/FAC, which had realized the efficient separation of photogenerated carriers and reduced the electrochemical impedance. The active species quenching results showed that ·O₂^- and h⁺ played key roles in the photocatalytic process.

Key words: fly-ash cenosphere, polyaniline, zinc ferrite, composite material, photocatalytic degradation, sulfamethazine

中图分类号:

O643.3

沈登绪, 楚留声. 粉煤灰漂珠负载聚苯胺/ZnFe₂O₄复合材料制备及光催化降解性能研究[J]. 日用化学工业（中英文）, 2026, 56(10): 1327-1336.

Dengxu Shen, Liusheng Chu. Preparation and photocatalytic degradation performance of polyaniline/ZnFe₂O₄ composites loaded on fly-ash cenospheres[J]. China Surfactant Detergent & Cosmetics, 2026, 56(10): 1327-1336.

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参考文献 30

[1]	左卫元, 谭微, 陀丽媚, 等. 构建可见光驱动的缺陷型Bi₂WO₆用于光催化降解磺胺甲恶唑[J]. 水处理技术, 2025, 51 (3) : 96-101. doi: 10.16796/j.cnki.1000-3770.2025.03.016
[2]	Xu T F, Yao J, Sui X J, et al. Construction of sulfur-doped spherical carbon nitride photocatalysts for the efficient removal of sulfonamide antibiotics[J]. Materials Letters, 2025, 406: 139846. doi: 10.1016/j.matlet.2025.139846
[3]	Qin Z Q, Zhu L, Ge X, et al. Flower-spherical Ag-Bi₂WO₆ photocatalytic degradation of sulfamethazine[J]. Inorganic Chemistry Communications, 2025, 171: 113618. doi: 10.1016/j.inoche.2024.113618
[4]	Zeng X L, Shu S, Wang X L, et al. Photocatalytic degradation of sulfamethazine using g-C₃N₄/TiO₂ heterojunction photocatalyst: Performance, mechanism insight and degradation pathway[J]. Materials Science in Semiconductor Processing, 2024, 181: 108595. doi: 10.1016/j.mssp.2024.108595
[5]	罗司玲, 艾建平, 李文魁, 等. 高级氧化技术降解典型抗生素的研究进展[J]. 化工进展, 2025, 44 (7) : 4169-4189. doi: 10.16085/j.issn.1000-6613.2024-0959
[6]	郑禾山, 朱芷薇, 李硕, 等. 高级氧化降解抗生素及降解产物的生态毒性评估[J]. 哈尔滨工业大学学报, 2025, 57 (2) : 44-56.
[7]	孙宇, 刘宝震, 安呈泰, 等. 基于高级氧化技术降解水中OPPs的研究进展[J]. 应用化工, 2024, 53 (2) : 428-432, 457.
[8]	胡怀生, 张鹏会. S型TiO₂/C₃N₅异质结光催化剂的制备及降解亚甲基蓝性能[J]. 日用化学工业 (中英文), 2025, 55 (8) : 980-988.
[9]	Yang H, Xie J B, Li X Y, et al. Flower-like ZnFe₂O₄/BiOI type p-n heterojunction nanorods facilitating the efficient degradation of tetracycline[J]. Applied Surface Science, 2025, 719: 164963. doi: 10.1016/j.apsusc.2025.164963
[10]	Chen Y, Zhong Y W, Diao Z H, et al. Photocatalytic generation of electron and hole for peroxymonosulfate activation to degrade levofloxacin over ZnO/ZnFe₂O₄ heterojunction[J]. Journal of Environmental Chemical Engineering, 2025, 13: 118233. doi: 10.1016/j.jece.2025.118233
[11]	Xu Z Y, Liu C Y, Cong H K, et al. Oxygen vacancy-engineered Z-scheme Bi₂O₂CO₃/ZnFe₂O₄ heterojunction for day-night tribo-photocatalytic removal of pollutants[J]. Journal of Environmental Chemical Engineering, 2025, 13: 118459. doi: 10.1016/j.jece.2025.118459
[12]	Sanei A, Kolvari E, Dashtian K. Molecular insights into selective alcohol oxidation on a biomass-derived ZnFe₂O₄/carbon photocatalyst[J]. Inorganic Chemistry Communications, 2025, 182: 115606. doi: 10.1016/j.inoche.2025.115606
[13]	Zhang J, Wang X Y, Zhang Y N, et al. Degradation of norfloxacin by magnetic recyclable Z-scheme heterojunctions CoWO₄/ZnFe₂O₄ photocatalysts[J]. Journal of Alloys and Compounds, 2025, 1014: 178740. doi: 10.1016/j.jallcom.2025.178740
[14]	Li Y Q, Dai Y M, Cai L, et al. Efficient adsorption and photocatalytic degradation of organic dyes by novel chitosan/polyaniline/MnFe₂O₄ composites[J]. Journal of Molecular Liquids, 2025, 424: 126995. doi: 10.1016/j.molliq.2025.126995
[15]	Jamuna M, Sulochana D. Synthesis of PANi-Ag nanocomposites using interfacial polymerization and its investigation as a photocatalyst for hazardous organic dyes[J]. Micro and Nanostructures, 2025, 210: 208462. doi: 10.1016/j.micrna.2025.208462
[16]	Farzadkia M, Esrafili A, Asgari E, et al. Investigating the toxicity of photocatalytic degradation products from metronidazole using ZnO/polyaniline and TiO₂/polyaniline nanocomposites: A bioassay study[J]. Desalination and Water Treatment, 2025, 321: 101005. doi: 10.1016/j.dwt.2025.101005
[17]	Low W L, Liew C W, Juan J C, et al. Development of polyaniline-tin oxide (PAni-SnO₂) as binary photocatalyst for toxic pollutant removal[J]. Polymer Bulletin, 2024, 82: 1-22. doi: 10.1007/s00289-024-05525-1
[18]	Shayista G, Amit K, Javed A, et al. Efficient visible light-induced photocatalytic degradation of tetracycline hydrochloride using CuFe₂O₄ and PANI/CuFe₂O₄ nanohybrids[J]. Environmental Science and Pollution Research International, 2023, 30: 108878-108888. doi: 10.1007/s11356-023-29976-7
[19]	张霞, 白羽石, 常熙, 等. BiOCl/聚苯胺的制备及其光催化降解罗丹明B性能[J]. 无机化学学报, 2025, 41 (5) : 913-922.
[20]	Bitaraf M, Amoozadeh A. A covalently engineered magnetically recyclable TiO₂/WO₃ heterojunction for visible-light-driven selective photooxidation[J]. Solid State Sciences, 2025, 171: 108113. doi: 10.1016/j.solidstatesciences.2025.108113
[21]	Fomenko E V, Akimochkina G V, Anshits N N. Dispersed PM10 microspheres from coal fly ash: fine fraction separation, characterisation, and glass-ceramic preparation[J]. Molecules, 2025, 30: 2600-2609. doi: 10.3390/molecules30122600
[22]	Zhang J, Wang B, Cui H, et al. Synthesis of CeO₂/fly ash cenospheres composites as novel photocatalysts by modified pyrolysis process[J]. Journal of Rare Earths, 2014, 32: 1120-1125. doi: 10.1016/S1002-0721(14)60192-7
[23]	Zhang J, Cui H, Wang B, et al. Fly ash cenospheres supported visible-light-driven BiVO₄ photocatalyst: Synthesis, characterization and photocatalytic application[J]. Chemical Engineering Journal, 2013, 223: 737-746. doi: 10.1016/j.cej.2012.12.065
[24]	Li L, Du X, Lin X, et al. One-step synthesis of floatable BiOCl/BiOBr@FACs enriched in oxygen vacancies for improved photocatalytic activity via peroxymonosulfate activation[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 676: 132165. doi: 10.1016/j.colsurfa.2023.132165
[25]	Raj A, Tembhurkar A R. Taguchi optimization for synthetization of novel Fe₂O₃/TiO₂/fly ash nanophotocatalyst via hydrothermal combined waterbath precipitation method for the degradation of sodium isopropyl xanthate[J]. Inorganic Chemistry Communications, 2025, 181: 115149. doi: 10.1016/j.inoche.2025.115149
[26]	岑凤, 李俊. 改性尖晶石催化盐酸四环素降解性能及机理研究[J]. 日用化学工业 (中英文), 2025, 55 (4) : 472-480.
[27]	朱砚, 李薇, 邱小燕. CdS/g-C₃N₄复合材料的制备及对刚果红的光催化降解[J]. 日用化学工业(中英文), 2025, 55 (5) : 573-580.
[28]	何妍妍, 申乾宏, 曹子林, 等. 1D/2D型AgVO₃/Bi₂WO₆复合光催化材料制备及其可见光催化性能[J]. 材料科学与工程学报, 2025, 43 (5) : 715-721, 764.
[29]	Song Y Y, Ding J J, Zhou T, et al. Precious metal-free Bi₅O₇I/CoS rod-like type-II heterostructures for efficient photocatalytic hydrogen production[J]. International Journal of Hydrogen Energy, 2025, 198: 152644. doi: 10.1016/j.ijhydene.2025.152644
[30]	Lu B W, Wang L, Zhu X Y, et al. Coral like g-C₃N₄/Br-Bi₂O₂CO₃ type-II heterojunction with efficient photocatalytic performance and mechanism for degradation of tetracycline[J]. Solid State Sciences, 2025, 160: 107765. doi: 10.1016/j.solidstatesciences.2024.107765

序号	因素				SMZ降解率/%
序号	ANI和ZnFe₂O₄/FAC质量比	ANI和APS摩尔比	盐酸浓度/（mol/L）	反应时间/h	SMZ降解率/%
1	2:1	2:1	0.5	6	65.01
2	2:1	1:1	1.0	8	65.51
3	2:1	1:2	1.5	10	70.15
4	1:1	2:1	1.0	10	80.17
5	1:1	1:1	1.5	6	74.35
6	1:1	1:2	0.5	8	98.90
7	1:2	2:1	1.5	8	61.98
8	1:2	1:1	0.5	10	61.49
9	1:2	1:2	1.0	6	72.11
均值1	66.890	69.053	75.133	70.490
均值2	84.473	67.117	72.597	75.463
均值3	65.193	80.387	68.827	70.603
极差	19.280	13.270	6.306	4.973

材料	原子分数/%
材料	O	Al	Si	Fe	Zn	C	N
ZnFe₂O₄/FAC	30.81	10.48	12.86	35.84	10.01
PANI@ZnFe₂O₄/FAC	15.41	0.91	1.12	13.44	4.39	57.33	7.40

粉煤灰漂珠负载聚苯胺/ZnFe₂O₄复合材料制备及光催化降解性能研究

Preparation and photocatalytic degradation performance of polyaniline/ZnFe₂O₄ composites loaded on fly-ash cenospheres

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