活性炭纤维毡负载N-TiO2/MoS2/N-TiO2固定化漆酶降解双酚A

doi:10.16085/j.issn.1000-6613.2024-0248

化工进展 ›› 2025, Vol. 44 ›› Issue (2): 887-898.DOI: 10.16085/j.issn.1000-6613.2024-0248

活性炭纤维毡负载N-TiO₂/MoS₂/N-TiO₂固定化漆酶降解双酚A

李章良¹^,³^,⁴(), 杨月珠¹^,³^,⁴, 伍传田¹^,², 吕源财²

^1.莆田学院环境与生物工程学院，福建莆田 351100
^2.福州大学环境与安全工程学院，福建福州 350108
^3.福建省新污染物生态毒理效应与控制重点实验室，福建莆田 351100
^4.生态环境及其信息图谱福建省高等学校重点实验室，福建莆田 351100

收稿日期:2024-02-01 修回日期:2024-05-24 出版日期:2025-02-25 发布日期:2025-03-10
通讯作者: 李章良
作者简介:李章良（1975—），男，硕士，教授，研究方向为污水处理与资源化。E-mail：ptulizhangliang@126.com。
基金资助:
国家自然科学基金(51908132);福建省自然科学基金(2020J01912);莆田学院科研项目(2024036)

Degradation of bisphenol A by N-TiO₂/MoS₂/N-TiO₂immobilized laccase on activated carbon fiber felt

LI Zhangliang¹^,³^,⁴(), YANG Yuezhu¹^,³^,⁴, WU Chuantian¹^,², LYU Yuancai²

^1.College of Environmental and Biological Engineering, Putian University, Putian 351100, Fujian, China
^2.College of Environment and Safety Engineering, Fuzhou University, Fuzhou 350108, Fujian, China
^3.Fujian Provincial Key Laboratory of Ecology-Toxicological Effects ＆ Control for Emerging Contaminants, Putian 351100, Fujian, China
^4.Key Laboratory of Ecological Environment and Information Atlas, Fujian Provincial University, Putian 351100, Fujian, China

Received:2024-02-01 Revised:2024-05-24 Online:2025-02-25 Published:2025-03-10
Contact: LI Zhangliang

摘要/Abstract

摘要：

以活性炭纤维毡（ACFF）为基底，采用水热法与超声法相结合方式制备了活性炭纤维毡负载N-TiO₂/MoS₂/N-TiO₂光催化剂（NT/MS/NT/ACFF），并以此作为载体，通过共价结合法制得NT/MS/NT/ACFF固定化漆酶。利用扫描电子显微镜、X射线衍射仪、比表面积分析、拉曼光谱、紫外-可见分光光度计和傅里叶变换红外光谱等手段对样品的形貌、微观结构进行了表征，研究了不同体系对双酚A（BPA）的降解效果、反应动力学及矿化率，考察了催化剂的重复使用性能。结果表明，与其他体系相比，可见光下NT/MS/NT/ACFF固定化漆酶对BPA降解率高达82.5%，表观速率常数k_obs为0.00764min^-1，矿化率可达64.5%。NT/MS/NT/ACFF固定化漆酶具有良好的光催化、酶催化的活性及稳定性，循环使用4次后BPA降解率仍可达到69.4%。通过气相色谱-质谱（GC-MS）结果分析，推断BPA被NT/MS/NT/ACFF固定化漆酶的催化降解过程包括断裂重组、氧化分解、开环等反应。

关键词: 催化剂载体, 纳米二氧化钛, 二硫化钼, 漆酶, 固定化, 双酚A

Abstract:

N-TiO₂/MoS₂/N-TiO₂ (NT/MS/NT/ACFF) photocatalyst supported by activated carbon fiber felt (ACFF) was prepared by ultrasound assisted hydrothermal method, and used as the carrier of laccase. The NT/MS/NT/ACFF immobilized laccase was then obtained by covalent bonding method. The morphology and microstructure of the catalyst were characterized by means of SEM, XRD, BET, Raman, UV-vis DRS and FTIR. The effects of different systems on the degradation of bisphenol A (BPA). The reaction kinetics, mineralization rate and reusability of NT/MS/NT/ACFF immobilized laccase were studied. The results showed that compared with other systems, NT/MS/NT/ACFF immobilized laccase in visible light had the best degradation rate of BPA (82.5%), the apparent rate constant k_obs was 0.00764 min^-1, and the mineralization rate was up to 64.5%. NT/MS/NT/ACFF immobilized laccase has good photocatalysis performance, enzyme catalytic activity and stability, and the degradation rate of BPA can still reach 69.4% after 4 cycles. Through GC-MS analysis, we concluded that the catalytic degradation of BPA by NT/MS/NT/ACFF immobilized laccase includes steps of fracture recombination, oxidative decomposition and ring-opening reactions.

Key words: catalyst support, N-TiO₂, MoS₂, laccase, immobilization, bisphenol A

中图分类号:

X703.1

李章良, 杨月珠, 伍传田, 吕源财. 活性炭纤维毡负载N-TiO₂/MoS₂/N-TiO₂固定化漆酶降解双酚A[J]. 化工进展, 2025, 44(2): 887-898.

LI Zhangliang, YANG Yuezhu, WU Chuantian, LYU Yuancai. Degradation of bisphenol A by N-TiO₂/MoS₂/N-TiO₂immobilized laccase on activated carbon fiber felt[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 887-898.

图/表 18

图1 NT/MS/NT/ACFF制备流程图

图2 ACFF、NT/MS/NT/ACFF的SEM图

图3 ACFF、TiO2、NT/MS/NT/ACFF、MoS2的XRD图

图4 ACFF、NT/MS/NT/ACFF的N2吸附-脱附等温线及孔径分布图

表1 ACFF、NT/MS/NT/ACFF的比表面积、总孔容及平均孔径

样品	比表面积/m²·g^-1	总孔容/cm³·g^-1	平均孔径/nm
ACFF	1084.73	0.57	2.89
NT/MS/NT/ACFF	443.98	0.24	3.59

图5 ACFF、NT、NT/ACFF、NT/MS/NT/ACFF的Raman图

图6 ACFF、MoS2、NT/ACFF、NT/MS/NT/ACFF的漫反射光谱和带隙图

图7 NT/MS/NT/ACFF的XPS谱图

图8 固定化漆酶的SEM图

图9 NT/MS/NT/ACFF氨基改性和漆酶固定化的FTIR图

图10 不同体系对BPA的降解效果

表2 不同体系对BPA降解的拟一级动力学拟合参数

不同体系	拟一级动力学拟合方程	k_obs/min^-1	R²
固定化灭活漆酶	y = 0.000162x	0.000162	0.8731
可见光下固定化灭活漆酶	y = 0.00176x	0.00176	0.9526
固定化漆酶	y = 0.0022x	0.0022	0.9493
可见光下固定化漆酶	y = 0.00764x	0.00764	0.9858

图11 固定化漆酶循环使用对BPA降解效果的影响

图12 固定化漆酶循环使用的SEM图与XRD图

图13 NT/MS/NT/ACFF/PMS体系的EPR图及猝灭剂对BPA降解效果的影响

图14 N-TiO2和MoS2的能带结构图和光催化机理

图15 固定化漆酶对BPA的催化降解示意图

表3 GC-MS测定的BPA中间产物

序号	停留时间/min	化合物	化学式	质核比（m/z）
1	29.083	双酚A	C₁₅H₁₆O₂	228
2	10.708	2,4-二叔丁基苯酚	C₁₄H₂₂O	206
3	9.133	3-异丙基苯甲酸	C₁₀H₁₂O₂	164
4	7.258	对苯甲酸	C₈H₈O₂	136
5	10.308	2,5-二甲基对苯醌	C₈H₈O₂	136
6	7.808	丁烯二酸	C₅H₆O₄	130

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活性炭纤维毡负载N-TiO₂/MoS₂/N-TiO₂固定化漆酶降解双酚A

Degradation of bisphenol A by N-TiO₂/MoS₂/N-TiO₂immobilized laccase on activated carbon fiber felt

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