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

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

Abstract

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

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

CLC Number:

X703.1

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.

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.

Figures/Tables 18

References 41

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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

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

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

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

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

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

活性炭纤维毡负载N-TiO₂/MoS₂/N-TiO₂固定化漆酶降解双酚A

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