Preparation of molecularly imprinted-TiO2 and its properties of photoelectrocatalytic degradation of solubilized PHE

doi:10.11949/0438-1157.20230304

Abstract

Abstract:

Three types of molecularly imprinted-TiO₂ (MIP-TiO₂) were prepared by sol-gel method using phenanthrene (PHE), the Triton X-100 (TX-100) and their mixture as templates, respectively, and n-butyl titanate as the functional monomer. The corresponding thin film electrodes were prepared for treating simulated soil washing effluent within solubilized PHE by photoelectrocatalytic method. The properties of the MIP-TiO₂ and their thin film electrodes were characterized by XRD, nitrogen adsorption-desorption and SEM. The results showed that MIP-(TX-100) TiO₂ present outstanding property of removal solubilized PHE. With TX-100 as imprinted molecules, the crystallization of MIP-(TX-100) TiO₂ appears rutile phase, its specific surface area reached 63.533 m²/g, and the agglomeration of nanoparticles was also improved. The adsorption process of MIP-(TX-100) electrode towards solubilized PHE (30 mg/L) by TX-100 (5 g/L) followed the secondary kinetic model, which suggested that the process was mainly controlled by chemisorption. It is speculated that TiO₂ produces a large number of imprinted holes due to the molecular imprinting process. After the imprinted holes are enriched in TX-100 during the photocatalytic process, PHE breaks the micelle barrier, thereby improving the degradation efficiency of PHE.

Key words: molecular imprinting, TiO₂, catalyst, surfactants, PHE, waste water

摘要：

分别以菲（PHE）、非离子表面活性剂曲拉通X-100及两者的混合物作为模板，钛酸正丁酯为功能单体，通过溶胶-凝胶法，制备得到三种分子印迹-TiO₂[MIP-(TX-100)TiO₂，MIP-(PHE)TiO₂，MIP-(TX-100+PHE)TiO₂]，并且制备对应的薄膜电极，用于光电催化处理模拟土壤淋洗增溶废水PHE。通过XRD、氮气吸附脱附、SEM对MIP-TiO₂材料及其薄膜电极进行性能表征。结果表明，MIP-(TX-100)TiO₂中，TX-100印迹分子的引入会改变晶体结构，出现金红石晶相TiO₂，且其比表面积达到63.533 m²/g，TiO₂颗粒大小及分散性较为良好，团聚现象也得到了一定的改善，其对TX-100（5 g/L）增溶的PHE（30 mg/L）溶液光电催化降解率可达74.45%。MIP-(TX-100)TiO₂电极对增溶废水PHE的吸附过程更符合二级动力学模型，该过程主要受化学吸附所控制。推测分子印迹过程使TiO₂产生大量印迹空穴，在光电催化过程中印迹空穴富集TX-100后，使PHE破除胶束障碍，从而提高了PHE的降解效率。

关键词: 分子印迹, TiO₂, 催化剂, 表面活性剂, 菲, 废水

CLC Number:

O 643

Xin YANG, Xiao PENG, Kairu XUE, Mengwei SU, Yan WU. Preparation of molecularly imprinted-TiO₂ and its properties of photoelectrocatalytic degradation of solubilized PHE[J]. CIESC Journal, 2023, 74(8): 3564-3571.

杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.

Figures/Tables 8

Fig.1 Schematic diagram of photoelectrocatalytic degradation

Fig.2 XRD patterns of molecularly imprinted-TiO2 and NIP-TiO2

Table 1 Pore structure parameters of molecularly imprinted-TiO2 and NIP-TiO2

样品	比表面积/(m²/g)	总孔容/(cm³/g)	平均孔径/nm
NIP-TiO₂	11.31	0.01942	6.869
MIP-(PHE)TiO₂	67.75	0.08322	4.914
MIP-(TX-100)TiO₂	63.53	0.06229	3.922
MIP-(TX-100+PHE)TiO₂	69.61	0.07274	4.180

Fig.3 SEM images of molecularly imprinted-TiO2 and NIP-TiO2 electrode of magnification factor of 10000

Fig.4 Photoelectrocatalytic degradation performance diagram of NIP-TiO2 and MIP-TiO2 electrode

Fig.5 Adsorption kinetic model of molecularly imprinted-TiO2 electrode for TX-100 solubilized phenanthrene

Table 2 Kinetic parameters of photoelectrocatalytic degradation of TX-100 solubilized phenanthrene by MIP-TiO2 electrode

MIP-TiO₂电极	准一级动力学			准二级动力学
MIP-TiO₂电极	q_e/(mg/g)	K₁/min^-1	R²	q_e/(mg/g)	K₂/(mg/(g·min))	R²
MIP-(PHE)TiO₂	0.1348	0.0220	0.7880	0.1605	0.1607	0.8445
MIP-(TX-100)TiO₂	0.1918	0.0539	0.9405	0.2071	0.4950	0.9620
MIP-(TX-100+PHE)TiO₂	0.1553	0.0431	0.8629	0.1737	0.3705	0.9141

Fig.6 Mechanism of MIP-(TX-100)TiO2 degradation and solubilization PHE

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Preparation of molecularly imprinted-TiO₂ and its properties of photoelectrocatalytic degradation of solubilized PHE

分子印迹-TiO₂光电催化降解增溶PHE废水性能研究

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