酞菁铁/MXene复合阴极的制备及电芬顿降解磺胺间二甲氧嘧啶

doi:10.15541/jim20240176

无机材料学报 ›› 2025, Vol. 40 ›› Issue (1): 61-69.DOI: 10.15541/jim20240176 CSTR: 32189.14.10.15541/jim20240176

酞菁铁/MXene复合阴极的制备及电芬顿降解磺胺间二甲氧嘧啶

刘会来¹^,²(), 李志豪¹^,², 孔德峰¹^,², 陈星¹^,²()

1.合肥工业大学资源与环境工程学院, 合肥 230009
2.合肥工业大学工业与装备技术研究院, 合肥 230009

收稿日期:2024-04-10 修回日期:2024-06-20 出版日期:2025-01-20 网络出版日期:2024-06-24
通讯作者: 陈星, 研究员. E-mail: xingchen@hfut.edu.cn
作者简介:刘会来(1996-), 男, 博士研究生. E-mail: 1141749101@qq.com
基金资助:
国家重点研发计划(2019YFC0408500);安徽生态文明研究院重点实验室(中心)开放基金(W2023JSKF0152)

Preparation of FePc/MXene Composite Cathode and Electro-Fenton Degradation of Sulfadimethoxine

LIU Huilai¹^,²(), LI Zhihao¹^,², KONG Defeng¹^,², CHEN Xing¹^,²()

1. School of Resources and Environmental Engineering, Hefei University of Technology, Hefei 230009, China
2. Institute of Industry and Equipment Technology, Hefei University of Technology, Hefei 230009, China

Received:2024-04-10 Revised:2024-06-20 Published:2025-01-20 Online:2024-06-24
Contact: CHEN Xing, professor. E-mail: xingchen@hfut.edu.cn
About author:LIU Huilai (1996-), male, PhD candidate. E-mail: 1141749101@qq.com
Supported by:
National Key R&D Program of China(2019YFC0408500);Open Foundation of the Key Lab (Center) of Anhui Institute of Ecological Civilization(W2023JSKF0152)

摘要/Abstract

摘要：

研发具有高活性和高稳定的电极材料, 是实现电芬顿体系高效降解磺胺类抗生素污染物的关键。本工作以MXene材料作为载体负载酞菁铁(FePc), 制备了FePc/MXene纳米复合材料, 并利用其作为阴极催化剂构建的电芬顿体系对磺胺间二甲氧嘧啶(SDM)进行降解。负载FePc后, 纳米复合材料依然保持手风琴状的片层结构, 并且表面略粗糙, 层间间距变小; FePc/MXene中FeN_x的配位数约为4, 且FePc与MXene之间的相互作用促进了电极表面的电子转移。在构建的电芬顿体系中, FePc/MXene电极在50 min内对SDM的降解率达到97.2%, 且在较宽的pH范围内表现出优异的催化性能和稳定性。降解性能显著提高主要归因于复合材料中引入FeN₄增强了O₂电催化还原为H₂O₂的活性。电芬顿体系主要通过自由基(·OH和·O₂^-)与非自由基(¹O₂)共同降解SDM。利用前沿轨道理论和Fukui函数阐明了SDM被不同活性物种攻击的位点, 降解途径主要有苯环的羟基化、苯环上氨基的氧化、C-S和S-N键断裂。此外, 循环和离子浸出实验证明所制备的阴极催化剂具有优异的稳定性。

关键词: 电芬顿, FePc/MXene, 磺胺间二甲氧嘧啶, 活性氧物种, 降解路径

Abstract:

Development of electrode materials with high activity and stability is a key issue to achieve efficient degradation of sulfonamide pollutants by electro-Fenton (EF) system. In this work, FePc/MXene nanocomposites were prepared by using MXene material as carrier to load iron phthalocyanine (FePc) and employed as cathodic catalyst to construct EF system for the degradation of sulfadimethoxine (SDM). After loading FePc, the nanomaterials retained accordion-like lamellar structure with slightly roughened surface and narrowed interlayer spacing. Coordination number of FeN_x in FePc/MXene was about 4, in which the interaction between FePc and MXene was favorable to promote the electron transfer at the electrode surface. In the EF system, the FePc/MXene electrode achieved a 97.2% degradation rate of SDM within 50 min, showing excellent catalytic performance and stability over wide pH range. The significant improvement in degradation performance was mainly attributed to the enhanced activity of O₂ electrocatalytic reduction to H₂O₂ by the introduction of FeN₄ in the composites. Free radical (·OH and ·O₂^-) and non-radical (¹O₂) pathways were co-operative in the degradation of SDM by EF system. Frontier orbital theory and Fukui function theoretically elucidated the sites where SDM was attacked by different reactive oxygen species, primarily degrading through hydroxylation of the benzene ring, oxidation of the amino group on the benzene ring, and cleavage of C-S and S-N bonds. In addition, cycling and ion leaching experiments demonstrated the excellent stability of the prepared cathode catalysts.

Key words: electro-Fenton, FePc/MXene, sulfadimethoxine, reactive oxygen species, degradation pathway

中图分类号:

刘会来, 李志豪, 孔德峰, 陈星. 酞菁铁/MXene复合阴极的制备及电芬顿降解磺胺间二甲氧嘧啶[J]. 无机材料学报, 2025, 40(1): 61-69.

LIU Huilai, LI Zhihao, KONG Defeng, CHEN Xing. Preparation of FePc/MXene Composite Cathode and Electro-Fenton Degradation of Sulfadimethoxine[J]. Journal of Inorganic Materials, 2025, 40(1): 61-69.

图/表 14

图1 FePc/MXene的SEM照片(a)、TEM照片(b)和EDS元素映射图像(c)

Fig. 1 (a) SEM image, (b) TEM image, and (c) EDS elemental mappings of FePc/MXene

图2 MXene、FePc和FePc/MXene纳米复合材料的XRD图谱

Fig. 2 XRD patterns of MXene, FePc, and FePc/MXene

图3 FePc/MXene的XPS谱图

Fig. 3 XPS spectra of FePc/Mxene (a) Survey; (b) N1s; (c) C1s; (d) O1s; (e) Ti2p; (f) Fe2p

图4 Fe箔、FePc和FePc/MXene的Fe K-edge XANES曲线(a)和R空间EXAFS曲线(b)

Fig. 4 Fe K-edge XANES curves (a) and EXAFS curves in R space (b) of Fe foil, FePc and FePc/MXene

图5 MXene/GCE、FePc/GCE和FePc/MXene/GCE的CV曲线(a)和Nyquist谱图(b)

Fig. 5 CV curves (a) and Nyquist plots (b) of MXene/GCE, FePc/GCE and FePc/MXene/GCE

图6 电芬顿体系中不同实验条件下SDM的降解率和动力学曲线

Fig. 6 SDM degradation rates and kinetics curves in the electro-Fenton system under different experimental conditions (a) Different cathode materials; (b) Initial SDM concentration; (c) Current density; (d) Initial pH

图7 BQ、TBA和L-组氨酸对SDM降解的影响(a)以及电芬顿体系中产生的·OH、·O2-和1O2的ESR谱图(b)

Fig. 7 (a) Effects of BQ, TBA and L-tryptophan radical scavengers on SDM degradation, and (b) ESR spectra of ·OH, ·O2- and 1O2 generated by catalyst in the electro-Fenton system

图8 SDM的几何优化构型

Fig. 8 Molecular geometry optimization of SDM (a) Optimized geometric structure; (b) HOMO and (c) LUMO distributions; (d) Molecular electrostatic potential; (e) Calculated Fukui index; (f) Degradation pathways of SDM

图S1 MXene和FePc/MXene的N2吸附-脱附等温线(a)及相应的孔径分布曲线(b)

Fig. S1 N2 adsorption-desorption isotherms (a) and corresponding pore size distribution curves (b) of MXene and FePc/MXene Colorful figure is available on website

图S2 MXene和FePc/MXene的FT-IR谱图

Fig. S2 FT-IR spectra of MXene and FePc/MXene Colorful figure is available on website

图S3 FePc(a)和FePc/MXene(b)在R空间的EXAFS拟合曲线

Fig. S3 EXAFS fitting curves in R space of FePc (a) and FePc/MXene (b)

图S4 FePc/MXene的循环稳定性(a)和循环实验中铁的浸出浓度(b)

Fig. S4 Cycling stability of FePc/MXene (a) and iron leaching concentration in the cycle experiment (b)

图S5 FePc/MXene电极反应前后的SEM照片(a)和XRD图谱(b)

Fig. S5 SEM images (a) and XRD patterns (b) of FePc/MXene electrode before and after reaction Colorful figure is available on website

表S1 FePc和FePc/MXene中Fe K-edge的EXAFS拟合参数

Table S1 EXAFS fitting parameters of Fe K-edge in FePc and FePc/MXene

Sample	Shell	CN	R/Å	σ²/(×10^-3, Å²)	ΔE₀/eV	R factor/%
FePc	Fe-N	4.0	1.93	7.9	3.2	1.8
FePc/MXene	Fe-N	4.1	1.96	1.1	5.1	1.5

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酞菁铁/MXene复合阴极的制备及电芬顿降解磺胺间二甲氧嘧啶

Preparation of FePc/MXene Composite Cathode and Electro-Fenton Degradation of Sulfadimethoxine

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