配体诱导制备NM88（D）/COF-OMe复合材料及可见光芬顿联合降解抗生素磺胺甲嘧啶研究

doi:10.11949/0438-1157.20210289

摘要/Abstract

摘要：

基于配体诱导界面生长策略，制备了具有优异光芬顿降解性能与稳定性的NM88（D）/COF-OMe复合材料，并对该材料的结构形貌与光电性能进行表征。表征结果说明：DMTP的锚定能够诱导复合材料内部形成紧密连接的异质界面，并提高COF-OMe在NM88（D）表面的分散度，提升该材料的比表面积、可见光吸收能力和光生载流子分离能力，从而增强复合材料的光催化能力。光芬顿降解性能测试表明：NM88（D）/COF-OMe对磺胺甲嘧啶（SMR）的降解速率常数为0.0658 min^-1，明显高于原始材料和其他已报道的催化剂。经循环使用10次后复合材料的降解率仍能保持初始态的95%以上，表明NM88（D）/COF-OMe具有良好的结构稳定性。最后，对复合材料光芬顿降解SMR的催化机理进行推导，NM88（D）/COF-OMe优异的催化能力归因于异质界面的存在提升了光生载流子分离效率并促使·OH高效生成。

关键词: 配体诱导, NM88（D）/COF-OMe, 磺胺甲嘧啶, 光芬顿, 界面

Abstract:

Based on the “ligand-induced interfacial growth” strategy, NM88(D)/COF-OMe composite with excellent photo-Fenton degradation performance and photo-stability towards sulfamerazine (SMR) was constructed. The morphologies and photoelectric properties of the materials were characterized and the results showed that: the anchoring of DMTP induced the formation of a tightly connected hetero-interface inside the composite, improved the dispersion of COF-OMe on the surface of NM88(D), the specific surface area, visible light absorption and photogenerated carrier separation capacity. As a consequence, the photocatalytic ability of the composite was enhanced. The results of the composite catalytic performance measurements showed that the apparent rate constant of NM88(D)/COF-OMe was 0.0658 min^-1, which was significantly higher than that of the pristine materials and other reported catalysts. The catalytic activity of the composite remained more than 95% after 10 cycles of degradation, indicating that the NM88(D)/COF-OMe possessed superior structural stability. Finally, the catalytic mechanism for the degradation of SMR by photo-Fenton of the composite material is deduced. The excellent catalytic ability of NM88(D)/COF-OMe is attributed to the existence of heterogeneous interface, which improves the separation efficiency of photogenerated carriers and promotes the high efficient generation of hydroxyl radical (·OH). The current study offered a promising strategy for developing high performance photo-Fenton active MOF/COF composites formed by the “ligand-induced interfacial growth” strategy for a range of practical applications.

Key words: ligand-induced, NM88(D)/COF-OMe, sulfamerazine, photo-Fenton, interface

中图分类号:

O 643

胡小龙, 公文学, 彭艺, 胡阳, 汤颖, 何辉, 李文愿, 赵钟兴, 赵祯霞. 配体诱导制备NM88（D）/COF-OMe复合材料及可见光芬顿联合降解抗生素磺胺甲嘧啶研究[J]. 化工学报, 2021, 72(9): 4730-4739.

Xiaolong HU, Wenxue GONG, Yi PENG, Yang HU, Ying TANG, Hui HE, Wenyuan LI, Zhongxing ZHAO, Zhenxia ZHAO. Construction of NM88(D)/COF-OMe composite via ligand-induced interfacial growth strategy for highly efficient photo-Fenton degradation of antibiotic sulfamerazine under visible light[J]. CIESC Journal, 2021, 72(9): 4730-4739.

图/表 8

图1 NM88、COF-OMe、NM88(D)、NM88/COF-OMe和NM88(D)/COF-OMe的扫描电镜图

Fig.1 SEM images of NM88, COF-OMe, NM88(D), NM88/COF-OMe and NM88(D)/COF-OMe

图2 不同材料的XRD谱图(a)、N2吸附-脱附等温线(b)和XPS谱图[(c)、(d)]

Fig.2 XRD patterns(a), N2 adsorption-desorption isotherms(b) and XPS spectra[(c), (d)] of different materials

表1 不同材料的孔隙结构参数

Table 1 The pore structure parameters of different materials

Sample	S_BET/ (m²/g)	S_mic/ (m²/g)	S_meso/ (m²/g)	S_meso/S_mic	V_t/ (cm³/g)	V_mic/ (cm³/g)
NM88	35.3	9.5	25.8	2.7	0.106	0.028
COF-OMe	2166.7	698.9	1467.8	2.1	1.364	0.443
NM88(D)	28.6	7.3	21.3	2.9	0.087	0.022
NM88/COF-OMe	442.9	138.4	304.5	2.2	0.437	0.136
NM88(D)/COF-OMe	639.9	159.9	480.0	3.0	0.613	0.153

表2 XPS测试的样品的表面元素（C、N、O和Fe）含量

Table 2 Surface element （C， N， O and Fe） distribution of samples determined from XPS

Sample	C 1s/ %(at.)	N 1s/ %(at.)	O 1s/ %(at.)	Fe 2p/ %(at.)
NM88	59.17	6.92	29.00	4.90
COF-OMe	84.32	6.92	8.76	0.00
NM88(D)	59.30	6.67	29.21	4.82
NM88/COF-OMe	67.73	6.40	22.64	3.23
NM88(D)/COF-OMe	70.10	7.33	19.53	3.05

图3 不同材料的紫外-可见漫反射吸收光谱(a)、(ahv)1/2对光能(hv)带隙图(b)、电化学阻抗谱(c)和光致发光光谱(d)

Fig.3 UV-Vis DRS spectra(a), plots of (ahv)1/2versus photon energy (hv)(b), electrochemical impedance spectroscopy(c) and PL spectra(d) for different materials

图4 在可见光下不同材料的光芬顿SMR降解(a)、降解动力学拟合(b)和NM88(D)/COF-OMe的循环性能(c)

Fig.4 Photo-Fenton degradation of SMR(a), calculated degradation kinetics constants under visible light for different materials(b) and recycling performance of NM88(D)/COF-OMe(c)

表3 对比不同材料降解相似磺胺类抗生素的降解速率

Table 3 Comparison of degradation rate of similar sulfonamide antibiotics by different materials

Catalyst	Pollutant	Concentration/(mg/L)	V^①/ml	Catalyst/mg	H₂O₂/ (mmol/L)	pH	k^②×10⁴/ (L/(mmol·min))	Ref.
SBC	SMT^③	10	78	40	10	7.4	1.1	[33]
Fe₂O₃-CeO₂	SMR	20	250	125	8	3.0	1.3	[6]
CuFeO	SMT	50	100	50	60	6.0	1.7	[34]
CUS-MIL-100(Fe)	SMT	20	80	40	6	3.0	3.1	[35]
FeCu@C	SMT	20	80	20	1.5	3.0	18.6	[36]
NM88(D)/COF-OMe	SMR	10	100	10	2	6.2	32.9	this work

图5 NM88(D)/COF-OMe捕获主要活性物种实验(a)和可见光照下DMPO-·OH的ESR谱图(b)

Fig.5 Trapping experiments for major active species(a) and ESR spectra of DMPO-·OH under visible light irradiation(b)

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