改性尖晶石催化盐酸四环素降解性能及机理研究

doi:10.3969/j.issn.2097-2806.2025.04.009

摘要/Abstract

摘要：

尖晶石光催化剂具有环境友好性和优异的稳定性，在光催化降解抗生素废水方面有着广阔的应用潜力。本研究用水热法制备了铬（Cr）掺杂的ZnAl₂O₄尖晶石光催化剂，通过XRD、SEM、EDS、FTIR、PL等手段表征了该催化剂的物相结构、微观形貌、光谱性能，以盐酸四环素为降解对象，通过氙灯照射探究了Cr掺杂ZnAl₂O₄尖晶石光催化剂的催化性能。研究结果表明：水热法制备的ZnAl₂O₄尖晶石属于正尖晶石结构，ZnAl₂O₄的形貌为180~400 nm的不规则的块体，具有多孔结构，Cr掺杂后没有改变ZnAl₂O₄的晶格结构，并且Cr均匀分布在ZnAl₂O₄中。Cr掺杂到ZnAl₂O₄后降低了带隙宽度，Zn_0.4Cr_0.6Al₂O₄试样的带隙宽度最小仅2.87 eV，光致发光强度显著降低。试样在光照180 min时对盐酸四环素的降解率最高为96.02%，在pH 3的酸性条件下降解率增大至97.95%，该试样循环试验5次后降解率保持在90%以上，具有优异的重复使用性能。

关键词: ZnAl₂O₄尖晶石, Cr掺杂, 盐酸四环素, 光催化, 重复使用

Abstract:

Spinel photocatalysts have environmental friendliness and excellent stability, which have broad application potential in the photocatalytic degradation of antibiotic wastewater. In this work, Cr-doped ZnAl₂O₄ spinel photocatalyst was prepared by hydrothermal method. The crystal structure, microstructure and spectral properties of the catalyst were characterized by XRD, SEM, EDS, FTIR and PL. Tetracycline hydrochloride was used as the degradation object. The catalytic performance of Cr-doped ZnAl₂O₄ spinel photocatalyst was investigated under xenon lamp irradiation. The results showed that the ZnAl₂O₄ spinel prepared by hydrothermal method was of normal spinel structure. The morphology of ZnAl₂O₄ was irregular blocks of 180-400 nm with porous structure. The lattice structure of ZnAl₂O₄ was not changed after Cr doping, and Cr was uniformly distributed in ZnAl₂O_4.The band gap width of Zn_0.4Cr_0.6Al₂O₄was only 2.87 eV, and the photoluminescence intensity of Zn_0.4Cr_0.6Al₂O₄ was significantly reduced. The highest percentage of degradation of tetracycline hydrochloride catalyzed by Zn_0.4Cr_0.6Al₂O₄ samples at 180 min irradiation was 96.02%, and the degradation percentage was increased to 97.95% at pH 3.The degradation percentage could still maintain above 90% after 5 cycles of testing, indicative of excellent reusability.

Key words: ZnAl₂O₄ spinel, Cr doping, tetracycline hydrochloride, photocatalysis, reuse

中图分类号:

O643.3

岑凤, 李俊. 改性尖晶石催化盐酸四环素降解性能及机理研究[J]. 日用化学工业（中英文）, 2025, 55(4): 472-480.

Feng Cen, Jun Li. Study on the catalytic degradation of tetracycline hydrochloride by modified spinel and its mechanism[J]. China Surfactant Detergent & Cosmetics, 2025, 55(4): 472-480.

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样品	2θ/（°）	a=b=c/nm	V/nm³	D/nm
x=0	36.88	0.809 6	0.530 65	242
x=0.2	36.89	0.809 2	0.529 87	206
x=0.4	36.86	0.808 3	0.528 10	215
x=0.6	36.82	0.807 5	0.526 54	218
x=0.8	36.78	0.807 6	0.526 73	221