Preparation of g⁃C3N4/Co3O4 and Its Photocatalytic Degradation of Tetracycline

doi:10.12422/j.issn.1006-396X.2024.05.007

Abstract

Abstract:

The use of solar photocatalytic degradation of pollutants is one of the most promising technologies to solve water pollution problems and achieve solar energy conversion. By changing the amount of g-C₃N₄ added, g-C₃N₄/Co₃O₄ catalysts with different g-C₃N₄ mass fractions are prepared based on the calcination method with cobalt nitrate hexahydrate (Co（NO₃)₂-6H₂O) and urea (NH₄CNO) as raw materials. The samples are analyzed and characterized using X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and ultraviolet visible absorption spectroscopy （UV-vis DRS）. To speculate on the active species of the catalyst, capture agent experiments are conducted on it. The results indicate that the synergistic effect between g-C₃N₄ and Co₃O₄ can improve the transfer and separation efficiency of charge carriers at the interface between the two phases. Under visible light, the degradation effect of 10% g-C₃N₄/Co₃O₄ is the best, with a degradation rate of 66.50%, which is higher than the degradation effect of single Co₃O₄ （degradation rate of 35.90%）. The active species of the catalyst are mainly superoxide radicals（·O₂-） and holes（h⁺）. After compounding with g-C₃N₄, the drawbacks of Co₃O₄ electron hole pair, such as too fast recombination and a deficient energy level structure, are improved, providing ideas for the degradation of organic pollutants in the future.

Key words: Photocatalysis, Cobalt tetroxide, Tetracycline, Heterojunction, Graphite nitride carbon

摘要：

利用太阳能光催化降解污染物，是解决水污染问题并实现太阳能转化最有前途的技术之一。应用煅烧法，以六水合硝酸钴（Co（NO₃）₂·6H₂O）、尿素（NH₄CNO）为原料，通过改变g-C₃N₄的加入量，制备了g-C₃N₄质量分数不同的g-C₃N₄/Co₃O₄催化剂；利用X射线衍射（XRD）、X射线光电子能谱（XPS）、紫外-可见吸收光谱（UV-vis DRS）测试，对催化剂进行了分析和表征；为推测催化剂的活性物种，对其进行了捕获剂实验。结果表明，g-C₃N₄与Co₃O₄的协同作用可提高两相界面间载流子的转移和分离效率；在可见光下，g-C₃N₄质量分数为10%的g-C₃N₄/Co₃O₄对四环素的降解效果最佳，降解率为66.50%，高于纯Co₃O₄对四环素的降解率（35.90%）；催化剂的活性物种主要为超氧自由基（·O₂-）和空穴（h⁺）；Co₃O₄与g-C₃N₄的复合，改善了Co₃O₄电子-空穴对复合过快、带隙小和光吸收能力弱等不足，为今后有机污染物的降解提供了思路。

关键词: 光催化, 四氧化三钴, 四环素, 异质结, 石墨氮化碳

CLC Number:

TQ123.4

Xinyue MA, Lei CHEN, Fangfang WANG, Changdong CHEN. Preparation of g⁃C₃N₄/Co₃O₄ and Its Photocatalytic Degradation of Tetracycline[J]. Journal of Petrochemical Universities, 2024, 37(5): 56-64.

马馨月, 陈雷, 王芳芳, 陈常东. g⁃C₃N₄/Co₃O₄的制备及其光催化降解四环素研究[J]. 石油化工高等学校学报, 2024, 37(5): 56-64.

Figures/Tables 10

Fig.1 XRD spectra of g?C3N4, Co3O4, and X? g?C3N4/Co3O4

Fig.2 SEM images of g?C3N4, Co3O4 and 10%?g?C3N4/Co3O4

Fig.3 Effect of g?C3N4， Co3O4 and X?g?C3N4/Co3O4 on the degradation performance of tetracycline

Table 1 Comparison of degradation of pollutants by different catalysts in photocatalytic reactions

催化剂	污染物	ρ（污染物）/（mg·L^-1）	反应速率常数/min^-1	降解时间/min	降解率/%	来源
Co₃O₄/Bi₂O₂CO₃	萘	10	0.014 01	150	91.02	[34]
MOF⁃Co₃O₄	罗丹明B	10	0.979 10	180	92.91	[35]
纳米Co₃O₄	罗丹明B	5	-	120	70.00	[36]
NCQDs/Co₃O₄	TC	20	-	120	81.20	[37]
Co₃O₄/MoO₃	茜素黄	10	0.008 83	120	67.00	[38]
g⁃C₃N₄/Co₃O₄	TC	50	0.005 82	150	66.50	本文

Fig.4 XPS diagram of g?C3N4, Co3O4 and 10%?g?C3N4/Co3O4

Fig.5 OCP, MS, and EIS plots of g?C3N4, Co3O4 and 10%?g?C3N4/Co3O4

Fig.6 UV?VIS absorption spectra and Tauc diagram of g?C3N4, Co3O4 and 10%?g?C3N4/Co3O4, and valence band diagram of g?C3N4, Co3O4

Fig.7 Effect of capture agents on the photocatalytic performance of 10%?g?C3N4/Co3O4

Fig.8 Migration path of photogenerated electrons

Fig.9 Cyclic test of 10%?g?C3N4/Co3O4

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Preparation of g⁃C₃N₄/Co₃O₄ and Its Photocatalytic Degradation of Tetracycline

g⁃C₃N₄/Co₃O₄的制备及其光催化降解四环素研究

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