cRP NRs/MIL-101-NH<sub>2</sub>复合材料的制备及其光催化降解四环素

朱靖雨; 高志邦; 王驰; 李凯; 梅毅

cRP NRs/MIL-101-NH₂复合材料的制备及其光催化降解四环素

朱靖雨¹,
高志邦¹,
王驰^1, ,,
李凯²,
梅毅¹

1.
昆明理工大学　化学工程学院, 昆明 650500
2.
昆明理工大学　环境科学与工程学院, 昆明 650500

基金项目: 国家自然科学基金 (52260013)；云南省重大科技项目(202202AG050005)；云南省磷资源技术创新中心资助(202305AK340002)

详细信息

通讯作者:
王驰，博士，教授，博士生导师，研究方向为纳米材料、环境净化以及能源光催化　E-mail: wangchikg@163.com

中图分类号: TB333
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- 文章访问数: 72
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- 被引次数: 0
出版历程
- 收稿日期: 2024-04-12
- 修回日期: 2024-05-07
- 录用日期: 2024-05-13
- 网络出版日期: 2024-06-13

Preparation of cRP NRs/MIL-101-NH₂ composites and photocatalytic degradation of tetracycline

ZHU JingYu¹,
GAO ZhiBang¹,
WANG Chi^{1
, ,},
Li Ki²,
MEI Yi¹

1.
Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500
2.
Faculty of Environmental Science Engineering, Kunming University of Science and technology, Kunming 650500

Funds: National Natural Science Foundation of China (No. 52260013); Key Science and Technology Project of Yunnan Province (202202AG050005); Supported by Innovation Center of Phosphorus Resource, Yunnan Province (NO. 202305AK340002)

摘要

摘要: 晶态红磷纳米带(cRP NRs)是一种具有条带状结构的新型材料，其结构赋予了晶态红磷纳米带独特的物理和化学性质，使其在光催化领域具有广泛的应用前景。然而cRP NRs因其光生电子空穴复合较快和自由基产生种类单一等问题影响了其在光催化中的应用。为了提高cRP NRs的光催化降解效率，通过结合铁基MOF材料MIL-101-NH₂具有高比表面积和孔隙率的优点，利用构造异质结的方法来对材料进行改性。本文采用溶剂热法成功将cRP NRs与MIL-101-NH₂铁基金属有机框架材料复合。随后，对复合材料进行了SEM、TEM等表征，并通过元素分布扫描和XRD特征峰等分析，证实了cRP NRs与MIL-101-NH₂材料的成功复合。在光催化降解四环素的对比实验中，cRP NRs/MIL-101-NH₂表现出优异的降解效率，在光照90 min后降解了约80%。接着深入进行了XPS元素能谱分析、禁带宽度测量、Mott-Schottky曲线测定以及自由基捕获实验，确定了cRP NRs/MIL-101-NH₂形成了Z型异质结。
- 晶态红磷纳米带 /
- MOF /
- 溶剂热法 /
- 光催化 /
- 四环素
Abstract: The crystalline red phosphorus nanoribbons (cRP NRs) are a new type of material with banded structure, which gives the crystalline red phosphorus nanoribbons unique physical and chemical properties, and makes it have a wide application prospect in the field of photocatalysis. However, the application of cRP NRs in photocatalysis is affected by the problems such as the fast recombination of photogenerated electron holes and the single type of free radicals. In order to improve the photocatalytic degradation efficiency of cRP NRs, the iron-based MOF material MIL-101-NH₂ has the advantages of high specific surface area and porosity, and the material was modified by constructing heterojunction. In this paper, we have successfully synthesized cRP NRs with MIL-101-NH₂ organic framework materials by solvothermal method. Subsequently, the composite was characterized by SEM and TEM, and the successful composite of cRP NRs and MIL-101-NH₂ was confirmed by element distribution scanning and XRD characteristic peaks. In the comparative experiment of photocatalytic degradation of tetracycline, cRP NRs/MIL-101-NH₂ showed excellent degradation efficiency, degrading about 80% after 90 min of light. Then, XPS spectral analysis, band gap measurement, Mott-Schottky curve determination and free radical trapping experiments were carried out, and it was confirmed that cRP NRs/MIL-101-NH₂ formed Z-scheme heterojunction.
- Crystalline Red Phosphorus nanoribbons /
- MOF /
- solvothermal /
- Photocatalytic /
- tetracycline

HTML全文

图 1 (a)晶态红磷纳米带(cRP NRs)，(b)MIL-101-NH₂和(c)cRP NRs/MIL-101-NH₂的SEM图像

Figure 1. SEM images of (a) crystalline red phosphorus nanoribbons (cRP NRs), (b) MIL-101-NH₂ and (c) cRP NRs/MIL-101-NH₂

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图 2 (a，b，c) cRP NRs， MIL-101-NH₂和 cRP NRs/ MIL-101-NH₂的TEM图像，(d) cRP NRs/ MIL-101-NH₂的元素分布，(e) cRP NRs/ MIL-101-NH₂的晶格条纹图像，(f) cRP NRs， MIL-101-NH₂和 cRP NRs/ MIL-101-NH₂的XRD图像

Figure 2. (a, b, c) TEM images of cRP NRs, MIL-101-NH₂ and cRP NRs/ MIL-101-NH₂, (d) elemental distribution of cRP NRs/ MIL-101-NH₂, (e) lattice fringe images of cRP NRs/ MIL-101-NH₂, (f) XRD images of cRP NRs, MIL-101-NH₂, and cRP NRs/ MIL-101-NH₂

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图 3 cRP NRs， MIL-101-NH₂和 MIL-101-NH₂的XPS全谱图像

Figure 3. XPS full spectrum images of cRP NRs, MIL-101-NH₂, and MIL-101-NH₂

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图 4 cRP NRs/MIL-101-NH₂的C 1s、O 1s、Fe 2p和P 2p图谱

Figure 4. C 1s, O 1s, Fe 2p and P 2p of cRP NRs/MIL-101-NH₂

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图 5 cRP NRs、MIL-101-NH₂及cRP NRs/MIL-101-NH₂的N₂吸脱附曲线

Figure 5. N₂ absorption and desorption curves of cRP NRs, MIL-101-NH₂ and cRP NRs/MIL-101-NH₂

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图 6 (a)cRP NRs、MIL-101-NH₂及cRP NRs/MIL-101-NH₂的UV-Vis图，(b) Tauc's 图，(c)Mott-Schottky曲线

Figure 6. (a) UV-Vis diagram of cRP NRs, MIL-101-NH₂ and cRP NRs/MIL-101-NH₂, (b) Tauc's diagram, (c) Mott-Schottky curve

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图 7 cRP NRs、MIL-101-NH₂及cRP NRs/MIL-101-NH₂的瞬态光电流响应对比

Figure 7. Comparison of transient photocurrent responses of cRP NRs,MIL-101-NH₂ and cRP NRs/MIL-101-NH₂

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图 8 cRP NRs、MIL-101-NH₂、cRP NRs/MIL-101-NH₂ (2∶1)、 cRP NRs/MIL-101-NH₂ (4∶3)、cRP NRs/MIL-101-NH₂ (1∶1)、cRP NRs/MIL-101-NH₂ (4∶5)的降解曲线

Figure 8. (a) cRP NRs, MIL-101-NH₂, cRP NRs/MIL-101-NH₂ (2∶1), cRP NRs/MIL-101-NH₂ (4∶3), cRP NRs/MIL-101-NH₂ (1∶1), cRP Degradation curves of NRs/MIL-101-NH₂ (4∶5)

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图 9 cRP NRs、MIL-101-NH₂、cRP NRs/MIL-101-NH₂ (2∶1)、 cRP NRs/MIL-101-NH₂ (4∶3)、cRP NRs/MIL-101-NH₂ (1∶1)、cRP NRs/MIL-101-NH₂ (4∶5)动力学拟合曲线

Figure 9. Kinetic fitting curve of cRP NRs, MIL-101-NH₂, cRP NRs/MIL-101-NH₂ (2∶1), cRP NRs/MIL-101-NH₂ (4∶3), cRP NRs/MIL-101-NH₂ (1∶1), cRP NRs/MIL-101-NH₂ (4∶5)

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图 10 MIL-101-NH₂和cRP NRs/MIL-101-NH₂的循环降解曲线

Figure 10. Cyclic degradation curves of MIL-101-NH₂ and cRP NRs/MIL-101-NH₂

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图 11 cRP NRs/MIL-101-NH₂的自由基捕获曲线

Figure 11. Free radical trapping curves of cRP NRs/MIL-101-NH₂

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图 12 cRP NRs/MIL-101-NH₂的光催化降解机理图

Figure 12. Photocatalytic degradation mechanism of cRP NRs/MIL-101-NH₂

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图 13 cRP NRs/MIL-101-NH₂降解TC可能的路径

Figure 13. Possible pathways of TC degradation by cRP NRs/MIL-101-NH₂

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表 1 其他文献材料降解四环素效果对比

Table 1. Comparison of tetracycline degradation effects of other materials in literature

Materials	Catalyst concentration/ (mg·L⁻¹)	Dosage/mg	TC concentration/ (mg·L⁻¹)	Reaction time/min	Degradation efficiency	Reference
cRP/MIL-101(Fe)-NH₂	0.2	10	50	120	82%	This study
MIL-101(Fe)/MIL-100(Fe)	0.125	10	50	140	80%	[31]
TiO₂	0.2	20	10	120	76.60%	[32]
BiOI/MIL-125(Ti)	0.25	25	20	120	70%	[33]
CDs/MIL-101(Fe)	0.5	50	75	120	81%	[34]
RP/MIL-101(Fe)	0.5	50	50	80	90.10%	[15]
PSCN-50	1	100	10	60	85.50%	[35]
MIL-101(Fe)/MoS₂	0.3	30	100	40	85%	[36]
RP/HAp	1	100	10	30	100%	[10]
P-BiOCl	0.5	50	20	30	81%	[37]
Notes：TiO₂ is titanium dioxide, BiOI is a compound of bismuth oxide and iodine, CDs are carbon dots, RP is red phosphorus, PSCN is phosphorus-sulfur co-doped g-C₃N₄, MoS₂ is molybdenum disulfide, HAp is a hollow hydroxyapatite, P is phosphorus, BiOCl is a compound of bismuth oxide and chlorine.

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