Preparation of cRP NRs/MIL-101-NH2 composites and photocatalytic degradation of tetracycline
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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。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.
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Key words:
- Crystalline Red Phosphorus nanoribbons /
- MOF /
- solvothermal /
- Photocatalytic /
- tetracycline
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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
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/minDegradation
efficiencyReference 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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