Preparation and photocatalytic properties of NH2—Fe3O4@polyethylene glycol@ZnO nanospheres
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摘要: 首先合成氨基功能化Fe3O4(NH2—Fe3O4)，并以NH2—Fe3O4为磁核，六水合硝酸锌(Zn(NO3)2·6H2O)为锌源，在表面活性剂聚乙二醇(PEG，PEG-400)辅助下通过水热法制备PEG修饰的ZnO(NH2—Fe3O4@PEG@ZnO)磁性复合材料。利用XRD、SEM、TEM、XPS、紫外-可见-近红外分光光度计、比表面吸附仪(BET)、振动样品磁强计(VSM)等对NH2—Fe3O4@PEG@ZnO复合材料组成、形貌、磁性能等进行表征。并进一步以罗丹明B(RhB)染料为模拟污染物，对NH2−Fe3O4@PEG@ZnO复合材料的光催化降解性能进行研究，采用单因素法探究Fe与Zn的原子比(n(Fe)∶n(Zn))、合成温度、表面活性剂种类及用量对NH2—Fe3O4@PEG@ZnO复合材料光催化降解性能的影响。结果表明，n(Fe)∶n(Zn)=1∶15、水热合成温度为180℃制备的NH2—Fe3O4@ZnO复合材料具有良好的光降解性能，0.0500 g NH2—Fe3O4@ZnO复合材料在紫外光照射20 min内对50 mL RhB(1.0×10−5 mol·L−1)溶液降解率为90.36%。而相同条件制备的NH2—Fe3O4@PEG@ZnO复合材料呈微球状，比表面积为11.43 m2·g−1，禁带宽度为2.51 eV，对RhB的光催化降解率可提高至99.36%，循环使用10次后，其对RhB的光催化降解率仍可达96.48%，PEG-400对NH2—Fe3O4@ZnO复合材料的光催化活性具有较大的协同效应。Abstract: The amino functionalized Fe3O4(NH2—Fe3O4) had been successfully prepared as magnetic core. With zinc nitrate hexahydrate (Zn(NO3)2·6H2O) as zinc source and polyethylene glycol(PEG, PEG-400) as surfactant, the magnetic composite based on zinc oxide and PEG-400-modified (NH2—Fe3O4@PEG@ZnO) composite was synthesized by hydrothermal process. The composition, morphology and magnetic properties of the NH2—Fe3O4@PEG@ZnO composite were characterized by a series of techniques including XRD, SEM, TEM, XPS, UV-VIS-NIR spectroscopy, specific surface area analyzer(BET), vibrating sample magnetometer(VSM) and so on. The photocatalytic performance of NH2—Fe3O4@PEG@ZnO composite under ultraviolet light was investigated by using the degradation of Rhodamine B (RhB) dye as a simulated pollutant. The influencing factors such as the atomic ratio of Fe to Zn(n(Fe)∶n(Zn)), reaction temperature, types and dosages of surfactant on photocatalytic degradation performance were investigated by one-factor method. The results show that NH2—Fe3O4@ZnO composite has good photocatalytic activity which is synthesized by n(Fe)∶n(Zn) is 1∶15 and the hydrothermal temperature is 180℃. The degradation rate of 50 mL RhB(1.0×10−5 mol·L−1) is 90.36% when use 0.0500 g NH2—Fe3O4@ZnO composite as a catalyst under ultraviolet light within 20 min. The specific surface area of NH2—Fe3O4@PEG@ZnO composite is 11.43 m2·g−1, the forbidden band width is about 2.51 eV and degradation rate of RhB is up to 99.36%. After 10 times of recycling, the photocatalytic degradation rate of RhB can still reach 96.48%. The combination of NH2−Fe3O4@ZnO composite and PEG-400 has a synergistic effect on improving the photocatalytic activity.
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Key words:
- magnetic composites /
- photocatalytic degradation /
- nano ZnO /
- amino functionalized /
- Rhodamine B
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图 1 氨基功能化Fe3O4(NH2—Fe3O4)@聚乙二醇(PEG)@ZnO的制备
Figure 1. Synthesis of amino functionalized Fe3O4 (NH2—Fe3O4)@ polyethylene glycol(PEG)@ZnO
图 2 NH2—Fe3O4@ZnO-1(a)、 NH2—Fe3O4@ZnO-2(b)、 NH2—Fe3O4@ZnO-3(c)、NH2—Fe3O4@PEG@ZnO(d)和循坏后NH2—Fe3O4@PEG@ZnO(e)复合材料的XRD图谱
Figure 2. XRD patterns of NH2—Fe3O4@ZnO-1(a), NH2—Fe3O4@ZnO-2(b), NH2—Fe3O4@ZnO-3(c), NH2—Fe3O4@PEG@ZnO(d) and recycled NH2—Fe3O4@PEG@ZnO(e) composites
图 3 NH2—Fe3O4@ZnO-2(a)、NH2—Fe3O4@PEG@ZnO(b)和循环后NH2—Fe3O4@PEG@ZnO(c)复合材料的SEM图像及NH2—Fe3O4@PEG@ZnO(d)复合材料的TEM图像
Figure 3. SEM images of NH2—Fe3O4@ZnO-2(a), NH2—Fe3O4@PEG@ZnO(b) and recycled NH2—Fe3O4@PEG@ZnO(c) composite, TEM image of NH2—Fe3O4@PEG@ZnO(d) composite
图 5 ZnO、NH2—Fe3O4@ZnO-2和NH2—Fe3O4@PEG@ZnO复合材料的紫外漫反射光图谱
Figure 5. Diffused reflectance spectra of ZnO, NH2—Fe3O4@ZnO-2 and NH2—Fe3O4@PEG@ZnO composites
图 6 NH2—Fe3O4@PEG@ZnO复合材料的磁滞回线
Figure 6. Magnetic hysteresis loop of NH2—Fe3O4@PEG@ZnO composite
图 7 不同Fe与Zn原子比(n(Fe)∶n(Zn))对NH2—Fe3O4@ZnO复合材料光催化降解罗丹明B(RhB)的影响
Figure 7. Effect of different atomic ratios of Fe to Zn(n(Fe)∶n(Zn)) on degradation of Rhodamine B(RhB) by NH2—Fe3O4@ZnO composite
图 8 不同合成温度对NH2—Fe3O4@ZnO-2复合材料光催化降解RhB的影响
Figure 8. Effect of different synthesis temperatures on degradation of RhB by NH2—Fe3O4@ZnO-2 composite
图 9 表面活性剂种类对NH2—Fe3O4@ZnO-2复合材料光催化降解RhB的影响
Figure 9. Effect of different surfactant types on degradation of RhB by NH2—Fe3O4@ZnO-2 composite
图 10 PEG-400用量对NH2—Fe3O4@PEG@ZnO复合材料光催化降解RhB的影响
Figure 10. Effect of different PEG-400 dosages on degradation of RhB by NH2—Fe3O4@PEG@ZnO composite
图 11 NH2—Fe3O4@PEG@ZnO复合材料光催化降解RhB拟一级动力学曲线
Figure 11. Pseudo first-order kinetic curves of NH2—Fe3O4@PEG@ZnO composite degrading RhB
图 12 NH2—Fe3O4@PEG@ZnO复合材料光催化降解RhB的循环使用性能
Figure 12. Reusability of NH2—Fe3O4@PEG@ZnO composite for degradation of RhB
表 1 NH2—Fe3O4@ZnO和NH2—Fe3O4@PEG@ZnO复合材料配比
Table 1. Component contents of NH2—Fe3O4@ZnO and NH2—Fe3O4@PEG@ZnO composite
Sample n(Fe)∶n(Zn) NH2—Fe3O4/g Zn(NO3)2·6H2O/g PEG-400/mL NH2—Fe3O4@ZnO-1 1∶10 0.0773 2.970 − NH2—Fe3O4@ZnO-2 1∶15 0.0773 4.455 − NH2—Fe3O4@ZnO-3 1∶20 0.0773 5.940 − NH2—Fe3O4@PEG@ZnO 1∶15 0.0773 4.455 15 Note: n(Fe) : n(Zn)—Atomic ratio of Fe to Zn. 
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表 2 NH2—Fe3O4@ZnO-2和NH2—Fe3O4@PEG@ZnO复合材料比表面积
Table 2. BET surface areas of NH2—Fe3O4@ZnO-2 and NH2—Fe3O4@PEG@ZnO composites
Catalyst BET surface area/(m2·g−1) NH2—Fe3O4@ZnO-2 0.0756 NH2—Fe3O4@PEG@ZnO 11.43
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表 3 NH2—Fe3O4@PEG@ZnO复合材料光催化降解RhB拟一级动力学方程及参数
Table 3. Pseudo first-order kinetic equations and parameters of NH2—Fe3O4@PEG@ZnO composite degrading RhB
Composite Kinetic equations R2 K/min−1 NH2—Fe3O4 Y=0.0049x+0.0073 0.8288 0.0049 ZnO Y=0.0859x+0.0028 0.9841 0.0859 NH2—Fe3O4 @ZnO-2 Y=0.1220x+0.1135 0.9115 0.1220 NH2—Fe3O4@PEG@ZnO Y=0.2016x+0.1160 0.9669 0.2016 Notes: R2—Correlation coefficient; K—Apparent rate constant.
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