Preparation and tetracycline degradation performance of MoO3-Cu2O/CN ternary photocatalyst
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摘要: 本文通过水热法先在g-C3N4(CN)上原位生长MoO3,继而在其表面电沉积Cu2O构建了MoO3-Cu2O/CN三相复合光催化剂。采用XRD、SEM、TEM、XPS和FTIR等手段对催化剂进行表征,证明了复合光催化剂的成功制备。以四环素为目标污染物,探究了所制备光催化剂对四环素的降解效果及光催化剂的作用机制。结果表明,在可见光下,1.5 MoO3-Cu2O-100/CN复合材料对四环素的降解效果最佳,150 min时降解率为97.75%,分别是CN(45.28%)和1.5 MoO3/CN(63.24%)的2.2和1.5倍。采用自由基捕获实验及电子顺磁共振光谱(EPR)对机制进行了探究,证实了羟基自由基(·OH)和超氧自由基(·O2−)是光催化过程的主要活性物质。综合各项测试计算 CN、MoO3 和Cu2O 的价带和导带位置,表明三相复合光催化剂形成了双Z型异质结。同时光催化活性的提高主要归因于双Z机制的构建,拓宽了可见光吸收范围,保留了氧化还原能力较高的空穴电子,降低了光生电子与空穴的复合率。稳定性实验结果表明制备的催化剂在经过四次循环后,对四环素的降解率仍达到90%以上,具有优异的稳定性,可循环使用。
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关键词:
- MoO3-Cu2O/CN /
- 双Z机制 /
- 四环素 /
- 降解 /
- 光催化
Abstract: In this paper, MoO3 was in-situ grown on g-C3N4 (CN) by hydrothermal method, followed by the electrodeposition of Cu2O to construct a ternary MoO3-Cu2O/CN composite photocatalyst. The catalyst was characterized by XRD, SEM, TEM, XPS and FTIR, which proved the successful preparation of the composite photocatalyst. Taking tetracycline as the target pollutant, the degradation effect of the prepared photocatalyst on tetracycline and the action mechanism of the photocatalyst were investigated. The results showed that 1.5 MoO3-Cu2O-100/CN composite had the best degradation effect of tetracycline at 150 min under visible light, up to 97.75%. They are 2.2 and 1.5 times of CN (45.28%) and 1.5 MoO3/CN (63.24%) respectively. The mechanism was investigated by free radical capture experiment and electron paramagnetic resonance spectroscopy (EPR). It was confirmed that hydroxyl radical (·OH) and superoxide radical (·O2−) were the main active substances in the photocatalytic process. The valence band and conduction band positions of CN, MoO3, and Cu2O are calculated based on various tests. It is shown that the double Z-type heterojunction is formed by the ternary composite photocatalyst. At the same time, the improvement of photocatalytic activity is mainly due to the construction of double Z mechanism, which widens the visible light absorption range, retains the hole electrons with high REDOX ability, and reduces the recombination rate of photogenerated electrons and holes. The results of stability test show that the catalytic degradation rate of tetracycline is still over 90% after four cycles, which has excellent stability and can be recycled.The results of stability test show that the catalytic degradation rate of tetracycline is still over 90% after four cycles, which has excellent stability and can be recycled.-
Key words:
- MoO3-Cu2O/CN /
- dual Z-scheme /
- tetracycline /
- degradation /
- photocatalytic
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图 7 (a) 不同光催化剂对四环素的 (a) 降解曲线, (b) 一级动力学曲线,(c) 降解速率常数 (k, min−1), (d) 不同MoO3含量的四环素光降解效率
Figure 7. (a) Tetracycline degradation curves, (b) first-order kinetics curves, and (c) degradation rate constants (k, min−1) of different photocatalysts,(d) Tetracycline photo-degradation efficiency of with different MoO3 contents
图 10 (a) 1. MoO3-Cu2O-100/CN在不同清除剂存在下对四环素的降解曲线, (b) DMPO-捕获·OH和 (c) ·O2−与1.5MoO3-Cu2O-100/CN复合材料的EPR光谱
Figure 10. (a) Degradation curve of tetracycline by 1.5MoO3-Cu2O-100/CN in the presence of different scavengers, EPR spectra of (b) DMPO− to capture ·OH and (c)·O2− with 1.5MoO3-Cu2O-100/CN composite
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