氧化亚铜的控制合成及其光催化性质研究
摘要
本论文旨在研究过渡金属氧化物氧化亚铜(Cu20)的合成及其光催化性质。利用室温液相还原法,成功制备了Cu20纳米颗粒和微米立方块。探讨了不同形貌氧化亚铜的形成机理。研究了纳米颗粒和微米立方块对有机染料的光催化降解性能。利用低温水热法制备了球状氧化亚铜,研究了球状氧化亚铜对阴离子染料甲基橙的光催化降解性能。在此基础上,制备了Cu2O-WO3及Cu2O-ZnO复合物,并对复合物的性质进行了研究。
论文主要内容概述如下：
1.Cu2O纳米颗粒和微米立方块的合成及其光催化性质
采用室温液相还原法以抗坏血酸在碱性条件下还原硫酸铜,成功制备了Cu2O纳米颗粒和微米立方块。无需添加表面活性剂,合成方法简单可行。考察了OH-浓度对合成产物形貌的影响。通过研究OH-浓度对氧化亚铜{100}面的生长情况的影响,探讨了两种形貌氧化亚铜的形成机理。利用XRD,IR,SEM等手段对产物进行了表征。利用固体紫外可见光谱测试不同形貌Cu2O的带隙能,经测定,微米立方块状氧化亚铜的带隙能小于纳米小颗粒的带隙能。研究了两种形貌合成产物对阳离子染料和阴离子染料的光催化降解性能,结果表明,合成产物对阴离子染料有较好的降解效果,对阳离子染料降解效果不明显,氧化亚铜微米立方块的光催化活性高于氧化亚铜纳米颗粒。比较了两种形貌的样品光致发光性质。此外,还对氧化亚铜的抑菌性能做了初步研究。在金黄色葡萄球菌和大肠杆菌培养过程中加入氧化亚铜,可形成明显的抑菌圈。表明所合成氧化亚铜有显著的抑菌效果。
2.低温水热法制备球状氧化亚铜及其光催化性质
利用低温水热法分别以抗坏血酸和葡萄糖为还原剂制备了球形氧化亚铜。通过控制反应条件,使氧化亚铜晶体以聚集生长模式为主,爆发式成核,得到球形产物。并考察了反应温度对产物形貌的影响。利用X射线衍射、扫描电子显微镜对合成产物进行了表征。以合成产物光催化降解偶氮染料甲基橙为模型,研究了球状Cu2O的光催化性能,结果表明球状氧化亚铜对甲基橙的脱色率达89.0%。探讨了氧化亚铜光催化降解甲基橙的机理。此外,研究了球状氧化亚铜/Fenton复合体系的光催化性质。结果表明,此体系中甲基橙的脱色率高达98.1%。
3. Cu2O-WO3及Cu2O-ZnO复合物的制备及其光催化性质
采用室温液相还原法制备了Cu2O-WO3及Cu2O-ZnO复合物。利用XRD对产物进行了表征,研究了太阳光照下两种复合物对阳离子染料次甲基蓝的光催化降解性能。结果表明,两种复合物比单纯的氧化亚铜对阳离子染料次甲基蓝的光催化效果有了明显的提高。分析了复合物能提高阳离子染料次甲基蓝的光催化效果的原因,探讨了Cu2O复合物光催化降解次甲基蓝的机理。
In this thesis, the synthesis and property of Cu2O were investigated. Cuprous oxide (Cu2O) nanoparticles and microcubes have been successfully fabricated by solution-phase reducing method. The mechanism of the formation of different morphology of cuprous oxide was discussed. Novel Cu2O nanospheres were prepared by hydrothermal treatment. Moreover, the Cu2O-WO3 and Cu2O-ZnO particles were prepared successfully. The properties of as-synthessized products were discussed. The details are summarized as follows:
1. Cuprous oxide (Cu2O) nanoparticles and microcubes have been successfully fabricated by reduce of CUSO4 using ascorbic acid at room temperature. The synthesis of Cu2O was simple. There were no template or surfactant has been introduced. It suggested that OH- have effects on stability of{100} which lead to morphology of cubic. All of the samples were characterized by X-ray powder diffractometer (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectrometer (FT-IR). The band gaps of as-prepared products were determined by UV-vis absorption spectra, the band gap of cuprous oxide microcubes was lower. The photocatalytic activities of as-synthesized Cu2O nanoparticles and microcubes for dyes were studied. The effects of different conditions on decoloration rate of dyes were discussed. Moreover, the photoluminescence properties of the products were investigated.
2. Novel Cu2O nanospheres were prepared by hydrothermal treatment. The products were characterized via X-ray diffraction (XRD) and field emitted scanning electron microscopy (FESEM). The photocatalytic activities of as-synthesized Cu2O nanospheres for methyl orange were studied. The decoloration rate of methyl orange in as-synthesized Cu2O nanospheres system was 89.0%. In the Cu2O/Fenton composite system, the decoloration rate of methyl orange could reach 98.1%. The photocatalytic degradation mechanism of Cu2O for methyl orange was suggested. Moreover, the antibacterial performance of Cu2O was studied as well. The result suggested Cu2O have good antibacterial performance for staphylococcus and E. coli.
3. Cu2O-WO3 and Cu20-ZnO complexes were successfully fabricated by solution-phase reducing method. The products were characterized via X-ray diffraction (XRD). The photocatalytic activities of as-synthesized complexes for methylene blue were studied. It was found that as-synthesized complexes have higher photocatalytic activity than Cu2O. Moreover, photocatalytic degradation mechanism of the complexes for methylene blue was discussed.
论文主要内容概述如下：
1.Cu2O纳米颗粒和微米立方块的合成及其光催化性质
采用室温液相还原法以抗坏血酸在碱性条件下还原硫酸铜,成功制备了Cu2O纳米颗粒和微米立方块。无需添加表面活性剂,合成方法简单可行。考察了OH-浓度对合成产物形貌的影响。通过研究OH-浓度对氧化亚铜{100}面的生长情况的影响,探讨了两种形貌氧化亚铜的形成机理。利用XRD,IR,SEM等手段对产物进行了表征。利用固体紫外可见光谱测试不同形貌Cu2O的带隙能,经测定,微米立方块状氧化亚铜的带隙能小于纳米小颗粒的带隙能。研究了两种形貌合成产物对阳离子染料和阴离子染料的光催化降解性能,结果表明,合成产物对阴离子染料有较好的降解效果,对阳离子染料降解效果不明显,氧化亚铜微米立方块的光催化活性高于氧化亚铜纳米颗粒。比较了两种形貌的样品光致发光性质。此外,还对氧化亚铜的抑菌性能做了初步研究。在金黄色葡萄球菌和大肠杆菌培养过程中加入氧化亚铜,可形成明显的抑菌圈。表明所合成氧化亚铜有显著的抑菌效果。
2.低温水热法制备球状氧化亚铜及其光催化性质
利用低温水热法分别以抗坏血酸和葡萄糖为还原剂制备了球形氧化亚铜。通过控制反应条件,使氧化亚铜晶体以聚集生长模式为主,爆发式成核,得到球形产物。并考察了反应温度对产物形貌的影响。利用X射线衍射、扫描电子显微镜对合成产物进行了表征。以合成产物光催化降解偶氮染料甲基橙为模型,研究了球状Cu2O的光催化性能,结果表明球状氧化亚铜对甲基橙的脱色率达89.0%。探讨了氧化亚铜光催化降解甲基橙的机理。此外,研究了球状氧化亚铜/Fenton复合体系的光催化性质。结果表明,此体系中甲基橙的脱色率高达98.1%。
3. Cu2O-WO3及Cu2O-ZnO复合物的制备及其光催化性质
采用室温液相还原法制备了Cu2O-WO3及Cu2O-ZnO复合物。利用XRD对产物进行了表征,研究了太阳光照下两种复合物对阳离子染料次甲基蓝的光催化降解性能。结果表明,两种复合物比单纯的氧化亚铜对阳离子染料次甲基蓝的光催化效果有了明显的提高。分析了复合物能提高阳离子染料次甲基蓝的光催化效果的原因,探讨了Cu2O复合物光催化降解次甲基蓝的机理。
In this thesis, the synthesis and property of Cu2O were investigated. Cuprous oxide (Cu2O) nanoparticles and microcubes have been successfully fabricated by solution-phase reducing method. The mechanism of the formation of different morphology of cuprous oxide was discussed. Novel Cu2O nanospheres were prepared by hydrothermal treatment. Moreover, the Cu2O-WO3 and Cu2O-ZnO particles were prepared successfully. The properties of as-synthessized products were discussed. The details are summarized as follows:
1. Cuprous oxide (Cu2O) nanoparticles and microcubes have been successfully fabricated by reduce of CUSO4 using ascorbic acid at room temperature. The synthesis of Cu2O was simple. There were no template or surfactant has been introduced. It suggested that OH- have effects on stability of{100} which lead to morphology of cubic. All of the samples were characterized by X-ray powder diffractometer (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectrometer (FT-IR). The band gaps of as-prepared products were determined by UV-vis absorption spectra, the band gap of cuprous oxide microcubes was lower. The photocatalytic activities of as-synthesized Cu2O nanoparticles and microcubes for dyes were studied. The effects of different conditions on decoloration rate of dyes were discussed. Moreover, the photoluminescence properties of the products were investigated.
2. Novel Cu2O nanospheres were prepared by hydrothermal treatment. The products were characterized via X-ray diffraction (XRD) and field emitted scanning electron microscopy (FESEM). The photocatalytic activities of as-synthesized Cu2O nanospheres for methyl orange were studied. The decoloration rate of methyl orange in as-synthesized Cu2O nanospheres system was 89.0%. In the Cu2O/Fenton composite system, the decoloration rate of methyl orange could reach 98.1%. The photocatalytic degradation mechanism of Cu2O for methyl orange was suggested. Moreover, the antibacterial performance of Cu2O was studied as well. The result suggested Cu2O have good antibacterial performance for staphylococcus and E. coli.
3. Cu2O-WO3 and Cu20-ZnO complexes were successfully fabricated by solution-phase reducing method. The products were characterized via X-ray diffraction (XRD). The photocatalytic activities of as-synthesized complexes for methylene blue were studied. It was found that as-synthesized complexes have higher photocatalytic activity than Cu2O. Moreover, photocatalytic degradation mechanism of the complexes for methylene blue was discussed.
引文
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