铜氧族化合物的合成与性质研究
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摘要
金属铜氧化物和硒化物半导体纳米材料因其优良的催化、发光、光电转化、气敏、磁性能，成为材料、化学、物理等领域的重要研究方向之一。由于材料的结构、组成、晶型、形貌及尺寸影响材料的性能和应用，因此，设计并控制合成具有特定结构和形貌的铜氧化物和硒化物半导体纳米材料具有重要的理论和实际意义。本论文采用超声微波辅助法，结合热转化反应合成出了方砖状CuO多孔材料；在温和水热条件下制备了具有纳米棒状和纳米片状次级结构的CuO微米球及六角状Cu_(2-x)Se微米板，并对所合成的微纳米材料进行了详细的结构表征、形貌及光学性质研究，探讨了不同反应条件对产物形貌的影响。具体的研究内容包括：
1、以氯化铜和草酸钾为原料，以价格低廉的十二烷基苯磺酸钠为导向剂，采用超声微波辅助法，合成了草酸铜前驱物，通过在300°C下灼烧草酸铜前驱体快速制得了方砖状CuO多孔材料。通过XRD、SEM、TEM对合成产物的晶型、形貌及颗粒大小进行研究，以XPS研究了产物的元素组成及纯度，通过N2吸附-脱附实验对产物的比表面积和孔径分布进行研究。分别以FT-IR、UV-Vis及PL研究了产物的表面结构、光吸收特性和荧光性质，并研究了产物的表面光伏特性。探讨了不同反应条件对产物形貌的影响，提出了方砖状CuO多孔材料的生成机理。
2、采用水热合成法，以氯化铜为原料，使用易溶于水且无毒的十二烷基苯磺酸钠SDBS作导向剂在水-氨水体系中，制备出了具有纳米棒状次级结构的CuO微球，并研究反应条件对产物形貌的影响。通过XRD、SEM、TEM等表征了所合成的CuO微球的晶型、结构形貌及颗粒大小，并测试了产物的BET比表面积。采用FT-IR对产物的表面结构进行了研究，以UV-Vis及PL光谱对产物的光吸收特性和荧光性质进行了研究。结果表明，氨水的用量影响微球的结构，SDBS的用量是影响纳米棒自组装成球的关键因素。此外，在水-氨水-氢氧化钠体系中，在低温条件下制备出了具有纳米片状次级结构的CuO微球。
3、用硒粉、氯化铜为原料，在水-NaOH-N_2H_4·H_2O体系中，以油胺OLA为导向剂，采用水热合成法制备了六角状Cu_(2-x)Se微米板。通过XRD、SEM、TEM对所合成产物的晶型、形貌及颗粒大小进行研究。通过一系列控制实验，得到了最佳反应条件，进而探讨了产物的生成机理。对所制备的Cu_(2-x)Se微米板进行了FT-IR、UV-Vis、PL、SPS测试，研究了产物的表面结构及光电性质。
Metal oxides and semiconductor nanomaterials have become one of importantresearches in fields of materials, chemistry and physics etc. because of their excellentproperties in catalysis, optics, photoelectric conversion, gas sensitivity and magnetism. Due tothe structure, composition, crystal structure, morphology and size of materials influence theperformance and applications of the materials, designing and controlling synthesis ofcopper oxides and copper selenide semiconductor materials with a specific structure andmorphology are of significance from theortical and practical point of view. In this thesis theporous square-brick-like hierarchical CuO was synthesized by ultrasound and microwaveassisted method, combing with thermal conversion reaction. The nanorod and nanosheethierarchical CuO microspheres and hexagonal Cu2-XSe microplates were preparedunder mild hydrothermal conditions. The detailed structure and morphology characterizationand optical properties of the synthesized micro/nano materials were studied. The effect ofdifferent reaction conditions on the morphology was explored and discussed. This thesisincludes the following aspects:
1. Using low cost SDBS as a directing agent, CuCl_2·2H_2O and K_2C_2O_4as the rawmaterials, square-brick CuC_2O_4.xH_2O precursor were synthesized by ultrasound-microwavemethod. After calcination of the CuC_2O_4.xH_2O precursor at 300℃, the square-brick porousCuO materials were fast obtained. The crystal structure, morphology and particle size of theproducts were characterized by XRD, SEM and TEM, and the elementalcomposition and purity of the products were studied by XPS, the surface area and pore sizedistribution of the products were obtained by N2adsorption - desorption experiments.The surface structure, absorption and fluorescence properties of the products were studied byFT-IR, UV-Vis absorption spectra and PL. The surface photovoltaic property of the productwas also studied. In addition, effect of different reaction conditions on the morphology wasdiscussed and the formation mechanism of square-brick porous CuO materials was proposed.
2. CuO microspheres with a nanorod-like hierarchical structure were synthesized by mildhydrothermal method in a water-ammonia system, where CuCl_2·H_2O was used as the rawmaterial and non-toxic water soluble SDBS as a directing agent, the dependence of CuOmicrosphere morphology on reaction conditions was investigated. The crystal structure,morphology and particle size of the products were characterized by XRD, SEM and TEM,and the surface area of products were obtained by N2adsorption-desorption experiments.The surface structure, absorption and fluorescence properties of the products were studied byFT-IR, UV-Vis absorption spectra and PL. It was found that the amount of SDBS andammonia plays an important role on formation of spherical CuO by self-assemble ofnanorod-like structures. Moreover, CuO microspheres with a hierarchical nanosheet-like structure were synthesized by mild hydrothermal method in a water-ammonia system at lowtemperature.
3. Hexaonal Cu_(2-x)Se microplates were synthesized by mild hydrothermal method in awater-NaOH-N2H4·H2O system, where selenium power and CuCl_2·H_2O were used as the rawmaterials and OLA as a directing agent. The crystal structure, morphology and particle size ofthe products were characterized by XRD, SEM and TEM. The effect of differentreaction conditions on the morphology was also discussed and the formation mechanism ofhexaonal Cu_(2-x)Se microplates was proposed. The surface structure, absorption andfluorescence properties of the products were studied by FT-IR, UV-Vis absorption spectraand PL, the p surface hotovoltaic properties of the products was also studied.
1、以氯化铜和草酸钾为原料，以价格低廉的十二烷基苯磺酸钠为导向剂，采用超声微波辅助法，合成了草酸铜前驱物，通过在300°C下灼烧草酸铜前驱体快速制得了方砖状CuO多孔材料。通过XRD、SEM、TEM对合成产物的晶型、形貌及颗粒大小进行研究，以XPS研究了产物的元素组成及纯度，通过N2吸附-脱附实验对产物的比表面积和孔径分布进行研究。分别以FT-IR、UV-Vis及PL研究了产物的表面结构、光吸收特性和荧光性质，并研究了产物的表面光伏特性。探讨了不同反应条件对产物形貌的影响，提出了方砖状CuO多孔材料的生成机理。
2、采用水热合成法，以氯化铜为原料，使用易溶于水且无毒的十二烷基苯磺酸钠SDBS作导向剂在水-氨水体系中，制备出了具有纳米棒状次级结构的CuO微球，并研究反应条件对产物形貌的影响。通过XRD、SEM、TEM等表征了所合成的CuO微球的晶型、结构形貌及颗粒大小，并测试了产物的BET比表面积。采用FT-IR对产物的表面结构进行了研究，以UV-Vis及PL光谱对产物的光吸收特性和荧光性质进行了研究。结果表明，氨水的用量影响微球的结构，SDBS的用量是影响纳米棒自组装成球的关键因素。此外，在水-氨水-氢氧化钠体系中，在低温条件下制备出了具有纳米片状次级结构的CuO微球。
3、用硒粉、氯化铜为原料，在水-NaOH-N_2H_4·H_2O体系中，以油胺OLA为导向剂，采用水热合成法制备了六角状Cu_(2-x)Se微米板。通过XRD、SEM、TEM对所合成产物的晶型、形貌及颗粒大小进行研究。通过一系列控制实验，得到了最佳反应条件，进而探讨了产物的生成机理。对所制备的Cu_(2-x)Se微米板进行了FT-IR、UV-Vis、PL、SPS测试，研究了产物的表面结构及光电性质。
Metal oxides and semiconductor nanomaterials have become one of importantresearches in fields of materials, chemistry and physics etc. because of their excellentproperties in catalysis, optics, photoelectric conversion, gas sensitivity and magnetism. Due tothe structure, composition, crystal structure, morphology and size of materials influence theperformance and applications of the materials, designing and controlling synthesis ofcopper oxides and copper selenide semiconductor materials with a specific structure andmorphology are of significance from theortical and practical point of view. In this thesis theporous square-brick-like hierarchical CuO was synthesized by ultrasound and microwaveassisted method, combing with thermal conversion reaction. The nanorod and nanosheethierarchical CuO microspheres and hexagonal Cu2-XSe microplates were preparedunder mild hydrothermal conditions. The detailed structure and morphology characterizationand optical properties of the synthesized micro/nano materials were studied. The effect ofdifferent reaction conditions on the morphology was explored and discussed. This thesisincludes the following aspects:
1. Using low cost SDBS as a directing agent, CuCl_2·2H_2O and K_2C_2O_4as the rawmaterials, square-brick CuC_2O_4.xH_2O precursor were synthesized by ultrasound-microwavemethod. After calcination of the CuC_2O_4.xH_2O precursor at 300℃, the square-brick porousCuO materials were fast obtained. The crystal structure, morphology and particle size of theproducts were characterized by XRD, SEM and TEM, and the elementalcomposition and purity of the products were studied by XPS, the surface area and pore sizedistribution of the products were obtained by N2adsorption - desorption experiments.The surface structure, absorption and fluorescence properties of the products were studied byFT-IR, UV-Vis absorption spectra and PL. The surface photovoltaic property of the productwas also studied. In addition, effect of different reaction conditions on the morphology wasdiscussed and the formation mechanism of square-brick porous CuO materials was proposed.
2. CuO microspheres with a nanorod-like hierarchical structure were synthesized by mildhydrothermal method in a water-ammonia system, where CuCl_2·H_2O was used as the rawmaterial and non-toxic water soluble SDBS as a directing agent, the dependence of CuOmicrosphere morphology on reaction conditions was investigated. The crystal structure,morphology and particle size of the products were characterized by XRD, SEM and TEM,and the surface area of products were obtained by N2adsorption-desorption experiments.The surface structure, absorption and fluorescence properties of the products were studied byFT-IR, UV-Vis absorption spectra and PL. It was found that the amount of SDBS andammonia plays an important role on formation of spherical CuO by self-assemble ofnanorod-like structures. Moreover, CuO microspheres with a hierarchical nanosheet-like structure were synthesized by mild hydrothermal method in a water-ammonia system at lowtemperature.
3. Hexaonal Cu_(2-x)Se microplates were synthesized by mild hydrothermal method in awater-NaOH-N2H4·H2O system, where selenium power and CuCl_2·H_2O were used as the rawmaterials and OLA as a directing agent. The crystal structure, morphology and particle size ofthe products were characterized by XRD, SEM and TEM. The effect of differentreaction conditions on the morphology was also discussed and the formation mechanism ofhexaonal Cu_(2-x)Se microplates was proposed. The surface structure, absorption andfluorescence properties of the products were studied by FT-IR, UV-Vis absorption spectraand PL, the p surface hotovoltaic properties of the products was also studied.
引文
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