硫化物半导体纳米材料的制备及光催化性质研究
摘要
半导体纳米材料所具有的量子尺寸效应、小尺寸效应和表面效应等使得它们呈现出许多新奇的特性，在非线性光学、磁介质、催化、医药、及功能材料等方面具有极为广阔的应用前景，同时亦将对生命科学和信息技术的发展以及物质领域的基础研究发生深刻的影响。在本论文中，我们选取了硫化锌和硫化镉两种非常重要的半导体材料，以不同胺为模板剂，在低温下制备了不同形貌的硫化锌、硫化镉纳米材料，并对它们的光催化活性进行的研究。
采用乙二胺、1，3-丙二胺、丁胺和β-羟乙基乙二胺等不同胺为模板剂，它们与CS_2反应生成的H_2S为硫源，在50℃与ZnSO_4搅拌反应20分钟制备了有孔的ZnS亚微米球。用SEM表征了有孔ZnS亚微米球的形貌、粒子大小为100～850nm以及孔的大小为250～600nm，XRD和HRTEM阐明了其为β型立方晶系，并由2～5纳米的ZnS纳米晶构成，UV-vis最大吸收峰蓝移表明其在室温下具有一定的量子尺寸效应。通过实验分析可知，所制备的有孔硫化锌亚微米空心球的形貌是可控的：陈化时间可控制球的粒径的大小，反应物二硫化碳和乙二胺的摩尔比可控制球的形状。对产物光催化实验降解可溶性染料曙红结果表明所制备的有孔纳米空心球均具有较强的光催化活性，而且，空心球的粒径越小，光催化活性越高。胺模板剂的两个氨基有利于与Zn~(2+)作用而形成均匀、相对光滑的有孔ZnS亚微米球，引入羟乙基则不利，提出了由H_2S冲出形成孔的合理机理。
采用正丁胺为模板剂制备了不同形貌的CdS纳米材料。研究发现二硫化碳和正丁胺的摩尔比对反应产物的结构和形貌有较大的影响：当n_(CS2)：n_(CH3CH2CH2CH2NH2)＜1：2时，得到的产物是晶型较好的平均粒径约为10nm的CdS纳米颗粒，而当n_(CS2)：n_(CH3CH2CH2CH2NH2)＞1：2时，得到的产物是CdS(CH_3CH_2CH_2CH_2NHCSCH_2CH_2CH_2CH_3)(CS_2)配合物纳米线或纳米带。对CdS纳米颗粒的光催化研究表明，60 min内对染料直接黑EX溶液的光降解率达到了98％以上，体现了较高的光催化活性。元素分析、XRD、FT-IR、TG分析表明CdS／有机配合物结构较为稳定，不受陈化时间的改变而改变，且随着陈化时间的增长，配合物形貌发生较大的改变，逐渐由直径为10-30nm、长约1μm以上的纳米线过渡到宽约4μm、长约10μm、厚约30nm的带状纳米结构。
Semiconductive nanomaterials may exhibit lots of novel and amazing properties deriving from their effects such as quantum size, small size, and surface, which give rise to their potential use in the fields of nonlinear optics, magnetics, catalysis, medicine, and functional materials, as well as other areas. And the development of life science, information technology and even the basic research in material area can also been greatly influenced by those effects simultaneously. In this thesis, the selected two kinds of important semiconductive materials, ZnS and CdS, were synthesized with different morphology and nanostructure by employing different amine templates.
The ZnS holey submicrospheres were prepared by reacting ZnSO_4 with the sulfide source, H_2S, formed in the reaction of CS_2 with ethylenediamine, 1,3-propylenediamine, butylamine or 2-(2-Aminoethylamino)ethanol, which acted as template agent also, at 50℃ under agitating. The shape, particle size of about 100-850nm and hole size of about 250-600nm of ZnS holey submicrospheres were shown by SEM images. ZnS holey submicrospheres with β cubic ZnS phase and composed by 2-5nm of nanocrystals were proved by XRD and HRTEM. The blue shift of λ_(max) in UV-vis displayed the effect of quantum size. The ZnS submicrospheres is controllable: the size of them can be controlled by the aging time and the shape can be controlled by the molar ratio of CS_2 and ethylenediamine. These ZnS holey submicrospheres showed high photocatalytic activity by photodegrading eosin and the smaller ZnS holey submicrospheres showed higher activity of photocatalysis. The two aminos of amine template favor to act with Zn~(2+) form uniform and relatively smooth ZnS holey submicrospheres, while hydroxyethyl take disadvantage. Rational mechanism of hole by H_2S rushing out is suggested.
CdS nanomaterials of different morphology were prepared by template agent of butylamine. Experiment shows the structure and morphology were effected by the molar ratio of CS2 and butylamine: When n cs2:n CH3CH2CH2CH2NH2<1: 2, we obtained pure CdS nanoparticles with an average diameter of about 10nm; while n cs2:n
采用乙二胺、1，3-丙二胺、丁胺和β-羟乙基乙二胺等不同胺为模板剂，它们与CS_2反应生成的H_2S为硫源，在50℃与ZnSO_4搅拌反应20分钟制备了有孔的ZnS亚微米球。用SEM表征了有孔ZnS亚微米球的形貌、粒子大小为100～850nm以及孔的大小为250～600nm，XRD和HRTEM阐明了其为β型立方晶系，并由2～5纳米的ZnS纳米晶构成，UV-vis最大吸收峰蓝移表明其在室温下具有一定的量子尺寸效应。通过实验分析可知，所制备的有孔硫化锌亚微米空心球的形貌是可控的：陈化时间可控制球的粒径的大小，反应物二硫化碳和乙二胺的摩尔比可控制球的形状。对产物光催化实验降解可溶性染料曙红结果表明所制备的有孔纳米空心球均具有较强的光催化活性，而且，空心球的粒径越小，光催化活性越高。胺模板剂的两个氨基有利于与Zn~(2+)作用而形成均匀、相对光滑的有孔ZnS亚微米球，引入羟乙基则不利，提出了由H_2S冲出形成孔的合理机理。
采用正丁胺为模板剂制备了不同形貌的CdS纳米材料。研究发现二硫化碳和正丁胺的摩尔比对反应产物的结构和形貌有较大的影响：当n_(CS2)：n_(CH3CH2CH2CH2NH2)＜1：2时，得到的产物是晶型较好的平均粒径约为10nm的CdS纳米颗粒，而当n_(CS2)：n_(CH3CH2CH2CH2NH2)＞1：2时，得到的产物是CdS(CH_3CH_2CH_2CH_2NHCSCH_2CH_2CH_2CH_3)(CS_2)配合物纳米线或纳米带。对CdS纳米颗粒的光催化研究表明，60 min内对染料直接黑EX溶液的光降解率达到了98％以上，体现了较高的光催化活性。元素分析、XRD、FT-IR、TG分析表明CdS／有机配合物结构较为稳定，不受陈化时间的改变而改变，且随着陈化时间的增长，配合物形貌发生较大的改变，逐渐由直径为10-30nm、长约1μm以上的纳米线过渡到宽约4μm、长约10μm、厚约30nm的带状纳米结构。
Semiconductive nanomaterials may exhibit lots of novel and amazing properties deriving from their effects such as quantum size, small size, and surface, which give rise to their potential use in the fields of nonlinear optics, magnetics, catalysis, medicine, and functional materials, as well as other areas. And the development of life science, information technology and even the basic research in material area can also been greatly influenced by those effects simultaneously. In this thesis, the selected two kinds of important semiconductive materials, ZnS and CdS, were synthesized with different morphology and nanostructure by employing different amine templates.
The ZnS holey submicrospheres were prepared by reacting ZnSO_4 with the sulfide source, H_2S, formed in the reaction of CS_2 with ethylenediamine, 1,3-propylenediamine, butylamine or 2-(2-Aminoethylamino)ethanol, which acted as template agent also, at 50℃ under agitating. The shape, particle size of about 100-850nm and hole size of about 250-600nm of ZnS holey submicrospheres were shown by SEM images. ZnS holey submicrospheres with β cubic ZnS phase and composed by 2-5nm of nanocrystals were proved by XRD and HRTEM. The blue shift of λ_(max) in UV-vis displayed the effect of quantum size. The ZnS submicrospheres is controllable: the size of them can be controlled by the aging time and the shape can be controlled by the molar ratio of CS_2 and ethylenediamine. These ZnS holey submicrospheres showed high photocatalytic activity by photodegrading eosin and the smaller ZnS holey submicrospheres showed higher activity of photocatalysis. The two aminos of amine template favor to act with Zn~(2+) form uniform and relatively smooth ZnS holey submicrospheres, while hydroxyethyl take disadvantage. Rational mechanism of hole by H_2S rushing out is suggested.
CdS nanomaterials of different morphology were prepared by template agent of butylamine. Experiment shows the structure and morphology were effected by the molar ratio of CS2 and butylamine: When n cs2:n CH3CH2CH2CH2NH2<1: 2, we obtained pure CdS nanoparticles with an average diameter of about 10nm; while n cs2:n
引文
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[2] Rajeshwar K, Tacconi N R, Chenthamarakshan C R, Semiconductor-based composite materials: peparation, poperties, and prformance, Chem. Mater. 2001, 13: 2765.
[3] Manna L, Milliron D J, Meisel A, Scher E C, Alivisatos A P, Controlled growth of tetrapod-branched inorganic nanocrystals, Nature Mater., 2003, 2: 382.
[4] Peng X, Shape control of CdSe nanocrystals, Nature, 2000, 404: 59.
[5] Hu J, Li L, Yang W, Manna L, Wang L, Alivisatos A P, Linearly polarized emission from colloidal semiconductor quantum rods, Science, 2001, 292: 2060.
[6] 丁秉钧，纳米材料，机械工业出版社，2004，31．
[7] Qian Y T, Su Y, Xie Y, Chen Q W, Chen Z Y, Hydrothermal preparation and characterization of nanocrystalline powder of sphalerite, Mater. Res. Bull.,1995,30:601.
[8] 苏宜，谢毅，陈乾旺，钱逸泰，纳米ZnS、CdS水热合成及其表征，应用化学，1996，13(5)：56．
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[10] Kumta P N, Phule P P, Risbud S H, Low-temperature wet-chemical synthesis of amorphous indium sulfide powders, Mater. Lett., 1987, 5: 401.
[11] Variano B F, Hwang D M, Sandreff C J, Wiltzius, P, Jing T W, Ong N P, Quantum effects in anisotropic semiconductor clusters: colloidal suspensions of bismuth sesquisulfide and antimony sesquisulfide, Phys. Chem., 1987, 91: 6455.
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[14] Bianconi P A, Lin J, Stzelecki A R, Crystallization of an inorganic phase controlled by a polymer matrix, Nature, 1991, 349: 315.
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