【作者】 徐支有；

【导师】 张永才；

【作者基本信息】 扬州大学 ， 材料物理与化学， 2009， 硕士

【摘要】 本论文旨在探索掺杂ⅡB族金属硫化物半导体纳米材料的溶剂热合成新方法、新路线,通过调节掺杂金属离子的浓度,合成了系列带隙可调控的ZnS:Mn, CdS:Mn, ZnS:Cu纳米棒状材料,并初步探讨了其合成机理。所得产物用X–射线衍射（XRD）、透射电镜（TEM）、能谱（EDS）、紫外–可见吸收光谱（UV–vis）及傅立叶转换红外光谱（FTIR）等多种现代分析测试手段进行表征。并以合成的产物为催化剂进行光催化降解MO（甲基橙）或MB（亚甲基蓝）溶液实验的研究,现对本论文的主要内容总结如下:1.以Cd_1-xMn_x-（DDTC）₂（x=0–0.35）为单源分子前驱体,控制合成了六方相Cd_1-xMn_xS（x=0–0.35）纳米棒,主要包括以下两步:首先在常温常压下通过醋酸锰（Mn（CH₃COO）₂·2H₂O）、硫酸镉（3CdSO4·8H2O）和二乙基二硫代氨基甲酸钠（DDTC）在水溶液中的沉淀反应制得单源分子前驱体Cd_1-xMn_x-（DDTC）₂ （x=0–0.35）;然后将前驱体在乙二胺中180 oC下溶剂热处理12 h,得到了六方相的Cd_1-xMn_xS纳米棒。研究了x值的大小对产品形貌、尺寸和光学性质的影响,并探讨了反应机理。利用XRD、TEM、EDS、UV–vis及FTIR等测试手段对所得产物进行表征。最后,以合成的Cd_1-xMn_xS纳米棒为催化剂进行光催化降解MO溶液实验的研究,实验结果表明,x = 0.02的产物(即Cd_0.98Mn_0.02S)具有最好的光催化降解效果,当其用量为0.1 g,光照时间为4.5 h,对250 ml浓度为10 mg/L甲基橙溶液的脱色率为99.9%。2.以Zn_1-xMn_x-（DDTC）₂（x=0–0.10）为单源分子前驱体,控制合成了六方相Zn_1-xMn_xS（x=0–0.10）纳米棒,主要包括以下两步:首先在常温常压下通过醋酸锰（Mn（CH₃COO）₂·2H₂O）、醋酸锌（Zn（CH₃COO）₂·2H₂O）和二乙基二硫代氨基甲酸钠（DDTC）在水溶液中的沉淀反应制得单源分子前驱体Zn_1-xMn_x-（DDTC）₂ （x=0–0.10）;然后将前驱体在40%的水合肼溶液中180 oC下溶剂热处理12 h,得到了六方相的Zn_1-xMn_xS纳米棒。研究了x值的大小对产品形貌、尺寸和光学性质的影响,并探讨了反应机理。利用XRD、TEM、EDS、UV–vis及FTIR等测试手段对所得产物进行表征。最后,以合成的Zn_1-xMn_xS纳米棒为催化剂进行光催化降解MB溶液实验的研究,实验结果表明,随着掺锰量的增加,所得Zn_1-xMn_xS纳米棒对MB溶液的光催化降解效果越来越差。x = 0的产物（即硫化锌纳米棒）的光催化性能最好,当其用量为0.1 g,光照时间为5.5 h,对250 ml亚甲基蓝溶液（10 mg/L）的脱色率为98%。3.以Zn_1-xCu_x-（DDTC）₂（x=0–0.10）为单源分子前驱体,控制合成了Zn_1-xCu_xS （x=0–0.10）纳米棒和纳米颗粒（x=0–0.01）,主要包括以下两步:首先在常温常压下通过醋酸锌（Zn（CH3COO）₂?2H2O）、氯化铜（CuCl2·2H2O）和二乙基二硫代氨基甲酸钠（DDTC）在水溶液中的沉淀反应制得单源分子前驱体Zn_1-xCu_x-（DDTC）₂（x=0–0.10）;然后将前驱体在50%的乙二胺溶液中180 oC下溶剂热处理12 h,分别得到了六方相的（当x = 0, 0.01时）和混合相的Zn_1-xCu_xS（当x = 0.03, 0.05时）的Zn_1-xCu_xS纳米棒,而将前驱体在蒸馏水中180 oC下水热处理12 h,则得到了混合相的（当x = 0, 0.002, 0.005时）和六方相的（当x = 0.01时）的Zn_1-xCu_xS纳米颗粒。研究了溶剂和x值的大小对产品晶型、形貌、尺寸和光学性质的影响,并探讨了反应机理。利用XRD、TEM、EDS、UV–vis及FTIR等测试手段对所得产物进行表征。最后,以合成的Zn_1-xCu_xS纳米材料为催化剂进行光催化降解MB溶液实验的研究。实验结果表明,随着掺铜量的增加,所得Zn_1-xCu_xS纳米材料对MB溶液的光催化降解效果越来越差,其中ZnS纳米棒及其颗粒具有最好的脱色效果。当硫化锌纳米棒的用量为0.1 g时,光照时间为5.5 h,对250 ml亚甲基蓝溶液（10 mg/L）的脱色率为94.5%;而以0.1 g以硫化锌颗粒为催化剂,光照时间为5.5 h时,对250 ml亚甲基蓝溶液（10 mg/L）的脱色率为78.4%。更多还原

【Abstract】 The present thesis is aimed at exploring novel solvothermal methods to synthesize the semiconductor nanomaterials of dopedⅡB-sulfide. By doping different concentrations of metal ions (such as Mn²⁺, Cu²⁺), we can obtain ZnS:Mn, CdS:Mn, ZnS:Cu nanorods or nanopaticles with tuneable bandgaps. And the corresponding formation mechanisms of the products were also discussed. X–ray diffraction （XRD）, Transmission electron microscopy （TEM）, Energy dispersive spectroscopy （EDS）, UV–vis absorption spectrum, and Fourier transform infrared spectroscopy （FTIR） were used to characterize the as–obtained products. At the same time, we did some photodegradation experiments of MO（methyl orange） or MB（methylence blue） solution under UV irradiation with our homemade products as catalysts. The main works achieved are summed up as following:1. The controllable synthesis of hexagonal Mn-doped CdS (Cd_1-xMn_xS, x=0–0.35) nanorods from a class of solid air-stable single-source molecular precursors (cadmium manganese bis（N,N-diethyldithiocarbamate）, Cd_1-xMn_x-（DDTC）₂) has been achieved by two facile steps: first, Cd_1-xMn_x-（DDTC）₂ （x=0–0.35） was prepared directly through the precipitation reactions of stoichiometric cadmium sulfate, manganese acetate, and sodium diethyldithiocarbamate in distilled water under the ambient condition; second, pure hexagonal phase Cd_1-xMn_xS （x=0–0.35） nanorods with different aspect ratios were produced via solvothermal treatment of the precursors in ethylenediamine at 180 oC for 12 h. It was observed that the values of x played an important role in shape, size and optical characteristic of the products. The possible formation mechanism was also discussed. The homemade products were characterized by XRD, TEM, EDS, Uv-vis and FTIR. At last, we did some photodegradation experiments of MO（methyl orange） solution under UV irradiation with Cd_1-xMn_xS as catalyst. The photocatalytic experiments indicated that Cd_0.98Mn_0.02S has the best photocatalytic performance. The decolorization efficiency of 250 mL MO solution （10 mg/L） would reach 99.9% after 4.5h’photodegradation with 0.1 g of Cd0.98Mn0.02S as catalyst.2. The controllable synthesis of hexagonal Zn_1-xMn_xS （x=0–0.10） nanorods from a class of solid air-stable single-source molecular precursors (zinc manganese bis（N,N-diethyldithiocarbamate）, Zn_1-xMn_x-（DDTC）₂) has been achieved by two facile steps: first, Zn_1-xMn_x-（DDTC）₂ （x=0–0.10） was prepared directly through the precipitation reactions of stoichiometric manganese acetate, zinc acetate, and sodium diethyldithiocarbamate in distilled water under the ambient condition; second, pure hexagonal phase Zn_1-xMn_xS （x=0–0.10） nanorods with different aspect ratios were produced via solvothermal treatment of the precursors in 40 vol.% hydrate hydrazine aqueous solution at 180 oC for 12 h, It was observed that the value of x was important to shape, size and optical characteristic of the products. The possible formation mechanism was also discussed. The homemade products were characterized by XRD, TEM, EDS, Uv-vis and FTIR. Finally, we do some photodegradation experiments of MB（methylence blue） solution with Zn_1-xMn_xS as catalyst. The photocatalytic experiments indicated that the decolorization efficiency of MB solution would decrease with increasing x values in the as-syntheiszed Zn_1-xMn_xS, and ZnS nanorods have the best photocatalytic performance. The decolorization efficiency of 250 mL MB solution （10 mg/L） will arrive at 98% after 5.5 hours, photodegradation, when 0.1 g of ZnS nanorods were used as catalyt.3. The controllable synthesis of hexagonal phase Zn_1-xCu_xS （x=0–0.10） nanorods or nanoparticles （x=0–0.01） from a class of solid air-stable single-source molecular precursors (zinc copper bis（N,N- diethyldithiocarbamate）, Zn_1-xCu_x-（DDTC）₂) has been achieved by two facile steps: first, Zn_1-xCu_x-（DDTC）₂ （x=0–0.10） was prepared directly through the precipitation reactions of stoichiometric copper chloride, zinc acetate, and sodium diethyl- dithiocarbamate in distilled water under the ambient condition; second, pure hexagonal phase （x=0, 0.01） and mixed phase （x = 0.03, 0.05） Zn_1-xCu_xS nanorods were produced via solvothermal treatment of the precursors in 50 vol.% en aqueous solution at 180 oC for 12 h, while the mixed phase （x=0, 0.002, 0.005） and single hexagonal phase （x=0.01） Zn_1-xCu_xS nanoparticles were produced via hydrothermal treatment of the precursors in distilled water at 180 oC for 12 h. It was observed that the value of x affected phase, shape, size and optical characteristic of the products. The possible formation mechanism was also discussed. The homemade products were characterized by XRD, TEM, EDS, Uv-vis and FTIR. At last, we do some photodegradation experiments of MB solution with Zn_1-xCu_xS nanorods as catalyst, the experiment indicated that the decolorization efficiency of 10 mg/L MB solution will decrease with increasing of Cu²⁺, ZnS nanorods have the best photocatalytic effect, The decolorization efficiency will arrive at 94.5% after 5.5 hours, photodegradation. Whlie it will arrive at 78.4% after 5.5 hours, photodegradation with ZnS nanoparticles as catalyst.更多还原