L-半胱氨酸辅助金属硫化物微米材料的合成与表征
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摘要
随着对纳米／微米材料的进一步深入研究,如何通过控制纳米／微米材料的结晶与成核生长过程来合成具有特殊形貌结构、性能和尺寸大小的材料成为当前材料研究的重点。截止目前为止,各种不同的方法先后被应用于纳米／微米材料的制备合成,应用生物分子为模板或辅助剂来合成纳米／微米材料已成为当前材料制备合成的一大热点,因生物分子具有独特的结构和出色的自组装功能,它们特殊的性能使其成为设计和合成具有复杂结构材料的极佳模板。
金属硫化物作为材料的一大类,具有广泛的用途。目前大部分金属硫化物都是通过无机硫源与各种金属阳离子反应来制备合成的。L半胱氨酸作为生物体的基本成分之一,其分子结构中具有-SH基团,因此可以作为硫源来合成金属硫化物纳米／微米材料；同时其分子结构具有普通氨基酸的结构能够发生缩合反应来形成多肽进而作为模板来控制材料的合成。怎样使用L-半胱氨酸特殊的结构和强自组装功能来合成具有复杂结构的金属硫化物成为当前研究的热点之一,受到广泛的关注。
本文研究了以L-半胱氨酸为模板水热合成金属硫化物微米材料的不同方法,通过这些方法成功制备了多种金属硫化物微米材料,并通过各种表征手段如：X-射线衍射(XRD)、透射电镜(TEM)、高分辨电镜(HRTEM),扫描电镜(SEM)、电子衍射(SAED)、红外光谱(FTIR)及荧光光谱分析(PL)等技术对所制备的材料进行了详细的表征和性能研究。主要内容如下：
(1)利用L-半胱氨酸为模板,在水热条件下合成了管状的γ-MnS微米晶体。通过控制水热反应的温度、时间及添加适当的表面活性剂可得到不同相如α、γ相,不同形貌如片状、海胆状、胶囊状的γ-MnS及八面体状的α-MnS。荧光检测表明不同相、不同形貌的MnS皆具有良好的光学性能。
(2)基于以上方法,通过调节溶液的pH值或添加不同的螯合剂成功制备了不同形貌的NiS、Bi2S3等硫化物微米晶体。
该制备方法丰富和发展了金属硫化物微米材料的制备技术,丰富了金属硫化物微米材料的形貌,并为进一步应用生物分子辅助合成微纳米材料提供了理论支持。
Accompanying with nanomaterial's further study, it has became important to synthesize materials with special morphologies, characters, and sizes by controlling the nucleation and growth progress. Until recently, different methods have been applied to synthesize nanomaterials. Now, it is a hot topic to apply biomolecule as template or assist agent to synthesize materials due to biomolecule's special structure and fascinating self-assembling functions. Their special properties make them templates of unmatched type for the design and synthesis of complicated structures.
As a kind of useful materials, metal sulfides have been used widely in different field. Recently, most metal sulfides are synthesized by inorganic sulfur sources and metal cations. As one of life's basic building blocks, L-cysteine contains-SH in its molecule structure, which can act as sulfur source to synthesize metal sulfides. Besides, its molecule structure also contains the-NH2 and-COOH structure in average amino acid and can form peptide by condensation. How to use L-cysteine's special structure and self-assembling function for the synthesis of complicated structures has became a hot topic.
In this thesis, a hydrothermal way was developed to synthesize several metal sulfide micromaterials. Various methods including X-ray powder diffraction (XRD), Transmission Electron Microscope (TEM), High-resolution Transmission Electron Microscope (HRTEM), Selected Area Electron Diffraction (SAED), Infrared Spectrum (IR) and Photoluminescence (PL) were used for characterization. The main summarized as follows.
(1) Using L-cysteine as template, tube-likeγ-MnS microcrystals were synthesized under hydrothermal condition. Different phases and morphologies of MnS, such asαandγphase, thin flake like, sea urchin like, octahedral like, and capsule like, were synthesized by controlling reaction temperature, time, or adding certain surfactant. Photoluminescence experiments under room temperature have indicted that these pure MnS have good optical properties.
(2) Based on above methods, different morphologies of NiS、Bi2S3 and other sulfides were prepared by changing pH values or adding chelating agent.
The preparation method enriched and developed the technology of the preparation of metal sulfide micromaterials, whose size and morphology were enriched, besides, it also provides the theory supports of biomolecule assist synthesis of micro/nanomaterilas.
金属硫化物作为材料的一大类,具有广泛的用途。目前大部分金属硫化物都是通过无机硫源与各种金属阳离子反应来制备合成的。L半胱氨酸作为生物体的基本成分之一,其分子结构中具有-SH基团,因此可以作为硫源来合成金属硫化物纳米／微米材料；同时其分子结构具有普通氨基酸的结构能够发生缩合反应来形成多肽进而作为模板来控制材料的合成。怎样使用L-半胱氨酸特殊的结构和强自组装功能来合成具有复杂结构的金属硫化物成为当前研究的热点之一,受到广泛的关注。
本文研究了以L-半胱氨酸为模板水热合成金属硫化物微米材料的不同方法,通过这些方法成功制备了多种金属硫化物微米材料,并通过各种表征手段如：X-射线衍射(XRD)、透射电镜(TEM)、高分辨电镜(HRTEM),扫描电镜(SEM)、电子衍射(SAED)、红外光谱(FTIR)及荧光光谱分析(PL)等技术对所制备的材料进行了详细的表征和性能研究。主要内容如下：
(1)利用L-半胱氨酸为模板,在水热条件下合成了管状的γ-MnS微米晶体。通过控制水热反应的温度、时间及添加适当的表面活性剂可得到不同相如α、γ相,不同形貌如片状、海胆状、胶囊状的γ-MnS及八面体状的α-MnS。荧光检测表明不同相、不同形貌的MnS皆具有良好的光学性能。
(2)基于以上方法,通过调节溶液的pH值或添加不同的螯合剂成功制备了不同形貌的NiS、Bi2S3等硫化物微米晶体。
该制备方法丰富和发展了金属硫化物微米材料的制备技术,丰富了金属硫化物微米材料的形貌,并为进一步应用生物分子辅助合成微纳米材料提供了理论支持。
Accompanying with nanomaterial's further study, it has became important to synthesize materials with special morphologies, characters, and sizes by controlling the nucleation and growth progress. Until recently, different methods have been applied to synthesize nanomaterials. Now, it is a hot topic to apply biomolecule as template or assist agent to synthesize materials due to biomolecule's special structure and fascinating self-assembling functions. Their special properties make them templates of unmatched type for the design and synthesis of complicated structures.
As a kind of useful materials, metal sulfides have been used widely in different field. Recently, most metal sulfides are synthesized by inorganic sulfur sources and metal cations. As one of life's basic building blocks, L-cysteine contains-SH in its molecule structure, which can act as sulfur source to synthesize metal sulfides. Besides, its molecule structure also contains the-NH2 and-COOH structure in average amino acid and can form peptide by condensation. How to use L-cysteine's special structure and self-assembling function for the synthesis of complicated structures has became a hot topic.
In this thesis, a hydrothermal way was developed to synthesize several metal sulfide micromaterials. Various methods including X-ray powder diffraction (XRD), Transmission Electron Microscope (TEM), High-resolution Transmission Electron Microscope (HRTEM), Selected Area Electron Diffraction (SAED), Infrared Spectrum (IR) and Photoluminescence (PL) were used for characterization. The main summarized as follows.
(1) Using L-cysteine as template, tube-likeγ-MnS microcrystals were synthesized under hydrothermal condition. Different phases and morphologies of MnS, such asαandγphase, thin flake like, sea urchin like, octahedral like, and capsule like, were synthesized by controlling reaction temperature, time, or adding certain surfactant. Photoluminescence experiments under room temperature have indicted that these pure MnS have good optical properties.
(2) Based on above methods, different morphologies of NiS、Bi2S3 and other sulfides were prepared by changing pH values or adding chelating agent.
The preparation method enriched and developed the technology of the preparation of metal sulfide micromaterials, whose size and morphology were enriched, besides, it also provides the theory supports of biomolecule assist synthesis of micro/nanomaterilas.
引文
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