以蛋白质为模板制备二氧化钛纳米材料及机理探讨
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摘要
近年来,以生物组织(例如生物有机体的某一部分、微生物和生物大分子等)为模板合成各种材料受到了广泛的关注,而蛋白质模板则为科学家们更加青睐。这主要是由于蛋白质有先天的优势,它在生物体内能与很多无机物质紧密结合在一起,形成诸如人体骨骼,节肢动物的外壳和硅藻属的骨架等,而且蛋白质来源广泛、价格低廉又容易购得,因此成为研究生物模板时的重点。
目前,国内外学者们普遍用作模板的蛋白质主要是去铁铁蛋白,人铁蛋白,清蛋白以及蚕丝蛋白,利用蛋白的空腔或胶连网状结构来产生模板效应。
本论文主要研究了常见的两种廉价蛋白,酪蛋白和蛋清蛋白,将这两种蛋白应用到合成中,以它们作模板来尝试合成具有光催化活性的二氧化钛和氧化锌。
首先以酪蛋白为模板,在水相体系中合成二氧化钛。经过10天的静置,在室温条件下合成制得了TiO2纳米薄片,薄片为无定形TiO2,表面光滑。纳米薄片的长度和宽度均为微米级,厚度约为20nm。经过500℃焙烧后可部分保持形貌,在紫外光及可见光照下降解苯酚效果良好。
然后又在以蛋清蛋白为模板的水相体系中合成TiO2,制得了分散均匀、形状规则的TiO2小颗粒,颗粒直径约为9nm。通过TEM, XPS, FTIR, TG-DTA和Uv-Vis等表征手段对反应的机理进行了深入的研究,提出了变性的蛋清蛋白形成网状胶连体作模板的机理,简单描述如下：蛋清蛋白和无定形二氧化钛在室温下形成无机一蛋白混合物,当温度升高至80℃,蛋白分子伸展,变性并聚集成一个巨大的网状结构,同时无定形二氧化钛吸附在网状结构的表面或内部。当温度升高至150℃时,胶连网状结构分解,无定形二氧化钛形成均匀的二氧化钛小晶核,再经过适当时间的晶化,形成了均匀且分散良好的二氧化钛纳米颗粒。对产物的光催化测试结果表明其在紫外光照下对甲基橙的降解效率优于普通的无模板合成的TiO2。
最后对以酪蛋白为模板合成ZnO颗粒进行了初步探讨,得到了形状较规则的ZnO颗粒,且产物的光催化效果比商用TiO2(P25)更加优异。
In recent years, a variety of biological tissues for the template synthesis of materials have attracted extensive attention. Amongst, proteins are of particular interests due to their inherent advantages. Proteins can closely integrate with many inorganic materials in vivo to form the body such as bone, shell of arthropods and skeleton of diatoms. Moreover, proteins are cheap and accessible with a wide range of sources.
Casein and egg albumin are employed as bio-templates to synthesize titania and zinc oxide with good photocatalytic activities.
We employ casein as template with water as solvent and obtain titania nanosheets from static solution at room temperature after 10 days. The titania nanosheets are amorphous with smooth surface. Their length and width are in micron-level and their thickness is about 20 nm. The morphology of nanosheets can be preserved to some extent after calcined at 500℃. The calcined titania nanosheets exhibit good photocatalytic activity in the degradation of phenol under UV and visible light irradiation.
Egg albumin has been used as a template in water solution for the synthesis of titania. Uniform and well dispersed TiO2 nanoparticles with a diameter of ca.9 nm can be obtained. The as-prepared TiO2 nanoparticles are characterized by means of TEM, XPS, FTIR, TG-DTA and UV-Vis. Based on the characterization results, a possible mechanism of heat-induced denatured protein network as template matrix to fabricate TiO2 nanoparticles was carefully proposed, which is described as below:egg albumin solutions and amorphous TiO2 could form inorganic-protein conjugation complexes at room temperature. As temperature increased to 80℃, the protein molecules unfolded, denatured and formed a huge network matrix, with TiO2 embedding in the inner and absorbing on the outer surface of the matrix. At higher temperatures up to 150℃, the gelation network decomposed and uniform TiO2 nanoparticles were obtained after proper crystallization process. The as-prepared TiO2 nanoparticles exhibit superior photocatalytic activity in degradation of methyl orange under UV light irradiation.
In the second part of work, casein has been applied as a bio-template for synthesis of zinc oxide, which acts as a potential photocatalyst, and some results have been obtained. ZnO particles with regular shape are obtained by means of bio-template and good photocatalytic activity was achieved.
目前,国内外学者们普遍用作模板的蛋白质主要是去铁铁蛋白,人铁蛋白,清蛋白以及蚕丝蛋白,利用蛋白的空腔或胶连网状结构来产生模板效应。
本论文主要研究了常见的两种廉价蛋白,酪蛋白和蛋清蛋白,将这两种蛋白应用到合成中,以它们作模板来尝试合成具有光催化活性的二氧化钛和氧化锌。
首先以酪蛋白为模板,在水相体系中合成二氧化钛。经过10天的静置,在室温条件下合成制得了TiO2纳米薄片,薄片为无定形TiO2,表面光滑。纳米薄片的长度和宽度均为微米级,厚度约为20nm。经过500℃焙烧后可部分保持形貌,在紫外光及可见光照下降解苯酚效果良好。
然后又在以蛋清蛋白为模板的水相体系中合成TiO2,制得了分散均匀、形状规则的TiO2小颗粒,颗粒直径约为9nm。通过TEM, XPS, FTIR, TG-DTA和Uv-Vis等表征手段对反应的机理进行了深入的研究,提出了变性的蛋清蛋白形成网状胶连体作模板的机理,简单描述如下：蛋清蛋白和无定形二氧化钛在室温下形成无机一蛋白混合物,当温度升高至80℃,蛋白分子伸展,变性并聚集成一个巨大的网状结构,同时无定形二氧化钛吸附在网状结构的表面或内部。当温度升高至150℃时,胶连网状结构分解,无定形二氧化钛形成均匀的二氧化钛小晶核,再经过适当时间的晶化,形成了均匀且分散良好的二氧化钛纳米颗粒。对产物的光催化测试结果表明其在紫外光照下对甲基橙的降解效率优于普通的无模板合成的TiO2。
最后对以酪蛋白为模板合成ZnO颗粒进行了初步探讨,得到了形状较规则的ZnO颗粒,且产物的光催化效果比商用TiO2(P25)更加优异。
In recent years, a variety of biological tissues for the template synthesis of materials have attracted extensive attention. Amongst, proteins are of particular interests due to their inherent advantages. Proteins can closely integrate with many inorganic materials in vivo to form the body such as bone, shell of arthropods and skeleton of diatoms. Moreover, proteins are cheap and accessible with a wide range of sources.
Casein and egg albumin are employed as bio-templates to synthesize titania and zinc oxide with good photocatalytic activities.
We employ casein as template with water as solvent and obtain titania nanosheets from static solution at room temperature after 10 days. The titania nanosheets are amorphous with smooth surface. Their length and width are in micron-level and their thickness is about 20 nm. The morphology of nanosheets can be preserved to some extent after calcined at 500℃. The calcined titania nanosheets exhibit good photocatalytic activity in the degradation of phenol under UV and visible light irradiation.
Egg albumin has been used as a template in water solution for the synthesis of titania. Uniform and well dispersed TiO2 nanoparticles with a diameter of ca.9 nm can be obtained. The as-prepared TiO2 nanoparticles are characterized by means of TEM, XPS, FTIR, TG-DTA and UV-Vis. Based on the characterization results, a possible mechanism of heat-induced denatured protein network as template matrix to fabricate TiO2 nanoparticles was carefully proposed, which is described as below:egg albumin solutions and amorphous TiO2 could form inorganic-protein conjugation complexes at room temperature. As temperature increased to 80℃, the protein molecules unfolded, denatured and formed a huge network matrix, with TiO2 embedding in the inner and absorbing on the outer surface of the matrix. At higher temperatures up to 150℃, the gelation network decomposed and uniform TiO2 nanoparticles were obtained after proper crystallization process. The as-prepared TiO2 nanoparticles exhibit superior photocatalytic activity in degradation of methyl orange under UV light irradiation.
In the second part of work, casein has been applied as a bio-template for synthesis of zinc oxide, which acts as a potential photocatalyst, and some results have been obtained. ZnO particles with regular shape are obtained by means of bio-template and good photocatalytic activity was achieved.
引文
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