TiO_2纳米花和HAP/TiO_2的制备、表征及其光催化降解有机污染物的研究
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摘要
自从在1972年Fujishima和Honda发现n—型半导体材料TiO2可以通过光电催化分解水制氢以来,光催化技术得到了广泛关注,被应用于全球密切关注的太阳能的转换、环境污染治理和清洁燃料的生产。几十年来,人们一直努力开发高活性的半导体光催化剂,目前世界各国已经成功地生产出了多种高效的半导体光催化材料。在众多的半导体氧化物催化剂中,TiO2由于生物和化学惰性、强光催化氧化能力、低成本、长期的稳定性等优点使它得到了广泛的应用：作为光催化剂、去除水和空气中的有机污染物、去除水体的重金属污染物和光解水制氢等等。特别是具有特殊微结构的TiO2半导体材料,它们作为光催化剂在这些方面可能具有更出色的性能和应用潜力。最近,人们在分子水平上对TiO2光催化剂的表面结构进行了研究探索,研究发现锐钛矿TiO2的{001}晶面具有比其它晶面高的化学活性。因此有关{001}晶面TiO2材料合成的研究是目前光催化领域的热点课题之一
另一方面,多环芳烃(PAHs)是一类典型的具有“致癌、致畸和致基因突变”特性的持久性有机污染物,来源分布广泛。PAHs在大气颗粒物表面的光化学反应是其重要的转化途径,研究PAHs在催化剂表面光催化降解转化特性具有重要的理论和实际意义。
围绕着上面的内容,我们主要开展了以下三个方面的工作：
(1)本文采用水热法,利用硫酸钛和氟化氢作为原料合成出TiO2纳米花。同时结合扫描电子显微镜(SEM)、X-射线衍射(XRD)、紫外-可见吸收光谱(DRS)、氮气-吸附脱附(BET)、瞬态光伏技术(TPV)、X射线电子能谱(XPS)等手段对样品的结构、形貌及其光学特性进行一系列的表征,并用其降解罗丹明B,使其与P25作对比,发现其催化活性高于P25。
(2)由于生物材料羟基磷灰石具有较强的吸附性能,我们通过沉淀法将其与TiO2纳米花负载在一起,这样就把羟基磷灰石的吸附性能与TiO2的光催化活性结合起来,并通过一系列的现代物理手段进行表征,证明羟基磷灰石已经成功的负载到了TiO2上,提高了对光的利用率,通过降解罗丹明B,发现其具有很高的催化活性。
(3)本文用原位红外技术作为检测手段来研究TiO2纳米花和HAP/TiO2对典型PAHs——萘的光催化降解行为。实验结果表明,在紫外光的照射下,萘受到光催化作用会发生开环反应,生成酸酐、芳酮、苯酯、羧酸、苯醛等中间产物,这些中间产物最后可被进一步氧化为二氧化碳和水。
Since the demonstration by Honda and Fujishima of the photoelectrolysis of water using a TiO2 electrode under an anodic bias potential, intensive research efforts have been devoted to the development of photocatalytic materials, with the aim of utilizing solar energy and thus addressing the increasing global concerns of environmental remediation and clean fuel production. Decades of efforts have successfully produced a wide range of efficient semiconductor—based photocatalytic materials for solar energy conversion and environmental remedy. Photocatalysts with high performance have been successfully fabricated by the investigators all over the world. Among various oxide semiconductor photocatalysts, TiO2 was generally recognized as the most promising one due to its biological and chemical inertness, superior photo oxidative, low cost and long—term stability. It has been widely used in photocatalytic applications, including the degradation of organic pollutants in aqueous and gaseous phases, removal of heavy metals from contaminated waters, hydrogen gas generation from photocatalytic water splitting, etc. Especially, TiO2 based photocatalysts with advanced mircrostructures would possess higher performances and potential in these applications.
Recently, people investigated the TiO2 materials at molecular level through a lot of research and found that the meta—stable{001} facets of anatase are more reactive than the other ones. The investigations related to{001} facets of anatase TiO2 has now become a hot topic in the field.
On the other hand, PAHs has been known as typical POPs, which are carcinogenic, teratogenic, mutagenic or endocrine disrupting to organisms. The photochemical behaviors of PAHs over atmospheric particles is an typical transforming pathway, so that studies on PAHs photocatalytic degradation over the surface of catalyst particles would make an important contribution to theretical and practical aspects.
In this thesis, we carried out the following three aspects of investigations about the anatase TiO2 with{001} facets:
(1) Flower—like anatase TiO2 assemblies with dominant{001} facets exposed were synthesized by a simple, economical hydrothermal route with titanium sulfate and hydrofluoric acid. Their surface morphology and structure were investigated by scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, X—ray diffraction, and Brunauer—Emmet—Teller N2 gas adsorption—desorption isotherms. The optical property and the photo—induced charge carriers of the flower—like TiO2 were studied by UV—vis diffuse reflectance spectroscopy and transient photovoltage technique. The flower—like TiO2 particles exhibited a good photocatalytic activity in degrading rhodamine B.
(2) Due to the strong adsorptive capability of the biological material—hydroxyapatite, we loaded it with the flower—like TiO2 together, so that we could combine the adsorption of the hydroxyapatite and the photocatalytic of the flower—like TiO2. Through some modern characterization techniques such as SEM, XRD, DRS, EDS, FTIR, XPS and so on, we proved that hydroxyapatite was successfully loaded on the flower—like TiO2. At the same time, we used them to degrading rhodamine B to compare their photocatalytic activity.
(3) The in-situ transmission infrared spectroscopy was used to study the photocatalytic reaction of the naphthalene on flower—like TiO2 and HAP/TiO2, and the experimental was carried out under UV irradiation. And the results showed that under the UV irradiation, the nanphthalene's ring will be opened, and the reaction intermediate products were aromatic ketons, Propyl hydroxybenzoate, carboxylic acid, benzene formaldehyde, and the final products are carbon dioxide and water.
另一方面,多环芳烃(PAHs)是一类典型的具有“致癌、致畸和致基因突变”特性的持久性有机污染物,来源分布广泛。PAHs在大气颗粒物表面的光化学反应是其重要的转化途径,研究PAHs在催化剂表面光催化降解转化特性具有重要的理论和实际意义。
围绕着上面的内容,我们主要开展了以下三个方面的工作：
(1)本文采用水热法,利用硫酸钛和氟化氢作为原料合成出TiO2纳米花。同时结合扫描电子显微镜(SEM)、X-射线衍射(XRD)、紫外-可见吸收光谱(DRS)、氮气-吸附脱附(BET)、瞬态光伏技术(TPV)、X射线电子能谱(XPS)等手段对样品的结构、形貌及其光学特性进行一系列的表征,并用其降解罗丹明B,使其与P25作对比,发现其催化活性高于P25。
(2)由于生物材料羟基磷灰石具有较强的吸附性能,我们通过沉淀法将其与TiO2纳米花负载在一起,这样就把羟基磷灰石的吸附性能与TiO2的光催化活性结合起来,并通过一系列的现代物理手段进行表征,证明羟基磷灰石已经成功的负载到了TiO2上,提高了对光的利用率,通过降解罗丹明B,发现其具有很高的催化活性。
(3)本文用原位红外技术作为检测手段来研究TiO2纳米花和HAP/TiO2对典型PAHs——萘的光催化降解行为。实验结果表明,在紫外光的照射下,萘受到光催化作用会发生开环反应,生成酸酐、芳酮、苯酯、羧酸、苯醛等中间产物,这些中间产物最后可被进一步氧化为二氧化碳和水。
Since the demonstration by Honda and Fujishima of the photoelectrolysis of water using a TiO2 electrode under an anodic bias potential, intensive research efforts have been devoted to the development of photocatalytic materials, with the aim of utilizing solar energy and thus addressing the increasing global concerns of environmental remediation and clean fuel production. Decades of efforts have successfully produced a wide range of efficient semiconductor—based photocatalytic materials for solar energy conversion and environmental remedy. Photocatalysts with high performance have been successfully fabricated by the investigators all over the world. Among various oxide semiconductor photocatalysts, TiO2 was generally recognized as the most promising one due to its biological and chemical inertness, superior photo oxidative, low cost and long—term stability. It has been widely used in photocatalytic applications, including the degradation of organic pollutants in aqueous and gaseous phases, removal of heavy metals from contaminated waters, hydrogen gas generation from photocatalytic water splitting, etc. Especially, TiO2 based photocatalysts with advanced mircrostructures would possess higher performances and potential in these applications.
Recently, people investigated the TiO2 materials at molecular level through a lot of research and found that the meta—stable{001} facets of anatase are more reactive than the other ones. The investigations related to{001} facets of anatase TiO2 has now become a hot topic in the field.
On the other hand, PAHs has been known as typical POPs, which are carcinogenic, teratogenic, mutagenic or endocrine disrupting to organisms. The photochemical behaviors of PAHs over atmospheric particles is an typical transforming pathway, so that studies on PAHs photocatalytic degradation over the surface of catalyst particles would make an important contribution to theretical and practical aspects.
In this thesis, we carried out the following three aspects of investigations about the anatase TiO2 with{001} facets:
(1) Flower—like anatase TiO2 assemblies with dominant{001} facets exposed were synthesized by a simple, economical hydrothermal route with titanium sulfate and hydrofluoric acid. Their surface morphology and structure were investigated by scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, X—ray diffraction, and Brunauer—Emmet—Teller N2 gas adsorption—desorption isotherms. The optical property and the photo—induced charge carriers of the flower—like TiO2 were studied by UV—vis diffuse reflectance spectroscopy and transient photovoltage technique. The flower—like TiO2 particles exhibited a good photocatalytic activity in degrading rhodamine B.
(2) Due to the strong adsorptive capability of the biological material—hydroxyapatite, we loaded it with the flower—like TiO2 together, so that we could combine the adsorption of the hydroxyapatite and the photocatalytic of the flower—like TiO2. Through some modern characterization techniques such as SEM, XRD, DRS, EDS, FTIR, XPS and so on, we proved that hydroxyapatite was successfully loaded on the flower—like TiO2. At the same time, we used them to degrading rhodamine B to compare their photocatalytic activity.
(3) The in-situ transmission infrared spectroscopy was used to study the photocatalytic reaction of the naphthalene on flower—like TiO2 and HAP/TiO2, and the experimental was carried out under UV irradiation. And the results showed that under the UV irradiation, the nanphthalene's ring will be opened, and the reaction intermediate products were aromatic ketons, Propyl hydroxybenzoate, carboxylic acid, benzene formaldehyde, and the final products are carbon dioxide and water.
引文
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