二氧化钛基光催化材料的微结构调控与性能增强
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摘要
21世纪,环境和能源问题是人类面临的最大挑战。半导体光催化技术,为我们提供了一种有效治理环境污染和高效利用太阳能的有效途径。纳米二氧化钛是最常用的半导体光催化材料,广泛应用于污水处理、空气净化、抗菌杀毒、光分解水制氢等领域。但是,二氧化钛光响应范围较窄,只能吸收太阳光中的紫外光,同时其量子效率偏低,阻碍了其实际应用和商业化发展。本博士论文围绕二氧化钛基光催化材料的组成、组织、结构与性能的关系,开展了系统深入的研究工作,在高活性二氧化钛的微结构调控、掺杂、复合、性能增强和新型光催化材料的制备等方面的研究中取得了创新性研究成果,其主要研究内容如下：
第一,不同形貌二氧化钛的制备和光催化活性比较。首先,我们选用硫酸钛为前驱体,以氟化氢铵为形貌控制剂,通过一步水热法合成了几种不同形貌锐钛矿二氧化钛微结构,包括实心微球、空心球和暴露{001}晶面块状锐钛矿微晶。研究发现,表面氟化二氧化钛空心微球具有最好的光催化活性,而暴露{001}晶面块状锐钛矿微晶具有最好的比光催化活性。这主要是由于一方面空心微球有利于增强对光的吸收和利用效率；另一方面,二氧化钛空心球具有大的比表面积和分级多孔结构,有利于增强对污染物的富集和反应物与产物在催化材料中的扩散,从而增强光催化活性。随后,以钛酸盐纳米管为前躯体,在HF-H2O-C2H5OH的混合溶液中,采用一种无模板和表面活性剂的醇热法合成了暴露{001}面二氧化钛纳米片自组装形成的分等级花状超结构。该花状二氧化钛超结构在气相光催化降解丙酮和液相光催化降解甲基橙中表现出非常高的光催化活性,其活性明显高于国际标准光催化材料Degussa P-25。这主要是由该材料具有分等级多孔结构,暴露高活性{001}晶面和增强的光吸收能力引起的。
第二,暴露高活性{001}面二氧化钛纳米片的制备及其光催化活性的研究。首先,以钛酸四丁酯为前驱体,在氢氟酸和水的混合溶液中通过一步水热法制备了表面氟化暴露不同比例{001}晶面的锐钛矿二氧化钛纳米片粉末材料。该材料在光催化分解空气中丙酮的实验中表现出增强的光催化活性,特别是表面氟化和暴露适当比例(～70%){001}晶面的二氧化钛纳米片显示出最高的光催化活性,其表观速率常数是P25样品的9倍多。这主要是由于表面氟化和暴露最佳比例的{001}晶面具有协同增强二氧化钛光催化活性的作用。随后,基于暴露{001}晶面表现出较高光催化活性,我们以钛片为基底,通过一步水热法合成了暴露{001}面花状二氧化钛微球薄膜。该花状二氧化钛微球薄膜在光催化降解偶氮染料溶液时,表现出光催化选择性,并且通过改变二氧化钛微球表面性质和{001}晶面的腐蚀程度能够进一步调控二氧化钛微球薄膜的光催化选择性。这主要是由于通过改变二氧化钛表面电荷性质,使二氧化钛优先吸附带相反电荷的污染物分子,从而选择性降解被吸附的污染物分子。
第三,等离子光催化剂Ag-TiO2复合空心球的微波水热制备及其可见光催化活性。通过微波水热、化学诱导自转变和光还原的方法,制备了可见光响应的等离子体光催化剂Ag-TiO2复合空心球。这种金属-半导体纳米复合等离子体光催化剂在降解水中的罗丹明时显示出较高的可见光光催化活性和稳定性。这主要是由于吸附在二氧化钛空心球上的银纳米粒子具有表面等离子体效应,它能够吸收可见光,使复合催化剂具有可见光响应。在可见光照射下,银纳米颗粒的表面等离子体响应诱导产生光生电子-空穴对,银纳米粒子上的电子受到激发并转移到Ti02导带上,接着与溶液中的分子氧反应形成超氧自由基O2,然后质子化生成HOO·自由基,HOO·自由基与被捕获的电子结合生成H2O2,最后生成·OH自由基,这些活性基团都能降解和矿化罗丹明。
第四,石墨烯修饰二氧化钛的制备及其增强光分解水产氢活性。首先,在H2O-C2H5OH混合溶液中,采用微波水热法合成了石墨烯修饰暴露{001}面锐钛矿二氧化钛纳米片复合光催化材料。该复合材料表现出较好的光催化活性,在以甲醇为牺牲剂和无Pt为助催化剂条件下光分解水产氢实验中,其产氢速率是纯二氧化钛纳米片的41倍多。这主要是由于石墨烯是较好的电子接受体,并且石墨烯的氧化还原电势位于二氧化钛导带底端和氢电极电势之间,因此能够促进二氧化钛导带上光生电子转移到石墨烯上,从而还原氢离子产氢,增强光催化分解水产氢活性。随后,采用两步水热反应策略,合成了层状MoS2/graphene复合二氧化钛光催化材料,该复合材料表现出极好的光催化分解水产氢活性,远远超过纯二氧化钛,MoS2与石墨烯单独复合Ti02的光分解水产氢活性。这主要是由于MoS2和石墨烯作为共催化剂的协同作用,包括减少载流子复合、增强界面载流子转移速率、增加反应活性位和光催化反应中心,从而极大地增强了二氧化钛的光催化分解水产氢活性。最后,对暴露{001}面二氧化钛纳米片进行氮元素掺杂,使其具有可见光分解水产氢活性。以TiN为原料,采用溶剂热法一步制备了氮自掺杂暴露65%{001)晶面锐钛矿二氧化钛纳米片光催化材料。该材料表现出非常高的可见光光催化分解水产氢活性和光催化氧化性。这主要是由于氮掺杂二氧化钛,降低了二氧化钛的禁带宽带,使其具有可见光响应；同时该材料暴露了高活性{001}晶面并具有较大的比表面积,从而增加反应物在催化材料中的吸附和提供更多活性中心位,因而增强了可见光光催化活性。
第五,基于石墨烯半导体光催化材料的制备与性能研究。石墨烯具有均一的二维机构,优良的导电性,高的载流子迁移率和极高的比表面积,并且能够大规模廉价生产。因此,石墨烯已经作为各种功能化复合材料的重要组成部分。特别是石墨烯基半导体光催化材料在环境和能源方面的快速发展和广泛应用,引起了人们越来越多的关注。在本章中,以三聚氰胺聚合物和氧化石墨烯为前驱体,水合肼为还原剂,通过浸渍和化学还原相结合的方法,随后在550℃氮气氛围中热处理制备了graphene/C3N4复合光催化材料。该复合材料表现出非常高的光催化分解水产氢活性,其活性是纯g-C3N4光催化剂的3倍多。这主要是由于石墨烯作为电子传输通道,能够有效分离光生电子和空穴,降低它们的复合速率,增强其寿命,从而增强g-C3N4的可见光催化分解水产氢活性。随后,在此基础上进一步总结了石墨烯基半导体光催化剂的各种设计策略与制备方法,包括原位生长、溶液混合、水热和溶剂热等方法。进一步讨论了制备石墨烯基复合系统的光催化性能,主要涉及到环境和能源方面的应用,包括光催化降解污染物、光催化产氢、光催化杀菌；并且对石墨烯基半导体光催化剂今后的研究方向和挑战进行总结和展望。
第六,各种半导体光催化材料羟基自由基产生速率的定量表征。以香豆素为探针分子,通过荧光(PL)光谱技术检测了氙灯照射下各种半导体光催化材料羟基自由基的产生速率,通过定量比较各种半导体材料在同样条件下羟基自由基的形成速率,可以间接确定光催化材料的光催化活性高低。结果显示P25和锐钛矿二氧化钛产生羟基自由基的速率远高于金红石二氧化钛、氧化锌、三氧化钨、硫化镉、钨酸铋和铋氧氯等其它半导体,我们进一步提出了“羟基自由基指数”的新概念,用于表征各种半导体光催化材料羟基自由基的形成速率和国际标准光催化材料Degussa P-25羟基自由基的形成速率的相对比值,为以后比较不同光催化剂的催化活性和设计与制备新型光催化剂提供了一条新的思路。
Energy and environmental issues are the biggest challenges in the21century. Semiconductor photocatalytic materials exhibit great potentials in environmental protection and solar energy conversion. TiO2nano-material is the most widely used material because of its wide potential application in waste water treatment, air purification, bacillus resistance and water splitting to generate hydrogen. However, owing to its low quantum efficiency and relatively wide band gap, which can only absorb the UV light, and thus greatly restricts its practical applications and commercial benefit. In this dissertation, our main ideas are tuning the electronic structure, surface property, band gap structure and photocatalytic performance of TiO2-based photocatalytic material, and developing highly activity semiconductor photocatalyst with modifying, doping and assembling to absorb visible light and to enhance the photocatalytic activity. The main points could be summarized as follows:
Firstly, fabrication of TiO2photocatalysts with different morphology and comparison of their photocatalytic activity. Surface-fluorinated TiO2hollow microspheres and tabular-shaped anatase single mico-crystals with highly energetic (001) facets exposed were prepared by a one-step hydrothermal strategy using ammonium bifluoride (NH4HF2) as a morphology controlling agent. It was found that with increasing NH4HF2concentration, the average crystallite size and average pore size increase, whilst the specific surface area, pore volume and porosity steadily decrease. The TiO2hollow microsphere exhibits the highest photocatalytic activity for the photocatalytic decolorization of RhB in aqueous solution, and is higher than pure TiO2or P25due to the enhancement of crystallization, formation of hollow structures and surface fluorination. Subsequently, hierarchical flower-like TiO2superstructures (HFTS) self-assembled from anatase TiO2nanosheets with exposed {001} facets (up to87%) have been synthesized by a simple alcohothermal strategy in a HF-H2O-C2H5OH mixed solution using titanate nanotubes as precursor. The study shows that the activity of HFTS for photocatalytic oxidation decomposition of acetone in air and methyl orange (MO) in aqueous solution is greatly higher than that of commercial Degussa P25(P25) and tabular-shaped anatase TiO2obtained in pure water. A significant enhancement in the photocatalytic activity can be related to several factors, including hierarchical porous structure, exposed {001} facets, and the increased light-harvesting abilities.
Secondly, we investage the effects of surface fluorination and exposed {001} facets on the photocatalytic decomposition of acetone in air and photocatalytic selectivity towards decomposition of azo dyes in water. Firstly, surface-fluorinated anatase TiO2nanosheets with dominant {001} facets were fabricated by a simple hydrothermal route in a Ti(OC4H9)4-HF-H2O mixed solution. All fluorinated TiO2nanosheets exhibit much higher photocatalytic activity than Degussa P-25TiO2(P25) and pure TiO2nanoparticles prepared in pure water. The fluorinated TiO2nanosheet with an optimal relative percentage of exposed anatase {001} facets exhibits the highest photocatalytic activity, and its photoactivity exceeds that of P25by a factor of more than9times due to the synergistic effect of surface fluorination and exposed {001} facets on the photoactivity of TiO2. Subsequently, the flower-like TiO2microspheres films were directly synthesized on the Ti foil in a dilute aqueous HF solution by a simple one-pot hydrothermal treatment. The photocatalytic selectivity of TiO2films towards decomposition of azo dyes in water can be tuned by modifying the surface of TiO2microspheres as well as by varying the degree of etching of {001} facets. In addition, the percentage of exposed {001} facets can be also controlled to some extent by adjusting the reaction time of the selective chemical etching. This is because that the selective photocatalytic degradation of charged contaminants can be tuned by altering the surface charge of TiO2depending on pH.
Thirdly, microwave-hydrothermal preparation and visible-light photoactivity of plasmonic photocatalyst Ag-TiO2nanocomposite hollow spheres. Conventional TiO2photocatalyst possesses excellent activities and stabilities, but requires near-ultraviolet irradiation for effective photocatalysis thereby severely limiting its practical application. It is highly desirable to develop a photocatalyst that can use visible light in high efficiency under sunlight irradiation. Noble metal Ag nanoparticles can dramatically amplify the absorption of visible light and is therefore utilized to develop efficient visible-light-driven plasmonic photocatalysts. In this work, a visible-light-driven plasmonic photocatalyst Ag-TiO2nanocomposite hollow spheres was prepared using the template-free chemically-induced self-transformation method under microwave-hydrothermal condition, then reducing the Ag+ions on the surface of TiO2nanoparticles to Ag0species under xenon lamp irradiation. The surface plasmon absorption band of the silver clusters supported on the TiO2hollow spheres is observed. The prepared plasmonic photocatalyst exhibits a highly visible-light photocatalytic activity for the photocatalytic degradation of RhB aqueous solution. This is due to the fact that the photoexcited electrons at the silver nanoparticles are injected into the TiO2conduction band, and the injected electrons can be transferred to the ubiquitously present molecular oxygen to form first the superoxide radical anions, O2-, then on protonation yields the HOO radicals, and HOO· radicals and the trapped electrons combine to produce H2O2, finally forming HO·radicals. These active species will result in the degradation and mineralization of RhB. This study may provide new insight into design and preparation of advanced visible-light photocatalytic materials.
Fourthly, enhanced photocatalytic H2-production activity of graphene-modified titania. Firstly, graphene-modified TiO2nanosheets with exposed (001) facets were prepared by microwave-hydrothermal treatment of graphene oxide and the hydrothermally-synthesized TiO2nanosheets with exposed (001) facets in an ethanol-water solvent. These nanocomposite samples showed high photocatalytic H2-production activity in aqueous solutions containing methanol as sacrificial reagent even without Pt co-catalyst. The potential of graphene/graphene-are deemed to be less negative than the conduction band of TiO2and more negative than H+/H2potential, which favors the electron transfer from CB of TiO2to graphene and the reduction of H+, thus enhancing photocatalytic H2-production activity. Subsequently, the proposed two-step hydrothermal synthesis of titania-based composite photocatalysts with layered MoS2/graphene co-catalyst afforded an effective photocatalyst for H2production. The TiO2/MoS2/graphene composite photocatalysts showed high photocatalytic H2-production activity with the rate as high as165.3μmol h-1for the sample having0.5%of co-catalyst that consisted of MoS2(95%) and of graphene (5.0%). The corresponding apparent quantum efficiency reached9.7%at365nm even without noble metal co-catalyst. At last, a novel and facile solvothermal route for the preparation of visible-light responsive nitrogen self-doped TiO2nanosheets with exposed{001} facet is proposed by treating TiN in a HNO3-HF ethanol solution. Due to nitrogen doping, the presence of highly reactive {001} facets and large specific surface area, nitrogen self-doped TiO2nanosheets with exposed {001} facets exhibited much higher visible-light photocatalytic H2-production activity than nitrogen doped TiO2microcrystallites with exposed{001} facets (ca.60%).
Fifthly, we investigate graphene-based semiconductor photocatalysts. Graphene, a single layer of graphite, possesses a unique two-dimensional structure, high conductivity, superior electron mobility and extremely high specific surface area, and can be produced on a large scale at low cost. Thus, it has been regarded as an important component for making various functional composite materials. Especially, graphene-based semiconductor photocatalysts have attracted extensive attention because of their usefulness in environmental and energy applications. Firstly, graphene and graphitic carbon nitride (g-C3N4) composite photocatalysts were prepared by a combined impregnation-chemical reduction strategy involving polymerization of melamine in the presence of graphene oxide (precursors) and hydrazine hydrate (reducing agent) followed by thermal treatment at550℃under flowing nitrogen. Graphene sheets act as electronic conductive channels to efficiently separate the photogenerated charge carriers, and consequently, to enhance the visible-light photocatalytic H2-production activity of g-C3N4. Subsequently, we summarize the recent progress in the design and fabrication of graphene-based semiconductor photocatalysts via various strategies including in situ growth, solution mixing, hydrothermal and/or solvothermal methods. Furthermore, the photocatalytic properties of the resulting graphene-based composite systems are also discussed in relation to the environmental and energy applications such as photocatalytic degradation of pollutants, photocatalytic hydrogen generation and photocatalytic disinfection. This chapter ends with a summary and some perspectives on the challenges and new directions in this emerging area of research.
Sixthly, quantitative characterization of hydroxyl radicals produced by various photocatalysts. The·OH produced on various semiconductor photocatalysts in aqueous solution under Xenon lamp irradiation was quantitatively investigated by the photoluminescence technique using coumarin as a probe molecule. The formation rates of·OH on anatase TiO2and P25were much higher than that of·OH on the other semiconductors (such as rutile TiO2, ZnO, WO3, CdS, Bi2WO4and BiOCl, etc.). A new "OH-index" was introduced by comparing the relative-OH formation rate of the target photocatalyst to that of P25, which was proposed to compare oxidation activity of various photocatalysts. This study would provide new insights and understanding on the photocatalytic mechanism.
第一,不同形貌二氧化钛的制备和光催化活性比较。首先,我们选用硫酸钛为前驱体,以氟化氢铵为形貌控制剂,通过一步水热法合成了几种不同形貌锐钛矿二氧化钛微结构,包括实心微球、空心球和暴露{001}晶面块状锐钛矿微晶。研究发现,表面氟化二氧化钛空心微球具有最好的光催化活性,而暴露{001}晶面块状锐钛矿微晶具有最好的比光催化活性。这主要是由于一方面空心微球有利于增强对光的吸收和利用效率；另一方面,二氧化钛空心球具有大的比表面积和分级多孔结构,有利于增强对污染物的富集和反应物与产物在催化材料中的扩散,从而增强光催化活性。随后,以钛酸盐纳米管为前躯体,在HF-H2O-C2H5OH的混合溶液中,采用一种无模板和表面活性剂的醇热法合成了暴露{001}面二氧化钛纳米片自组装形成的分等级花状超结构。该花状二氧化钛超结构在气相光催化降解丙酮和液相光催化降解甲基橙中表现出非常高的光催化活性,其活性明显高于国际标准光催化材料Degussa P-25。这主要是由该材料具有分等级多孔结构,暴露高活性{001}晶面和增强的光吸收能力引起的。
第二,暴露高活性{001}面二氧化钛纳米片的制备及其光催化活性的研究。首先,以钛酸四丁酯为前驱体,在氢氟酸和水的混合溶液中通过一步水热法制备了表面氟化暴露不同比例{001}晶面的锐钛矿二氧化钛纳米片粉末材料。该材料在光催化分解空气中丙酮的实验中表现出增强的光催化活性,特别是表面氟化和暴露适当比例(～70%){001}晶面的二氧化钛纳米片显示出最高的光催化活性,其表观速率常数是P25样品的9倍多。这主要是由于表面氟化和暴露最佳比例的{001}晶面具有协同增强二氧化钛光催化活性的作用。随后,基于暴露{001}晶面表现出较高光催化活性,我们以钛片为基底,通过一步水热法合成了暴露{001}面花状二氧化钛微球薄膜。该花状二氧化钛微球薄膜在光催化降解偶氮染料溶液时,表现出光催化选择性,并且通过改变二氧化钛微球表面性质和{001}晶面的腐蚀程度能够进一步调控二氧化钛微球薄膜的光催化选择性。这主要是由于通过改变二氧化钛表面电荷性质,使二氧化钛优先吸附带相反电荷的污染物分子,从而选择性降解被吸附的污染物分子。
第三,等离子光催化剂Ag-TiO2复合空心球的微波水热制备及其可见光催化活性。通过微波水热、化学诱导自转变和光还原的方法,制备了可见光响应的等离子体光催化剂Ag-TiO2复合空心球。这种金属-半导体纳米复合等离子体光催化剂在降解水中的罗丹明时显示出较高的可见光光催化活性和稳定性。这主要是由于吸附在二氧化钛空心球上的银纳米粒子具有表面等离子体效应,它能够吸收可见光,使复合催化剂具有可见光响应。在可见光照射下,银纳米颗粒的表面等离子体响应诱导产生光生电子-空穴对,银纳米粒子上的电子受到激发并转移到Ti02导带上,接着与溶液中的分子氧反应形成超氧自由基O2,然后质子化生成HOO·自由基,HOO·自由基与被捕获的电子结合生成H2O2,最后生成·OH自由基,这些活性基团都能降解和矿化罗丹明。
第四,石墨烯修饰二氧化钛的制备及其增强光分解水产氢活性。首先,在H2O-C2H5OH混合溶液中,采用微波水热法合成了石墨烯修饰暴露{001}面锐钛矿二氧化钛纳米片复合光催化材料。该复合材料表现出较好的光催化活性,在以甲醇为牺牲剂和无Pt为助催化剂条件下光分解水产氢实验中,其产氢速率是纯二氧化钛纳米片的41倍多。这主要是由于石墨烯是较好的电子接受体,并且石墨烯的氧化还原电势位于二氧化钛导带底端和氢电极电势之间,因此能够促进二氧化钛导带上光生电子转移到石墨烯上,从而还原氢离子产氢,增强光催化分解水产氢活性。随后,采用两步水热反应策略,合成了层状MoS2/graphene复合二氧化钛光催化材料,该复合材料表现出极好的光催化分解水产氢活性,远远超过纯二氧化钛,MoS2与石墨烯单独复合Ti02的光分解水产氢活性。这主要是由于MoS2和石墨烯作为共催化剂的协同作用,包括减少载流子复合、增强界面载流子转移速率、增加反应活性位和光催化反应中心,从而极大地增强了二氧化钛的光催化分解水产氢活性。最后,对暴露{001}面二氧化钛纳米片进行氮元素掺杂,使其具有可见光分解水产氢活性。以TiN为原料,采用溶剂热法一步制备了氮自掺杂暴露65%{001)晶面锐钛矿二氧化钛纳米片光催化材料。该材料表现出非常高的可见光光催化分解水产氢活性和光催化氧化性。这主要是由于氮掺杂二氧化钛,降低了二氧化钛的禁带宽带,使其具有可见光响应；同时该材料暴露了高活性{001}晶面并具有较大的比表面积,从而增加反应物在催化材料中的吸附和提供更多活性中心位,因而增强了可见光光催化活性。
第五,基于石墨烯半导体光催化材料的制备与性能研究。石墨烯具有均一的二维机构,优良的导电性,高的载流子迁移率和极高的比表面积,并且能够大规模廉价生产。因此,石墨烯已经作为各种功能化复合材料的重要组成部分。特别是石墨烯基半导体光催化材料在环境和能源方面的快速发展和广泛应用,引起了人们越来越多的关注。在本章中,以三聚氰胺聚合物和氧化石墨烯为前驱体,水合肼为还原剂,通过浸渍和化学还原相结合的方法,随后在550℃氮气氛围中热处理制备了graphene/C3N4复合光催化材料。该复合材料表现出非常高的光催化分解水产氢活性,其活性是纯g-C3N4光催化剂的3倍多。这主要是由于石墨烯作为电子传输通道,能够有效分离光生电子和空穴,降低它们的复合速率,增强其寿命,从而增强g-C3N4的可见光催化分解水产氢活性。随后,在此基础上进一步总结了石墨烯基半导体光催化剂的各种设计策略与制备方法,包括原位生长、溶液混合、水热和溶剂热等方法。进一步讨论了制备石墨烯基复合系统的光催化性能,主要涉及到环境和能源方面的应用,包括光催化降解污染物、光催化产氢、光催化杀菌；并且对石墨烯基半导体光催化剂今后的研究方向和挑战进行总结和展望。
第六,各种半导体光催化材料羟基自由基产生速率的定量表征。以香豆素为探针分子,通过荧光(PL)光谱技术检测了氙灯照射下各种半导体光催化材料羟基自由基的产生速率,通过定量比较各种半导体材料在同样条件下羟基自由基的形成速率,可以间接确定光催化材料的光催化活性高低。结果显示P25和锐钛矿二氧化钛产生羟基自由基的速率远高于金红石二氧化钛、氧化锌、三氧化钨、硫化镉、钨酸铋和铋氧氯等其它半导体,我们进一步提出了“羟基自由基指数”的新概念,用于表征各种半导体光催化材料羟基自由基的形成速率和国际标准光催化材料Degussa P-25羟基自由基的形成速率的相对比值,为以后比较不同光催化剂的催化活性和设计与制备新型光催化剂提供了一条新的思路。
Energy and environmental issues are the biggest challenges in the21century. Semiconductor photocatalytic materials exhibit great potentials in environmental protection and solar energy conversion. TiO2nano-material is the most widely used material because of its wide potential application in waste water treatment, air purification, bacillus resistance and water splitting to generate hydrogen. However, owing to its low quantum efficiency and relatively wide band gap, which can only absorb the UV light, and thus greatly restricts its practical applications and commercial benefit. In this dissertation, our main ideas are tuning the electronic structure, surface property, band gap structure and photocatalytic performance of TiO2-based photocatalytic material, and developing highly activity semiconductor photocatalyst with modifying, doping and assembling to absorb visible light and to enhance the photocatalytic activity. The main points could be summarized as follows:
Firstly, fabrication of TiO2photocatalysts with different morphology and comparison of their photocatalytic activity. Surface-fluorinated TiO2hollow microspheres and tabular-shaped anatase single mico-crystals with highly energetic (001) facets exposed were prepared by a one-step hydrothermal strategy using ammonium bifluoride (NH4HF2) as a morphology controlling agent. It was found that with increasing NH4HF2concentration, the average crystallite size and average pore size increase, whilst the specific surface area, pore volume and porosity steadily decrease. The TiO2hollow microsphere exhibits the highest photocatalytic activity for the photocatalytic decolorization of RhB in aqueous solution, and is higher than pure TiO2or P25due to the enhancement of crystallization, formation of hollow structures and surface fluorination. Subsequently, hierarchical flower-like TiO2superstructures (HFTS) self-assembled from anatase TiO2nanosheets with exposed {001} facets (up to87%) have been synthesized by a simple alcohothermal strategy in a HF-H2O-C2H5OH mixed solution using titanate nanotubes as precursor. The study shows that the activity of HFTS for photocatalytic oxidation decomposition of acetone in air and methyl orange (MO) in aqueous solution is greatly higher than that of commercial Degussa P25(P25) and tabular-shaped anatase TiO2obtained in pure water. A significant enhancement in the photocatalytic activity can be related to several factors, including hierarchical porous structure, exposed {001} facets, and the increased light-harvesting abilities.
Secondly, we investage the effects of surface fluorination and exposed {001} facets on the photocatalytic decomposition of acetone in air and photocatalytic selectivity towards decomposition of azo dyes in water. Firstly, surface-fluorinated anatase TiO2nanosheets with dominant {001} facets were fabricated by a simple hydrothermal route in a Ti(OC4H9)4-HF-H2O mixed solution. All fluorinated TiO2nanosheets exhibit much higher photocatalytic activity than Degussa P-25TiO2(P25) and pure TiO2nanoparticles prepared in pure water. The fluorinated TiO2nanosheet with an optimal relative percentage of exposed anatase {001} facets exhibits the highest photocatalytic activity, and its photoactivity exceeds that of P25by a factor of more than9times due to the synergistic effect of surface fluorination and exposed {001} facets on the photoactivity of TiO2. Subsequently, the flower-like TiO2microspheres films were directly synthesized on the Ti foil in a dilute aqueous HF solution by a simple one-pot hydrothermal treatment. The photocatalytic selectivity of TiO2films towards decomposition of azo dyes in water can be tuned by modifying the surface of TiO2microspheres as well as by varying the degree of etching of {001} facets. In addition, the percentage of exposed {001} facets can be also controlled to some extent by adjusting the reaction time of the selective chemical etching. This is because that the selective photocatalytic degradation of charged contaminants can be tuned by altering the surface charge of TiO2depending on pH.
Thirdly, microwave-hydrothermal preparation and visible-light photoactivity of plasmonic photocatalyst Ag-TiO2nanocomposite hollow spheres. Conventional TiO2photocatalyst possesses excellent activities and stabilities, but requires near-ultraviolet irradiation for effective photocatalysis thereby severely limiting its practical application. It is highly desirable to develop a photocatalyst that can use visible light in high efficiency under sunlight irradiation. Noble metal Ag nanoparticles can dramatically amplify the absorption of visible light and is therefore utilized to develop efficient visible-light-driven plasmonic photocatalysts. In this work, a visible-light-driven plasmonic photocatalyst Ag-TiO2nanocomposite hollow spheres was prepared using the template-free chemically-induced self-transformation method under microwave-hydrothermal condition, then reducing the Ag+ions on the surface of TiO2nanoparticles to Ag0species under xenon lamp irradiation. The surface plasmon absorption band of the silver clusters supported on the TiO2hollow spheres is observed. The prepared plasmonic photocatalyst exhibits a highly visible-light photocatalytic activity for the photocatalytic degradation of RhB aqueous solution. This is due to the fact that the photoexcited electrons at the silver nanoparticles are injected into the TiO2conduction band, and the injected electrons can be transferred to the ubiquitously present molecular oxygen to form first the superoxide radical anions, O2-, then on protonation yields the HOO radicals, and HOO· radicals and the trapped electrons combine to produce H2O2, finally forming HO·radicals. These active species will result in the degradation and mineralization of RhB. This study may provide new insight into design and preparation of advanced visible-light photocatalytic materials.
Fourthly, enhanced photocatalytic H2-production activity of graphene-modified titania. Firstly, graphene-modified TiO2nanosheets with exposed (001) facets were prepared by microwave-hydrothermal treatment of graphene oxide and the hydrothermally-synthesized TiO2nanosheets with exposed (001) facets in an ethanol-water solvent. These nanocomposite samples showed high photocatalytic H2-production activity in aqueous solutions containing methanol as sacrificial reagent even without Pt co-catalyst. The potential of graphene/graphene-are deemed to be less negative than the conduction band of TiO2and more negative than H+/H2potential, which favors the electron transfer from CB of TiO2to graphene and the reduction of H+, thus enhancing photocatalytic H2-production activity. Subsequently, the proposed two-step hydrothermal synthesis of titania-based composite photocatalysts with layered MoS2/graphene co-catalyst afforded an effective photocatalyst for H2production. The TiO2/MoS2/graphene composite photocatalysts showed high photocatalytic H2-production activity with the rate as high as165.3μmol h-1for the sample having0.5%of co-catalyst that consisted of MoS2(95%) and of graphene (5.0%). The corresponding apparent quantum efficiency reached9.7%at365nm even without noble metal co-catalyst. At last, a novel and facile solvothermal route for the preparation of visible-light responsive nitrogen self-doped TiO2nanosheets with exposed{001} facet is proposed by treating TiN in a HNO3-HF ethanol solution. Due to nitrogen doping, the presence of highly reactive {001} facets and large specific surface area, nitrogen self-doped TiO2nanosheets with exposed {001} facets exhibited much higher visible-light photocatalytic H2-production activity than nitrogen doped TiO2microcrystallites with exposed{001} facets (ca.60%).
Fifthly, we investigate graphene-based semiconductor photocatalysts. Graphene, a single layer of graphite, possesses a unique two-dimensional structure, high conductivity, superior electron mobility and extremely high specific surface area, and can be produced on a large scale at low cost. Thus, it has been regarded as an important component for making various functional composite materials. Especially, graphene-based semiconductor photocatalysts have attracted extensive attention because of their usefulness in environmental and energy applications. Firstly, graphene and graphitic carbon nitride (g-C3N4) composite photocatalysts were prepared by a combined impregnation-chemical reduction strategy involving polymerization of melamine in the presence of graphene oxide (precursors) and hydrazine hydrate (reducing agent) followed by thermal treatment at550℃under flowing nitrogen. Graphene sheets act as electronic conductive channels to efficiently separate the photogenerated charge carriers, and consequently, to enhance the visible-light photocatalytic H2-production activity of g-C3N4. Subsequently, we summarize the recent progress in the design and fabrication of graphene-based semiconductor photocatalysts via various strategies including in situ growth, solution mixing, hydrothermal and/or solvothermal methods. Furthermore, the photocatalytic properties of the resulting graphene-based composite systems are also discussed in relation to the environmental and energy applications such as photocatalytic degradation of pollutants, photocatalytic hydrogen generation and photocatalytic disinfection. This chapter ends with a summary and some perspectives on the challenges and new directions in this emerging area of research.
Sixthly, quantitative characterization of hydroxyl radicals produced by various photocatalysts. The·OH produced on various semiconductor photocatalysts in aqueous solution under Xenon lamp irradiation was quantitatively investigated by the photoluminescence technique using coumarin as a probe molecule. The formation rates of·OH on anatase TiO2and P25were much higher than that of·OH on the other semiconductors (such as rutile TiO2, ZnO, WO3, CdS, Bi2WO4and BiOCl, etc.). A new "OH-index" was introduced by comparing the relative-OH formation rate of the target photocatalyst to that of P25, which was proposed to compare oxidation activity of various photocatalysts. This study would provide new insights and understanding on the photocatalytic mechanism.
引文
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