Ti~(3+)自掺杂的纳米TiO_2的制备及其可见光催化性能

以TiH2为Ti源,H2O2为氧化剂,首先通过表面氧化得到不同状态的前驱体凝胶,然后采用后续水热处理制备Ti3+自掺杂的纳米Ti O2.考察了前驱体凝胶状态及水热处理时间对材料结构和性能的影响.利用X射线衍射、透射电子显微镜、X射线光电子能谱、电子顺磁共振波谱和紫外-可见漫反射光谱手段对样品进行表征.以次甲基蓝溶液为模拟废水评价样品的可见光催化降解性能.结果表明,与纯Ti O2相比,Ti3+的自掺杂使材料在可见光区有明显的吸收,并具有良好的可见光催化降解性能和循环使用性能.当采用黄色凝胶为前驱体时,在160°C下水热处理24 h所得样品在可见光下光催化降解次甲基蓝的反应速率常数(0.0439 min-1)是纯Ti O2的18.3倍.     

N掺杂TiO_2纳米粉体的制备及其可见光催化性能

首次以钛酸纳米管(NTA)为Ti的前驱体,以尿素为N源,采用水热法制备N掺杂TiO2纳米微粒,并用X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)、紫外-可见漫反射光谱仪(UV-Vis DRS)、透射电镜(TEM)、傅立叶变换红外光谱(FT-IR)等技术对不同条件下制备的产物进行了表征.探讨了尿素的掺杂量、水热温度对N掺杂TiO2形貌和结构的影响,并以亚甲基蓝为模型反应物考察了其在可见光下的催化性能,结果表明样品UN-130-1/2催化活性最高.     

可见光响应的硫掺杂TiO2的制备、表征及其光催化活性

采用溶胶-凝胶法制备了硫掺杂TiO2光催化剂粉末.光催化降解罗丹明B实验结果表明,钛酸四丁酯与硫脲的摩尔比Ti/S=2.7∶ 1,经600℃热处理后光催化活性最佳.通过紫外可见漫反射吸收光谱(DRS)、X-射线衍射(XRD)、X-射线光电子能谱(XPS)、傅立叶变换红外光谱(FT-IR)以及表面光电压谱(SPS)等研究结果表明,适量的硫掺杂导致TiO2有效地抑制晶相转变.在热处理过程中由S2-被氧化为S4+并进入TiO2晶格中取代部分Ti4+,发生晶格畸变,带隙变窄,使催化剂吸收光谱红移至550 nm,诱发可见光活性.     

氮铋共掺杂TiO2的合成及其可见光催化性能研究

以纳米管钛酸为钛的前驱体,Bi(NO₃)₃·5H₂O为N源和Bi源,采用水热法制备了N、Bi共掺杂的TiO₂;并以甲基橙为目标降解物考察了所制备样品的可见光催化性能(λ≥420 nm).利用XRD、XPS、UV-Vis DRS、TEM等技术对不同条件下制备的产物进行了表征.结果表明,所得样品主要为锐钛矿型,粒径20 nm左右,掺杂的Bi主要以Bi₂O₃和BiONO₃两种形式存在.N元素除了以NO₃^-的形式存在于BiONO₃中,还有少量N以间隙氮掺杂于TiO₂中形成Ti-O-N键.N、Bi共掺杂的TiO₂在可见光下表现出了优越的光催化性能,其中水热温度为130 ℃,Bi/Ti摩尔比为1%时,催化活性最高.催化活性的提高源于N和Bi的掺杂增加了样品对可见光的利用效率,降低了光生电子空穴的复合速率.     

S掺杂S-TiO_2/SiO_2可见光响应光催化剂的制备及性能

以四氯化钛为钛源,硫脲为硫源,采用液相水解-沉淀法制备了S掺杂的TiO2/SiO2(S-TiO2/SiO2)催化剂,并以苯酚为模型物,考察了催化剂在可见光区、紫外光区和太阳光下的光催化活性,以及催化剂的使用寿命和分离性能.采用X射线光电子能谱、傅里叶变换红外光谱、紫外-可见漫反射光谱、X射线衍射、透射电镜及N2吸附-脱附等技术对催化剂进行了表征.结果表明,S以+6价形式进入TiO2体相并置换晶格中的Ti4+,适量S掺杂的S-TiO2/SiO2在紫外光区、可见光区和太阳光下均表现出较高的光催化活性.SiO2与TiO2界面间有Ti-O-Si键形成,结合牢固.S掺杂在TiO2表面生成Ti-O-S键,形成新的能级结构,使光催化剂在450～550nm产生吸收,诱发TiO2可见光催化活性;同时提高了TiO2表面羟基数量.SiO2的加入可减小TiO2颗粒的平均尺寸,增大催化剂的比表面积,改善催化剂的分离性能,提高催化剂的使用寿命.     

钆及双稀土元素掺杂TiO2可见光催化降解罗丹明B的研究

以钛酸丁酯为前驱体，采用溶胶一凝胶法制备了钆及双稀土元素共掺杂纳米TiO2光催化剂，研究了自制催化剂在可见光下对有机染料罗丹明B催化降解反应的活性。稀土掺杂后的TiO2在可见光下催化活性比纯的TiO2有显著的提高。当Gd^3＋与TiO2的摩尔比为1．5％，催化剂经过500℃焙烧，对罗丹明B的降解率达到99．5％；Gd^3＋：La^3＋：TiO2的摩尔比为O．5：0．5：100，焙烧温度为600℃，降解率高达99．9％，比双元素掺杂的结果更好。     

铋掺杂二氧化钛纳米颗粒的制备及其可见光催化性能

采用水热法,以纳米管钛酸为前驱物制备了Bi掺杂的TiO₂,并利用X射线衍射、透射电子显微镜、X射线光电子能谱、紫外-可见漫反射光谱等手段对样品进行了表征. 以甲基橙的光催化降解为模型反应评价了样品的可见光催化性能. 结果表明,Bi离子并没有进入TiO₂的晶格中,而是以BiOCl的形式存在. 所制得的BiOCl/TiO₂复合物对甲基橙降解表现出较优越的可见光催化活性;当Bi/Ti摩尔比为1%,水热温度为130℃时,所制催化剂的光催化性能最佳,并对光催化活性提高的机理进行了讨论. 同时,该催化剂对4-氯苯酚降解也表现出较高的光催化性能.     

锌掺杂TiO_2的制备及其可见光催化性能

以钛酸纳米管[H2Ti2O2(OH)2,NTA]作为钛的前驱体、ZnCl2为锌源,采用水热法制备了锌掺杂的TiO2光催化剂;采用X射线衍射仪和透射电镜分析了催化剂产物的晶体结构和微观形貌;同时以亚甲基蓝为模型反应物,研究了锌掺杂量和水热温度对催化剂可见光光催化性能的影响.结果表明,水热温度为130℃,锌掺杂量为0.5%时,所得样品的光催化性能最佳.     

铬和硫共掺杂二氧化钛催化剂的制备及其可见光催化性能

以钛酸四丁酯为前驱体,硝酸铬和硫脲为掺杂离子给体,通过溶胶-凝胶法成功制备了纯TiO2、不同浓度的铬掺杂和铬/硫共掺杂TiO2光催化剂.以靛红为目标污染物,进行了可见光催化降解活性测试实验.结果表明,共掺杂催化剂的活性高于未掺杂和单掺杂催化剂.当共掺杂催化剂含0.60%(原子比)的铬,1.2%(原子比)的硫,焙烧温度为500℃时具有最高的光催化降解活性.X射线衍射、N2吸附、X射线光电子能谱和紫外-可见漫反射吸收光谱表征结果显示,共掺杂催化剂为锐钛矿型,具有较高的比表面积,对可见光有较强的吸收能力.共掺杂TiO2具备较高可见光催化活性的原因可能是铬掺杂降低了TiO2的禁带宽度,拓展了可见光吸收区域,而硫掺杂能够维持体系的电荷平衡,增强催化剂对可见光的吸收.     

氮掺杂TiO2/SiO2核壳型复合微球的制备及其可见光催化性能

 以单分散性良好的SiO2微球为模板,以钛酸四丁酯为钛源,利用化学吸附和原位水解方法制备了TiO2/SiO2核壳结构复合微球,并在氨气气氛下进行了氮掺杂. 以罗丹明B水溶液的光催化降解为模型反应,评价了所制试样在可见光照射下的光催化活性,并借助透射电镜、高分辨透射电镜、 X射线衍射、紫外-可见漫反射光谱、红外光谱和X射线光电子能谱等测试手段对其结构、形貌和光谱性质进行了表征. 结果表明,氮掺杂TiO2/SiO2为核壳结构, TiO2包覆层厚约10 nm. 由于SiO2核与TiO2壳间形成了 Ti-O-Si 键, TiO2的热稳定性增强. 掺杂的氮形成了 Ti-O-N 键. 600 ℃下氮化1 h得到的试样的可见光活性最佳. 由于结合了SiO2核优良的吸附性能及氮掺杂TiO2壳的可见光响应性能,该复合微球在整体上表现出比P25更优的光催化活性.     

Facile one-pot hydrothermal synthesis of B/N-codoped TiO2 hollow spheres with enhanced visible-light photocatalytic activity and photoelectrochemical property

B/N-codoped TiO₂ hollow spheres (B/N-THs) were synthesized by facile one-pot hydrothermal method. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption isotherms, UV–vis diffuse reflectance spectrum (DRS) and X-ray photoelectron spectroscopy (XPS). The B/N-THs have large surface areas (up to 172.1 m² g⁻¹). The photocatalytic activities of as-prepared THs were evaluated by degradation of Reactive Brilliant Red dye X-3B solution under visible light irradiation. The results showed that B/N-THs exhibited the highest photocatalytic activity due to their high surface area and synergetic effect of B/N-codoped. A photocurrent–time spectrum was examined by anodic photocurrent response to characterize the electron-transferring efficiency in the process of photocatalysis reaction.     

Low-temperature hydrothermal synthesis of S-doped TiO2 with visible light photocatalytic activity

A one-step low-temperature hydrothermal route was developed for the synthesis of S-doped TiO₂ photocatalysts from TiS₂ and HCl. Crystalline TiO₂ was formed and sulfur could be efficiently doped into the anatase lattice under hydrothermal conditions. When the initial TiS₂ concentration is increased, the content of S-dopant and optical absorption in the visible region also increase. The photocatalytic activity of the S-doped TiO₂ was evaluated through the degradation of 4-chlorophenol under visible light irradiation. Our results show that the S-doped TiO₂ prepared by this hydrothermal approach possesses much higher photocatalytic activity than that obtained by the traditional high-temperature thermal annealing method.     

Synthesis of sponge-like TiO2 with surface-phase junctions for enhanced visible-light photocatalytic performance

Maximizing adsorption and catalytic active sites and promoting the photo-excited charge separation are two key factors to achieve excellent photocatalytic performance. In this study, we report a sol-gel synthesis approach to obtain non-metal doped TiO₂ with sponge-like structure and surface-phase junctions all at once. While doping of carbon and nitrogen shifted the activation wavelength to the visible-light region, the innovative use of perchloric acid as a pore-making agent led to the formation of three-dimensional lamellar and porous structure with surface-phase junctions. High surface area with catalytic active sites rendered by the sponge-like structure and surface-phase junctions contributed to the much improved photocatalytic degradation efficiency toward rhodamine B, tetracycline and Disperse Red 60 with excellent reusability and stability. The improved generation and separation efficiency of the photo-induced charge carriers of the as-prepared TiO₂ were supported by electrochemical impedance measurements and transient photocurrent responses. This method could also be applied to other photocatalysts to achieve structural alteration and element doping simultaneously.     

Defect induced nickel,nitrogen-codoped mesoporous TiO2 microspheres with enhanced visible light photocatalytic activity

Nickel, nitrogen-codoped mesoporous TiO₂ microspheres (Ni–N–TiO₂) with high surface area, and an effective direct band gap energy of ∼2.58 eV. Nickel sulfate used as the Ni source and ammonia gas as the N source here. The efficiency of the as-prepared samples was investigated by monitoring the degradation of Rhodamine B under visible light irradiation. The experimental results indicate that Ni-doped mesoporous TiO₂ microspheres show higher photocatalytic activity than mesoporous TiO₂ microspheres under visible light irradiation. It mainly due to that the electron trap level (Ni²⁺/Ni⁺) promoting the separation of charge carriers and the oxygen vacancies inducing the visible light absorption. In addition, Ni–N–TiO₂ shows enhanced activity compared with Ni–TiO₂. Codopants and dopants are found to be uniformly distributed in TiO₂ matrix. Among the all samples the 0.5% molar quantity of Ni dopant and 500 °C 2 h nitriding condition gives the highest photocatalytic activity. The treatment of ammonia gas on Ni–TiO₂ sample induced oxygen vancancies, substitutional and interstitial N. A suitable treatment by ammonia gas also promote separation of charge carriers and the absorption of visible light. The active species generated in the photocatalytic system were also investigated. The strategy presented here gives a promising route towards the development of a metal and non-metal codoped semiconductor materials for applied photocatalysis and related applications.     

In-situ polymerization for PPy/g-C3N4 composites with enhanced visible light photocatalytic performance

Polypyrrole-modified graphitic carbon nitride composites (PPy/g-C₃N₄) are fabricated using an in-situ polymerization method to improve the visible light photocatalytic activity of g-C₃N₄. The PPy/g-C₃N₄ is applied to the photocatalytic degradation of methylene blue (MB) under visible light irradiation. Various characterization techniques are employed to investigate the relationship between the structural properties and photoactivities of the as-prepared composites. Results show that the specific surface area of the PPy/g-C₃N₄ composites increases upon assembly of the amorphous PPy nanoparticles on the g-C₃N₄ surface. Owing to the strong conductivity, the PPy can be used as a transition channel for electrons to move onto the g-C₃N₄ surface, thus inhibiting the recombination of photogenerated carriers of g-C₃N₄ and improving the photocatalytic performance. The elevated light adsorption of PPy/g-C₃N₄ composites is attributed to the strong absorption coefficient of PPy. The composite containing 0.75 wt% PPy exhibits a photocatalytic efficiency that is 3 times higher than that of g-C₃N₄ in 2 h. Moreover, the degradation kinetics follow a pseudo-first-order model. A detailed photocatalytic mechanism is proposed with ·OH and ·O₂^? radicals as the main reactive species. The present work provides new insights into the mechanistic understanding of PPy in PPy/g-C₃N₄ composites for environmental applications.     

Synthesis of 3D hierarchical porous TiO2/InVO4 nanocomposites with enhanced visible-light photocatalytic properties

Three-dimensional (3D) hierarchical porous TiO₂/InVO₄ nanocomposites were fabricated by loading TiO₂ nanoparticles on the surface of porous InVO₄ microspheres. X-ray diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis spectroscopy and photoluminescence spectroscopy (PL) were adopted to analyze the structure–property relationship of samples. The results show that the surface of as-prepared TiO₂/InVO₄ nanocomposites are composed of uniformly interconnected bi-phase nanocrystals, forming a close interface between these two components, which is favorable for the highly efficient interparticle electron transfer to achieve enhanced photocatalytic properties. However, the adsorption ability is decreased due to the loading of TiO₂ nanoparticles on the surface of InVO₄. Therefore, under the joint action of these factors, the TiO₂/InVO₄ nanocomposites achieve the best photocatalytic activity when the mole ratio of In:Ti reaches 4:1, and the visible-light photocatalytic activity is about as 3.3 times high as that of pure InVO₄ without modification.     

碳和钇共掺杂对混相TiO2光催化性能的影响

TiO2因其毒性低、稳定性高、制备成本低廉而获得广泛应用,特别是作为光催化剂在降解环境污染物方面受到了广泛关注;然而,纯TiO2较大的光生载流子复合率和较宽的带隙限制了其应用.元素掺杂作为一种拓宽光催化剂光吸收能力的方法广泛应用于各种光催化剂的修饰改性,而两种具有光催化性能的TiO2相共存则能有效抑制光生载流子的复合,因此采取合适的方法有效利用这两种TiO2改性的方法制备得到更具实际应用潜质的光催化剂具有一定的可行性.本文通过简单的溶胶-凝胶过程向锐钛矿相与金红石相组成的混相TiO2中共掺杂碳和钇得到了一种活性较高的可见光响应光催化剂.采用粉末X射线衍射、拉曼光谱、X射线光电子能谱和透射电镜等表征手段研究了碳和钇掺杂对TiO2结构的影响,发现碳掺杂有利于金红石相的形成且材料具有更大的晶粒尺寸,钇掺杂则有利于锐钛矿相的形成且能细化材料的晶粒尺寸,提高材料的比表面积,导致材料更好的光催化活性.材料在30 W荧光灯光照条件下的光催化降解亚甲基蓝(MB)性能的研究显示,C-Y-TiO2样品具有比单掺杂和未掺杂样品更高的光催化活性,其顺序为C-Y-TiO2>Y-TiO2>C-TiO2>TiO2≈P25.此外,降解反应动力学研究表明C-Y-TiO2样品光降解MB的速率是未掺杂样品在相同条件下降解速率的3.5倍.不同钇掺杂含量样品的结构和光催化降解MB的研究结果表明,钇掺杂显著促进了锐钛矿相TiO2的形成.这说明钇可能仅掺杂进入锐钛矿相,因此合适的钇掺杂量才能有效形成最优化的光催化性能的混相TiO2.不同热处理温度下获得的样品的光降解MB特性也表明,一定的热处理温度有利于合适的锐钛矿相和金红石相的组成,从而有利于相间的协同效应.紫外-可见光谱和荧光光谱表征分析表明,碳和钇的掺杂都拓展了其吸收光谱到可见光区域,且抑制了光生电子和空穴对的复合,进而提高了材料的光催化活性.碳和钇共掺杂的混相TiO2具有较高可见光光催化活性的主要原因有两个方面:一是元素掺杂减小了TiO2的带隙使得材料具有可见光响应;二是金属和非金属元素在锐钛矿相与金红石相TiO2中不同的掺杂特性形成的协同效应,抑制了光生电子和空穴的复合.     

Highly enhanced visible-light photocatalytic hydrogen evolution on g-C3N4 decorated with vopc through π-π interaction

Photocatalytic H₂ evolution reactions on pristine graphitic carbon nitrides (g-C₃N₄), as a promising approach for converting solar energy to fuel, are attractive for tackling global energy concerns but still suffer from low efficiencies. In this article, we report a tractable approach to modifying g-C₃N₄ with vanadyl phthalocyanine (VOPc/CN) for efficient visible-light-driven hydrogen production. A non-covalent VOPc/CN hybrid photocatalyst formed via π-π stacking interactions between the two components, as confirmed by analysis of UV-vis absorption spectra. The VOPc/CN hybrid photocatalyst shows excellent visible-light-driven photocatalytic performance and good stability. Under optimal conditions, the corresponding H₂ evolution rate is nearly 6 times higher than that of pure g-C₃N₄. The role of VOPc in promoting hydrogen evolution activity was to extend the visible light absorption range and prevent the recombination of photoexcited electron-hole pairs effectively. It is expected that this facile modification method could be a new inspiration for the rational design and exploration of g-C₃N₄-based hybrid systems with strong light absorption and high-efficiency carrier separation.     

磷掺杂TiO2薄膜的制备与表征及其可见光照射下光催化降解邻苯二甲酸丁苄酯性能（英文）

P‐doped TiO2 (PTIO) thin‐films with different P contents were prepared using a sol‐gel method. The thin‐film samples were characterized using various techniques. The photocatalytic activity was evaluated by decomposing butyl benzyl phthalate under visible‐light irradiation. The results showed that the transformation of anatase to the rutile phase was inhibited and grain growth of TiO2 was prevented by P doping. The results confirm that the doped P atoms existed in two chemical forms, and those incorporated in the TiO2 lattice may play a positive role in photocatalysis. The high photocatalytic activities of the PTIO thin‐films may be the result of extrinsic absorption through the creation of oxygen vacancies, rather than excitation of the intrinsic absorption band of bulk TiO2 . The PTIO can be recycled with little depression of the photocatalytic activity. After six cycles, the photocatalytic activity of the PTIO film was still higher than 98%.