TiO_2光催化材料掺杂改性的研究进展

TiO2是当前最有应用潜力的光催化材料,但其量子效率低、降解效果不理想、难以充分利用太阳能。选用合适的掺杂组分、制备方法和载体,制备出具有宽光谱响应范围、光量子效率高、易于回收利用的TiO2/载体光催化材料,对实现TiO2的工业化应用具有重大意义。根据半导体能带理论和异质结构的工作原理,研究各种表面改性技术和研制新的光催化剂,将是今后研究的主要方向。     

TiO2薄膜光催化剂的性能研究

采用溶胶-凝胶法在玻璃管上制备了透明的TiO₂薄膜，并利用XRD、Raman、UV-Vis和XPS技术对薄膜进行了表征。结果表明,在773 K焙烧的TiO₂样品在290～330 nm处的吸收明显强于573 K焙烧的样品。在573 K焙烧的情况下，薄膜基本为非晶态，但却表现出良好的光催化活性，并随着负载层数的增加，薄膜的光催化活性逐渐增加。在573 K以上，随焙烧温度的升高，TiO₂薄膜的光催化活性逐渐降低。     

N、Mn共掺杂TiO2的制备、表征及光催化性能研究

应用溶胶凝胶法,以尿素、氯化锰和钛酸丁酯为原料制备了纯Ti O2、N掺杂、Mn掺杂及N、Mn共掺杂的Ti O2纳米粉体。采用XRD、SEM、EDS、UV-VIS等分析手段对样品的物相、形貌、成分和吸光性能进行了表征,并且以亚甲基蓝溶液为模拟污染物在阳光下进行了光催化实验。结果表明,样品主要为锐钛矿相二氧化钛及少量的金红石型二氧化钛;样品呈颗粒状,有一定程度的团聚;N掺杂、Mn掺杂及N、Mn共掺杂样品的吸收光谱分别红移至470、440、490 nm;光催化实验表明,在可见光照射下的光催化能力由强到弱依次为N、Mn共掺杂N掺杂Mn掺杂纯Ti O2。     

Study on properties and synthesis of sulfonated coal supported nanostructure TiO2 photocatalysts

Nano-TiO₂ was synthesized with titanium sulfate by a simple economical microwave-assisted-hydrolysis method, and it was successfully coated on semi-organic-matter sulfonated coal (SC). SC as a semi-organic matter was first chosen as the substrate of nano-TiO₂. Their surface morphology and structure were investigated by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The hybrid nano-composite photocatalyst exhibited a good photocatalytic activity in degrading methylene blue (MB). Results revealed that under the assistance of microwave-process, the anatase TiO₂ can be synthesized at low temperature (around 100 °C), presents a strong crystalline and has a good photocatalytic performance.     

N和硫属元素掺杂及共掺杂TiO_2第一性原理计算

采用密度泛函理论(DFT)计算了N、S、Se和Te掺杂及共掺杂金红石TiO2的电子结构。针对DFT方法存在对过渡金属氧化物带隙能的计算结果与实际值严重偏离的缺陷,采用DFT+U(Hubbard系数)方法对掺杂体系的电子结构进行了计算。优化结构的结果表明,掺杂造成二氧化钛的体积膨胀和晶格畸变很明显。相比较于其他元素而言,Te更难掺杂进二氧化钛中是由于其大的原子半径和较大的取代能。能带总态密度图和分态密度图的分析表明,Ti 3d和O 2d轨道与N 2p、S 3p、Se 4p和Te 5p强烈地杂化在一起。与S、Se、Te单掺杂后带隙能比较,由计算的结果(S:2.43;Se:2.42;Te:2.46)可以看出,N/S、N/Se和N/Te共掺杂能明显地改善材料的电子结构及带隙。DFT+U计算结果与实验测量结果较好地吻合。     

TiO2光催化剂的研究进展

TiO2具有光催化效率高、稳定性好、不容易产生二次污染和成本低等特点,已广泛应用于抑菌抗癌、制备氢气、废水处理、太阳能电池、防晒、自清洁等领域.首先,介绍了TiO2光催化作用机理,探讨了晶型、粒径和缺陷对TiO2光催化活性的影响;然后,综述了近年来国内外TiO2光催化剂的研究现状与进展;接着总结了目前TiO2光催化剂的改性方法;最后,阐述了TiO2光催化剂改性过程中所面临的问题,对未来发展提出了建议.     

掺钒二氧化钛的可见光催化性能研究

制备高活性可见光响应型掺钒TiO2光催化剂,以荧光灯为光源,光催化降解亚甲基蓝为模型反应,对可见光下TiO2的催化活性进行评价。研究了掺钒TiO2制备方法、掺钒量及氧化剂对光催化氧化的影响。结果表明,溶胶-凝胶法制备的TiO2催化活性较高,且工序简单,钒离子掺杂均匀;掺钒能使TiO2具有可见光响应,最佳掺钒量为1%;外加氧化剂H2O2能提高掺钒TiO2催化活性。     

共沉淀法制备Mo/N共掺杂TiO_2可见光光催化剂

采用共沉淀法制备了Mo/N共掺杂TiO2光催化剂(Mo-N-TiO2)。结果表明,所得光催化剂为锐钛矿晶型,Mo/N共掺杂使样品对可见光吸收增强,吸收带边明显红移。在Mo∶N∶Ti摩尔比为0.012 5∶0.02∶1,煅烧温度为500℃的最优制备条件下,样品在白炽灯下照射2 h对亚甲基蓝溶液脱色率达55.7%。Mo以+6价的形式存在,并取代Ti4+进入TiO2晶格中,导致TiO2表面的Lew is酸性增强,有利于其导带中光生电子向表面迁移,促进了光生电子-空穴对的分离,同时与共掺杂引起的带边红移和较完整的锐钛矿相的协同作用有效提高了TiO2的可见光催化活性。     

Effect of the sonication and coating time on the photocatalytic degradation of TiO2, TiO2-Ag,and TiO2-ZnO thin film photocatalysts

Abstract

Today, the ultrasound utilizing for material synthesis has been extensively investigated. The unusual acoustic cavitation phenomenon caused by ultrasonic waves has created a new world for the production of high efficiency photocatalysts with new structures. In this study, TiO₂, TiO₂-Ag, and TiO₂-ZnO thin film photocatalysts were prepared using titanium isopropoxide Ti[OCH(CH₃)₂]₄, zinc acetate dehydrates (CH₃COO)₂Zn·2H₂O, and silver nitrate AgNO₃ by a sol–gel method under the ultrasonic irradiation. The prepared photocatalysts were characterized by UV–vis diffuse reflectance spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), and energy dispersive spectroscopy. The SEM images showed that the Ag and ZnO particles were evenly dispersed in the photocatalysts due to the ultrasonic irradiation, and Ag particles were approximately 90?nm, which is relatively small compared to the photocatalysts which is not treated with ultrasonic irradiation. The catalytic activity of the photocatalysts was determined using Acid Red 27 dye. The most excellent catalytic degradation was obtained with TiO₂-ZnO thin film photocatalyst. In comparison to the conventional photocatalyst, the efficiency of photocatalytic activity of the photocatalyst produced under ultrasonication has been increased due to the reduced size of Ag and ZnO and its uniform dispersion.     

稀土氢氧化物纳米线掺杂二氧化钛光催化性能

利用水热法合成稀土Y(OH)3和Eu(OH)3纳米线,取一定稀土纳米线掺入以钛酸四丁酯为主要原料的溶胶-凝胶体系中,制备出不同煅烧温度不同稀土掺杂量的TiO2材料。以甲基橙为目标降解物,研究了该材料的光催化性能。结果表明,稀土的掺入量对材料的光催化性能有明显的影响,甲基橙的脱色率随着稀土掺入量的增加降低;不同煅烧温度也影响材料的光催化性能,实验条件下,煅烧温度较高的材料催化甲基橙的脱色率更高,当煅烧温度为600℃,Y(OH)3或Eu(OH)3纳米线掺入量为1%时,光催化效果最佳,光反应1 h后甲基橙的降解率可达99%以上。     

铁掺杂二氧化钛空心球的制备及性能

以TiF₄为钛源、九水合硝酸铁为掺杂前体,采用水热法制备铁掺杂的TiO₂空心微球。采用SEM、TEM、XRD、BET、XPS等技术对样品的形貌、结构、晶型、比表面积、元素组成等进行表征,以亚甲基蓝（MB）的光催化降解为目标反应,评价其光催化活性。结果表明,160℃下水热反应生成的纳米TiO₂空心微球晶型为锐钛矿,少量掺铁并不影响微球的形貌及晶体结构。光催化实验表明,160℃下水热反应12 h生成的TiO₂空心微球样品均匀性好、光催化活性最佳;铁掺杂能显著提高TiO₂空心微球的催化活性,当铁钛比为1.5:100时,所得样品粒径最小,比表面积最大,光催化活性最高。     

TiO2 photocatalysts promoted by alkali metals

The new photocatalysts have been obtained by calcination titanium dioxide of anatase type (Tytanpol A11, “Police” Chemical Factory, Poland) with hydroxides (Li, Na, K, Ba) and carbonate (Sr). The obtained materials have been characterised by several analytical methods, like XRD, FT-IR/DRS, DR–UV–vis. The photocatalytic oxidation of phenol as model contamination has been investigated over obtained alkali metals–TiO₂. From all investigated photocatalysts only materials based on titanates in perovskite forms (BaTiO₃, SrTiO₃) have higher activity than pure titanium dioxide A11.     

掺杂ZnO光催化剂研究进展

ZnO作为半导体光催化剂,具有无毒性、高效性和低成本等优点得到广泛研究。但是ZnO禁带宽度较宽,为3.37 eV,仅能吸收紫外光,而且光生电子和空穴较容易复合,在太阳光照射下,表现出较低的光催化活性,不能满足工业应用要求。对ZnO进行改性能够提高ZnO对可见光的利用率及光催化活性。其中,对ZnO进行掺杂能够有效改变光催化剂的比表面积、颗粒大小和光催化活性等性质,适当引入一些金属或非金属离子有可能使催化剂对光的吸收范围扩展到可见光区。金属掺杂能使ZnO形成更多的晶格缺陷,降低电子和空穴的复合几率;而非金属掺杂能够在ZnO晶格中引入氧空位以及引起ZnO晶格膨胀,使ZnO禁带变窄,进而能吸收可见光;同时,掺杂两种非金属有可能比掺杂单一非金属更能改善ZnO对可见光的吸收。结合金属掺杂与非金属掺杂的优点,金属与非金属共同掺杂到ZnO中,使ZnO的各种缺点得到全面改善。此外,利用金属氧化物对ZnO进行掺杂,可改变ZnO晶格结构以及表面电子状态,提高ZnO光催化活性。需加强对掺杂理论的研究,掺杂虽能使ZnO能够吸收可见光,但是对可见光吸收不强,对太阳能利用率不高,需要对ZnO改性方法进行更深入研究,同时,光催化要进一步在工业上进行应用,应加强对光催化降解多组分废水及真实废水进行研究,其稳定性、固载化及其回收利用方面也应该得到更多关注。     

Microwave hydrothermal synthesis and photocatalytic properties of TiO2/BiVO4 composite photocatalysts

TiO₂/BiVO₄ composite photocatalysts with heterojunction structures were synthesized by the one-step microwave hydrothermal method. The physical and photophysical properties of the as-prepared photocatalysts were fully characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), UV–vis diffuse reflectance spectra, photoluminescence (PL) and BET surface area analysis. The photocatalytic activities were evaluated by the decolorization of rhodamine B under UV and simulated sun-light irradiation. The results reveal that the as-prepared TiO₂/BiVO₄ composites exhibit higher photocatalytic activities than pure BiVO₄. The 20% TiO₂/BiVO₄ sample shows the best photocatalytic activity. The enhancement of photocatalytic activity is mainly attributed to the increasing separation rate of photogenerated charge carriers. The possible photocatalytic mechanism is discussed on the basis of the calculated energy band positions.     

稀土元素La对TiO_2光催化剂的改性作用

采用溶胶-凝胶法制备系列不同掺杂量的稀土元素La改性的TiO2光催化剂,借助X射线衍射、X射线光电子能谱和固体光致发光光谱等对催化剂进行表征,以光催化降解甲基橙染料溶液为反应模型,探讨稀土元素La对TiO2光催化剂的改性作用。结果表明,稀土元素La可明显促进锐钛矿相的形成并显著细化晶粒;La以La2O3化学态形式高度分散在TiO2表面,增加了催化剂表面氧空位,有助于提高光催化活性。当掺杂稀土元素La质量分数为1%时,可使TiO2催化剂催化活性提高约22%。     

Zn2+ doped TiO2/C with enhanced sodium-ion storage properties

To improve the performance of anatase TiO₂ as an anode material for sodium-ion batteries, Zn²⁺-doped TiO₂/C composites are synthesized by a co-precipitation method. The results of XRD, EPR and XPS demonstrate that Zn²⁺ occupies at the Ti⁴⁺ site of TiO₂ to form a solid-solution, resulting in an expansion of lattice and an increase of Ti³⁺ content. The expansion of lattice can enhance the stability of the crystal structure of TiO₂. The increase of Ti³⁺ content can improve the conductivity of TiO₂. Therefore, Ti_0.94Zn_0.06O₂/C delivers a reversible capacity of 160 mA h g⁻¹ with a capacity retention of 96% after 100 cycles at 5 C. Even charged/discharged at 10 C, this sample still exhibits a reversible capacity of 117 mA h g⁻¹, comparing to 86 mA h g⁻¹ for TiO₂/C. The enhanced electrochemical performances can be ascribed to the improvement of the conductivity and the structural stability of TiO₂ due to Zn²⁺-doping. Therefore, Ti_0.94Zn_0.06O₂/C is an attractive anode material of sodium-ion batteries.     

Surface properties of iron-titania photocatalysts employed for 4-nitrophenol photodegradation in aqueous TiO2 dispersion

Iron(III) doped specimens (0.01–5% atomic Fe Ti) have been prepared by impregnating polycrystalline home prepared TiO₂ (mainly anatase) and have been studied for photocatalytic degradation of 4-nitrophenol in aqueous dispersions. Some structural and surface properties have been studied by X-ray diffraction, specific surface area and porosity measurements and FTIR monitoring of pyridine, ammonia and methanoic acid adsorption for surface acidity and basicity. Their surface properties were compared with a corresponding series of photocatalysts prepared by a coprecipitation method. Adsorption of pyridine and ammonia indicates the presence of surface acid Lewis sites, a low concentration of surface Brønsted sites being present only in the samples prepared by impregnation. The photocatalytic experiments indicated that the presence of iron ions does not influence or is detrimental for the occurrence of the 4-nitrophenol photodegradation.