Zr 掺杂对锐钛矿型TiO2 电子结构和光学性质的影响

本文采用密度泛函理论的平面波超软赝势方法研究了Zr 掺杂对锐钛矿型TiO₂ 电子结构和光学性质的影响, 计算了Zr 掺杂前后锐钛矿型TiO₂ 的电子态密度分布、能带结构、光吸收系数等性质, 定性地分析了掺杂前后电子结构和光学性质的变化. 研究结果表明: Zr 掺杂锐钛矿型TiO₂, 导致带隙减小, 掺杂后在360~400nm 附近的光吸收系数增大, TiO₂ 的吸收带产生红移, 增强了TiO₂ 的光催化活性, 理论与实验结果 一致.     

Zn掺杂锐钛矿TiO2的电子结构及光学性质的研究

采用基于密度泛函理论(DFT)的第一性原理对Zn掺杂锐钛矿TiO_2进行了结构优化,并对掺杂前后的能带结构、电子态密度和吸收光谱进行了计算。研究表明:Zn掺杂锐钛矿TiO_2体系为间接带隙半导体,在价带顶部引入了杂质能级,杂质能级主要由O-2p轨道和Zn-3d轨道贡献,杂质能级的引入增强了TiO_2对可见光区的响应,增大TiO_2的光吸收范围。实验结果表明:Zn掺杂使锐钛矿TiO_2吸收边红移,并能增强TiO_2的光电效应,可用于材料的光阴极保护。     

Synthesis,characterization, and theoretical study of N,S-codoped nano-TiO<Subscript>2</Subscript> with photocatalytic activities

Nitrogen and sulfur doped titanium dioxide photocatalysts were prepared by the sol-gel method. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-visible diffuse reflectance spectra (DRS). Photocatalytic activities of the samples were investigated on the degradation of methyl orange (MO). The effect of the dopants on the electronic structure of TiO₂ was studied by the first-principles calculations based on the density functional theory (DFT). The orbital hybridization resulted in energy gap narrowing and electronic delocalization in the crystal of doped TiO₂. Mobile electrons of varied energetic states could offer enhanced electron transfer, together with optical absorption improvement. The results show that the doping elements of N and S play a cooperative role in the modification of electronic structure, which enhances the photocatalytic performance. The experimentally observed absorption edges of N-doped TiO₂, S-doped TiO₂, and N, S-codoped TiO₂ are 420, 413, and 429 nm, respectively, which can be explained by the theoretical calculation results.     

A kinetic model for describing effect of the external surface concentration of TiO2 on the reactivity of eggshell activated carbon supported TiO2 photocatalyst

The porous support supported TiO2 is considered to be the promising photocatalyst due to the fact that it is easily recovered from water and has high capacity to mineralize pollutants. Obviously, the expected structure of this kind of photocatalyst is egg-shell, that is, TiO2 is mainly on the external surface of the porous support. The reactivity of the supported photocatalyst strongly depends on the concentration of TiO2 on the external surface of the porous support. In this study, a kinetic model was developed to describe the effect of the external surface concentration of TiO2 （CESC） on the reactivity of egg-shell activated carbon （AC） supported TiO2 photocatalysts. It was found that the obtained model precisely described the effect of CESC, on the reactivity of TiO2/AC photocatalysts. This study can be used to deeply understand the performance of TiO2/AC catalysts and to provide valuable information on designing efficient supported TiO2 photocatalysts.     

A review of TiO<Subscript>2</Subscript> nanoparticles

Climate change and the consumption of non-renewable resources are considered as the greatest problems facing humankind.Because of this,photocatalysis research has been rapidly expanding.TiO2 nanoparticles have been extensively investigated for photocatalytic applications including the decomposition of organic compounds and production of H2 as a fuel using solar energy. This article reviews the structure and electronic properties of TiO2,compares TiO2 with other common semiconductors used for photocatalytic applications and clarifies the advantages of using TiO2 nanoparticles.TiO2 is considered close to an ideal semi- conductor for photocatalysis but possesses certain limitations such as poor absorption of visible radiation and rapid recombination of photogenerated electron/hole pairs.In this review article,various methods used to enhance the photocatalytic characteristics of TiO2 including dye sensitization,doping,coupling and capping are discussed.Environmental and energy applications of TiO2, including photocatalytic treatment of wastewater,pesticide degradation and water splitting to produce hydrogen have been summarized.     

水热法制备TiO2-ZnO纳米棒分级结构及其光电性能研究

为了增加光电极光生电子传输通道并提高其光敏剂的负载能力,采用两步水热法制备了一种新颖的TiO_2-ZnO纳米棒分级结构。采用水热法在FTO导电玻璃基底上生长TiO_2纳米棒有序阵列膜,通过浸泡提拉在TiO_2纳米棒上包覆一层ZnO溶胶,经烧结形成ZnO种子层;再次采用水热法于TiO_2纳米棒上生长ZnO纳米棒,形成TiO_2-ZnO纳米棒分级结构,通过旋涂辅助连续离子反应分别在TiO_2纳米棒阵列和TiO_2-ZnO纳米棒分级结构中沉积光敏剂CdS纳米晶,形成CdS/TiO_2纳米棒复合膜和CdS/TiO_2-ZnO纳米分级结构复合膜。利用SEM,TEM,XRD、紫外-可见吸收光谱、瞬态光电流图谱等表征和测试手段,对样品的形貌、结构、光吸收和光电性能进行了表征和测试。结果表明,与单纯的TiO_2纳米棒阵列相比,TiO_2-ZnO分级结构可以沉积更多的CdS光敏剂,CdS/TiO_2-ZnO纳米分级结构复合膜的光吸收性能和瞬态光电流均明显优于CdS/TiO_2纳米复合薄膜。凭借优异的光电性能,TiO_2-ZnO分级结构在太阳电池光阳极材料中具有很好的应用前景。     

N,Cd TiO2光催化活性的实验与理论研究

 采用热分解法制备了N, Cd共掺杂纳米TiO₂光催化剂,通过XRD、XPS和UV-DRS等对样品进行了分析表征,并以甲基橙为目标降解物考察了其光催化性能。实验表明产物N, Cd TiO₂为锐钛矿型,颗粒约为10~15 nm,N取代了TiO₂晶格中的O原子,而Cd以游离态分布在TiO₂表面;其光吸收发生明显红移;光催化活性提高,N、Cd在提高TiO₂的光催化活性方面具有协同作用。采用第一性原理方法,对其电子结构和光学性质进行了理论计算。结果发现在N,Cd TiO₂的带隙中出现了N2p和Cd5s的杂质能级,价带的电子可以吸收较小的能量跃迁到杂质能级上,接着二次激发跃迁到导带上,电子跃迁变得容易,吸收波长向可见光区移动。计算结果很好地解释了实验现象。     

Low energy H+ effects on the photovoltaic and optical properties of polycrystalline silicon solar cells

Low energy hydrogen ion was used to passivate the electrically active defects existing in grains and grain boundaries of polycrystalline silicon solar cells. Short-circuit current of H⁺ implanted cells remarkably increased before and after preparing TiO₂AR (antireflective) coating. The measurements (at λ=6328 Å) of the optical properties of H⁺ implanted silicon samples show that: the value of absorption coefficient reached the level of a-Si; refractive indexn and ref?ectivityR significantly decreased; the optical band gap increased from 1.1 eV to 1.3 eV. The results indicate that Si-H bonds have been formed after H⁺ implantation. The calculation shows that the optical thickness cycle of TiO₂ AR coating will reduce correspondingly in order to obtain the optimum optical match between AR coating and implanted silicon since refractive index decreases after H⁺ implantation.     

二氧化钛-硫化镉/氧化石墨烯复合材料光催化降解废水中有机物的研究

本论文采用溶剂热法制备出TiO₂-CdS/rGO三元复合光催化材料,并对其降解亚甲基蓝、罗丹明B的光催化活性进行研究,发现TiO₂-CdS/rGO对于亚甲基蓝、罗丹明B的光催化降解活性优于TiO₂-CdS,催化效率明显提高,降解时间大大缩短;在可见光照射下,以TiO₂-CdS/rGO为光催化剂,光反应时间40 min,亚甲基蓝、罗丹明B的降解率可达100%。本文还研究了催化材料的稳定性、催化剂用量对光催化降解效果的影响。     

Blue TiO2 polymorph: An efficient material for dye-sensitized solar cells fabricated using a low-temperature sintering process

Recently,surface-disordered or non-stoichiometric TiO_2,such as blue TiO_2(B-TiO_2),has received much attention owing to its unique properties,such as structural disorder near the surface and the existence of Ti~(3+)ions and oxygen vacancies.Therefore,surface-disordered TiO_2has been applied for microwave absorption,photocatalysis,in photoelectrochemical sensors and rechargeable lithium-ion batteries.In this work B-TiO_2,a polymorph consisting of nanoparticles,nanotubes and nanosheets,was successfully synthesized and employed as a semiconductor layer in dye-sensitized solar cells(DSSCs)fabricated using a low-temperature heat treatment process(120°C).Based on the analyses of the experimental results regarding the structure and those from the characterization of B-TiO_2,and its application to DSSCs,it has been found that the B-TiO_2 material has an effect on electron-hole pair separation.The conversion efficiency of the B-TiO_2 DSSC(BTiO_2-DSSC)was 6.18%,whereas that of the TiO_2-P25 DSSC(P25-DSSC)was 3.61%,and that of the TiO_2 polymorph DSSC(PTiO_2-DSSC)which is the precursor of B-TiO_2 was 4.51%.     

Preparation, characterization and photocatalytic activity of N-doped TiO2 nanocrystals

N-doped TiO₂ nanocrystals were prepared using titanium alkoxide as precipitant with different proportional materials. The products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and UV-vis diffuse reflectance spectra. It is confirmed experimentally that the photocatalytic activity of N-doped TiO₂ is much higher than that of Degussa P25, when used for the degradation of crystal violet. The degradation kinetics follows an apparent first-order reaction, which is consistent with a generally observed Langmuir-Hinshelwood mechanism. The doping of TiO₂ with nitrogen significantly increases the absorption in the region of visible light. The energy of the band gap of N-doped TiO₂ is 2.92 eV. The better performance of N-doped TiO₂ can be explained by the fact that it is also excited with longer-wavelength light.     

纳米TiO2晶体的制备及光催化性能

采用Sol-Gel法成功地合成了TiO     

新型TiO2-铜卟啉催化剂的合成及其光催化甲基橙降解研究

为了研究不同长度侧链催化剂对光催化降解甲基橙溶液的影响,更好地解决水污染治理问题,以1-萘酚为原料,经两步反应得到中间体4-(3-萘氧基-烷氧基)-苯甲醛,利用Lindsey法合成4个结构新颖的卟啉及铜卟啉衍生物,中间体和目标产物的结构经MS,NMR和元素分析进行确认,制备了TiO_2-铜卟啉催化剂,并进行了光催化甲基橙降解实验。结果表明:当铜卟啉衍生物苯环上连有侧链时,其光催化活性优于四苯基铜卟啉催化剂,但侧链的长度对活性的影响不明显。该研究为今后合成高效催化剂提供了思路。     

CdS修饰低密度TiO2纳米棒阵列复合膜的制备及光电性能

为了提高CdS光敏层在TiO₂一维纳米棒阵列中的填充率,在TiO₂种子层的基础上,采用水热法于FTO导电玻璃表面生长了棒长较短、棒间距较大的低密度TiO₂一维纳米棒阵列膜,通过化学浴沉积在TiO₂纳米棒表面包覆CdS种子层,以此为基底采用水热法于TiO₂一维纳米阵列中生长CdS光敏层。采用SEM,XRD及紫外-可见吸收光谱对不同CdS水热生长时间的TiO₂/CdS复合膜结构进行了表征,并对其光电性能进行了研究。结果表明,低密度TiO₂纳米棒阵列有利于CdS生长液在阵列中渗入形成完全包覆的CdS种子层,CdS光敏层通过水热过程在整个TiO₂纳米棒表面均匀生长,逐渐形成CdS对TiO₂纳米棒阵列的完全填充和包覆,并在阵列顶端形成由CdS纳米短棒组成的花状修饰层;CdS的修饰将TiO₂一维纳米阵列膜的光吸收拓展至可见光区,水热生长7 h所得到的TiO₂/CdS复合膜具有最高光电流。所制备的CdS修饰低密度TiO₂纳米棒复合膜在太阳电池器件中具有很好的应用前景。     

Hydrotalcite-supported Pd-Cu catalyst for nitrate adsorption and reduction from water

With the rapid development of industry and agricul- ture, the nitrate contamination in groundwater becomes increasingly serious in many countries [1]. Therefore, the remediation of nitrate-contaminated groundwater is one of the targets urgently confronted…     

Fabrication of TiO2 nanoparticles/nanorod composite arrays via a two-step method for efficient dye-sensitized solar cells

Ti O2nanoparticles/nanorod composite arrays were prepared on the F-doped tin oxide(FTO)substrate through a two-step method of hydrothermal and d.c.magnetron sputtering.The microstructure and optical properties of the samples were characterized respectively by means of X-ray diffraction(XRD),field-emission scanning electron microscopy(FESEM)and UV–vis spectrometer.The results showed that the Ti O2composite nanorod arrays possess the nature of high surface area for more dye molecule absorption and the strong light scattering effects.The dye sensitized solar cells(DSSCs)based on Ti O2composite nanorod arrays exhibited a 80%improvement in the overall energy conversion efficiency compared with the pure Ti O2nanorod arrays photoanode.     

Preparation, characterization and photodegradation of methylene blue based on TiO2 microparticles modified with thiophene substituents

The new microparticles,2-formylthiophene(FT)/TiO2 and(E)-1,2-bis(5-formyl-2-thienyl) ethylene(EBFTE)/TiO2 were synthesized with a silane coupling agent.The prepared TiO2 composites were characterized using Ultraviolet-Vis absorption(UV-Vis),X-ray diffraction(XRD),scanning electron microscope(SEM) and thermogravimetric analyzer(TGA).Methylene blue was used as a model material to examine the photocatalytic activities of the prepared catalysts under both Ultraviolet-Vis(UV) and visible(Vis) light.The enhanced photocatalytic activities were observed in the presence of(FT)/TiO2 and EBFTE/TiO2 under Vis light.It suggests that FT or EBFTE plays a block or active role in the photodegradation mechanisms under UV and Vis light irradiation,respectively.     

A novel TiO2 with a large amount of bulk intrinsic defects-Visible-light-responded photocatalytic activity induced by foreign trap

A novel TiO2 (anatase) containing a large amount of single electron trapped oxygen vacancies (SETOV) was prepared by dehydration of titanic acid nanotubes. This novel TiO2 contains high concentration intrinsic defects in bulk structure, while its surface still remains the stoichiometric structure to protect them. And this novel TiO2 itself has the visible light absorption without any doping, so we call it as the third generation of TiO2 . However, it is regretted that this novel TiO2 (A) only has photocatalytic activity under UV light irradiation, and was inactive for the visible light. The true reasons for this phenomenon were investigated by the transient IR absorption and photoluminescence spectra. Through constructing the foreign electron traps (PdO, PtO2 ), the photocatalytic oxidation of propylene under visible light irradiation was successfully achieved. The removal yield of propylene (C3H6 ) reached 7.6% and 28% on 2 wt.% PtO2 /novel TiO2 and 2 wt.% PdO/novel TiO2 , respectively. By comparison with the noble metal electron traps (Pt, Pd), we found that the effective foreign electron traps need to satisfy two conditions: (1) its work function should situate in the range of Eg(TiO2 ); (2) O2 adsorbes on it undissociatively. This work opens up a new route for the investiga- tion of solar-energy-available TiO2 .     

预制层结构对CZTS薄膜微观组织和光学性能的影响

研究了叠层顺序对磁控溅射沉积铜锌锡硫（CZTS）吸收层的微观结构、表面形貌和光学性能的影响.试验结果表明：当预制层结构为Cu/ZnS/SnS₂时,制备的CZTS薄膜在（112）晶面具有择优生长取向,并具有较好的结晶一致性,在288,335和368 cm^-1处呈现出特征拉曼（Raman）峰,薄膜表面晶粒较大、形状规则、薄膜空隙较少、比较致密,可见光范围内的吸收系数较高,光学带隙1.5 eV,适合作为CZTS薄膜太阳能电池的吸收层;当预制层结构为SnS₂/Cu/ZnS和ZnS/SnS₂/Cu时,由于在预制层硫化过程中造成一定的Zn和Sn流失,使CZTS薄膜中含有CuS杂相,导致薄膜表面质量下降,禁带宽度增加,不适合做CZTS薄膜太阳能电池的吸收层.     

Preparation, structure, and properties of polyurethane foams modified by nanoscale titanium dioxide with three different dimensions

TiO2-based nanosheets (TiNSs), TiO2-based nanotubes (TiNTs) were prepared by hydrothermal processing, and polyurethane foams with TiO2 nanopowders (P25), TiNSs and TiNTs were synthesized by free-rising foaming method. The Fourier-transform infrared (FT-IR) spectra show that the addition of titanium dioxide does not affect the chemical structure of polyurethane foam. However, microscope observations show that PU/TiNSs composite foams have more uniform cells and the average aperture smaller than that of pure poly-urethane foams. According to the results of thermal analysis, the PU/TiNSs composite foams have better thermal stability, the temperature of decompostion occurring with a maximum weight loss rate is about 30 ℃ higher than that of pure PU foams. The decompostion temperatures are 167 ℃ and 148 ℃ for the PU/P25 composite foams and the PU/TiNTs composite foams respectively, which are lower than that of pure PU foams. Moreover, with the addition of the fillers, the sound absorption property also has changed; the addition of TiNSs improved the sound absorbing property efficiently. The better thermal stability and sound absorption of PU/TiNSs composite foams are mainly due to the uniform cells diffuse and smaller aperture.