Engineering the Band Gap States of the Rutile TiO2(110) Surface by Modulating the Active Heteroatom

Introducing band gap states to TiO₂ photocatalysts is an efficient strategy for expanding the range of accessible energy available in the solar spectrum. However, few approaches are able to introduce band gap states and improve photocatalytic performance simultaneously. Introducing band gap states by creating surface disorder can incapacitate reactivity where unambiguous adsorption sites are a prerequisite. An alternative method for introduction of band gap states is demonstrated in which selected heteroatoms are implanted at preferred surface sites. Theoretical prediction and experimental verification reveal that the implanted heteroatoms not only introduce band gap states without creating surface disorder, but also function as active sites for the Cr^VI reduction reaction. This promising approach may be applicable to the surfaces of other solar harvesting materials where engineered band gap states could be used to tune photophysical and ‐catalytic properties.     

CrO2 (1 0 0) and TiO2 (1 0 0) film heteroepitaxy on a BaF2 (1 1 1)/Si (1 0 0) substrate

Multi-domained heteroepitaxial rutile-phase TiO₂ (1 0 0)-oriented films were grown on Si (1 0 0) substrates by using a 30-nm-thick BaF₂ (1 1 1) buffer layer at the TiO₂–Si interface. The 50 nm TiO₂ films were grown by electron cyclotron resonance oxygen plasma-assisted electron beam evaporation of a titanium source, and the growth temperature was varied from 300 to 600 °C. At an optimal temperature of 500 °C, X-ray diffraction measurements show that rutile phase TiO₂ films are produced. Pole figure analysis indicates that the TiO₂ layer follows the symmetry of the BaF₂ surface mesh, and consists of six (1 0 0)-oriented domains separated by 30° in-plane rotations about the TiO₂ [1 0 0] axis. The in-plane alignment between the TiO₂ and BaF₂ films is oriented as [0 0 1] TiO₂ || BaF₂ or [0 0 1] TiO₂ || BaF₂ . Rocking curve and STM analyses suggest that the TiO₂ films are more finely grained than the BaF₂ film. STM imaging also reveals that the TiO₂ surface has morphological features consistent with the BaF₂ surface mesh symmetry. One of the optimally grown TiO₂ (1 0 0) films was used to template a CrO₂ (1 0 0) film which was grown via chemical vapor deposition. Point contact Andreev reflection measurements indicate that the CrO₂ film was approximately 70% spin polarized.     

X射线荧光光谱法测定金红石中主次组分

采用Li2B4O7和LiBO2的混合熔剂(67∶33)熔融制样,波长色散X射线荧光光谱法测定金红石中TiO2,TFe,P,SiO2,Al2O3,MnO,CaO,Cr2O3,MgO,ZrO2,HfO2等组分。实验中样品和熔剂的质量比为1∶14,以溴化锂(LiBr)作脱模剂,采用高频熔炉在1 150℃熔融90s进行制样,所得熔片均匀、强度高、成型良好。方法用于金红石实际样品的测定,结果同参考值或化学分析方法的结果相吻合,相对标准偏差(RSD,n=10)P为3.8%、Al2O3为2.8%,其它均小于2%,能够满足实际测定工作的需要。     

Preparation of synthetic rutile from high titanium slag using microwave heating

In this work, we demonstrate a novel synthesis of synthetic rutile from high titanium slag. This rutile TiO₂ was obtained by a simple one-step microwave roasting route. The influence of microwave roasting temperature and duration on the phase transformation of high titanium slag has been assessed. X-ray diffraction (XRD) results indicate that the intensity of anosovite (Fe₃Ti₃O₁₀) phase, which were the major phase of high titanium slag of carbon thermal reduction of ilmenite ores, decreased rapidly while the peaks for rutile TiO₂ phase increased with increase in the microwave roasting temperature. The scanning electron microscope (SEM) images revealed formation and the particle-size distribution of rutile TiO₂ phase. Based on XRD and SEM analysis, confirmed the dependence of phase structure, composition and crystallite size on the process conditions of microwave roasting.     

高温氧气热处理对TiO_2晶体结构和铁磁性的影响

金红石TiO_2晶体先在真空中进行退火处理,随后在1173 K的氧气中进行不同时间(2 h、5 h、8 h)的热处理.理论上,通过Doppler程序计算了晶体中存在单空位、双空位和间隙O原子时的正电子湮没寿命.实验上,利用正电子湮没寿命谱仪、符合多普勒能谱仪和超导量子干涉仪分别表征了氧气退火后晶体内部的缺陷结构和常温铁磁性.分析结果得出:真空退火晶体的常温铁磁性主要与O空位的存在相关联;而经过氧气退火后,虽然极大地减少了氧空位,但晶体中却产生了大量的Ti双空位,这使得晶体的常温铁磁性有所增加.     

DFT calculations for Au adsorption onto a reduced TiO2 (110) surface with the coexistence of Cl

Residual chlorines, which originate from HAuCl₄, enhance the aggregation of gold (Au) nanoparticles and clusters, preventing the generation of highly active supported Au catalysts. However, the detailed mechanism of residual-chlorine-promoted aggregation of Au is unknown. Herein to investigate this mechanism, density functional theory (DFT) calculations of Au and Cl adsorption onto a reduced rutile TiO₂ (110) surface were performed using a generalised gradient approximation Perdew, Burke, and Ernzerhof formula (GGA–PBE) functional and plane-wave basis. Although both Au and Cl atoms prefer to mono-absorb onto oxygen defect sites, Cl atoms have a stronger absorption onto a reduced TiO₂ (110) surface, abbreviated as rTiO₂ (110) in the following, than Au atoms. Additionally, co-adsorption of a Cl atom and a Au atom or Au nanorod onto a rTiO₂ surface was investigated; Cl adsorption onto an oxygen defect site weakens the interaction between a Au atom or Au nanorod and rTiO₂ (110) surface. The calculation results suggest that the depletion of interaction between Au and rTiO₂ surface is due to strong interaction between Cl atoms at oxygen defect sites and neighbouring bridging oxygen (O^B) atoms.     

Photocatalytic Effects of Rutile Phase TiO2 Ultrafine Powder with High Specific Surface Area Obtained by a Homogeneous Precipitation Process at Low Temperatures

The photocatalytic characteristics of nanostructured TiO₂ ultrafine powder with rutile phase produced using the homogeneous precipitation process at low temperatures (HPPLT) were compared with those of commercial P-25 TiO₂ powder by flame hydrolysis. The TiO₂ powder by the HPPLT showed much higher photoactivity in the removal rate, showing lower pH values in the solution than the P-25 powder when eliminating metal ions such as Pb and Cu from the aqueous metal-EDTA solutions. This can be inferred as the more rapid photo-oxidation or -reduction of metal ions from the aqueous solution, together with relatively higher efficiencies in the use of an electron-hole pair formed on the surface of the TiO₂ particles under UV light irradiation. Also, in the view of the TiO₂ particle morphology, compared to the well-dispersed spherical P-25 particles, the agglomerated TiO₂ secondary particles by the HPPLT consist of acicular typed primary particles with a thickness in the range of 3–7 nm and the primary particles radialize in all directions, which would be more effective to photocatalytic reactions without the large electron-hole recombination on the surface of the TiO₂ particle under UV light irradiation. It can be, therefore, thought that the higher photoactivity of the rutile TiO₂ powder by the HPPLT in the aqueous solutions results mainly from having a larger surface area by the acicular shaped primary particles with very thin thickness and radialization in all directions.     

化学镀镍-高磷合金的微观结构及晶化行为研究

分别以SnCl2.2H2O和SnCl2.5H2O为锡源,采用胶溶晶核法,经沉淀和胶溶过程,在液相中一步合成了金红石型TiO2。详细考察了各种胶溶条件对产物结构的影响,并通过两种锡源实验结果的比较对异相晶核法中两种锡源的成晶机理进行了分析,所合成的金红石型TiO2晶粒度为20－50nm,两种方法获得完全红金石型TiO2所需引入SnO2的最低物质的量的分数分别为10％和8％。     

纳米级金红石型TiO2放大试验

以 H2 Ti O3为原料 ,经过 Ti O(NO3) 2 水解的放大实验 ,制备了金红石型 Ti O2 纳米粒子 ,通过 X射线衍射 (XRD)、透射电镜 (TEM)和比表面吸附 (BET) ,对纳米粒子的结构、形貌、粒径进行了分析和表征 .结果表明 ,粒子的平均粒径在 11nm左右 ,晶型为金红石型 ,粒子分布较松散 ,部分颗粒呈纤维状排列 .     

TiOCl2溶液微波加热制备金红石型TiO2纳米粒子

本文报道了一种由TiOCl2液相直接合成金红石型TiO2纳米粒子的新方法,即微波诱导沸腾回流强迫水解法,用该法制备出常规条件下不能得到的产品.所得产物用粉末X射线衍射仪和透射电子显微镜表征,证明产物为金红石型,粒子尺寸5～30nm可控.研究表明,产物物相取决于Ti4+的初始水解速率,水解速率越快,越有利于金红石相成核;通过控制初始Ti4+的浓度,可改变纳米TiO2的粒径.另外还讨论了该金红石型TiO2纳米粒子的成核机理.