Identifying the effect of photo-generated carriers on the phonons in rutile TiO_(2) through Raman spectroscopy

Investigating lattice vibrations through Raman spectroscopy is a crucial method for studying crystalline materials.Carriers can interact with lattices and influence lattice vibrations;thus,it is feasible to study the effect of photo-generated carriers on phonons by analyzing changes in the Raman spectra of semiconductors.Rutile is one of the predominant crystalline phases of TiO_(2),which is a widely utilized metal oxide semiconductor.In this work,rutile TiO_(2) is coated on a thinned optical fiber to concentrate ultraviolet light energy within the material,thereby enhancing the generation of carriers and amplifying the changes in the Raman spectra.A Raman detection laser with a wavelength of 532 nm is utilized to collect the Raman spectra of rutile TiO_(2) during irradiation.Using this setup,the impact of photo-generated carriers on the phonons corresponding to Raman vibrational modes is researched.The localization and non-radiative recombination of photo-generated carriers contribute to a reduction in both the frequencies and lifetimes of phonons.This work provides a novel approach to researching the effect of carriers on phonons.

Activity and Adsorption Behavior of Oxygen on Rutile TiO_(2)(110)

The activity and adsorption behavior of oxygen on rutile TiO_(2)(110)(RTiO_(2)(110))were investigated using the temperature programmed desorption(TPD)method with methanol(CH_(3)OH)as the probe molecule.By controlling the coverage of molecular O_(2)on the surface via increasing or decreasing O_(2)exposure,two chemisorbed O_(2)species on the surface are confirmed,one at the bridging oxygen vacancy(Ov)site(O_(2)^(2-)/Ov)and the other at the five-fold coordinated titanium(Ti_(5c))site(O^(2-)/Ti_(5c)).At low O_(2)exposure,O^(2-)/Ov is the main species on the surface,which only leads to the O-H bond cleavage of CH_(3)OH,producing methoxy groups(CHgO).However,after the Ov sites are nearly filled by O_(2)at about 0.1 L O_(2)exposure,O_(2)/Tisc species begins to appear on R-TiO_(2)(110)surface,resulting in the formation of formaldehyde(CH_(2)O)via the reaction of O_(2)/Tisc species with CH_(3)OH or CH3O to break the C-H bond at low surface temperature.Moreover,the yield of CH_(2)O increases linearly with that of H_(2)O.In addition,when the 1 L O_(2)covered surface is irradiated with 355 nm UV irradiation to desorb and dissociate O_(2)/Ti_(5c)species,the yield of CH_(2)O decreases linearly with that of H_(2)O.Further analysis suggests that the charge state of O_(2)/Ti_(5c)may not change as the exposure of O_(2)changes on the R-TiO_(2)(110)surface,and O_(2)is most likely to adsorb on the Ti_(5c)sites in the form of O_(2)^(2-),not O_(2)^(-),The result not only advances our understanding on the adsorption state of O_(2)on TiO_(2),but also provides clues for low temperature C-H bond activation with O_(2)on TiO_(2).

Surface Chemistry and Photochemistry of Cyclohexane on Rutile TiO_(2)(110)

Cyclohexane is a high-valued chemical receivingsignificant interest in liquid hydrogen storage technology.TiO_(2)-based catalysts show high performance in the photocatalytic dehydrogenation of cyclohexane under mild conditions,but the detailed reaction mechanism is not well understood.With the surface science approaches,we have studied the adsorption and surface chemistry of cyclohexane on rutile TiO_(2)(110).The thermal desorption spectroscopy and X-ray photoelectron spectroscopy results both demonstrate the molecular adsorption of cyclohexane on rutile TiO_(2)(110).Upon the UV Hg light irradiation,photodesorption of cyclohexane occurs from both the chemisorbed monolayer and the multilayer.No decomposition nor dehydrogenation of cyclohexane occurs on rutile TiO_(2)(110).These results deepen the fundamental understanding of the surface chemistry of cyclohexane on the TiO_(2)surface.

Time-resolved photoluminescence of anatase/rutile TiO_2 phase junction revealing charge separation dynamics

Junctions are an important structure that allows charge separation in solar cells and photocatalysts. Here, we studied the charge transfer at an anatase/rutile TiO2 phase junction using time-resolved photoluminescence spectroscopy. Visible （-S00 nm） and near-infrared （NIR, -830 nm） emissions were monitored to give insight into the photoinduced charges of anatase and rutile in the junction, respectively, New fast photoluminescence decay components appeared in the visible emission of futile-phase dominated TiO2 and in the NIR emission of many mixed phase TiO2samples. The fast decays confirmed that the charge separation occurred at the phase junction. The visible emission intensity from the mixed phase TiO2 increased, revealing that charge transfer from rutile to anatase was the main pathway. The charge separation slowed the microsecond time scale photolumines- cence decay rate for charge carriers in both anatase and rutile. However, the millisecond decay of the charge carriers in anatase TiO2 was accelerated, while there was almost no change in the charge carrier dynamics of rutile TiO2. Thus, charge separation at the anatase/rutile phase junction caused an increase in the charge carrier concentration on a microsecond time scale, because of slower electron-hole recombination. The enhanced photocatalytic activity previously observed at ana- tase/rutile phase junctions is likely caused by the improved charge carrier dynamics we report here. These findings may contribute to the development of improved photocatalytic materials.

Nitrate-group-grafting-induced assembly of rutile TiO2 nanobundles for enhanced photocatalytic hydrogen evolution

In this study,an acid-induced assembly strategy for a rutile TiO2 photocatalyst was proposed on the basis of the treatment of lamellar protonated titanate with a concentrated HNO3 solution.Nitrate groups were successfully grafted onto a TiO2 surface and induced the assembly of rutile TiO2 nanorods into uniform spindle-like nanobundles.The resulting TiO2 product achieved a photocatalytic hydrogen evolution rate of 402.4μmol h^?1,which is 3.1 times higher than that of Degussa P25-TiO2.It was demonstrated that nitrate group grafting caused the rutile TiO2 surface to become negatively charged,which is favorable for trapping positive protons and improving charge carrier separation,thereby enhancing photocatalytic hydrogen production.Additionally,surface charges were crucial to structural stability based on electrostatic repulsion.This study not only developed a facile surface modification strategy for fabricating efficient H2 production photocatalysts but also identified an influence mechanism of inorganic acids different from that reported in the literature.

水对甲醇在Rutile-TiO_2(110)-(1×1)表面光催化解离的影响(英文)

采用程序升温脱附方法研究了甲醇分子吸附在真空退火后的二氧化钛(110)表面的光催化过程,对比分析了单独吸附甲醇分子以及甲醇分子与水分子共吸附情况下的光催化解离过程.结果表明,在二氧化钛(110)表面吸附的甲醇分子对共吸附水分子的光催化解离过程并没有直接的帮助作用.共吸附状态下的水分子也同样没有影响到甲醇的光致解离过程,但是水分子的存在抑制了甲醇光解产物甲醛的光致脱附过程,同时促进了甲酸甲酯的形成.

The discovery of TiO_(2)-Ⅱ,the α-PbO_(2)-structured high-pressure polymorph of rutile,in the Suizhou L6 chondrite

We report the discovery of TiO_(2)-Ⅱ in the unmelted rock of the shocked Suizhou L6 chondrite.Natural TiO_(2)-Ⅱ was previously found in ultrahigh-pressure metamorphic and mantle-derived rocks,terrestrial impact structures,and tektite.Our microscopic,Raman spectroscopic,electron microprobe and transmission electron microscopic investigations have revealed:(1) All observed TiO_(2)-Ⅱ grains are related with ilmenite and pyrophanite;(2) TiO_(2)-Ⅱ occurs as needle-and leaf-shaped inclusions in llmenite and patch-,tape-shaped body in pyrophanite;(3)The composition of TiO_(2)-Ⅱ is identical with that of its precursor rutile;(4) The Raman spectrum of TiO_(2)-Ⅱ is in good agreement with that of natural and synthesized α-PbO_(2)-type TiO_(2);(5) TiO_(2)-Ⅱ occurs mainly in the form of well-ordered nano-domains and small mis-orientation among the domains can be observed.(6) All electron diffraction reflections from TiO_(2)-Ⅱ can be indexed to α-PbO_(2)structure in space group Pbcn with lattice parameters of a=4.481 ?,b=5.578 A and c=4.921 A;(7) The exsolution inclusions of rutile from host ilmenite are mostly connected with an alternation process along the lamellar twinning plane of ilmenite induced by shockinduced high pressure and high temperature;(8) The P-T regime of 20-25 GPa and 1000 ℃ estimated for the Suizhou unmelted rock is suitable for phase transition of rutile into TiO_(2)-Ⅱ phase.

Facile synthesis of single-crystalline rutile TiO_2 nano-rods by solution method

A convenient and scalable technique for the synthesis of rutile titanium dioxide(TiO2) nano-rods was presented by using bulk TiO2 powder, sodium hydroxide(NaOH) and distilled water as raw materials. X-ray diffraction(XRD) and field emission scanning electron microscopy(FESEM) studies indicate that the prepared sample is crystalline and free from any impurities, however, it has no distinct shape and possesses a huge degree of agglomeration, and the average crystal size is around 40 nm. After annealing the sample at 600 °C for 2 h, it is observed through FESEM that nano-rods are formed. And XRD analysis shows that the nano-rods are single crystalline with distinct and smooth surfaces in different sizes with average length of about 1 μm and diameter of about 80 nm. Further UV-visible spectroscopy and Raman studies were conducted for the prepared sample and the band gap of the final product is found to be 3.40 eV.

Fabrication and characteristics of rutile TiO_2 nanoparticles induced by laser ablation

The laser ablation technique was employed to prepare TiO2 nanoparticles by pulsed laser ablation of a titanium target immersed in the poly-(vinylpyrrolidone) solution using wavelength of 1 064 nm. The as-prepared products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the rutile TiO2 nanoparticles are synthesized at room temperature and the average size is about 35 nm with narrow size distribution. A possible formation mechanism was discussed and the UV-vis absorption and photoluminescence were measured. The optical study shows that rutile nanoparticle possesses direct optical transition with band gap of 3.15 eV.

Electronic structure and optical properties of rutile RuO_2 from first principles

The systematic trends of electrionic structure and optical properties of rutile （P42/mnm） RuO2 have been cal- culated by using the plane-wave norm-conserving pseudopotential density functional theory （DFT） method within the generalised gradient approximation （GGA） for the exchange-correlation potential. The obtained equilibrium structure parameters are in excellent agreement with the experimental data. The calculated bulk modulus and elastic constants are also in good agreement with the experimental data and available theoretical calculations. Analysis based on elec- tronic structure and pseudogap reveals that the bonding nature in RuO2 is a combination of covalent, ionic and metallic bonds. Based on a Kramers Kronig analysis of the reflectivity, we have obtained the spectral dependence of the real and imaginary parts of the complex dielectric constant （~1 and z2, respectively） and the refractive index （n）; and comparisons have shown that the theoretical results agree well with the experimental data as well. Meanwhile, we have also calculated the absorption coefficient, reflectivity index, electron energy loss function of RuO2 for radiation up to 30 eV. As a result, the predicted reflectivity index is in good agreement with the experimental data at low energies.

Photoinduced Decomposition of Formaldehyde on Rutile TiO2（100）-（1×1）

We have investigated the photoinduced decomposition of formaldehyde （CH2O） on a rutile TiO2（100）-（1×1） surface at 355 nrn using ternperature-prograrnrned desorption. Products, formate （HCOO）, methyl radical （CH3.）, ethylene （C2H4）, and methanol （CH3OH） have been detected. The initial step in the decomposition of CH2O on the futile TiO2（100）-（1×1） surface is the formation of a dioxyrnethylene intermediate in which the carbonyl O atom of CH2O is bound to a Ti atom at the five-fold-coordinated Ti4＋ （Tisc） site and its carbonyl C atom bound to a nearby bridge-bonded oxygen （Oh） atom, respectively. During 355 nrn irradiation, the dioxymethylene intermediate can transfer an H atom to the Ob atom, thus forming HCOO directly, which is considered as the main reaction channel. In addition, the dioxyrnethylene intermediate can also transfer methylene to the Ob row and break the C-O bond, thus leaving the original carbonyl O atom at the Tisc site. After the transfer of methylene, several pathways to products are available. Thus, we have found that Ob atoms are intimately involved in the photoinduced decomposition of CH2O on the futile TiO2 （100）-（1× 1） surface.

Nanostructure of Rutile TiO₂Thin Films Prepared on Unheated Substrate by Dual Cathode DC Unbalanced Magnetron Sputtering

In this work, structural and optical properties of the TiO2 films deposited on unheated substrates by dual cathode dc unbalanced magnetron sputtering at long substrate-target distance (ds-t) were studied. Titanium dioxide (TiO2) thin films were deposited on unheated Si (110) wafers, glass slides and carbon coated copper grids at different substrate to target (ds-t) distances. The structural properties of TiO2 thin films were characterized by X-ray diffraction (XRD) and transmission electron microcopy (TEM) with selected-area electron diffraction (SAED), surface morphology using atomic force microscopy (AFM) and optical transmission spectra using a spectrophotometer. XRD results show that TiO2 films deposited at various ds-t distances have only rutile crystal structure. The crystallinity and thickness of the films increased while the roughness decreased with decreasing ds-t distance. The refractive indices of the deposited films were found to be in the range of 2.51 - 2.82 and increased with decreasing ds-t distance.

Defect-induced ferromagnetism in rutile TiO_2 : A first-principles study

Based on first-principles calculations, the electronic and magnetic properties of undoped and Li-doped rutile TiO2 have been studied. The results demonstrate that a cation vacancy can arouse ferromagnetism in TiO2 and the magnetic moment mainly comes from p orbitals of O atoms around the Ti vacancy. However, the Ti vacancy under normal conditions is very difficult to form due to its high formation energy. Our calculations indicate that Li-doped TiO2 can reduce the formation energy while keeping the magnetism. The large magnetization energy indicates that Li-doped TiO2 is a promising room-temperature diluted magnetic semiconductor.

影响喷雾造粒Al_2O_3/nano-TiO_2复合陶瓷粉体流动特性的流变学因素研究

本文研究了分散剂、粘结剂及固相含量等流变学因素对喷雾造粒粉体流动性的影响。结果表明 ,Al2 O3 3wt.%nano TiO2 浆料具有剪切变稀的特性 ,有利于复合陶瓷粉体的喷雾造粒。当固相含量为浆料总质量的6 0 % ,分散剂和粘结剂分别为固相质量的 0 3%和 1 0 %时 ,浆料具有合适的粘度和最佳的分散稳定性 ,喷雾造粒所得到的粉体形状为球形或近球形 ,具有较高的松装密度和良好的流动性 ,满足用于热喷涂的需要。

PS/弹性体/Nano-TiO2复合材料形态及力学性能

采用熔融共混法制备PS/弹性体/nano-TiO2复合材料,利用扫描电子显微镜（SEM）观察材料刻蚀断面和冲击断面的形貌,电子万能拉伸试验机及组合冲击试验机分别表征材料的拉伸和冲击性能,研究对比PS/SEBS/nano-TiO2和PS/SEBS-g-MAH/nano-TiO2复合材料的形态及力学性能.结果表明：PS/SEBS/nano-TiO2复合材料刻蚀断面的分散相SEBS粒径在0.6～1.4 μm之间,而PS/SEBS-g-M AH/nano-TiO2复合材料分散相SEBS-g-MAH粒径显著减小,在0.5 μm以下.与PS/SEBS/nano-TiO2复合材料相比,PS/SEBS-g-MAH/nano-TiO2复合材料的拉伸强度降低幅度减弱,在弹性体质量分数为16％时缺口冲击强度提高20％.复合材料冲击断面显示SEBS-g-MAH粒子比SEBS粒子更细微、更均匀地分散在PS基体中.

谷胱甘肽在nano-TiO_2-咖啡酸复合修饰碳糊电极上的电催化氧化及电分析方法

研究了还原型谷胱甘肽(GSH)在nano-TiO2-咖啡酸(CFA)复合修饰碳糊电极(nano-TiO2-CFA/CPE)上的电催化氧化行为,并进行了测定。结果表明,GSH在CPE和nano-TiO2/CPE上的直接电化学氧化过程十分迟缓,nano-TiO2-CFA/CPE比CFA/CPE对GSH的电化学氧化具有更好的催化作用。采用循环伏安法(CV)、计时电流法(CA)探讨了GSH在nano-TiO2-CFA/CPE上的电极过程动力学性质。用线性扫描伏安法(LSV)测得催化氧化峰电流与GSH的浓度在9.0×10-6～1.0×10-3 mol.L-1范围内呈良好线性,检出限为8.85×10-7 mol.L-1。将该方法用于市售还原型谷胱甘肽药物含量的测定,结果满意。

新型CNT／nano-TiO2复合膜电极的制备及其异相电催化性能

采用溶胶-凝胶法制备了碳纳米管/纳米TiO2(CNT/nano-TiO2)复合溶胶,通过提拉法将复合溶胶涂覆在Ti基体上制得CNT/nano-TiO2复合膜修饰电极(C电极),其电化学性能经循环伏安、计时库仑、交流阻抗谱(EIS)等方法研究。研究结果表明,CNT可阻碍nano-TiO2粒子团聚。在循环伏安图中,C电极的氧化还原峰电流比nano-TiO2膜修饰电极(P电极)的高出两倍多。通过对草酸溶液的异相电催化反应进一步证明C电极比P电极具有更高的电催化活性,而且对双氧水也有很强的异相电催化还原能力。

痕量Pb^(2+)在nano-TiO_2膜电极上的电化学行为及应用研究

利用纳米二氧化钛(nano-TiO2)的结构特性制备了一种nano-TiO2膜修饰的玻碳电极。采用阳极溶出伏安法详细研究了Pb2+在nano-TiO2膜修饰玻碳电极上的电化学响应行为,并对各种实验参数进行了优化。实验结果表明,在0.10 mol/L HAc-NaAc缓冲体系(pH 4.0)中,于-1.2 V富集搅拌480 s,再静置60 s后阳极化扫描,Pb2+在-0.48 V左右出现一灵敏的阳极溶出峰。Pb2+的溶出峰电流与其浓度在2.0×10-9~1.0×10-7mol/L范围内呈良好的线性关系,检出限可达1.0×10-10mol/L。该修饰电极具有一定的抗干扰能力,将其应用于实际水样中Pb2+的检测,结果令人满意。

家电用HIPS/nano-TiO_2多功能复合材料的性能

研究了家电用HIPS/nano TiO2 多功能复合塑料的加工流变性、母料分散性、吸光行为、抗菌、分解内毒素、分解异味气体及自清洁特性。结果表明 ,使用质量分数在0 5 %～ 2 0 %的nano TiO2 的复合材料加工流动性优于HIPS ;经EVA蜡改性的HIPS/nano TiO2 母料可得到良好分散效果 ;HIPS/nano TiO2 制品表现出良好的紫外吸收能力 ,nano TiO2 质量分数在 1 .0 %左右时 ,制品具有较好的抗菌、分解内毒素效果。