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.

早期CO_(2)养护与Nano-TiO_(2)协同作用下低热水泥基浆体的力学性能

为探究早期CO_(2)养护和纳米TiO_(2)(nano-TiO_(2),NT)协同作用对低热硅酸盐水泥(low-heat portland cement, LHPC)力学性能的影响规律,测试了不同CO_(2)养护时间和NT掺量下LHPC的抗折、抗压强度,并结合扫描电镜、热重分析等测试结果分析其对力学性能的协同作用机制。结果表明:仅考虑掺入NT或CO_(2)养护,NT掺量或CO_(2)养护时间均存在最佳范围。CO_(2)养护与NT协同作用下,CO_(2)养护24 h内,LHPC浆体在14 d和28 d龄期的抗压、抗折强度分别在NT掺量为1%~1.5%和1.5%~2%时提升幅度大,这归因于试样中水化硅酸钙凝胶(C-S-H)、钙矾石(AFt)和CaCO_(3)质量增加,长径比较小的纤维状C-S-H细化了大于50 nm的孔径。而CO_(2)养护超过24 h、NT掺量大于2%时,试样中孔隙数量增加、较大长径比的晶须状文石和微观裂缝的产生降低了力学性能。综合力学强度和经济性,建议CO_(2)养护时间为12 h, NT掺量为1%。研究结果为提升LHPC早期力学性能提供一定的参考依据。

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.

TBOEP和nano-TiO_(2)联合暴露诱导对土著鲫鱼的复合繁殖毒性效应

本研究以土著鲫鱼为受试生物,选择应用最为广泛的纳米二氧化钛(nano-TiO_(2))以及有机磷阻燃剂的典型代表磷酸三-(2-丁氧基)乙酯(TBOEP)作为暴露污染物,系统地研究nano-TiO_(2)与TBOEPP复合暴露对鲫鱼生殖系统的影响。实验设置空白对照组、0.05μg/L与0.5μg/L TBOEP暴露组0.5 mg/L nano-TiO_(2)暴露组以及TBOEP 0.05μg/L+nano-TiO_(2)0.5 mg/L、TBOEP 0.5μg/L+nano-TiO_(2)0.5 mg/L复合暴露组,暴露时间为7 d。研究结果表明:TBOEP能够在鲫鱼的组织中积累且nano-TiO_(2)能够加强TBOEP的生物累积。另外,TBOEP干扰鲫鱼血清中睾酮与雌二醇的水平,并造成鲫鱼下丘脑-垂体-性腺轴(HPG)基因异常表达,nano-TiO_(2)能够显著增强TBOEP对于鲫鱼性激素的干扰作用,加剧TBOEP对鲫鱼的繁殖毒性。

潮湿环境下金红石型纳米TiO_(2)掺杂聚乙烯的分子动力学模拟

为了从微观角度分析金红石型纳米TiO_(2)掺杂对聚乙烯(polyethylene,PE)材料性能的影响,采用分子动力学模拟方法,构建不同水分子质量分数的PE和TiO_(2)/PE复合模型,以温度为变量研究分析纳米TiO_(2)改性PE材料前后的热力学性能和微观结构以及水分子在复合体系中的扩散能力。结果表明:纳米TiO_(2)的掺杂使PE体系的玻璃化转变温度提高了33 K,杨氏模量提升了428.17%,剪切模量提升了338.62%。纳米TiO_(2)极大抑制了PE分子链的运动和水分子的扩散,增强了复合体系的稳定性。水分子的加入和温度的升高降低了复合体系的热力学性能,这两者均破坏了复合体系的稳定性。

Cu-BTC/nano-TiO_(2)的制备及其可见光催化性能

采用水热法制备了有机金属框架材料Cu-BTC,利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、比表面积分析仪(BET)等手段对Cu-BTC的微观结构和性能进行了表征,研究了Cu-BTC与nano-TiO_(2)混合后对染料(罗丹明B(RhB)、亚甲基蓝(MB)和刚果红(CR))吸附性能和光催化降解性能的影响。结果表明:Cu-BTC呈现典型的正八面体结构,比表面积高达935.44 m^(2)/g;引入nano-TiO_(2)后,混合材料对染料的吸附和光催化性能均有提升,当Cu-BTC和nano-TiO_(2)的质量比为3∶1时,240 min紫外光照后,RhB溶液的光催化降解效率达79.53%,对MB和CR的降解效率分别为94.66%和99.41%;同时,混合材料有较好的循环使用性能,3次循环使用后对MB和CR的降解效率仍保持在90.81%和97.60%以上。

STUDY ON THE SURFACE MODIFICATION OF NANO-TiO_2 BY GRAFTING PMMA/PBMA AND ITS THERMAL STABILITY

The surface of nano-TiO_2 was encapsulated with hydroxyl-propyl-methyl cellulose(HPMC),and then cograftedwith acrylates.Conditions of absorbing and grafting have been studied.Modified nano-TiO_2 particles were characterized byFT-IR spectra,TEM and TG analysis.It was convinced from FT-IR studies that both methyl methacrylate(MMA)and butyl-methacrylate(BMA)were co-grafted onto the surface of nano-TiO_2 particles.TEM images show that the surface of nano-TiO_2 particles was successfully modified by a thick layer of film-like polymer.TG results demonstrate that the decompositiontemperature of HPMC-g-PMMA/PBMA,which has been grafted onto the surface of nano-TiO_2,is 56.9 K higher than that ofHPMC-g-PMMA/PBMA.

Preparation of Nano-TiO_2 by Liquid Hydrolysis and Characterization of Its Antibacterial Activity

The nano-TiO_2 particles were prepared by liquid hydrolysis method and characterized using XRD. Its antibacterial activity against two representative bacterial, Escherichia eoli and Staphylococcus aureus, was also studied. The experimental results showed that the nano-TiO_2 caleinated at 600-700℃ contained the obvious anatase phase and exerted exeeUent antibacterial activity. The feature of antibacterial activity of nano- TiO_2 was non-strains specificity and exerted best antibacterial activity at concentration of 0.8 g/L.