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1.
A Fluorite Isotype of SnO2 and a New Modification of TiO2: Implications for the Earth's Lower Mantle
Liu LG 《Science (New York, N.Y.)》1978,199(4327):422-425
The existence of a cubic fluorite-type SnO(2) and a hexagonal TiO(2) (which may be related to the fluorite structure) have been demonstrated by an in situ x-ray diffraction study in which a diamond-anvil pressure cell was used after the samples had been heated by a continuous yttrium-aluminum-garnet laser. At room temperature, the lattice parameter for SnO(2) (fluorite) is a = 4.925 +/- 0.005 angstroms and those for TiO(2) (fluorite-related) are a = 9.22 +/- 0.01 angstroms and c = 5.685 +/- 0.006 angstroms at about 250 kilobars. The volume change associated with the transition from rutile to fluorite (or related structure) is about -8 percent for SnO(2) and -10.5 percent for TiO(2) at transition. Upon release of pressure, both the fluorite-type SnO(2) and the TiO(2) reverted to the alpha-PbO(2) structure at room temperature. The hypothesis that the earth's lower mantle is composed of oxide phases might be feasible if it were possible for SiO(2) to possess the fluorite structure or its related forms at high pressure, as shown for SnO(2) and TiO(2) in this study. The oxide hypothesis proposed here differs from that postulated by Birch in that the primary coordination of silicon is 6 for Birch's hypothesis and 8 for the hypothesis presented here. 相似文献
2.
El Goresy A Chen M Dubrovinsky L Gillet P Graup G 《Science (New York, N.Y.)》2001,293(5534):1467-1470
We report the discovery of an ultradense post-rutile polymorph of titanium dioxide in shocked gneisses of the Ries crater in Germany. The microscopic diagnostic feature is intense blue internal reflections in crossed polarizers in reflected light. X-ray diffraction studies revealed a monoclinic lattice, isostructural with the baddeleyite ZrO2 polymorph, and the titanium cation is coordinated with seven oxygen anions. The cell parameters are as follows: a = 4.606(2) angstroms, b = 4.986(3) angstroms, c = 4.933(3) angstroms, beta (angle between c and a axes) = 99.17(6) degrees; space group P2(1)/c; density = 4.72 grams per cubic centimeter, where the numbers in parentheses are standard deviations in the last significant digits. This phase is 11% denser than rutile. The mineral is sensitive to x-ray irradiation and tends to invert to rutile. The presence of baddeleyite-type TiO2 in the shocked rocks indicates that the peak shock pressure was between 16 and 20 gigapascals, and the post-shock temperature was much lower than 500 degrees C. 相似文献
3.
Sato H Endo S Sugiyama M Kikegawa T Shimomura O Kusaba K 《Science (New York, N.Y.)》1991,251(4995):786-788
A high-pressure phase of TiO(2), which had been observed by shock-wave experiments and remained unresolved, has been studied by in situ x-ray diffraction. The single phase was formed at 20 gigapascals and 770 degrees C with the use of sintered-diamond multianvils; it has the same structure as baddeleyite, the stable phase of ZrO(2) at ambient conditions. The coordination number of Ti increases from six to seven across the rutile to baddeleyite transition, and the volume is reduced by approximately 9 percent. 相似文献
4.
Silica (SiO2) exhibits extensive polymorphism at elevated pressures. X-ray diffraction measurements showed that a high-pressure form with a pyrite-type structure, denser than other known silica phases, is stable above 268 giga-pascals and 1800 kelvin. The silicon coordination number increases from 6 in the alpha-PbO2-type phase to 6+2 in the pyrite-type phase, leading to a large increase in density by about 5% at the phase transition. 相似文献
5.
Fe^3＋掺杂纳米TiO2的表征及其光催化性能的研究 总被引：1，自引：0，他引：1
[目的]提高TiO2的可见光响应和光催化活性。[方法]采用溶胶凝胶法制备掺铁纳米TiO2粉体,进而研究掺铁TiO2的光催化活性。[结果]450℃煅烧后掺铁TiO2出现了很明显的TiO2特征衍射峰,且峰形尖锐,结晶良好,均没有出现铁的掺杂新相。随着掺铁量的提高,TiO2的粒径逐渐减小,当掺杂量为0.4%时,TiO2的粒径最小,减少至纯TiO2的45%。掺铁抑制了锐钛矿向金红石矿的转变。随着焙烧温度的升高,TiO2的粒径逐渐增大。用溶胶-凝胶法制备的TiO2均为纳米级,基本成球形颗粒。纯TiO2粒子分布不是很均匀,团聚现象明显;掺铁TiO2颗粒分布均匀,没有明显的团聚现象。掺铁使TiO2在紫外灯和太阳光下的降解性能都有着不同程度的提高。[结论]溶胶-凝胶法制备的掺铁纳米TiO2细化了晶体晶粒,抑制了锐钛矿向金红石矿的转变。 相似文献
6.
利用溶胶-凝胶技术制备了TiO2纳米晶和掺杂Eu3+的TiO2纳米晶,测试了样品的X射线谱(XRD)和荧光光谱(PL),研究了不同煅烧温度下,TiO2:Eu3+的发光性质.Eu3+离子的掺入能抑制TiO2由锐钛矿相向金红石相的转变,464nm的激发波长对发射最有利,578nm处存在自吸收,随着退火温度增高,TiO2:Eu3+样品稀土发光强度下降. 相似文献
7.
Schaub R Wahlström E Rønnau A Lagsgaard E Stensgaard I Besenbacher F 《Science (New York, N.Y.)》2003,299(5605):377-379
Defects such as oxygen vacancies play a crucial role in the surface properties of transition metal oxides. By means of time-resolved, high-resolution scanning tunneling microscopy, we unraveled an adsorbate-mediated diffusion mechanism of oxygen vacancies on rutile TiO2(110). Adsorbed oxygen molecules mediate vacancy diffusion through the loss of an oxygen atom to a vacancy and the sequential capture of an oxygen atom from a neighboring bridging oxygen row, leading to an anisotropic oxygen vacancy diffusion pathway perpendicular to the bridging oxygen rows. 相似文献
8.
The Hugoniot of the rutile phase of titanium dioxide has been determined to 1.25 megabars, and data show the existence of a phase change at about 0.33 megabar. The volume decrease associated with this transformation appears to be quite large (approximately 21 percent). Rutile, when recovered from shockloading in excess of the transformation pressure, is found to be irreversibly transformed to the orthorhombic lead dioxide structure (a distortion of the fluorite structure) with parameters a, 4.529; b, 5.464; and c, 4.905 angstroms and a calculated density of 4.374 grams per cubic centimeter. The new phase reverts to rutile at temperatures above 450 degrees C. It is suggested that the new phase may be another diagnostic indicator of meteorite impact on the earth's surface. 相似文献
9.
Although n-type titanium dioxide (TiO2) is a promising substrate for photogeneration of hydrogen from water, most attempts at doping this material so that it absorbs light in the visible region of the solar spectrum have met with limited success. We synthesized a chemically modified n-type TiO2 by controlled combustion of Ti metal in a natural gas flame. This material, in which carbon substitutes for some of the lattice oxygen atoms, absorbs light at wavelengths below 535 nanometers and has a lower band-gap energy than rutile (2.32 versus 3.00 electron volts). At an applied potential of 0.3 volt, chemically modified n-type TiO2 performs water splitting with a total conversion efficiency of 11% and a maximum photoconversion efficiency of 8.35% when illuminated at 40 milliwatts per square centimeter. The latter value compares favorably with a maximum photoconversion efficiency of 1% for n-type TiO2 biased at 0.6 volt. 相似文献
10.
Wahlström E Vestergaard EK Schaub R Rønnau A Vestergaard M Laegsgaard E Stensgaard I Besenbacher F 《Science (New York, N.Y.)》2004,303(5657):511-513
Diffusion of oxygen molecules on transition metal oxide surfaces plays a vital role for the understanding of catalysis and photocatalysis on these materials. By means of time-resolved scanning tunneling microscopy, we provide evidence for a charge transfer-induced diffusion mechanism for O2 molecules adsorbed on a rutile TiO2(110) surface. The O2 hopping rate depended on the number of surface donors (oxygen vacancies), which determines the density of conduction band electrons. These results may have implications for the understanding of oxidation processes on metal oxides in general. 相似文献
11.
Wet electrons at the H2O/TiO2(110) surface 总被引：1，自引：0，他引：1
At interfaces of metal oxide and water, partially hydrated or "wet-electron" states represent the lowest energy pathway for electron transfer. We studied the photoinduced electron transfer at the H2O/TiO2(110) interface by means of time-resolved two-photon photoemission spectroscopy and electronic structure theory. At approximately 1-monolayer coverage of water on partially hydroxylated TiO2 surfaces, we found an unoccupied electronic state 2.4 electron volts above the Fermi level. Density functional theory shows this to be a wet-electron state analogous to that reported in water clusters and which is distinct from hydrated electrons observed on water-covered metal surfaces. The decay of electrons from the wet-electron state to the conduction band of TiO2 occurs in 相似文献
12.
Results show that PuO(2+x), a high-composition (x 相似文献
13.
Newton RC 《Science (New York, N.Y.)》1966,153(3732):170-172
The metastable kyaniteandalusite equilibrium in the Al(2)SiO(5) system has been reversed at 700 degrees , 750 degrees , and 800 degrees C at elevated water pressures, with a variety of natural and synthetic kyanites and andalusites as starting materials. Sillimanite, the stable form of Al(2)SiO(5) under these conditions, did not appear. The value of the transition pressure at 750 degrees C is 6.6 +/- 0.4 kilobars, several kilobars below pressures given by several convergent previous determinations. The Al(2)SiO(5) pressure-temperature triple point now indicated lies far from the points found by others. The revised aluminum silicate phase diagram indicates that many rocks crystallized at lower pressures than formerly thought possible. 相似文献
14.
Polychalcogenide compounds with open polymeric frameworks are rare, and they represent a class of compounds in which microporosity might be achieved. Microporous frameworks that are not oxide-based are now attracting interest because of the combination of catalytic and electronic properties they may simultaneously possess. Three new compounds that may be forerunners to such materials have been discovered and are reported here. The reaction of gallium (Ga), indium (In), and thallium (TI) metal with (Ph(4)P)(2)Se(5) (Ph, phenyl) and an excess of elemental selenium (Se) in a sealed, evacuated Pyrex tube at 200 degrees C yielded small red crystals of (Ph(4)P)[Ga(Se(6))(2)] (I), (Ph(4)P)[In(Se(6))(2)] (II), and (Ph(4)P)[TI(Se(6))(2)] (III), respectively. The [M(Se(6))(2)](-) (M = Ga, In, TI) ions form a two-dimensional, open framework filled with Ph(4)P(+) ions. The [M(Se(6))(2)](n)(n-) structure consists of tetrahedral M(3+) centers and bridging Se(6)(2-) ligands, leading to an extended structure in two dimensions. These layers stack perfectly one on top of the other giving rise to one-dimensional channels running down the c axis that are filled with Ph(4)P(+) cations. These cations are situated in the layers, as opposed to between the layers, and the whole structure can be viewed as a template. Compound II shows remarkable thermal stability and melts congruently at 242 degrees C. Upon cooling to room temperature it gives a glassy phase that recrystallizes upon subsequent heating to 160 degrees C. 相似文献
15.
The single-crystal elastic moduli of the modified spinel structure (beta phase) of magnesium orthosilicate (Mg(2)SiO(4)) have been measured by Brillouin spectroscopy under ambient conditions. Single crystals with dimensions up to 500 micrometers were grown at 22 gigapascals and 2000 degrees C over a period of 1 hour. Growth of crystals larger than 100 micrometers was achieved only when the pressure was within 5 percent of the pressure of the phase boundary separating the beta- and gamma-phase stability fields. A comparison of the elastic properties of the modified spinel phase with those of the olivine phase suggests that the 400-kilometer seismic discontinuity in the earth's mantle can be described by a mantle with 40 percent olivine. These results confirm that the 400-kilometer discontinuity can be due to the transition from olivine to modified spinel. The amount of olivine that must be present is less than that in a pyrolite model, although the results do not exclude pyrolite as a possible mantle model. 相似文献
16.
采用溶剂热法合成了MIL-53(Al),以此为载体负载TiO_2制备得到TiO_2/MIL-53(Al)光催化剂用于污水中次甲基蓝的催化降解研究,并与传统载体材料Al_2O_3负载的TiO_2催化剂的光催化效果进行比较。样品通过热重-差热扫描量热(TG-DSC)、红外光谱(FTIR)、扫描电镜(SEM)、X射线衍射(XRD)、N_2物理吸附-脱附等方法进行表征。采用光度吸收法分析污水中次甲基蓝的降解率,结果显示,TiO_2/MIL-53(Al)光催化剂对次甲基蓝的光催化降解率达到98.6%,而TiO_2/Al_2O_3光催化剂对次甲基蓝的降解率只有70.3%,TiO_2/MIL-53(Al)光催化剂对污水中次甲基蓝的降解去除能力明显优于TiO_2/Al_2O_3光催化剂对次甲基蓝的降解去除能力。 相似文献
17.
Matthey D Wang JG Wendt S Matthiesen J Schaub R Laegsgaard E Hammer B Besenbacher F 《Science (New York, N.Y.)》2007,315(5819):1692-1696
We studied the nucleation of gold clusters on TiO2(110) surfaces in three different oxidation states by high-resolution scanning tunneling microscopy. The three TiO2(110) supports chosen were (i) reduced (having bridging oxygen vacancies), (ii) hydrated (having bridging hydroxyl groups), and (iii) oxidized (having oxygen adatoms). At room temperature, gold nanoclusters nucleate homogeneously on the terraces of the reduced and oxidized supports, whereas on the hydrated TiO2(110) surface, clusters form preferentially at the step edges. From interplay with density functional theory calculations, we identified two different gold-TiO2(110) adhesion mechanisms for the reduced and oxidized supports. The adhesion of gold clusters is strongest on the oxidized support, and the implications of this finding for catalytic applications are discussed. 相似文献
18.
Hydrogen becomes a solid at 25 degrees C when subjected to a pressure of 57 kilobars. The high-pressure phase appears as a transparent crystalline mass. The refractive index of the high-pressure phase increases sharply with pressure, indicating a density increase of similar magnitude. At 360 kilobars the calculated density of the high-pressure phase is 0.6 to 0.7 grams per cubic centimeter. 相似文献
19.
Merte LR Peng G Bechstein R Rieboldt F Farberow CA Grabow LC Kudernatsch W Wendt S Lægsgaard E Mavrikakis M Besenbacher F 《Science (New York, N.Y.)》2012,336(6083):889-893
The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H(3)O(+)-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO(2)(110), where water dissociation is a key step in proton diffusion. 相似文献
20.
Shibata N Goto A Choi SY Mizoguchi T Findlay SD Yamamoto T Ikuhara Y 《Science (New York, N.Y.)》2008,322(5901):570-573
Determining the atomic structures of oxide surfaces is critical for understanding their physical and chemical properties but also challenging because the breaking of atomic bonds in the formation of the surface termination can involve complex reconstructions. We used advanced transmission electron microscopy to directly observe the atomic structure of reduced titania (TiO2) (110) surfaces from directions parallel to the surface. In our direct atomic-resolution images, reconstructed titanium atoms at the top surface layer are clearly imaged and are found to occupy the interstitial sites of the TiO2 structure. Combining observations from two orthogonal directions, the three-dimensional positioning of the Ti interstitials is identified at atomic dimensions and allows a resolution of two previous models that differ in their oxygen stoichiometries. 相似文献