Spectroscopic observation of dual catalytic sites during oxidation of CO on a Au/TiO₂ catalyst

The prevailing view of CO oxidation on gold-titanium oxide (Au/TiO(2)) catalysts is that the reaction occurs on metal sites at the Au/TiO(2) interface. We observed dual catalytic sites at the perimeter of 3-nanometer Au particles supported on TiO(2) during CO oxidation. Infrared-kinetic measurements indicate that O-O bond scission is activated by the formation of a CO-O(2) complex at dual Ti-Au sites at the Au/TiO(2) interface. Density functional theory calculations, which provide the activation barriers for the formation and bond scission of the CO-O(2) complex, confirm this model as well as the measured apparent activation energy of 0.16 electron volt. The observation of sequential delivery and reaction of CO first from TiO(2) sites and then from Au sites indicates that catalytic activity occurs at the perimeter of Au nanoparticles.     

掺镍TiO2的微波合成及催化降解有机废水

以氯化镍和硫酸钛为原料,以十二烷基硫酸钠为表面活性剂,通过直接投料微波合成了掺镍二氧化钛(Ni2+TiO2).以催化降解甲基橙为模型来考察其可见光光催化活性,研究了Ni的掺杂量、热处理温度、双氧水投加量、溶液酸度及掺Ni2+TiO2光催化剂用量等因素对光催化性能的影响.结果表明,当Ni2+/TiO2复合物的直接投料摩尔比为0.8％,在500℃的温度下热处理2h,催化剂用量为1.0 g/L,H2O2投加量为3 mL/L,溶液pH 5的条件下,可见光催化效果最好,此时2 mg/L的甲基橙溶液经光催化降解40min后,降解率达到94.5％.     

Efficient tandem polymer solar cells fabricated by all-solution processing

Tandem solar cells, in which two solar cells with different absorption characteristics are linked to use a wider range of the solar spectrum, were fabricated with each layer processed from solution with the use of bulk heterojunction materials comprising semiconducting polymers and fullerene derivatives. A transparent titanium oxide (TiO(x)) layer separates and connects the front cell and the back cell. The TiO(x) layer serves as an electron transport and collecting layer for the first cell and as a stable foundation that enables the fabrication of the second cell to complete the tandem cell architecture. We use an inverted structure with the low band-gap polymer-fullerene composite as the charge-separating layer in the front cell and the high band-gap polymer composite as that in the back cell. Power-conversion efficiencies of more than 6% were achieved at illuminations of 200 milliwatts per square centimeter.     

Nanometer-size alpha-PbO(2)-type TiO(2) in garnet: A thermobarometer for ultrahigh-pressure metamorphism

A high-pressure phase of titanium dioxide (TiO(2)) with an alpha-PbO(2)-type structure has been identified in garnet of diamondiferous quartzofeldspathic rocks from the Saxonian Erzgebirge, Germany. Analytical electron microscopy indicates that this alpha-PbO(2)-type TiO(2) occurred as an epitaxial nanometer-thick slab between twinned rutile bicrystals. Given a V-shaped curve for the equilibrium phase boundary of alpha-PbO(2)-type TiO(2) to rutile, the stabilization pressure of alpha-PbO(2)-type TiO(2) should be 4 to 5 gigapascals at 900 degrees to 1000 degrees C. This suggests a burial of continental crustal rocks to depths of at least 130 kilometers. The alpha-PbO(2)-type TiO(2) may be a useful pressure and temperature indicator in the diamond stability field.     

可见光响应氮杂化TiO2-N薄膜对水源水体的杀菌作用

以尿素为氮源,采用Sol-gel法及浸渍-提拉法制备氮杂化TiO2-N薄膜,并运用正交试验法优化TiO2-N薄膜的最佳制备条件;利用AFM分析技术对TiO2-N薄膜表面形貌进行表征;在太阳光光催化反应器中,探讨TiO2-N薄膜对饮用水供水水源水体中大肠菌群的杀菌作用。结果表明,热处理条件是影响TiO2-N薄膜制备的关键因素,各个影响因素的主次顺序为热处理温度〉停留温度〉热处理时间,在最佳条件下制备的TiO2-N薄膜,在太阳光作用下光解30min时,对饮用水供水水源水体中大肠菌群的杀菌率达到57.7%以上;Ag的协同掺杂（Ag-TiO2-N）或在TiO2-N薄膜表面的沉积（Ag/TiO2-N）,显著提高了TiO2-N薄膜的杀菌作用,对大肠菌群的杀菌率可达90%以上。     

金属掺杂TiO_2对中药渣裂解油特性的影响

以Ni、Fe、Co等3种不同金属掺杂的TiO2介孔材料作催化剂对中药渣进行催化裂解,研究不同催化剂对生物油产率及油品的影响,采用热值分析和气质联用(GC-MS)分析裂解油的特性,利用N2吸附-脱附对催化剂进行表征。研究表明,Ni/TiO2的催化效果优于Fe/TiO2和Co/TiO2,Ni/TiO2作催化剂时,裂解油中脂肪烃和烷基苯的种数最多,且其中与汽油或柴油相近的组分占大多数,而芳香族化合物数量明显较少。在Ni/TiO2的催化作用下,大分子中的氧多以H2O分子的形式脱去,因而生物油中含水率较高,导致其热值降低。     

纳米TiO_2与活性炭纤维复合材料降低室内污染物(Ⅰ)——纳米TiO_2气凝胶的制备

为了获得具有网络结构和纳米级粒子的TiO2光催化材料,使之负载到活性炭纤维(ACF)上,并在紫外光的作用下,达到有效降低室内空气中污染物的目的,以钛酸丁酯(Ti(OC4H9)4为原料,乙酸和乙酰丙酮为水解催化剂,利用Sol-Gel方法制备凝胶,并利用超临界流体干燥手段制备TiO2气凝胶.溶胶-凝胶反应溶液的配比为Ti(OR)4∶ EtOH∶ H2O∶ AcOR∶ ACACH=20∶ 40∶ 5∶ 0.2∶ 2(体积比,mL),可在120min左右得到醇凝胶.将醇凝胶置于-21℃条件下陈化1～3d,然后在12h内自然升温至室温,24h内置于超临界流体中进行干燥,可以得到具有纳米结构的TiO2气凝胶.该气凝胶可用于制备ACF/TiO2复合材料.     

TiO2/MIL-53(Al)和TiO2/Al2O3催化剂的制备及其光催化性能研究

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。     

二氧化钛/酞菁镁可见光催化降解的研究

[目的]研究与比较TiO2多项光催化降解,通过敏化剂与纳米TiO2复合来提高光催化剂的稳定性能。[方法]以酞酸正丁酯为原料,采用溶胶-凝胶法制备纳米TiO2光催化剂,然后再按一定的比例与酞菁镁（Mgpc）复合,制得TiO2/酞菁镁复合粉末,并通过亚甲基蓝溶液在可见光作用下的光催化降解,研究纳米TiO2/Mgpc复合催化剂粉末的光催化活性,考察了其催化性能。[结果]采用TiO2为催化剂可显著加快光催化氧化过程。采用酞菁镁敏化纳米TiO2制备的可见光催化剂,证实在可见光下,敏化与未敏化的TiO2相比,TiO2/Mgpc（1%）具有较强的可见光催化性能,TiO2/Mgpc复合粉末对亚甲基蓝的降解率已达36.2%,而未敏化的只达28.7%。[结论]TiO2与Mgpc的复合有利于不同能级之间光生载流子的输送和分离,提高系统的电荷分离效果,扩展其光谱响应范围,提高太阳光的利用率。     

水杨酸分子印迹掺氮TiO_2粉末的制备及在可见光下的选择性光催化研究

【目的】改善TiO_2在可见光下对污染物的选择性降解能力。【方法】采用改进的分子印迹溶胶-凝胶技术,以尿素、水杨酸分别为氮源和模板分子,制备水杨酸分子印迹掺氮TiO_2粉末。通过X射线衍射(XRD)、透射电镜(TEM)、紫外-可见光漫反射吸收光谱(UV-Vis DRS)和低温N_2物理吸附-脱附(BET)等技术对制备样品进行表征。【结果】样品均为锐钛矿相,氮掺杂致使TiO_2光吸收带边红移,分子印迹使TiO_2具有了更为发达的孔结构和孔型,掺杂和分子印迹均有效地增大了比表面积。可见光下,与催化降解苯甲酸及甲基橙相比,分子印迹掺氮TiO_2对水杨酸的选择性降解率较高,达96.0%。【结论】水杨酸分子印迹和氮掺杂有效地改善了TiO_2的选择性和可见光活性。     

Efficient photochemical water splitting by a chemically modified n-TiO2

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.     

The role of interstitial sites in the Ti3d defect state in the band gap of titania

Titanium dioxide (TiO2) has a number of uses in catalysis, photochemistry, and sensing that are linked to the reducibility of the oxide. Usually, bridging oxygen (Obr) vacancies are assumed to cause the Ti3d defect state in the band gap of rutile TiO2(110). From high-resolution scanning tunneling microscopy and photoelectron spectroscopy measurements, we propose that Ti interstitials in the near-surface region may be largely responsible for the defect state in the band gap. We argue that these donor-specific sites play a key role in and may dictate the ensuing surface chemistry, such as providing the electronic charge required for O2 adsorption and dissociation. Specifically, we identified a second O2 dissociation channel that occurs within the Ti troughs in addition to the O2 dissociation channel in O(br) vacancies. Comprehensive density functional theory calculations support these experimental observations.     

碱/酸两步催化法制备的“核—壳”SiO_2-TiO_2纳米材料及其光催化特性

以正硅酸乙酯(TEOS)为前驱体,以氨水为催化剂,制得含有SiO_2粒子的碱催化SiO_2溶胶;向碱催化SiO_2溶胶中加入前驱体钛酸丁酯(TBOT)和酸催化剂盐酸,得到以SiO_2粒子为核和以TiO_2为壳的"核—壳"SiO_2-TiO_2纳米材料.结果表明:SiO_2核的粒径约为13.5 nm;随着钛酸丁酯添加量的增加,SiO_2核表面不断有TiO_2壳形成,其粒径从13.5 nm增大至24.4 nm.XRD测定结果表明煅烧温度为500℃时,锐钛矿TiO_2的特征衍射峰明显增强.该温度下"核—壳"SiO_2-TiO_2复合粉末对罗丹明B的降解率从21.99%提高到94.86%.     

竹活性炭比表面积及其孔径对TiO_2/BAC光催化降解甲醛性能的影响

[目的]研究竹活性炭比表面积及其孔径对TiO2/BAC光催化降解甲醛性能的影响。[方法]以竹子为原料,按照不同浸渍比,用磷酸活化法制备不同孔径和比表面积的系列竹活性炭（BAC）作为载体;通过溶胶凝胶法制备负载型光催化剂（TiO2/BAC）,以水溶液中的甲醛作为目标污染物,考察所得的一系列负载型光催化剂的光催化性能;采用氮气吸附、SEM进行表征,研究了竹活性炭的孔径和比表面积对负载型光催化剂性能的影响。[结果]竹活性炭吸附和TiO2光解的协同效应使TiO2/BAC光催化剂对水溶液中甲醛的处理效率显著提高;比表面积较大、微孔较多、平均孔径为2~3 nm的竹活性炭有利于TiO2的负载,制备得到的复合光催化活性较高。[结论]为TiO2光催化剂的固化负载研究提供了理论依据。     

A Fluorite Isotype of SnO2 and a New Modification of TiO2: Implications for the Earth's Lower Mantle

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.     

Wet electrons at the H2O/TiO2(110) surface

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   

Multiple exciton collection in a sensitized photovoltaic system

Multiple exciton generation, the creation of two electron-hole pairs from one high-energy photon, is well established in bulk semiconductors, but assessments of the efficiency of this effect remain controversial in quantum-confined systems like semiconductor nanocrystals. We used a photoelectrochemical system composed of PbS nanocrystals chemically bound to TiO(2) single crystals to demonstrate the collection of photocurrents with quantum yields greater than one electron per photon. The strong electronic coupling and favorable energy level alignment between PbS nanocrystals and bulk TiO(2) facilitate extraction of multiple excitons more quickly than they recombine, as well as collection of hot electrons from higher quantum dot excited states. Our results have implications for increasing the efficiency of photovoltaic devices by avoiding losses resulting from the thermalization of photogenerated carriers.     

木质基g-C3N4/TiO2复合涂层的制备及光催化性能表征

为改善木材易污染,易霉变的缺点,采用真空浸渍和液相沉淀法,将g-C₃N₄/TiO₂复合涂层负载于木材表面,对木材进行功能化改良,赋予木材光催化自清洁功能。使用扫描电镜、能谱仪、X射线衍射、傅里叶红外光谱表征样品的表观形貌、相结构等。以罗丹明B为目标污染物,利用UV-VIS分光光度计测量降解效率,检测负载g-C₃N₄/TiO₂复合涂层的木质基材光催化性能。结果表明: g-C₃N₄/TiO₂复合涂层成功负载于木材表面,g-C₃N₄与TiO₂相互掺杂有效地提高了两者的光催化活性,负载g-C₃N₄/TiO₂复合涂层的木质基材具有一定的光催化功能。      

Enhanced bonding of gold nanoparticles on oxidized TiO2(110)

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.     

POMs/TiO_2复合催化剂光催化降解有机污染物的研究

[目的]采用溶胶-凝胶方法制备了几种POMs/TiO2复合光催化剂,考察了催化剂在紫外光照射下对模拟染料废水（酸性媒介黑PV溶液）的光催化降解行为,为降解有机污染物提供理论指导。[方法]研究了催化剂中的POMs含量、催化剂用量、溶液的pH及H2 O2浓度对PV溶液降解过程的影响。[结果]H4SiW12O40/TiO2复合催化剂光催化降解模拟染料废水（PV溶液）效果最佳。PV溶液初始浓度为300 mg/L时,脱色反应最佳条件：催化剂为H4SiW12O40/TiO2,α-H4SiW12O40质量分数为1.5%时,催化剂用量为60 mg、pH为2.0、H2 O2浓度为20 mmol/L时,PV降解质量分数可达到72.48%。[结论]POMs/TiO2复合催化剂较纯TiO2光催化降解PV溶液活性明显,其光催化降解有机污染物意义重大。