Cu/TiO2-NiO上光促表面催化CO2和H2O合成CH3OH反应规律

采用溶胶-凝胶法制备了n(电子型)-p(空穴型) 复合半导体材料0.5％Cu/TiO2-2.0％NiO (w),利用X射线衍射(XRD)、透射电镜(TEM)、红外光谱(IR)、紫外-可见光漫反射(UV-Vis)、程序升温脱附(TPD)技术对材料结构、吸光性能、化学吸附性能进行了表征,研究了该材料对CO2和H2O合成CH3OH的光促表面催化反应(PSSR)规律.结果表明,所制备材料能够明显促进目的反应,室温条件下即有CH3OH生成.在200 ℃下,由于光-表面-热的协同效应,CO2转化率得以提高,且CH3OH的选择性达到87.5％ .根据实验结果,得出CO2在材料表面的卧式吸附态为CH3OH的前驱物,并对PSSR机理进行了讨论.     

掺Cu对MoO3-TiO2/SiO2上光促甲烷和水表面反应的影响

 在固定床环隙反应器中,借助紫外光的激发,气相甲烷和水在MoO3-TiO2/SiO2催化剂表面生成了甲醇和氢气,当在催化剂中掺杂Cu2+后,光催化剂的活性明显提高. XRD,IR,UVDRS和TPD的研究结果表明,在催化剂表面形成了具有Mo-O-Ti和Mo-O-Cu基元的高度分散物种,不但使得吸光带边明显蓝移,而且扩展了催化剂的光响应范围. 所形成的复合结构还可以优化单组分的吸光性能并促进对反应物分子的吸附活化,同时可以有效地转移光生电子和空穴. 掺杂Cu2+能够进一步延长光生电子-空穴对的寿命,进而提高反应的量子产率.     

溶胶-凝胶-水热晶化法制备锐钛矿TiO2纳米膜的耐蚀性能

以钛酸正丁酯为前驱体, 采用溶胶-凝胶-水热晶化法在不锈钢(SS)表面制备TiO₂纳米膜. 利用X射线衍射(XRD)、Raman光谱、场发射扫描电子显微镜(SEM)、原子力显微镜(AFM)和俄歇电子能谱(AES)表征了TiO₂纳米膜的晶型、表面形貌和表面化学组成. 通过极化曲线和电化学阻抗谱(EIS)研究了TiO₂纳米膜的耐蚀性能. 170 °C下水热晶化制备的锐钛矿TiO₂与450 °C焙烧制备的锐钛矿TiO₂的结晶度类似, 但两种TiO₂薄膜的表面结构存在明显差异, 水热晶化法制备的TiO₂纳米膜在3.5% (w) NaCl溶液中的耐蚀性能优于焙烧法制备的.     

New Cu-based catalysts supported on TiO2 films for Ullmann S(N)Ar-type C-O coupling reactions

New routes for the preparation of highly active TiO(2)-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, (63)Cu nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO(2) catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO(2) at 120 °C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO(2) at 140 °C, corresponding to an initial reaction rate of 104 mmol g(cat) (-1) s(-1). The activation energy on the Cu/mesoporous TiO(2) catalyst was found to be (144±5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123±3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO(2) support (75±2 kJ mol(-1)).     

Low-temperature synthesis of soluble and processable organic-capped anatase TiO2 nanorods

We demonstrate the controlled growth of high aspect ratio anatase TiO2 nanorods by hydrolysis of titanium tetraisopropoxide (TTIP) in oleic acid (OLEA) as surfactant at a temperature as low as 80 degrees C. Chemical modification of TTIP by OLEA is proven to be a rational strategy to tune the reactivity of the precursor toward water. The most influential factors in shape control of the nanoparticles are investigated by simply manipulating their growth kinetics. The presence of tertiary amines or quaternary ammonium hydroxides as catalysts is essential to promote fast crystallization under mild conditions. The novelty of the present approach relies on the large-scale production of organic-capped TiO2 nanocrystals to which standard processing of colloidal nanocrystals, such as surface ligand exchange, can be applied for the first time. Concentrated colloidal titania dispersions can be prepared for a number of fundamental studies in homogeneous solutions and represent a new source of easily processable oxide material for many technological applications.     

钴前驱体对掺杂TiO2微结构和可见光催化性能的影响

In order to develop photoactive cobalt-doped TiO2 for the degradation of organic pollutants using visible light irradiation, the effects of cobalt precursor on TiO2 microstructure were investigated. Three cobaltprecursors, i.e. CoCl2, Co(NO3)2 and CoSO4 with two doping levels (nominally 1% and 10%), and two annealing temperatures (400 and 800 ℃) were adopted to prepare the doped titania through the sol-gel method. The powder samples were characterized with XRD, SEM, BET surface area analysis and UV-Vis absorption spectroscopy, and their photocatalytic activities were evaluated by the degradation of aniline under visible light irradiation. The results showed that the distribution of titania phases, particle size,morphology, surface area and the optical absorption of the catalysts were greatly dependent on the cobalt precursors. Samples prepared from Co(NO3)2, especially for those doped at 1% and calcined at 400 ℃,showed the highest photocatalytic activity towards the degradation of aniline, and the possible reasons are discussed briefly.     

Hydrothermal synthesis and characterization of nanorods of various titanates and titanium dioxide

The formation process of titania based nanorods during hydrothermal synthesis starting from an amorphous TiO2.nH2O gel has been investigated. Sodium tri-titanate (Na2Ti3O7) particles with a rodlike morphology were prepared by a simple hydrothermal process in the presence of a concentrated NaOH aqueous solution. The ion exchange reaction of the synthesized Na2Ti3O7 nanorods with HCl under ultrasonic treatment promotes a complete sodium substitution and the formation of H2Ti3O7 nanorods. Low-temperature annealing of the as-produced nanorods of Na2Ti3O7 and H2Ti3O7 leads to a loss of the layered crystal structure and the formation of nanorods of condensed framework phases-sodium hexa-titanate (Na2Ti6O13) and metastable TiO2-B phases, respectively. These transformations proceed without a significant change in particle morphology. The nanostructures were investigated by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), the Brunauer-Emmett-Teller (BET) method, thermogravimetric analysis (TGA), and Raman spectroscopy. The structural defects of the synthesized nanorods were investigated by high-resolution electron microscopy. The presence of planar defects can be attributed to the exfoliation of the zigzag ribbon layers into two-dimensional titanates as well as to the condensation of the layers of TiO6 octahedra into three-dimensional frameworks.     

A novel preparation of nano-Cu/ZnO by photo-reduction of Cu(OCH(Me)CH2NMe2)2 on ZnO at room temperature

Room-temperature preparation of nano-Cu on ZnO by UV light induced photo-reduction of Cu(OCH(Me)CH2NMe2)2 precursor was achieved, indicating a novel method of nano-Cu/ZnO synthesis from an organometallic copper precursor in non-aqueous media without further chemical reduction.     

EPR investigation of TiO2 nanoparticles with temperature-dependent properties

An in situ electron paramagnetic resonance (EPR) study has been carried out for anatase (Hombikat UV100) and rutile TiO(2) nanoparticles at liquid helium (He) temperature (4.2 K) under UV irradiation. Rutile titania was synthesized by ultrasonic irradiation with titanium tetrachloride (TiCl(4)) as the precursor. XRD and Raman results evidence the crystallinity of titania phases. The nature of trapped electrons and holes has been investigated by EPR spectroscopy under air and vacuum conditions. Illumination of TiO(2) powder (anatase and rutile) at 4.2 K resulted in the detection of electrons being trapped at Ti(4+) sites within the bulk and holes trapped at lattice oxide ions at the surface. The stability of electron traps was very sensitive to temperature in both phases of TiO(2). The annealing kinetics of the EPR detected radicals has been studied from 4.2 K to ambient temperature and also for calcined titania particles from 523 to 1273 K.     

Large-scale synthesis of TiO2 nanorods via nonhydrolytic sol-gel ester elimination reaction and their application to photocatalytic inactivation of E. coli

A simple method of synthesizing a large quantity of TiO(2) nanorods was developed. A nonhydrolytic sol-gel reaction between titanium(IV) isopropoxide and oleic acid at 270 degrees C generated 3.4 nm (diameter) x 38 nm (length) sized TiO(2) nanocrystals. The transmission electron microscopic image showed that the particles have a uniform diameter distribution. X-ray diffraction and selected-area electron diffraction patterns combined with high-resolution transmission electron microscopic image showed that the TiO(2) nanorods are highly crystalline anatase crystal structure grown along the [001] direction. The diameters of the TiO(2) nanorods were controlled by adding 1-hexadecylamine to the reaction mixture as a cosurfactant. TiO(2) nanorods with average sizes of 2.7 nm x 28 nm, 2.2 nm x 32 nm, and 2.0 nm x 39 nm were obtained using 1, 5, and 10 mmol of 1-hexadecylamine, respectively. The optical absorption spectrum of the TiO(2) nanorods exhibited that the band gap of the nanorods was 3.33 eV at room temperature, which is 130 meV larger than that of bulk anatase (3.2 eV), demonstrating the quantum confinement effect. Oleic acid coordinated on the nanorod surface was removed by the reduction of the carboxyl group of oleic acid, and the Brunauer-Emmett-Teller surface area of the resulting naked TiO(2) nanorods was 198 m(2)/g. The naked TiO(2) nanorods exhibited higher photocatalytic activity than the P-25 photocatalyst for the photocatalytic inactivation of E. coli.     

TiO_2光催化/膜分离耦合过程降解偶氮染料废水

以钛酸丁酯为前驱体,采用酸性溶胶法在低温下(<100oC)制备了纳米级TiO2粉末,X射线衍射分析表明,样品为锐钛矿型,晶粒尺寸为3.6nm.以250W紫外灯为光源,在自制悬浮式光催化膜反应器中进行降解活性艳红X-3B有机染料废水实验,采用尼龙6(N6)和混合纤维素(CN-CA)两类微滤膜对TiO2颗粒进行截留分离.综合考察了影响光催化和膜分离效率的因素.结果表明,反应起始pH值和催化剂用量对光催化膜反应器运行性能影响很大,该耦合体系的最佳pH值为4,染料和催化剂最佳浓度比为2:1,0.45和0.22μm的CN-CA膜对TiO2颗粒截留率可达96.5%以上.     

Facile synthesis and characterization of functionalized, monocrystalline rutile TiO2 nanorods

Functionalized, monocrystalline rutile TiO2 nanorods were prepared from TiCl4 in aqueous solution under acidic conditions in the presence of dopamine, followed by aging and hydrothermal treatment at 150 degrees C. The surface-bound organic ligand controls the morphology as well as the crystallinity and the phase selection of TiO2. The presence of monocrystalline rutile TiO2 was confirmed by X-ray powder diffraction and HRTEM investigations. The as-prepared nanorods are soluble in water at pH <3. The surface functionalization was analyzed by IR and 1H NMR, confirming the presence of dopamine on the surface. The surface amine groups can be tailored further with functional molecules such as dyes. Confocal laser scanning microscopy (CLSM) was used to characterize the binding of the fluorescent dye 4-chloro-7-nitrobenzofurazan (NBD) to the functionalized surface of the TiO2 nanorods.     

Role of water and carbonates in photocatalytic transformation of CO2 to CH4 on titania

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and (?)OH radicals (oxidation product) from water, and CO(3)(-) radical anions (oxidation product) from carbonates, was detected in CO(2)-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, (?)OCH(3), and methyl, (?)CH(3), radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO(2) on the surface of TiO(2) is supported by the results of first-principles calculations.     

TiO2纳米棒载Pd催化剂的制备及其对甲酸的电催化氧化

利用水热合成和无机溶胶法,分别制备了具有棒状(TiO2-R)和无规则结构(TiO2-I)的锐钛矿相TiO2,并以之为载体制备得到Pd/TiO2电催化剂.循环伏安测试显示,与无规则TiO2相比,具有棒状结构的TiO2载Pd催化剂对甲酸氧化的电催化性能提高了70%;计时电流测试显示,运行3000 s后,甲酸在棒状TiO2载Pd催化剂上的氧化电流是无规则TiO2载Pd催化剂的16倍.其原因可能与TiO2纳米棒拥有更好的电子传导性且表面拥有较多的活性含氧基团有关,从而能够有效提高催化剂对甲酸氧化的电催化活性和抗毒化性能.     

烷基胺为媒介的铜纳米棒的合成及其生长机制研究

以氯化铜为前躯体,葡糖糖为还原剂,烷基胺(十六胺和十八胺的混合物)为络合剂和表面包覆剂,经过络合反应和溶剂热两步反应首先得到形貌均一、直径约为100 nm的铜纳米颗粒, 随后自发生长为五重孪晶铜纳米棒(仍含有部分颗粒)。实验过程中分别对溶剂热反应1 h、3 h和5 h后的还原产物的形貌特征加以表征,可以推断被还原的铜原子首先均匀成核形成初级铜纳米颗粒,经过奥斯特瓦尔德老化过程生长为五重孪晶的次级铜纳米颗粒,由于孪晶结构具有很高的生长活性,在烷基胺的表面包覆作用下生长为各项异性的铜纳米棒。该方法提供了一种有效的铜纳米棒的制备方法并且降低了一维铜纳米材料的合成成本。     

Silica-supported Au nanoparticles decorated by TiO2: formation, morphology, and CO oxidation activity

Au-TiO(2) interface on silica support was aimed to be produced in a controlled way by use of Au hydrosol. In method A, the Au colloids were modified by hydrolysis of the water-soluble Ti(IV) bis(ammoniumlactato)dihydroxide (TALH) precursor and then adsorbed on Aerosil SiO(2) surface. In method B, Au sol was first deposited onto the SiO(2) surface and then TALH was adsorbed on it. Regular and high-resolution transmission electron microscopy (TEM and HRTEM) and energy dispersive spectrometry (EDS) analysis allowed us to conclude that, in method A, gold particles were able to retain the precursor of TiO(2) at 1.5 wt % TiO(2) loading, but at 4 wt % TiO(2) content the promoter oxide appeared over the silica surface as well. With method B, titania was detected on silica at each TiO(2) concentration. In Au-TiO(2)/SiO(2) samples, the stability of Au particles against sintering was much higher than in Au/TiO(2). The formation of an active Au-TiO(2) perimeter was proven by the greatly increased CO oxidation activity compared to that of the reference Au/SiO(2).     

Oxide thin films based on ordered arrays of 1D nanostructure. A possible approach toward bridging material gap in catalysis

TiO(2) thin films based on ordered arrays of 1D nanostructures (nanorods, nanotubes) are proposed as suitable model materials in studies for bridging material and complexity gap in catalysis. The samples were prepared by anodic oxidation of Ti foils. By changing the preparation conditions (pH, procedure of application of the potential), different types of 1D nanostructure and different characteristics of the ordered array of these 1D nanostructures could be obtained. This allows studying the effect of nanodimension and 3D nanoarchitecture on the characteristics and reactivity of these catalysts. It is also shown that TiO(2) thin films characterized by a well-ordered array of titania nanorod behave as photonic materials, thus showing unique properties of light harvesting efficiency.     

Characterization of Zr-doped TiO2 nanocrystals prepared by a nonhydrolytic sol-gel method at high temperatures

Highly crystalline and surface-modified Zr-doped TiO(2) nanorods were successfully prepared using a nonhydrolytic sol-gel method that involves the condensation of metal halides with alkoxides in anhydrous trioctylphosphine oxide (TOPO) at either 320 or 400 degrees C. In addition, the interaction of the cross-condensation between the Ti and Zr species was studied by characterizing the morphologies, crystalline structures, chemical compositions, surface properties, and band gaps of the nanocrystals obtained at different reaction temperatures and Zr-to-Ti stoichiometric ratios. Increases in the concentration of Zr(4+) and in the reaction temperature led to large nanorods and regular shapes, respectively. In addition, only the anatase form was observed in the Zr-doped TiO(2) nanorods. The Zr-to-Ti ratios obtained ranged from 0.01 to 2.05, all of which were far below the stoichiometric ratios used during the preparation of the samples (0.25-4). Moreover, the Zr(4+) units accumulated mainly at the surface of the TiO(2) nanocrystals. The band gaps of the Zr-doped TiO(2) nanorods ranged from 2.8 to 3.8 eV, which are smaller than those of pure TiO(2) (3.7 eV) or ZrO(2) (5.2 eV). The Zr-doped anatase TiO(2) nanorods prepared at 400 degrees C at an initial stoichiometric Zr-to-Ti ratio of 2:3 exhibited the highest photoactivities for the decomposition of rhodamine B because of the presence of trace amounts of Zr(4+) (Zr/Ti = 0.03) in the TiO(2) and the regular shapes of these particles. DSC analysis indicated that the temperatures for forming nanocrystalline TiO(2) and ZrO(2) were 207 and 340 degrees C, respectively. Moreover, the reactivities of condensation between the Ti species were reduced when Zr species were involved in the NHSG reactions. The results obtained in this study clearly demonstrate that the faster kinetics for the generation of TiO(2) controls the material properties as well as the photoactivities of the nonhydrolytic sol-gel-derived nanocrystals.     

FTIR study of adsorption and surface reactions of N(CH3)3 on TiO2

Fourier transform infrared spectroscopy has been employed to investigate the N(CH3)3 adsorption, thermal stability, and photochemical reactions on powdered TiO2. N(CH3)3 molecules are adsorbed on TiO2 without dissociation at 35 degrees C and are completely desorbed from the surface at 300 degrees C in a vacuum. The CH3 rocking frequencies of N(CH3)3 on TiO2 are affected via the interaction between N(CH3)3 and TiO2 surface OH groups. In the presence of O2, adsorbed N(CH3)3 decomposes thermally at 230 degrees C and photochemically under UV irradiation. In the latter case with comparative (16)O2 and (18)O2 studies, CO2(g), NCO(a), HCOO(a), and surface species containing C=N or NH(x) functional groups are identified to be the photoreaction products or intermediates. In the presence of (18)O2, the main formate species formed is HC(16)O(18)O(a). As H2O is added to the photoreaction system, a larger percentage of adsorbed N(CH3)3 is consumed. However, in the presence of (18)O2 and H2O, the amount of HC(16)O(18)O(a) becomes relatively small, compared to HC(16)O(16)O(a). A mechanism is invoked to explain these results. Furthermore, based on the comparison of isotopic oxygens in the formate products obtained from CH3O(a) photooxidation in (16)O2 and (18)O2, it is concluded that the N(CH3)3 photooxidation does not generate CH3O(a) in which the oxygen belongs to TiO2.     

Fabrication of hydroxyl group modified monodispersed hybrid silica particles and the h-SiO(2)/TiO(2) core/shell microspheres as high performance photocatalyst for dye degradation

The monodisperse hybrid silica particles (h-SiO(2)) were firstly prepared by a modified sol-gel process and the surface was modified in situ with double bonds, then abundant carboxyl moieties were introduced onto the surface of the silica core via thiol-ene click reaction. Afterward, the h-SiO(2)/TiO(2) core/shell microspheres were prepared by hydrolysis of titanium tetrabutoxide (TBOT) via sol-gel process in mixed ethanol/acetonitrile solvent, in which the activity of TBOT could be easily controlled. The carboxyl groups on the surface of silica particles promote the formation of a dense and smooth titania layer under well control, and the layer thickness of titania could be tuned from 12 to 100nm. The well-defined h-SiO(2)/TiO(2) core/shell structures have been confirmed by electron microscopy and X-ray photoelectron spectroscopy studies. After calcination at 500°C for 2h, the amorphous TiO(2) layer turned into anatase titania. These anatase titania-coated silica particles showed good photocatalytic performance in degradation of methyl orange aqueous solution under UV light.