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1.
We have obtained pKa values of p-nitrophenol–TiO2 by measuring the adsorption equilibrium constants of p-nitrophenol (PNP) on the TiO2 surface at different pH values. These values have been obtained from Langmuir isotherms and from a plot of 1/rate vs. 1/[PNP]o obtained during TiO2 catalyzed solar light photo-degradation of PNP. Two limit equilibrium constants are readily obtained depending on the solution pH: at pH 5 at which the TiO2 surface is mainly positively charged and at pH 8 when it is negatively charged. With these and other adsorption equilibrium constants and the PNP pKa value in solution, thermodynamic cycles are established in order to obtain the PNP pKa when it is adsorbed on positively charged, neutral and negatively charged TiO2 surfaces. From these pKa values useful information on the PNP–TiO2 interaction is readily obtained. For instance, the PNP nitro group interacts with the TiO2 surface via a hydrogen bond, arising from the complex of water molecules with the Ti4+ ions on its surface. The weaker the hydrogen bond donor, the stronger the oxygen nitro group basicity. Therefore, pKa changes on the phenolic hydroxyl group result from these interactions. Linear free energy correlations, maximum PNP adsorption capacity values (QL) and FTIR ATR, spectrum support this proposal. A kobs vs. pH degradation profile of p-nitrophenol is also provided. 相似文献
2.
Anna V. Korzhak Natalia I. Ermokhina Alexander L. Stroyuk Viktor K. Bukhtiyarov Alexandra E. Raevskaya Valentina I. Litvin Stepan Ya. Kuchmiy Vladimir G. Ilyin Piotr A. Manorik 《Journal of photochemistry and photobiology. A, Chemistry》2008,198(2-3):126-134
Na+ complex with the dibenzo-18-crown-6 ester was used as a template to synthesize mesoporous titanium dioxide with the specific surface area 130–140 m2/g, pore diameter 5–9 nm and anatase content 70–90%. The mesoporous TiO2 samples prepared were found to have photocatalytic activity in CuII, NiII and AgI reduction by aliphatic alcohols. The resulting metal–semiconductor nanostructures have remarkable photocatalytic activity in hydrogen evolution from water–alcohol mixtures, their efficiency being 50–60% greater than that of the metal-containing nano-composites based on TiO2 Degussa P25.The effects of the thermal treatment of mesoporous TiO2 upon its photocatalytic activity in hydrogen production were studied. The anatase content and pore size were found to be the basic parameters determining the photoreaction rate. The growth of the quantum yield of hydrogen evolution from TiO2/Ag0 to TiO2/Ni0 to TiO2/Cu0 was interpreted in terms of differences in the electronic interaction between metal nanoparticles and the semiconductor surface. It was found that there is an optimal metal concentration range where the quantum yield of hydrogen production is maximal. A decrease in the photoreaction rate at further increment in the metal content was supposed to be connected with the enlargement of metal nanoparticles and deterioration of the intimate electron interaction between the components of the metal–semiconductor nanocomposites. 相似文献
3.
Ag/TiO2光催化还原硝酸氮 总被引:3,自引:0,他引:3
利用化学还原法制备不同Ag掺杂量TiO2纳米催化剂,采用TEM、XRD、XRF和UV-Vis对催化剂进行表征。考察了催化剂在紫外光(254 nm)和可见光照射下还原初始浓度100 mgN·L-1水相硝酸氮的活性和效果。重点考察了紫外光照射下Ag掺杂量、不同空穴捕获剂(甲酸、甲醇、乙酸、乙醇、草酸、草酸钠等)及甲酸浓度对硝酸氮还原的影响;对硝酸氮转化率和总氮去除率、形成亚硝酸氮、氨氮浓度及氮气选择性的影响。甲酸浓度为0.030 mol·L-1、Ag掺杂量为1.0wt%时催化剂效果最佳。此时,硝酸氮、总氮的转化率分别为98.43%、78.13%;亚硝酸氮浓度为零,转化的硝酸氮中只有20.76%转化为氨氮,氮气选择性为79.24%。可见光下进行光催化还原反应时,硝酸氮转化率仅37.98%,但氮气的选择性较高。 相似文献
4.
以钛酸丁酯和季铵盐改性有机蒙脱石为原料,采用原位水解法和原位脱羟法制备了TiO2/蒙脱石纳米复合物。采用X射线衍射(XRD)、拉曼光谱(Raman)表征了不同焙烧温度下TiO2/蒙脱石纳米复合物中TiO2的结构相变,并与不同焙烧温度下纯TiO2的结构相变进行对比。结果发现TiO2/蒙脱石纳米复合物中TiO2从锐钛矿相开始转变为金红石的最低温度要比纯TiO2从锐钛矿开始相转变为金红石的最低温度高200℃,且在焙烧温度1 200℃时还存在锐钛矿相,而纯TiO2在焙烧温度800℃时就全部转换为金红石相。TiO2/蒙脱石纳米复合物中TiO2和纯TiO2的平均晶粒度都随焙烧温度升高而增大,但TiO2/蒙脱石纳米复合物中TiO2的平均晶粒度要小于相同温度下焙烧纯TiO2的平均晶粒度。表明蒙脱石结构层的硅氧结构抑制了TiO2晶型由锐钛矿相向金红石相的转变,进而使相变温度升高,同时阻碍了晶体的生长。 相似文献
5.
TiO2 nanoparticles incorporated with CuInS2 clusters were prepared in a solvothermal process and characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy-dispersion X-ray analysis (EDX). Compared with pure TiO2 nanoparticles, the TiO2 nanoparticles incorporated with CuInS2 clusters display higher photocatalytic activity with 99.9% of degradation ratio of 4-nitrophenol after 2 h irradiation. In order to investigate the effect of the CuInS2 clusters on the photocatalytic activity of TiO2 nanoparticles, diffuse reflectance UV–Vis spectra (DRS), photoluminescence (PL) spectra, and photocurrent action spectra were measured. The results indicate that the enhanced photocatalytic activity is probably due to the interface between TiO2 and CuInS2 as a trap of the photogenerated electrons to decrease the recombination of electrons and holes. 相似文献
6.
Defect microstructure of Zr-dissolved TiO2 polycrystals, homogenized as rutile structure at 1600 °C and then aged at 900 °C for 2-200 h in air, was characterized by analytical electron microscopy. Diffuse diffractions occurred at 1/2(211) as a result of Zr4+ substitution for Ti4+ with volume/charge compensating defect clusters. Upon annealing at 900 °C, plate-like Guinier and Preston (G.P.) zone appeared with the plate surface parallel to (100) and (010) and in association with dislocations. Commensurate superstructures with apparent triple {101} and {111} periodicity also occurred as metastable intermediates, which are presumably the precursor of the equilibrium ZrTi2O6 precipitate. 相似文献
7.
Chi-Chang Hu Hsin-Yi Guo Kuo-Hsin Chang Ching-Chun Huang 《Electrochemistry communications》2009,11(8):1631-1634
This communication demonstrates the first work on anodic composite deposition of oxide nanocomposites. Rutile TiO2 nanoflowers with an average petal size of ca. 10 nm in diameter and 100 nm in length were synthesized from a TiCl3 solution purged with air at 25 °C for 12 days prior to the composite deposition. Hydrous ruthenium oxide (RuO2·xH2O) and TiO2 nanoflowers were composite-deposited onto Ti substrates for supercapacitors. In comparing with RuO2·xH2O deposits, RuO2·xH2O–TiO2 nanocomposites with a highly porous nature exhibit the weakly mass-dependent specific capacitance and high-power capacitive characteristics. 相似文献
8.
本工作采用CVD法在阳极氧化TiO2纳米管阵列膜表面沉积一层非晶Si膜,通过退火后得到晶化了的Si膜/TiO2纳米管阵列的复合结构,并初步就其光催化还原CO2制备碳氢化合物的活性进行研究。拉曼光谱(Raman)、X射线衍射(XRD)、场发射扫描电镜(FE-SEM)、高分辨透射电子显微镜(TEM)等微结构表征结果表明所制备的TiO2纳米管阵列的厚度为270 nm左右,管直径约为70 nm,管壁厚度约为16 nm。覆盖的Si膜已晶化,其厚度约为300 nm。通过高效液相色谱(HPLC)及总有机碳(TOC)来检测光催化还原液相产物中的甲酸及总有机碳含量,发现负载Si膜后的TiO2纳米管阵列光催化性能有所提高,在装有400cut滤光片氙灯照射2 h下TOC含量从21.2 mg.L-1增长到29.5 mg.L-1,表明Si与TiO2的复合可有效的提高光催化还原CO2的活性,这可能与该异质结结构可增加对光的吸收并且可降低光生空穴-电子对复合有关。光催化循环实验表明所制得的催化剂在循环5次后仍可保持91.6%的催化活性。 相似文献
9.
采用固相反应法制备出BiNbO4,将其与TiO2耦合,得到TiO2/BiNbO4复合光催化剂。考察了催化剂在紫外光照射下催化降解气相苯的活性。结果表明,TiO2与BiNbO4耦合后催化活性明显提高,其中36%TiO2/BiNbO4紫外光照5 h对苯的降解率是P-25的3.7倍。紫外-可见漫反射谱(UV-Vis DRS)、XRD、XPS和低温氮吸附-脱附等表征结果表明TiO2与BiNbO4的能级匹配,二者之间存在能带协同效应。耦合后的TiO2/BiNbO4的光生电子和空穴能有效分离,从而提高了催化剂催化活性。 相似文献
10.
The bulk superconducting YCa2Cu3O7−δ compounds are prepared at an ordinary pressure of oxygen by conventional solid-state reaction method. The formation of sample is tested by means of XRD and is studied for their ac susceptibility below room temperature up to 77.5 K. The samples are found single-phase orthorhombic structure and found superconducting at 83.5 K. It is shown that the analysis is consistent with published data on YBa2Cu3O7−δ oxide superconductor. 相似文献
11.
A series of dye-modified TiO2 photocatalysts were synthesized using dye Chrysoidine G (CG), tolylene-2,4-diisocyanate (TDI), and commercial TiO2 (Degussa P25) as starting materials. TDI was used as a bridging molecule whose two -NCO groups reacted with Ti-OH of TiO2 and -NH2 groups of CG, respectively. As a result, special organic complexes were formed on the TiO2 surface via stable π-conjugated chemical bonds between TiO2 and dye molecules, confirmed by FT-IR, XPS, and UV-vis spectra. Due to the existence of π-conjugated surface organic complexes, the as-synthesized photocatalysts showed a great improvement in visible absorption (400-550 nm). Methylene blue, as a photodegradation target, was used to evaluate the photocatalytic performance, and the dye-modified TiO2 exhibited much better activity under the visible light irradiation than bare TiO2. 相似文献
12.
利用在钛箔表面沉积一层TiO2纳米粒子作为晶种,与NaOH反应,制备了一维物质TiO2纳米线。并用XRD、SEM、TEM、HRTEM及EDS等分析手段对TiO2纳米线的成分、形貌、结构进行表征。结果表明,采用该方法制得的TiO2纳米线直径在20~50 nm左右、长度可达几微米。反应温度能显著影响所得纳米线的形貌。研究了TiO2纳米线的光电化学性能。随反应温度的升高TiO2纳米线光电转换效率增大。 相似文献
13.
L. Reijnders 《Polymer Degradation and Stability》2009,94(5):873-876
There is a growing interest in the development of nanocomposites consisting of organic polymers and TiO2 or amorphous SiO2 nanoparticles. These nanoparticles may be released from nanocomposites. There is evidence that amorphous SiO2 and TiO2 nanoparticles can be hazardous. Thus, in the design of nanocomposites with such nanoparticles, hazard reduction extending to the full nanocomposite life cycle would seem a matter to consider. Options for hazard reduction include: changes of nanoparticle surface, structure or composition, better fixation of nanoparticles in nanocomposites, including persistent suppression of oxidative damage to polymers by nanoparticles, and design changes leading to the release of relatively large particles. 相似文献
14.
以TiCl_3和InCl_3为Ti源和In源,在不使用还原剂的条件下,首先通过液相沉淀反应制备前驱体沉淀,然后采用后续水热处理制备Ti~(3+)自掺杂的TiO_2(A)/TiO_2(R)/In_2O_3纳米异质结,考察了水热处理温度对材料结构和性能的影响。利用X射线衍射、透射电子显微镜、X射线光电子能谱和紫外-可见漫反射光谱对样品进行表征。分别以罗丹明B和苯酚溶液为模拟废水评价了样品的可见光催化降解性能。结果表明,与纯的TiO_2、In2O_3以及Ti~(3+)自掺杂的TiO_2相比,Ti~(3+)自掺杂的TiO_2(A)/TiO_2(R)/In_2O_3纳米异质结在可见光区有明显的吸收,并具有良好的可见光催化降解性能,200℃下水热处理24h所得样品光催化降解罗丹明B的反应速率常数(0.0444min-1)分别是纯TiO_2和In_2O_3的17.76倍和8.71倍。瞬态光电流时间响应结果表明样品的光催化性能主要来源于TiO_2(A)/TiO_2(R)/In_2O_3纳米异质结导致的提高的光生电子和空穴分离效率。 相似文献
15.
Hubert Huppertz Sandra Altmannshofer Gunter Heymann 《Journal of solid state chemistry》2003,170(2):320-329
In this work we report about a new rare-earth oxoborate β-Dy2B4O9 synthesized under high-pressure/high-temperature conditions from Dy2O3 and boron oxide B2O3 in a B2O3/Na2O2 flux with a walker-type multianvil apparatus at 8 GPa and 1000°C. Single crystal X-ray structure determination of β-Dy2B4O9 revealed:
, a=616.2(1) pm, b=642.8(1) pm, c=748.5(1) pm, α=102.54(1)°, β=97.08(1)°, γ=102.45(1)°, Z=2, R1=0.0151, wR2=0.0475 (all data). The compound exhibits a new structure type which is built up from bands of linked BO3- (Δ) and tetrahedral BO4-groups (□). The Dy3+-cations are positioned in the voids between the bands. According to the conception of fundamental building blocks β-Dy2B4O9 can be classified with the notation 2Δ6□:Δ3□=4□=3□Δ. Furthermore we report about temperature-resolved in situ powder diffraction measurements and IR-spectroscopic investigations on β-Dy2B4O9. 相似文献
16.
The crystal phase evolution of TiO2 nanoparticles, during hydrolysis and condensation of titanium tetraisopropoxide, was quenched at various reaction times by a freeze-drying method, followed by various characterizations. Three types of solutions with different acid input times were studied: (1) addition in infinite time (no addition), (2) addition at 24 h after the hydrolysis/condensation reaction started, and (3) addition from the beginning of the reaction. The acid-free solution yielded amorphous TiO2, which transformed to anatase very slowly. The acid input in 24 h resulted in a fast transformation of amorphous to a metastable anatase having a highly distorted atomic arrangement: thereby its transformation to a more stable phase, rutile, was suitable. The acid addition from the beginning of the reaction yielded the formation of a relatively stable anatase from the hydrolysis seed, thereby the subsequent transformation to rutile was sluggish. 相似文献
17.
以TiCl3和InCl3为Ti源和In源,在不使用还原剂的条件下,首先通过液相沉淀反应制备前驱体沉淀,然后采用后续水热处理制备Ti3+自掺杂的TiO2(A)/TiO2(R)/In2O3纳米异质结,考察了水热处理温度对材料结构和性能的影响。利用X射线衍射、透射电子显微镜、X射线光电子能谱和紫外-可见漫反射光谱对样品进行表征。分别以罗丹明B和苯酚溶液为模拟废水评价了样品的可见光催化降解性能。结果表明,与纯的TiO2、In2O3以及Ti3+自掺杂的TiO2相比,Ti3+自掺杂的TiO2(A)/TiO2(R)/In2O3纳米异质结在可见光区有明显的吸收,并具有良好的可见光催化降解性能,200℃下水热处理24 h所得样品光催化降解罗丹明B的反应速率常数(0.0444 min-1)分别是纯TiO2和In2O3的17.76倍和8.71倍。瞬态光电流时间响应结果表明样品的光催化性能主要来源于TiO2(A)/TiO2(R)/In2O3纳米异质结导致的提高的光生电子和空穴分离效率。 相似文献
18.
以钛酸丁酯为前驱体, 碘溶胶为碘源, 在室温下采用水解沉淀法制备了单质碘和纳米TiO2复合的双介孔结构光催化剂(M-I2-TiO2). 采用X射线衍射(XRD)、透射电子显微镜(TEM)、比表面分析(BET)、紫外-可见(UV-Vis)漫反射光谱和傅里叶变换-红外光谱(FT-IR)对M-I2-TiO2进行了表征. 以次甲基蓝(MB)溶液为模拟废水, 对M-I2-TiO2的光催化性能进行了评价, 研究了不同热处理温度对光催化活性的影响. 结果表明, M-I2-TiO2在可见光区有显著的吸收, 300 ℃热处理得到的样品比表面积高达227.6 m2/g, 600 ℃热处理所得样品的比表面积仍高达111.8 m2/g, 而400 ℃热处理所得样品具有最好的光催化降解性能. 双介孔结构纳米TiO2/I2复合材料的光催化降解性能显著高于相同方法制备的纯TiO2和Degussa P-25商业产品. 催化剂经6次重复使用其光催化活性基本保持不变. 相似文献
19.
采用共沉淀法将SnO_2组分掺入到V_2O_5-WO_3/TiO_2催化剂载体TiO_2中,并通过多种物理化学手段,考察了不同SnO_2掺入量时对催化剂结构,表面分散物种和SCR性能影响.结果表明,SnO_2掺入到TiO_2中,元素Sn与Ti以Sn—O—Ti键形式相互作用,促进锐钛矿型TiO_2向金红石型TiO_2转变.在特定条件下,VO_x与WO_x物种和SnTi氧化物之间以V—O—Ti(Sn)和W—O—Ti(Sn)键形式相互作用,提高了VO_x物种可还原能力、促进了具有更多B酸酸量四面体WOx物种和V~(5+)物种生成.VW/SnTi催化剂表面VO_x物种与WO_x物种之间的相互作用更强.因此,VW/SnTi催化剂具有更好的SCR活性. 相似文献
20.
Jinqiu Yu Lijuan Liu Shifeng Jin Haitao Zhou Xiaoling He Changlong Zhang Weining Zhou Xiaoyang Wang Xiaolong Chen Chuangtian Chen 《Journal of solid state chemistry》2011,184(10):2790-2793
The structure of the hydrothermal-grown nonlinear optical crystal KBe2BO3F2 was investigated. A new structure of the R3?c space group with cell parameters of a=4.422(1) Å and c=37.524(3) Å was obtained by powder X-ray diffraction and Rietveld refinement. The new structure is a 1×1×2 superstructure of the previously reported R32 structure with a different stacking sequence of (Be2BO3F2)∞ layers along the c axis. The relationship between the refined structure and the experimental results is discussed. A stacking fault mechanism is proposed for the formation of the superstructure as well as the nonuniformity of the hydrothermal-grown KBBF crystals. 相似文献