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1.
Hydrogen titanate nanotubes (H-TTNT) were synthesized by the alkali hydrothermal method followed by proton exchange and then submitted either to thermal treatment or to acid hydrothermal reaction to generate TiO2-anatase nanocrystals of different morphologies. The samples were characterized by XRPD, TGA, sulfur analysis, N2 physisorption, UV-Vis spectroscopy and TEM. Their photocatalytic activities were determined by measuring the NO conversion in inert gas stream passed through the powder catalyst bed under UV radiation. Incomplete transformation into anatase resulted in nanomaterials with low activity due to coexistence with H-TTNT or TiO2-B precursors. Anatase specimens derived from H-TTNT aged in strong sulfuric acid media contained equidimensional nanoparticles, but retention of sulfate negatively affected their photocatalytic activity. Combining milder acidic pH with higher aging temperature, allowed synthesis of a sulfate free anatase with the same optical properties and specific surface area as the counterpart produced by calcination of H-TTNT at 550°C; however, the former exhibited truncated bi-pyramid nanocrystals and the other adopted the form of nanorods. This latter showed the highest photocatalytic activity for NO abatement, outperforming the benchmark photocatatyst TiO2-P25; this improved activity was tentatively ascribed to the maximization of high energy {001} facets in anatase nanorods formed during calcination of H-TTNT.
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2.
A series of Ce–MnO x /TiO2 catalysts were prepared using a novel sol–gel template method and investigated for low-temperature selective catalytic reduction (SCR) of NO with NH3 at temperatures ranging from 353 to 473 K. The 0.07Ce–MnO x /TiO2 catalyst showed the highest activity and best resistance to SO2 poisoning. The structure and properties of the catalysts were characterized using X-ray diffraction (XRD) analysis, thermogravimetric analysis (TGA), thermogravimetry (TG)–differential scanning calorimetry (DSC)–mass spectroscopy (MS), high-resolution transmission electron microscopy (HRTEM), Brunauer–Emmett–Teller (BET) measurements, H2-temperature-programmed reduction (TPR), and NH3-temperature-programmed desorption (TPD). The superior catalytic activity of the 0.07Ce–MnO x /TiO2 catalyst was probably due to a change in the active components, an increase in surface active oxygen and surface acid sites, and lower crystallinity and larger surface area with Ce doping. Furthermore, the reduction ability also became stronger. The SO2 poisoning resistance of the 0.07Ce–MnO x /TiO2 catalyst improved because doping with Ce can effectively decrease the formation of ammonium salt on the catalyst surface and the sulfation of MnO x . In situ diffuse-reflectance infrared Fourier-transform (DRIFT) spectroscopy experiments indicated that addition of Ce could promote adsorption of NH3 and inhibit generation of some nitryl species. The SCR reactions over the catalysts mainly followed the Eley–Rideal mechanism accompanied with a partial Langmuir–Hinshelwood mechanism.  相似文献   

3.
Microcomposites consisting of TiO2 (or Ce-doped TiO2) and ThO2 (0.5–2% of the TiO2 mass) are produced by sol-gel synthesis of TiO2 in presence of ThO2. X-ray diffraction study reveals the effects of ThO2 (compared to the ThO2-free TiO2, obtained by the same method) on the anatase interplanar distances, crystallites size and phase composition. The photocatalytic tests in presence of the composites under UV irradiation reveal an increase of the Malachite Green degradation rate constant. The effect depends on the Th relative content, temperature of annealing of the catalyst and addition of other doping agent. The highest photocatalytic activity is observed for TiO2 obtained at 550°C and containing 1% ThO2. The composite exhibits activity in dark, also. The presence of Ce4+ ions is not an obligatory requirement for the realization of the ThO2 effect. The reported results suggest that the radioactivity of the Th and/or its decay products is one of the main factors responsible for the increased photocatalytic activity of TiO2.   相似文献   

4.
One-dimensional (1D) Ag/AgBr/TiO2 nanofibres (NFs) have been successfully fabricated by the one-pot electrospinning method. In comparison with bare TiO2 NFs and Ag/AgBr/PVP (polyvinylpyrrolidone) NFs, the 1D Ag/AgBr/TiO2 NFs photocatalyst exhibits much higher photocatalytic activity in the degradation of a commonly used dye, methylene blue (MB), under visible light. The photocatalytic removal efficiency of MB over Ag/AgBr/TiO2 NFs achieves almost 100 % in 20 min. The photocatalytic reaction follows the first-order kinetics and the rate constant (k) for the degradation of MB by Ag/AgBr/TiO2 NFs is 5.2 times and 6.6 times that of Ag/AgBr/PVP NFs and TiO2 NFs, respectively. The enhanced photocatalytic activity is ascribed to the stronger visible light absorption, more effective separation of photogenerated electron-hole pairs, and faster charge transfer in the long nanofibrous structure. The Ag/AgBr/TiO2 NFs maintain a highly stable photocatalytic activity due to its good structural stability and the self-stability system of Ag/AgBr. The mechanisms for photocatalysis associated with Ag/AgBr/TiO2 NFs are proposed. The degradation of MB in the presence of scavengers reveals that h+ and ?O 2 ? significantly contribute to the degradation of MB.  相似文献   

5.
Steady State Isotopic Transient Kinetic Analysis (SSITKA) experiments using on-line Mass Spectrometry (MS) and in situ Diffuse Reflectance Infrared Fourier-Transform Spectroscopy (DRIFTS) have been performed to study essential mechanistic aspects of the Selective Catalytic Reduction of NO by H2 under strongly oxidizing conditions (H2-SCR) in the 120–300°C range over a novel 0.1 wt % Pt/MgO-CeO2 catalyst. The N-path of reaction from NO to the N2 gas product was probed by following the 14NO/H2O215NO/H2/O2 switch (SSITKA-MS and SSITKA-DRIFTS) at 1 bar total pressure. It was found that the N-pathway of reaction involves the formation of two active NO x species different in structure, one present on MgO and the other one on the CeO2 support surface. Inactive adsorbed NO x species were also found on both the MgO-CeO2 support and the Pt metal surfaces. The concentration (mol/g cat) of active NO x leading to N2 was found to change only slightly with reaction temperature in the 120–300°C range. This leads to the conclusion that other intrinsic kinetic reasons are responsible for the volcano-type conversion of NO versus the reaction temperature profile observed.  相似文献   

6.
Interaction of N2O at low temperatures (473-603 K) with Fe-ZSM-5 zeolites (Fe, 0.01-2.1 wt %) activated by steaming and/or thermal treatment in He at 1323 K was studied by the transient response method and temperature-programmed desorption (TPD). Diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) of NO adsorbed at room temperature as a probe molecule indicated heterogeneity of surface Fe(II) sites. The most intensive bands were found at 1878 and 1891 cm(-1), characteristic of two types mononitrosyl species assigned to Fe2+(NO) involved in bi- and oligonuclear species. Fast loading of atomic oxygen from N2O on the surface and slower formation of adsorbed NO species were observed. The initial rate of adsorbed NO formation was linearly dependent on the concentration of active Fe sites assigned to bi- and oligonuclear species, evolving oxygen in the TPD at around 630-670 K. The maximal coverage of a zeolite surface by NO was estimated from the TPD of NO at approximately 700 K. This allowed the simulation of the dynamics of the adsorbed NO formation at 523 K, which was consistent with the experiments. The adsorbed NO facilitated the atomic oxygen recombination/desorption, the rate determining step during N2O decomposition to O2 and N2, taking place at temperatures > or =563 K.  相似文献   

7.
Zero-dimensional (0D)/two-dimensional (2D) heterojunctions have attracted great attention in photocatalysis due to their superior interfacial effects. In this work, 0D g-C3N4 quantum dots (CNQDs) were firstly used to modify {001}-faceted 2D TiO2 nanosheets by a simple solvothermal method. During the controlled growth of TiO2 nanosheets with exposed reactive {001} facets, the CNQDs can be simultaneously assembled on the surface of TiO2 nanosheets in a highly dispersive way. The 0D/2D composite containing only 0.5% of CNQDs shows the optimized solar photocatalytic activity for the degradation of rhodamine B and 4-chlorophenol. More importantly, the 0D/2D composite exhibits a better solar photocatalytic activity than the bulk g-C3N4/TiO2 nanosheets composite. This improvement can be ascribed to the close interfacial contact and strong interaction between the highly dispersed CNQDs and the TiO2 nanosheets, which could lead to efficient separation of the photogenerated electron–hole pairs, provide more catalytic active sites, and enhance the absorption of solar light. The 0D/2D composite also shows good stability for its practical applications.  相似文献   

8.
TiO2/WO3 nanocomposite with nanodisk morphology was prepared and successfully used as a photocatalyst. The nanocomposite was obtained via sonochemical and hydrothermal methods, using pomegranate juice as a capping agent. The products were characterized by FE-SEM imaging, BET, EDAX spectroscopy, X-ray diffraction, DRS, and FT-IR spectroscopy. TiO2/WO3 nanocomposite showed high sensitivity to absorb visible light in compared to TiO2. In an optimized condition, the yield of the aerobic photocatalytic oxidation of benzyl alcohol derivatives reached to 65% for the TiO2/WO3 nanocomposite, while the conversion percent of the derivatives was less than 8% and 50% on the TiO2 and WO3 nanoparticles, respectively. Experimental results were supported by density functional theory (DFT) calculations. The DFT results in several solvents of different dielectric constants, confirmed the strong dependence of light absorption and photocatalytic activity to adsorption energy of the substrates on the surface of the nanoparticles (Ead). In addition, the theoretical results showed an inverse correlation between the adsorption energy of benzyl alcohol and its conversion percent, accordance to the experimental trend.  相似文献   

9.
In this study, pure titanium dioxide (TiO2), Ta-doped TiO2, S-doped TiO2, and Ta-S-codoped rutile TiO2 photocatalysts were prepared by a sol-gel method. To evaluate the properties of the synthesized samples, X-ray diffraction analysis (XRD) and X-ray photoelectron spectroscopy (XPS) were applied. XRD detection results showed that the samples contained rutile phase basically. Scanning electron microscope observation showed that the morphology of Ta-S-TiO2 was nearly spherical. Transmission electron microscope investigation indicated that Ta-S-TiO2 had a flower-shaped structure consisting of many nanorods. The measurement of Brunauer-Emmett-Teller (BET)-specific surface areas (SBET) showed that tantalum and sulfur codoping can effectively increase the SBET of TiO2. XPS results indicated that Ta was in the form of Ta5+ in the TiO2 structure. Finally, the photocatalytic activities of synthesized photocatalyst samples were measured for the degradation of methylene blue in ultraviolet and visible light irradiation. The results demonstrated that the Ta-S-codoped rutile TiO2 photocatalyst had better photocatalytic performance than pure rutile TiO2, Ta-doped rutile TiO2 and S-doped rutile TiO2 photocatalyst.
Effects of pure TiO2, Ta-TiO2, S-TiO2, and Ta-S-TiO2 on degradation of MB under visible light irradiation (a) and ultraviolet (UV) irradiation (b) were studied. Ta-S-TiO2 exhibited a good photocatalytic performance under UV and visible light irradiation.
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10.
Kaolinite/TiO2 composites were prepared by using sol-gel method and raw kaolin, pretreated kaolinite and tetrabutyl titanate as the main raw materials. X-ray diffractometer, field-emission scanning electron microscope and infrared spectrometer analysis were carried out to characterize the phase composition and microstructure of the samples. The photocatalytic performance of the kaolinite/TiO2 composites were evaluated by degrading the methylene blue (MB) and phenol aqueous solution, respectively. The results show that intercalation and exfoliation reduced the size and thickness of kaolinite particles. Acid treatment improved the distribution and the loading quantity of TiO2 grains. When the kaolinite/TiO2 composites were calcined at 500?°C, the tetragonal structure of anatase particles of 30–100?nm in size were obtained, but the exfoliated kaolinite crystals were damaged. The degradation rate of MB increased gradually with the extension of photocatalytic reaction time and the enhancement of photocatalyst dosage. The adsorption performance of acid-treated kaolinite/TiO2 composite (AKT) was nearly the same as that of raw kaolin/TiO2 composite (RKT), but that of the exfoliated kaolinite/TiO2 composite (EKT) was the most excellent. The photocatalytic performance of AKT and EKT were better than that of RKT, and AKT exhibited the optimum property. Under a certain photocatalyst dosage and photocatalysis time, the absorption rate and the degradation rate decreased gradually with the enhancement of initial concentration of MB. Similar result was also acquired for the degradation of phenol. Both the acid treating and the exfoliating to kaolinite enhanced the photocatalytic performance of the kaolinite/TiO2 composite photocatalysts, but acid treatment may be more helpful to the preparation of high performance kaolinite/TiO2 composite photocatalyst.  相似文献   

11.
The photocatalytic reduction of nitrogen monoxide (NO) with ethane on the hollandite type catalyst (K2Ga2Sn6O16KGSO) was investigated. Using a closed-gas circulating system equipped with a Q-MASS detector and in-situ diffuse reflectance FT-IR spectroscopy. The reactant gases of NO and 13C2H6 decreased with the increasing irradiation time. In contrast, the N2 yield increased proportionally to the conversion of 13C2H6. Nitrogen oxides such as N2O did not reach their detectable levels. The NO adsorbed on KGSO was found to change to its activated species by UV irradiation. The oxidized products of C2H6 such as CH3CHO increased in proportion to the reaction time. The present results strongly suggest that KGSO has remarkable photocatalytic activity for the reduction of NO with C2H6.  相似文献   

12.
It was found that the photoelectrochemical performance and photocatalytic activity of rod-type TiO2 electrodes were affected by various post-calcination treatments, for example, calcination in NH3 or under vacuum. Post-calcination treatment in NH3 at 773 K was particularly effective in increasing the photoelectrochemical performance and photocatalytic activity of rod-type TiO2 electrodes. A unique photoelectrochemical circuit was constructed by connecting a rod-type TiO2 electrode to a Pt electrode through a silicon solar cell in which the negative bias was applied on the rod-type TiO2 electrode. It was found that the photoelectrochemical circuit can effectively oxidize ethanethiol in water into CO2.  相似文献   

13.
A combined study of intrinsic structural defects in reduced TiO2 was performed using mass spectrometry, optical diffuse-reflectance spectroscopy, and UV photoelectron spectroscopy (UPS). It was found that the reduction of TiO2 resulted in the appearance of absorption in the region 0.50 h 3.50 eV (400 2500 nm), which is formed by absorption due to free electrons (a continuum at h 1.50 eV), local centers—Ti3+ ions (a band at 2.00 eV), and oxygen vacancies (bands at 1.17, 2.81, and 2.55 eV). The spectrum of induced occupied electronic states in the forbidden gap and the position of oxygen vacancy levels with respect to the Fermi level were determined by UPS. The absorption of reduced TiO2 was stable on the sample to T = 800 K in a vacuum; however, it weakened in contact with O2, NO, and N2O molecules beginning at T = 300 K (surface sites) and T 400 K (subsurface sites) as a result of filling oxygen vacancies with atomic oxygen in the course of dissociative adsorption. The adsorption complexes formed by the interaction of O2, NO, and N2O with defects were analyzed by temperature-programmed desorption. The distribution of sites over the energies of oxygen binding was found with the use of a nonuniform surface model, and specific oxygen adsorption species were revealed. It was found that the irradiation of TiO2 activates the formation and decay of sites and results in the formation of specific O2 and N2O adsorption species.  相似文献   

14.
The efficiency of TiO2 (Degussa P-25) modified with an alkaline admixture (urea, BaO), sulfuric acid, or platinum in the photocatalytic oxidation of NO (50 ppm) with a flowing 7% O2 + N2 mixture under UV irradiation in a flow reactor at room temperature and atmospheric pressure is reported. Because of the progressive blocking of active sites of the photocatalyst by the reaction products (NO2, NO3), it is impossible to realize prolonged continuous removal of NO x (NO + NO2) from air without catalyst regeneration at elevated temperatures. The efficiency of the photocatalysts is characterized by specific photoadsorption capacity (SPC) calculated from the total amount of NO x adsorbed during 2-h-long irradiation. Modification of TiO2 with 5% BaO or 5% urea raises the SPC of the catalyst by a factor of 2–3. Presumably, this promoting effect is due to the basic properties of these dopants, which readily sorb NO2 and NO3. A considerable favorable effect on SPC is also attained by adding 0.5% Pt to (5% BaO)/TiO2. The SPC of the (0.5% Pt)/TiO2 catalyst depends on the state of the platinum. The samples calcined in air at 500°C, which contain Pt+ and Pt2+, have an approximately 2 times higher SPC than unpromoted TiO2 and ensure a much larger NO2/NO ratio at the reactor outlet. Conversely, the samples reduced in an H2 atmosphere at 200°C, whose platinum is in the Pt0 state, show a lower SPC than the initial TiO2 and cause no significant change in the NO2/NO ratio.  相似文献   

15.
The aim of this study was the development of low-cost tannin-formaldehyde xerogel/TiO2 (XTi-w) and carbon xerogel/TiO2 (XTiC-w) photocatalysts. The materials used as precursors were recycled titanium scraps and black wattle tannin extract, highlighting the low-cost approach employed in the synthesis. The materials were characterized by diffuse reflectance spectroscopy, scanning electron microscopy, dispersive energy spectrophotometry, X-ray diffractometry, infrared and Raman spectroscopy. X-ray diffractometry showed that the XTiC-w have tetragonal crystalline structure (anatase), whereas the XTi-w has an amorphous structure. The Raman and infrared analysis also showed the presence of titanium dioxide in the composition of both XTi-w and XTiC-w. XTi-w and XTiC-w showed photocatalytic activity at the visible wavelength. Titanium dioxide displayed no photocatalytic activity at the visible wavelength. The XTi-60 composite displayed the highest efficiency in the removal of the methylene blue from the system, as well as good reusability properties. The radicals with higher influence in the photocatalytic reaction mechanism are the photo generated electron and the singlet oxygen molecule. The effect of the heat treatment is negative on the photocatalytic properties of the hybrids produced, due to the removal of acid sites, adsorbed water and OH surface groups.
The graphical abstract displays an illustration of the materials obtained in this work and their respective efficiency in the adsorption and photocatalytic degradation of methylene blue under visible light.
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16.
TiO2/Ni metal-semiconductor composites were prepared from mesoporous titanium dioxide obtained by sol-gel precipitation in the presence of a structure-forming template. The photocatalytic activity of mesoporous TiO2/Ni composites in the generation of hydrogen from aqueous ethanol mixtures was discovered and studied in detail.__________Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol. 41, No. 1, pp. 24–29, January–February, 2005.  相似文献   

17.
ZnFe2O4 nanoparticles sensitized by C-modified TiO2 hybrids (ZnFe2O4–TiO2/C) were successfully prepared by a feasible method. The ZnFe2O4 nanoparticles were prepared by mechanical alloying and annealing. The residual organic compounds in the synthetic process of TiO2 were selected as the carbon source. The as-prepared composites were characterized by X-ray diffraction, Raman spectroscopy, X-ray fluorescence, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet–visible light diffuse reflectance spectroscopy (UV–Vis) and N2 adsorption–desorption analysis. The photocatalytic activity of the photocatalysts was measured by degradation of methyl orange under ultraviolet (UV) light and simulated solar irradiation, respectively. The results show that the carbon did not enter the TiO2 lattice but adhered to the surface of TiO2. The photocatalytic activity of the as-prepared C-modified TiO2 (TiO2/C) improved both under UV and simulated solar light irradiation, but the improvement was not dramatic. Introduction of ZnFe2O4 into the TiO2/C could enhance the absorption spectrum range. The ZnFe2O4–TiO2/C hybrids exhibited a higher photocatalytic activity both than that of the pure TiO2 and TiO2/C under either UV or simulated solar light irradiation. The complex synergistic effect plays an important role in improving the photocatalytic performance of ZnFe2O4–TiO2/C composites. The optimum photocatalytic performance was obtained from the ZnFe2O4(0.8 wt%)–TiO2/C sample.  相似文献   

18.
Eco-friendly biosynthesis of polycrystalline titanium dioxide (TiO2) nanoparticles (NPs) was synthesised using Justicia gendarussa (J. gendarussa) leaf extract as oxidizing agents. They were compared with TiO2 NPs synthesized using the glacial acetic acid and also studied was the combined effect of synthesis of TiO2 NPs. The crystalline nature and structural formation of TiO2 NPs synthesized by different methods were confirmed by the X-ray diffraction technique, and functional groups of materials were confirmed by FT-IR spectroscopy. The synthesized materials were investigated for photocatalytic activity for methylene blue under UV irradiation and toxicity activity against MCF-7 and MDA-MB-231 cells. The result indicates that TiO2 NPs synthesised by J. gendarussa showed superior and enhanced activity against MCF-7 and MDA-MB-231. Biosynthesized TiO2 NPs showed higher photodegradation of dyes when compared with other TiO2 NPs synthesized by different methods. This is due to the alterations in band gap; structural changes and surface area in nanoparticles that increased the activity. Also, nanosphere/disc like morphology of TiO2 NPs is confirmed using TEM.  相似文献   

19.
The degradation of ofloxacin (OFX) at low concentration in aqueous solution by UVA-LED/TiO2 nanotube arrays photocatalytic fuel cells (UVA-LED/TiO2 NTs PFCs) was investigated. TiO2 nanotube arrays (TiO2 NTs) photoanode prepared by anodization-constituted anatase–rutile bicrystalline framework. The results indicated that the degradation efficiency of OFX by UVA-LED/TiO2 NTs PFC was significantly enhanced by 14.3% compared with UVA-LED/TiO2 NTs photocatalysis. The pH affected the degradation efficiency markedly; the highest degradation efficiency (95.0%) and the pseudo-first-order reaction rate constant k value (0.049 min?1) were achieved in neutral condition (pH 7.0). The degradation efficiency increased with the increasing concentration of dissolved oxygen (DO) in the UVA-LED/TiO2 NTs PFC. The main reactive species of OFX degradation are positive holes (h+) and superoxide ion radicals (O 2 ·? ) in a DO sufficient condition. Furthermore, the possible pathways of OFX degradation were proposed.  相似文献   

20.
The extra electron on the hydrogenated anatase TiO2(101) is localized at the nearest Ti5c only, and the chargetransfer promoted NO and O2 adsorptions are also site-selective. These results are totally different from those at hydrogenated rutile TiO2(110).  相似文献   

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