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1.
The dispersion characteristics of nanosize silicon carbide (SiC) suspension were investigated in terms of surface charge, particle size, rheological measurement and adsorption study. Ammonium polycarboxylate has been used as dispersant to stabilize the suspension. It was found that the isoelectric point (iep) of SiC powder was pHiep (4.9). The surface charge of powder changed significantly in presence of the ammonium polycarboxylate dispersant and iep shifted significantly towards lower acidic pH (3.6). The shift in iep has been quantified in terms of ΔG 0 SP, the specific free energy of adsorption between the surface sites and the adsorbing polyelectrolyte (APC). The values of ΔG 0 SP (−10.85 RT unit) estimated by the electro kinetic data compare well with those obtained from adsorption isotherms (−9.521 RT unit). The experimentally determined optimum concentration of dispersant required for maximizing the dispersion was found to be 2.4 mg/g of SiC (corresponding to an adsorbed amount of 1.10 mg/g), at pH 7.5. This is much below the full monolayer coverage (corresponding to adsorbed amount of 1.75 mg/g) of the particles surface by the dispersant. The surface charge quantity, rheological, pH, electro kinetic and adsorption isotherm results were used to explain and correlate the stability of the nanosize silicon carbide in aqueous media. At pH 7.5, where both SiC surface and APC are negatively charged, the adsorption of APC was low because of limited availability of favourable adsorption sites. In addition, the brush-like configuration of the adsorbed polymer prevented close approach of any additional dispersant; hence stabilization of the slurry happens at a comparatively lower concentration than the monolayer coverage.  相似文献   

2.
There are many areas in the world where the ground water has been contaminated by arsenic. TiO2 is one of the most promising materials that can remove arsenic from groundwater supplies by the adsorption-based processes. The TiO2 surface is capable of photo-catalytic oxidation (PCO) changing the arsenite [As(III)] to arsenate [As(V)] which is more easily absorbed by the surface, increasing the efficiency of the process. In this paper, a density functional theory calculation has been performed to investigate the adsorption of As(III) on a perfect TiO2 anatase (1 0 1) surface. All the As(III) solution species such as H3AsO3, H2AsO3, HAsO32− and AsO33− are put onto the surface with many different possible attitudes to obtain the adsorption energy. Based on the adsorption energy and the concentration of H3AsO3, H2AsO3, HAsO32− and AsO33− in an aqueous solution, the bidentate binuclear (BB) adsorption configurations of H2AsO3 on the surface are more favorable at low As(III) concentrations, whereas BB form and monodentate mononuclear (MM) form may coexist at higher concentrations. By calculating H2AsO3 co-adsorption with water and oxygen, we can confirm the deep acceptor character of an adsorbed O2 molecule which implies that surface superoxide (or hydroperoxyl radical) plays an important role during the PCO process of As(III) on TiO2 surface.  相似文献   

3.
In this study, the surface of TiO2 nanoparticles was modified through plasma polymerization, which is a dry coating method at room temperature. The surface morphology of TiO2 nanoparticles was characterized by high-resolution transmission electron microscope (HRTEM). The dispersion behavior of TiO2 nanoparticles in water and ethyl glycol was investigated by laser size distribution and ultraviolet–visible absorption spectrum. TiO2 nanoparticles were coated with a thin film through plasma polymerization, which prevents the agglomeration and improves the dispersion behavior of TiO2 nanoparticles.  相似文献   

4.
In the preparation of nanocomposites, there is competition between the dispersion of nanoparticles and the formation of agglomerates. In this study, radical copolymerization of ethyl acrylate and methyl methacrylate initiated by 2,2‐azobis (isobutyro) nitrile (AIBN) was performed, in the presence of titanium oxide (TiO2) nanoparticles modified in a new approach; a good dispersion of the nanoparticles in the unsaturated polyester (UP) matrix was obtained. The TiO2 nanoparticles were exposed to 3‐(methacryloxy) propyl trimethoxy silane as the coupling agent. The presence of coupling agent‐grafted TiO2 nanoparticles in the copolymerization process resulted in the formation of a polymeric layer on the surface of the TiO2 nanoparticles (doubly modified‐TiO2). The grafting of coupling agent molecules and consequently copolymer macromolecular chains onto the surface of TiO2 nanoparticles was investigated using Fourier transform infrared (FTIR) analysis. It found that the formation of an acrylate layer on the surface of nanoparticles was successful. Then, unsaturated polyester (UP)/TiO2 nanocomposites were prepared. The morphology was studied using transmission electron microscopy (TEM). Mechanical properties and ultraviolet visible (UV/VIS) spectroscopy of various samples, including the doubly modified‐TiO2 nanoparticles, with different nanoparticle inclusions and the unmodified‐TiO2 nanoparticles, were also investigated. The results showed the doubly modified‐TiO2 nanoparticles, compared to those of unmodified‐TiO2, had better nanoparticle dispersion causing improvement in the mechanical properties and UV shielding.  相似文献   

5.
The effect of Cl ions on photooxidation of propylene on TiO2 semiconductor was investigated. Cl/TiO2 catalysts were prepared by annealing Degussa P25 TiO2 in the gas flow of N2 and Cl2 under 100-400 °C. The photocatalytic oxidation of propylene was carried out in a continuous flow system, with the chromatograph to analyze the products on line. The experimental results showed that the activity of Cl/TiO2 catalysts increased as heat-treated temperature decreased. The activity of the sample heat-treated at 100 °C was about two times higher than that of pure TiO2. Moreover, as to TiO2, the main product of the propylene photocatalytic oxidation was CO2, but with Cl/TiO2 catalysts, not only CO2 but also trace CO was determined. The adsorbed species on TiO2 surface before and after reaction were analyzed by X-ray photoelectron spectroscopy (XPS) and thermogravimetric/differential thermal analyses (TG-DTA) coupled to a mass spectrometer (MS). XPS analysis showed that there was Cl absorbed on the Cl/TiO2 surface, and the absorption amount of Cl decreased after the photooxidation reaction of propylene. TG-DTA-MS analysis confirmed chlorine absorbed on the surface of TiO2 in the form of Cl ion. These results illuminated that absorbed Cl on the surface of TiO2 formed a weak physical absorption on TiO2 at low temperature, and subsequently participated in the photooxidation of propylene, finally removed from TiO2 surface.  相似文献   

6.
The adsorption energies for physisorption and the most stable chemisorption of CO2 on the neutral charge of perfect anatase [TiO2] (0 0 1) are −9.03 and −24.66 kcal/mol on the spin-unpolarized and −12.98 and −26.19 kcal/mol on the spin-polarized surface. The small activation barriers of 1.67 kcal/mol on the spin-unpolarized surface and of 6.66 kcal/mol on the spin-unpolarized surface were obtained. The adsorption mechanism of CO2 on the oxygen vacancy defect [TiO2 + VO] surface of anatase TiO2 using density functional theory calculations was investigated. The energetically preferred conversion of CO2 to CO was found either on the spin-unpolarized or spin-polarized surfaces of oxygen vacancy defect surface [TiO2 + VO] as photocatalyst.  相似文献   

7.
The Sn-TiO2−X nanoparticles have been prepared via a rapid and simple stannous chemical reducing method. The as-prepared Sn-TiO2−X nanoparticles were investigated by means of surface photovoltage spectroscopy (SPS), XPS, and DRS technology as well as photocatalytic degradation of RhB were studied under illumination. The experiment results revealed that the reduction of the TiO2 particles raised their Fermi level, which can enhance the driven force of photoinduced electrons transferring from TiO2 to adsorbed O2 and SnO2 on the surface of TiO2. On the other hand, the amount of oxygen vacancies of the Sn-TiO2−X increased after the stannous chemical reduction. The oxygen vacancies can also effectively inhibit the recombination of photoinduced electrons and holes pairs. These factors are favorable to the photocatalytic reaction.  相似文献   

8.
Titanium dioxide (TiO2) nanoparticles were modified with poly(methyl methacrylate) (PMMA) to improve the dispersion stability of the nanoparticles in a dielectric medium and to reduce the density mismatch between TiO2 and a dielectric medium for a microcapsule‐type electrophoretic display application. Nanoparticles were coated with PMMA by in situ dispersion polymerization. The PMMA‐coated TiO2 nanoparticles were characterized by fourier transform‐infrared spectrometrey (FT‐IR), electrophoretic light scattering (ELS), and scanning electron microscopy (SEM). Density of PMMA‐coated TiO2 nanoparticles was found to be dependent on the thickness of the PMMA coating on the nanoparticles. An increase of thermal stability of the PMMA layer and the contents of PMMA on the surface of the nanoparticles were measured via thermogravimetric analysis (TGA).  相似文献   

9.
Nano-filled polyurethane coatings were prepared by incorporation of various amounts of untreated and amino propyltrimethoxy silane (APS) treated TiO2 nanoparticles. TEM and AFM techniques were employed to evaluate dispersion of nanoparticles and surface morphology of the coating, respectively. TEM observations revealed that the APS treated nanoparticles have a better dispersion and smaller agglomeration, compared with their untreated counterparts. AFM images revealed that, surface roughness of the coatings increased with increasing of nanoparticles content, however, at equal level of loadings; coatings containing untreated nanoparticles showed a higher surface roughness.Colour changes (colour coordinates data measurements), mechanical properties and surface morphology of the PU nanocomposite coatings, before and after being exposed to a QUV chamber for 1000 h were studied using various techniques. The results revealed that addition of 0.5 to 1.0 wt.% APS treated TiO2 nanoparticles reduces photocatalytic activity, and improves the weathering performance PU nanocomposite coatings. Tensile strength measurements showed significant improvement of mechanical properties of PU coatings containing modified TiO2 nanoparticles. Results also revealed that the colour measurement is a useful technique and non destructive method for evaluation of coating's performance against weathering conditions. The experimental results showed a good correlation between different techniques findings.  相似文献   

10.
Compared to conventional film photocatalysts, fiber photocatalyst has a greater surface-to-volume ratio and a 3-D open structure that allows its surface active sites to be accessible for reactants more easily and effectively. However, TiO 2 powder (Degussa P25), by itself, cannot be prepared in the form of fibers, but with the help of a polymer nanofiber, TiO 2 particles can be immobilized in a fibrous network of polyelectrolyte. Here, hybrid multilayered hollow nanofibers (HMHNFs) composed of TiO 2 /polyelectrolyte (PE) have been prepared by a combination of a electrospinning method and layer-by-layer (LBL) technology. The results show that both the average diameter and the wall thickness of the HMHNFs can be well controlled by the template, as well as the number of coating layers. The dried morphology of the obtained HMHNFs is dependent on the inner deposited numbers of the polyelectrolyte layers. When compared with other nanostructured TiO 2 materials, such as commercial TiO 2 nanoparticles (P25, Degussa) and TiO 2 films, the hollow TiO 2 /PE hybrid nanofibers exhibited higher photocatalytic activities.  相似文献   

11.
Understanding the environmental behavior of nanoparticles includes their interaction with biofilms, which is a covering on the surface of a living or nonliving substrate composed of microorganisms. This study focuses on nano-TiO2 sorption mechanism by synthetic biofilm that was prepared as superporous spherical beads from agarose, using batch stirred flasks kept at room temperature. The pH plays an important part in these phenomena, by its influence on the nanoparticles and biofilm chemistry, where the biofilm nanoTiO2 uptake at neutral pH was enhanced over acidic conditions. Hydroxylation of TiO2 nanoparticles, dependent on pH and the salinity of the solution, influences the stability of colloids, the sorption kinetics via the nature of limiting phases: diffusion through the boundary layer or intrabiofilm mass transfer and the sorption mechanism. The sorption follows pseudo first-order adsorption kinetics with estimated average rate constants of 2.2 (min? 1). Equilibrium isotherms were evaluated using Langmuir and Freundlich isotherms to obtain the maximum uptake at different solution pH and the free energy of the adsorption. The adsorption is apparently irreversible because biofilm limits diffusion of particles out of the pores and the complexation active binding sites on the surface hydrated biofilm to the hydrophilic TiO2 nanoparticles.  相似文献   

12.
Two kinds of hydrophilic polymers, poly(oxyethylene methacrylate) (POEM) and poly(styrene sulfonic acid) (PSSA), were grafted from TiO2 nanoparticles via the surface-initiated atom transfer radical polymerization (ATRP) technique. Chlorine modified TiO2 nanoparticles (TiO2-Cl), the ATRP initiators, were synthesized by the reaction of -OH in TiO2 with 2-chloropropionyl chloride (CPC). FT-IR, UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS) clearly showed that the polymer chains were successfully grafted from the surface of TiO2 nanoparticles. The hydrophilically modified TiO2 nanoparticles have a better dispersion in alcohol than unmodified nanoparticles, as revealed by transmission electron microscopy (TEM). It was also found that the polymer grafting did not significantly alter the crystalline structure of the TiO2 nanoparticles according to the X-ray diffraction (XRD) patterns. Grafting amounts were 10% of the weight for both TiO2-POEM and TiO2-PSSA nanoparticles, as determined by thermogravimetric analysis (TGA).  相似文献   

13.
Indium tin oxide (ITO) and titanium dioxide (TiO2) single layer and double layer ITO/TiO2 films were prepared using reactive pulsed laser ablation deposition (RPLAD) with an ArF excimer laser for applications in dye-sensitized solar cells (DSSCs). The films were deposited on SiO2 substrates either at room temperatures (RT) or heated to 200-400 °C. Under optimized conditions, transmission of ITO films in the visible (vis) range was above 89% for films produced at RT and 93% for the ones deposited at higher temperatures. Increasing the substrate temperature from RT to 400 °C enhances the transmission of TiO2 films in the vis-NIR from about 70% to 92%. High transmission (≈90%) was observed for the double layer ITO/TiO2 with a transmission cut-off above 900 nm. From the transmission data, the energies gaps (Eg), as well as the refractive indexes (n) for the films were estimated. n ≈ 2.03 and 2.04, respectively for ITO films and TiO2 film deposited at 400 °C in the visible region. Post-annealing of the TiO2 films for 3 h at 300 and 500 °C was performed to enhance n. The refractive index of the TiO2 films increases with the post-annealing temperature. The direct band gap is 3.6, 3.74 and 3.82 eV for ITO films deposited at RT, 200, and 400 °C, respectively. The TiO2 films present a direct band gap of 3.51 and 3.37 eV for as deposited TiO2 films and when annealed at 400 °C, respectively. There is a shift of about 0.1 eV between ITO and ITO/TiO2 films deposited at 200 °C. The shift decreases by half when the TiO2 film was deposited at 400 °C. Post-annealing was also performed on double layer ITO/TiO2.  相似文献   

14.
This paper investigated the gaseous formaldehyde degradation by the amine-functionalized SiO2/TiO2 photocatalytic films for improving indoor air quality. The films were synthesized via the co-condensation reaction of methyltrimethoxysilane (MTMOS) and 3-aminopropyltrimethoxysilane (APTMS). The physicochemical properties of prepared photocatalysts were characterized with N2 adsorption/desorption isotherms measurement, X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy (FT/IR). The effect of amine-functional groups and the ratio of MTMOS/APTMS precursors on the formaldehyde adsorption and photocatalytic degradation were investigated. The results showed that the formaldehyde adsorption and photocatalytic degradation of the APTMS-functionalized SiO2/TiO2 film was higher than that of SiO2/TiO2 film due to the surface adsorption on amine sites and the relatively high of the specific surface area of the APTMS-functionalized SiO2/TiO2 film (15 times higher than SiO2/TiO2). The enhancement of the formaldehyde degradation of the film can be attributed to the synergetic effect of adsorption and subsequent photocatalytic decomposition. The repeatability of photocatalytic film was also tested and the degradation efficiency was 91.0% of initial efficiency after seven cycles.  相似文献   

15.
A quantum modeling of the CO adsorption on illuminated anatase TiO2 (0 0 1) is presented. The calculated adsorption energy and geometries of illuminated case are compared with the ground state case. The calculations were achieved by using DFT formalism and the BH and HLYP. Upon photoexcitation, an electron-hole pair is generated. Comparing of natural population in the ground state and the exited state, shows that an electron is trapped in a Ti4+ ion and a hole is localized in an oxygen ion. The photoelectron helps generation of a CO2 molecule on the TiO2 surface. As shown by optimization of these systems, the CO molecule adsorbed vertically on the TiO2 (0 0 1) surface in the ground state case while the CO molecule made an angle of 134.3° to this surface at the excited state case. Based on the here used model the obtained adsorption energy was 0.36 eV which is in excellent agreement with the reported experimental value. In the present work the C-O stretch IR frequencies are calculated which are 1366.53 and 1423.16 cm−1. These results are in good agreement with the earlier reported works for the surface carbonaceous compounds, and oxygenated carbon species.  相似文献   

16.
Since the development of Scanning Tunnelling Microscopy (STM) technique, considerable attention has been devoted to various molecules adsorbed on various surfaces. Also, a new concept emerged with molecules on surfaces considered as nano machines by themselves. In this context, a thorough knowledge of surfaces and adsorbed molecules at an atomic scale are thus particularly invaluable. The present work describes the first Density Functional Theory (DFT) study of adsorption of CO, CO2 and NO molecules on a BaTiO3 surface following a first preliminary calculation of O and O2 adsorption on the same surface. In the previously considered work, we found that a (0 0 1) surface with BaO termination is more stable than the one with TiO2-termination. Consequently, we extended our study to CO, CO2 and NO molecules adsorbed on a (0 0 1) surface with BaO termination. The present calculation was performed on a (1 × 1) cell with one monolayer of adsorbed molecules. Especially, a series of cases implying CO molecules adsorbed in various geometrical configurations has been examined. The corresponding adsorption energy varies in the range of −0.17 to −0.10 eV. The adsorption energy of a CO2 molecule directly located above an O surface atom (called Os) is of the order of −0.18 eV. The O-C distance length is then 1.24 Å and the O-C-O and O-C-Os angles are 134.0° and 113.0°, respectively. For NO adsorption, the most important induced structural changes are the followings: (i) the N-O bond is broken when a NO molecule is absorbed on a Ba-Os bridge site. In that case, N and O atoms are located above an O and a Ba surface atom, respectively, whereas the O-Ba-Os and N-Os-Ba angles are 106.5° and 63.0°, respectively. The N-O distance is as large as 2.58 Å and the adsorption energy is as much as −2.28 eV. (ii) In the second stable position, the NO molecule has its N atom adsorbed above an Os atom, the N-O axis being tilted toward the Ba atom. The N-Os-Ba angle is then 41.1° while the adsorption energy is only −0.10 eV. At last, the local densities of states around C, O as well as N atoms of the considered adsorbed molecules have also been discussed.  相似文献   

17.
Iodine-doped mesoporous TiO2 (I/TiO2) was prepared by hydrothermal method, using tetrabutyl titanate as precursor, potassium iodate as iodine sources. The as-prepared I/TiO2 catalysts were characterized by UV-vis, XRD, TEM, BET, TG/DTA, XPS and photoluminescence (PL) spectroscopy. Production of OH radicals on the I/TiO2 surface was detected by the PL technique using terephthalic acid as a probe molecule. The effects of hydrothermal reaction temperature, calcination temperature and iodine doping content on the structure and properties of the catalysts were investigated. The results showed that iodine-doped TiO2 calcinated at 300 °C have good anatase crystal. The optimal hydrothermal conditions have been determined to be that reaction temperature 120 °C, calcinated temperature 300 °C and added 1.16 mmol iodine dopants. The average particle size of I/TiO2 synthesized under optimal condition (I-3 sample) is about 3.9 nm. The I-3 photocatalyst contains 100% anatase crystalline phase of TiO2. BET specific surface area of I-3 sample is184.8 m2 g−1 and is 3.67 times that of pure TiO2 (50.37 m2 g−1). Iodine in I/TiO2 catalyst mainly exists in the form of I2, and photoactivity of I/TiO2 catalyst in visible light comes from photosensitize of I2. I/TiO2 catalysis shows very high efficiency for the degradation of phenol under visible light.  相似文献   

18.
In this paper, TiO2:Sm3+ (0.75 mol%) nanoparticles doped with different amounts of Br were prepared by an improved sol-gel method and were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), VG ESCALAB MKIIX-ray photoelectron spectrometer (XPS) and ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS). Their photoluminescence (PL) properties were investigated at room temperature. The emissions of 4G5/2-6HJ (J=5/2, 7/2, 9/2) transitions of Sm3+ ions were observed under the excitation wavelength at 350 nm and the emission intensity depended strongly on the doping amount of Br. TiO2:Sm3+ (0.75 mol%) nanoparticles doped with 1 mol% of Br calcined at 700 °C exhibit highest intensity of luminescence, which is nearly three times than the undoped one. The mechanism of photoluminescence in the co-doped system was discussed.  相似文献   

19.
An amorphous acrylic acid (AA) polymer coating was generated on TiO2 nanoparticles through pulse radio frequency (RF) plasma polymerization. The AA plasma synthesis mechanism was studied by its optical emission spectrum. The chemical structures of AA–plasma‐polymer were carefully investigated by Fourier transform infrared spectroscopy (FTIR). The dispersion behaviors of AA‐coated and uncoated TiO2 nanoparticles in glycol solution were characterized by ultraviolet absorbency and particle size distribution measurements. The results showed that the aggregation of TiO2 nanoparticles in glycol solution was effectively lowered and the dispersion was improved a lot after AA–plasma‐polymer coating. The pulse plasma coating parameters played an important role in the dispersion enhancement of TiO2 nanoparticles. By properly regulating the pulse discharge parameters, the system could gain the highest radical–monomer reactions rate, the most compatible functional groups on the nanoparticles, and the best dispersion in the background media.  相似文献   

20.
Lipase B from Candida Antarctica (also known as Candida antarctica lipase B or CALB) was immobilized onto titanium dioxide (TiO2) in a buffer-free, bidistilled aqueous medium. The adsorption isotherm was determined by UV-vis analysis of supernatant solution at 280 nm, revealing that in 7 h 98% of the theoretical lipase monolayer on the TiO2 (with 45.7 m2/g BET area) was achieved.Samples withdrawn from the supernatant immobilization medium were analyzed by Fourier-transform infrared spectroscopy in the 1700-1600 cm−1 range (where the Amide I Proteins band appears) in order to obtain quantitative information on the evolution of the secondary-structure elements of the protein. The analysis performed revealed that lipase conformation suffers only minor changes during its adsorption onto TiO2. However, water associated to the lipase may interact of several ways with the surface of the hydrated oxide.Characterization of the immobilized biocatalyst (CALB/TiO2) implied SEM, fractal dimension analysis and FTIR techniques. A proposal of lipase-hydrated oxide interaction is presented.  相似文献   

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