A mechanism for enhanced photocatalytic activity of silver-loaded titanium dioxide

In this paper, silver-loaded TiO2 photocatalyst was prepared by photochemical impregnation method and characterized by transmission electron microscopy (TEM), diffuse reflectance spectra (DRS), photooxidation of phenol and photoreduction of Cr(VI). Electron paramagnetic resonance (EPR) was used to detect photoproduced paramagnetic radicals. The correlation of photocatalytic activity and photogenerated reactive species was discussed, and the mechanism of silver-loaded TiO2 for enhancement of photocatalytic activity was elucidated. The results show that deposited silver on TiO2 Surface acts as a site where electrons accumulate. The better separation between electrons and holes on the modified TiO2 surface allowed more efficiency for the oxidation and reduction reactions. The enhanced photocatalytic activity was mainly attributed to the increased amounts of O-2(.-) reactive species and surface Ti3+ reactive center on silver-loaded TiO2 photocatalyst. (C) 2004 Published by Elsevier B.V.

Probing into the catalytic nature of Co/sulfated zirconia for selective reduction of NO with methane

In this work, the structural and surface properties of Co-loaded sulfated zirconia (SZ) catalysts were studied by X-ray diffraction (XRD), N-2 adsorption, NH3-TPD, FT-IR spectroscopy, H-2-TPR, UV-vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), and NO-TPD. NH3-TPD and FT-IR spectra results of the catalysts showed that the sulfation process of the support resulted in the generation of strong Bronsted and Lewis acid sites, which is essential for the SCR of NO with methane. On the other hand, the N-2 adsorption, H-2-TPR, UV/vis DRS, and XPS of the catalysts demonstrated that the presence of the SO42- species promoted the dispersion of the Co species and prevented the formation Of Co3O4. Such an increased dispersion of Co species suppressed the combustion reaction of CH4 by O-2 and increased the selectivity toward NO reduction. The NO-TPD proved that the loading of Co increased the adsorption of NO over SZ catalysts, which is another reason for the promoting effect of Co. (C) 2004 Elsevier Inc. All rights reserved.

A study on the near-infrared luminescent properties of xerogel materials doped with dysprosium complexes

A series of dysprosium complex doped xerogels with the same first ligand (acac = acetylacetone) and different neutral ligands were synthesized in situ via a sol-gel process. The Fourier transform infrared (FTIR) spectra, diffuse reflectance (DR) spectra, and near-infrared (NIR) luminescent properties of dysprosium complexes and dysprosium complex doped xerogels are described in detail. The results reveal that the dysprosium complex is successfully synthesized in situ in the corresponding xerogel. Excitation at the maximum absorption wavelength of the ligands resulted in the characteristic NIR luminescence of the Dy3+ ion, which contributes to the energy transfer from the ligands to the central Dy3+ ion in both the dysprosium complexes and xerogels via an antenna effect.

Tunable Photoluminescence and Cathodoluminescence Properties of Eu3+-Doped LaInO3 Nanocrystalline Phosphors

LaInO3:Eu3+ phosphors were prepared by a Pechini sol-gel process. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), diffuse reflectance, photoluminescence, cathodoluminescence spectra, as well as lifetimes were utilized to characterize the synthesized phosphors. XRD results reveal that the sample begins to crystallize at 600 degrees C and pure LaInO3 phase can be obtained at 800 degrees C. The crystallinity increases upon raising the annealing temperature. The FE-SEM images indicate that LaInO3:Eu3+ phosphors are composed of fine and spherical grains around 40-80 nm in size. Under the excitation of UV light and low-voltage electron-beams, LaInO3:Eu3+ phosphors show the characteristic emissions of the Eu3+ (D-5(J)-F-7(J) J,J(')=0,1,2,3 transitions). The luminescence colors can be tuned from yellowish warm white to red by changing the doping concentration of Eu3+ to some extent. The corresponding luminescence mechanisms have been proposed.

Photoluminescence properties of LaF3: Eu3+ nanoparticles prepared by refluxing method

The europium-doped LaF3 nanoparticles were prepared by refluxing method in glycerol/water mixture and characterized with X-ray diffraction(XRD), field emission scanning electron microscopy(FE-SEM), UV-vis diffuse reflectance spectrum, and photoluminescence spectra. The results of XRD indicated that the obtained LaF3: Eu3+ nanoparticles were well crystallized with a hexagonal structure. ne FE-SEM image illustrated that the LaF3: Eu3+ nanoparticles were spherical with an average size around 30 nm. Under irradiation of UV light, the emission spectrum of LaF3: Eu3+ nanoparticles exhibited the characteristic line emissions arising front the D-5(0)-> F-7(J), (J=1, 2, 3, 4) transitions of the Eu3+ ions, with the dominating emission centered at 590 nm. In addition, the emissions from the 51), level could be clearly observed due to the low phonon energies (-350 cm(-1)) of LaF3 matrix. The optimum doping concentration for LaF3: Eu3+ nanoparticles was determined to be 20mol.%.

Host-sensitized luminescence of Dy3+, Pr3+, Tb3+ in polycrystalline SrIn2O4 for field emission displays

SrIn2O4:Dy3+/Pr3+/Tb3+ white/red/green phosphors were prepared by the Pechini sol-gel process. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), diffuse reflectance, photoluminescence, cathodoluminescence spectra, and lifetimes were utilized to characterize the samples. XRD reveal that the samples begin to crystallize at 800 degrees C and pure SrIn2O4 phase can be obtained at 900 degrees C. FE-SEM images indicate that the SrIn2O4:Dy3+, SrIn2O4:Pr3+, and SrIn2O4:Tb3+ samples consist of fine and spherical grains with size around 200-400 nm. Under the excitation of ultraviolet light and low-voltage electron beams (1 - 5 kV), the SrIn2O4:Dy3+, SrIn2O4: Pr3+, and SrIn2O4: Tb3+ phosphors show the characteristic emissions of Dy3+ (F-4(9/2) - H-6(15/2) at 492 nm and 4F(9/2) - 6H(13/2) at 581 nm, near white), Pr3+ (P-3(0) - H-3(4) at 493 nm, D-1(2) - H-3(4) at 606 nm, and P-3(0) - H-3(6) at 617 nm, red) and Tb3+ (D-5(4) - F-7(6,5,4,3) transitions dominated by D-5(4) - F-7(5) at 544 nm, green), respectively. All of the luminescence resulted from an efficient energy transfer from the SrIn2O4 host lattice to the doped Dy3+, Pr3+, and Tb3+ ions, and the luminescence mechanisms have been proposed.

Host-sensitized luminescence of Dy3+, Pr3+ , Tb3+ in polycrystalline CaIn2O4 for field emission displays

Caln(2)O(4):Dy3+/Pr3+/Tb3+ blue-white/green/green phosphors were prepared by the Pechini sol-gel process. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), diffuse reflectance, photoluminescence (PL) and cathodoluminescencc (CL) spectra as well as lifetimes were utilized to characterize the samples. The XRD results reveal that the samples begin to crystallize at 800 degrees C 3-1 and pure CaIn2O4 phase can be obtained after annealing at 900 degrees C. The FE-SEM images indicate that the CaIn2O4:Dy3+, CaIn2O4:Pr3+ and CaIn2O4:Tb3+ samples consist of spherical grains with size around 200-400nm. Under the excitation of ultraviolet light and low electron beams (1-5kV), the CaIn2O4:Dy3+, CaIn2O4:Pr3+ and CaIn2O4:Tb3+ phosphors show the characteristic emissions of Dy3+ ((F9/2-H15/2)-F-4-H-6 and (F9/2-H13/2)-F-4-H-6 transitions, blue-white), Pr3+ ((P0-H4)-P-3-H-3, (D2-H4)-D-1-H-3 and (P1-H5)-P-3-H-3 transitions, green) and Tb3+ ((D4-F6,5,4,3)-D-5-F-7 transitions, green), respectively. All the luminescence is resulted from an efficient energy transfer from the CaIn2O4 host lattice to the doped Dy3+ ,Pr3+ and Tb3+ ions, and the corresponding luminescence mechanisms have been proposed.

Effect of silver nanoparticles on luminescent properties of europium complex in di-ureasil hybrid materials

Organic-inorganic hybrids containing luminescent lanthanide complex Eu(tta)(3)Phen (tta = thenoyltrifluoroaceton, phen = 1,10-phenanthroline) and silver nanoparticles have been prepared via mixing rare earth complex and nanoparticles with the precursors of di-ureasil using a sol-gel process. The obtained hybrid materials with transparent and elastomeric features were characterized by transmission electron microscope, solid-state Si-29 magic-angle spinning NMR spectra, diffuse reflectance, UV-visible absorption and photoluminescence spectroscopies. The effect of the silver nanoparticles on the luminescence properties was investigated. The experimental results showed that the luminescence intensity of the Eu(tta)(3)phen complex could be enhanced by less than ca. 9.5 nM of silver nanoparticles with the average diameter of 4 nm, and reached its maximum at the concentration of ca. 3.6 nM. Further increasing the concentration of the silver nanoparticles (> 9.5 nM) made the luminescence quenched. The enchancement and quench mechnism was discussed.

Syntheses, structures and near-IR luminescent studies on ternary lanthanide (Er-III, Ho-III, Yb-III, Nd-III) complexes containing 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate

The ligand Hhfth [4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dione], which contains a heptafluoropropyl group, has been used to synthesize several new ternary lanthanide complexes (Ln = Er, Ho, Yb, Nd) in which the synergistic ligand is 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy). The two series of complexes are [Ln(hfth)(3)phen] [abbreviated as (Ln)1, where Ln = Er, Ho, Yb] and [Ln(hfth)(3)bipy] [abbreviated as (Ln)2, where Ln = Er, Ho, Yb, Nd]. Members of the two series have been structurally characterized. The growth morphology, diffuse reflectance (DR) spectra, thermogravimetric analyses, and photophysical studies of these complexes are described in detail. After ligand-mediated excitation of the complexes, they all show the characteristic near-infrared (NIR) luminescence of the corresponding Ln(3+) ions (Ln = Er, Ho, Yb, Nd). This is attributed to efficient energy transfer from the ligands to the central Ln(3+) ions, i.e. an antenna effect. The heptafluorinated substituent in the main hfth sensitizer serves to reduce the degree of vibrational quenching. With these NIR-luminescent lanthanide complexes, the luminescent spectral region from 1300 to 1600 nm, which is of particular interest for telecommunication applications, can be covered completely.

Preparation of TiO2 nanocrystallites by hydrolyzing with gaseous water and their photocatalytic activity

TiO2 nanocrystallites were prepared front precursors tetra-n-butyl titanate (Ti(OC4H9)(4)) and titanium tetrachloride (TiCl4). The precursors were hydrolyzed by gaseous water in autoclave, and then calcined at predetermined testing temperatures. The samples were characterized by X-ray diffraction (XRD), thermogravimetry-differential thermal analysis (TG-DTA), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectra (FT-IR), and UV-vis diffuse reflectance spectra (DRS). The photocatalytic activities of the samples were evaluated by the photobleaching of methylene blue (MB) in aqueous solution and the photocatalytic oxidation of propylene in gas phase at ambient temperature. The results showed that the anatase phase nanocrystalline TiO2 could be obtained at relatively low temperatures (for precursor Ti(OC4H9)4 at I I VC and for TiCl4 at 140 degrees C, respectively), and that the as prepared samples exhibited high photocatalytic activities to photobleach MB in aqueous solution. As the calcination temperatures increasing. the decolor ratio of MB increased and reached the maximum value of nearly 100% at 600 degrees C, and then decreased. The photobleaching of MB by all samples followed the pseudo-first-order kinetics with respect to MB concentration.

Study on the difference of photochromic and thermochromic mechanism of ethylenediamine trimolybdate

Ethylenediamine trimolybdate ((C2H10N2)[Mo3O10], denoted as ENTMo) shows unusual photochromic and thermochromic properties. The color of the white ENTMo compounds becomes reddish brown gradually under UV irradiation, and changes gradually to blue-black upon annealing. XRD patterns and FT-IR spectra verify that the crystal structure of the colored samples is almost unchanged except distortion. UV-vis diffuse reflectance spectra (DRS) and ESR spectra of the photochromic and the thermochromic samples could confirm that there must exist difference between thermochromic and photochromic mechanism.

Preparation and characterization of luminescent cubic MCM-48 impregnated with an Eu3+ beta-diketonate complex

We report on the preparation of luminescent silica mesoporous molecular sieves (MCM-48) activated by the europium complex Eu(DBM)(3) . 2H(2)O (where DBM = dibenzoylmethane), using a simple wet impregnation method. Different concentrations of Eu(DBM)(3) . 2H(2)O were introduced into the MCM-48 cubic structure, and the resulting samples were washed with ethanol for different times. UV-Vis absorption measurements and thermogravimetric analysis were used to estimate the amount of Eu complex that has been incorporated within the pores of the MCM-48 host. The various samples were characterized by X-ray powder diffraction (XRD), infrared spectroscopy, diffuse reflectance (DR) and fluorescence measurements. The results reveal that Eu complexes have been successfully introduced into the pores of MCM-48 without disrupting the structure. All the impregnated MCM-48 materials show the typical red luminescence of Eu3+ when excited with a UV lamp. Shifts of the absorption maxima were observed in the DR and fluorescence excitation spectra and will be discussed in relation with guest-host interactions between the organic complex and the silica matrix. The decay profiles of the europium luminescence in the different samples were also measured and discussed.