Studies on preparation of iron phenanthroline and 8-hydroxyquinoline complexes/Y zeolite, characterization and catalytic hydroxylation of phenol

Iron phenanthroline - and 8 - hydroxyquinoline complexes /Y zeolite, denoted a FePhen/Y and FeOx/Y respectively, were prepared; The formation of the metal complexes mentioned above within the cages of Y zeolite and their crystal structures were determined by elemental analyses, diffuse reflectance UV-Vis,SEM,BET,and XRD methods; The influence of experimental parameters upon phenol conversion and product selectivities were investigated as well.

Studies on preparation, characterization of cobalt(II) phenanthroline and 8-hydroxyquinoline complexes/Y zeolite, and catalytic hydroxylation of phenol

Cobalt(II) phenanthroline and 8-hydroxyquinoline complexes/Y zeolite, denoted as CoPhen/Y and CoOx/Y respectively, were prepared, The formation of the metal complexes mentioned above within the cages of Y zeolite and their crystal structures were determined by elementary analyses, TG-DTA, diffuse reflectance UV-Vis, SEM, BET and XRD methods. The influence of experimental parameters upon phenol conversion and product selectivities was investigated as well.

STUDIES ON PREPARATION OF IRON, COBALT AND COPPER PHTHALOCYANINES Y ZEOLITE - CHARACTERIZATION AND THEIR CATALYSIS FOR HYDROXYLATION OF PHENOL

Iron, cobalt and copper phthalocyanines/Y zeolite, denoted as FePcY, CoPcY and CuPcY respectively,were prepared. The formation of metal phthalocyanine compounds within the cages of Y zeolite and their crystal structures were determined by elementary analyses, IR, UV-Vis, TG, BET, and XRD methods; The influence of experimental parameters upon phenol conversion and product selectivities was investigated as well.

Growing process of CdS nanoclusters in zeolite Y studied by positron annihilation

Zeolite Y has been used as the host to generate CdS nanoclusters. The location of CdS nanoclusters inside zeolite hosts was confirmed by the blue-shifted reflection absorption spectra with respect to that of bulk CdS materials. But which kind of cage inside zeolite Y, sodalite cage or supercage, was preferred for the CdS clusters remained unclear. In this paper, we conducted positron annihilation spectroscopy (PAS) measurements for the first time on a series of CdS/Y zeolite samples and concluded that CdS clusters were not located in supercages but in smaller sodalite cages. The stability of CdS clusters inside the sodalite units was due to the coordination of Cd atoms with the framework oxygen atoms of the double six-ring windows. Moreover, PAS revealed some important information of surface states existing on the interfacial layers between CdS clusters and zeolite Y. (C) 2001 Elsevier Science B,V, All rights reserved.

On configuration of exchanged La3+ on ZSM-5: A theoretical approach to the improvement in hydrothermal stability of La-modified ZSM-5 zeolite

Density functional calculations have been employed to investigate the locating and binding of lanthanum cation, i.e., La(OH)(2)(+), on HZSM-5 zeolite. Through geometry optimization, it was determined that lanthanum ions are favorably accommodated in the two 6-T rings of the straight channels (Clusters 1 and 2, see Sec. III A for details). Cluster 1 was found to exist in prior to Cluster 2 due to the preference of Al substitution in the T11 site (Cluster 1) rather than in the T8 site (Cluster 2). Geometry-optimization of Cluster 1 containing another two lanthanide ions Nd3+ and Yb3+ was also carried out and it was found that a monotonic decrease in Ln-O bond length will take place as the atomic number increases, conforming well to the rule of lanthanide contraction. Some of the optimized parameters are comparable to the corresponding experimental values in Y zeolite, which confirms that the optimized configurations are acceptable. The average frequencies of hydroxyls attached to La3+ or Yb3+ in Cluster 1 fall at 3609.16 and 3579.76 cm(-1), respectively, with the gap of these two frequencies close to that in the sodalite cage of Y zeolite. Compared to H-form zeolite, the charges on both Al and O atoms in Ln-ZSM-5 zeolite show an obvious increase, which will undoubtedly lead to a stronger mutual interaction and hence enhance the stability of the [AlO4](-) anion. Moreover, the Ln(OH)(2)(+) seem to have thickened the zeolite framework, which can effectively retard the process of dealumination. Through the evaluation of the possibility for dimer formation, it turned out that when the exchange degree arrived to approximately 0.28, lanthanum monomers began to aggregate into dimers, and were completely converted into dimers when the exchange degree approached 0.60. (C) 2003 American Institute of Physics.

The effect of chromium on sulfur resistance of Pd/HY-Al2O3 catalysts for aromatic hydrogenation

Sulfur is a major poison to noble metal catalysts for deep aromatic hydrogenation in the petroleum refining industry. In order to study the sulfur resistance of Pd-based catalysts, a series of Pd, Cr, and PdCr catalysts supported on HY-Al2O3 were studied by NH3-TPD, pyridine-adsorption IR, TPR, IR spectra of adsorbed CO, and toluene hydrogenation in the presence of 3000 ppm sulfur as thiophene under the following conditions: 533-573 K, 4.2 MPa, and WHSV 4.0 h(-1). Cr has no influence on the acidity of the catalysts. TPR patterns and in situ IR spectra of adsorbed CO revealed a strong interaction between Cr and Pd, and the frequency shift of linear bonded CO on Pd indicates that the electron density of Pd decreases with the increase of the Cr/Pd atomic ratio. The catalytic performance of Pd, Cr, and PdCr catalysts shows that the sulfur resistance of Pd is strongly enhanced by Cr, and the activity reaches its maximum when the Cr/Pd atomic ratio equals 8. The active phase model "Pd particles decorated by Cr2O3" is postulated to explain the behavior of PdCr catalysts. (C) 2001 Academic Press.

Strong effect of transitional metals on the sulfur resistance of Pd/HY-Al2O3 catalysts for aromatic hydrogenation

In order to improve the sulfur resistance of noble metal catalysts in the aromatic hydrogenation of diesel fuel, the alloying effect of non-noble metals with Pd was studied. Toluene hydrogenation over Pd and Pd-M bimetallic catalysts (M = Cr, W,La, Mn, Mo, Ag) on a mixed HY-Al2O3 support was investigated in the presence of 3000 ppm sulfur as thiophene in the feedstock. The results showed that the addition of the second metals strongly affected the activity of toluene hydrogenation, which suggests that the sulfur resistibility of Pd-M bimetallic catalysts is much different from single Pd. La, Mn, Mo and Ag decreased the sulfur resistance of the palladium catalysts. For example, the toluene conversion at 553 K was observed to decrease sharply from 39.4 wt.% on Pd to 1.6 wt.% on Pd-Ag, which is by a factor of 25. One of the important findings in this article is that Cr and W increase hydrogenation activity of Pd catalysts. The reactions occurring on these catalysts include hydrogenation, isomerization and hydrocracking, The addition of the second metals has no noticeable effects on the hydrogenation and isomerization selectivity, but it slightly suppresses hydrocracking reactions. The four typical catalysts, Pd-Cr, Pd-W, Pd-Ag and Pd were characterized by infrared (IR) spectroscopy of pyridine and CO. LR spectra of CO revealed the strong interaction between Pd and the second metal as Cr, W and Ag (or their oxide), indicating that the improvement in sulfur resistance originates from electron-deficient Pd with the addition of second metals. (C) 2001 Elsevier Science B.V. All rights reserved.

Photostimulated luminescence of AgI clusters in zeolite-Y

AgI clusters in zeolite-Y (AgI/Y) were prepared by Ag+ exchange followed by reaction with NaI in solution. The formation of the clusters was determined by transmission electron microscopy and Auger electron spectroscopy. The clusters were uniform and even in size, 1.0-2.0 nm. The fluorescence spectrum of the clusters consists of two emission bands, which are attributed to AgI and Ag clusters, respectively. Photostimulated luminescence (PSL) is observed by stimulation at 675 or at 840 nm. The PSL spectrum of AgI/Y is consistent with the emission spectrum of Ag clusters and thus the PSL is considered to be caused by the charge transfer or carrier migration from the zeolite framework or from the AgI clusters to the Ag clusters. The appearance of PSL indicates that these materials may find application as a medium for erasable optical memory. (C) 1998 American Institute of Physics. [S0021-8979(98)02407-4].

Photoluminescence of ZnS clusters in zeolite-Y

Two obvious emissions are observed from the ZnS clusters encapsulated in zeolite-Y. The emission around 355 nm is sharp and weak, locating at the onset of the absorption edge. The band around 535 nm is broad, strong and Stokes-shifted. Both the two emissions shift to blue and their intensities firstly increase then decrease as the loading of ZnS in zeolite-Y or clusters size decreases. Through investigation, the former is attributed to the excitonic fluorescence, and the latter to the trapped luminescence from surface states. The cluster size-dependence of the luminescence may be explained qualitatively by considering both the carrier recombination and the nonradiative recombination rates. Four peaks appearing in the excitation spectra are assigned to the transitions of 1S-1S, 1S-1P, 1S-1D and surface state, respectively. The excitation spectra of the clusters do not coincide with their absorption spectra. The states splitted by quantum-size confinement are detected in the excitation spectra, but could not be differentiated in the optical absorption spectra due to inhomogeneous broadening. The size-dependence of the excitation spectra is similar to that of the absorption spectra. Both the excitation spectra of excitonic and of trapped emissions are similar, but change in relative intensity and shift in position are observed.

Photostimulated luminescence of silver clusters in zeolite-Y

Upon UV-irradiation at 254 nm, the photoluminescence of silver atoms in zeolite-Y decreases, meanwhile an absorption band shows up around 840 nm. By photostimulation at 840 nm, fluorescence of silver atoms is detected, which is called photostimulated luminescence, and the photoluminescence of silver atoms is increased slightly. These phenomena are attributed to the charge-transfer interaction between the zeolite framework and the entrapped silver atoms. (C) 1997 Published by Elsevier Science B.V.

Thermoluminescence of CdS clusters in zeolite-Y

Thermoluminescence (TL) of CdS clusters encapsulated in zeolite-Y is reported for the first time. The TL of the clusters is much stronger than that of the bulk CdS and increases as the CdS loading decreases. This inverse dependence of TL intensity upon CdS loading is caused mainly by the size-effect of the clusters. All samples exhibit almost the same glow peak position and shape, indicating that traps or surface states are not sensitive to the cluster sizes.

New observation on the luminescence of CdS clusters in zeolite-Y

The excitation spectrum of CdS dusters in zeolite-Y is consistent with their absorption spectrum, both showing two absorption bands that are assigned to the Is-is and Is-lp transitions, respectively. A new emission at 400 nn is considered to be the recombination of the bounded excitons. The emission firstly increases then decreases with increasing cluster size or loading. The emission by excitation into the Is-is band is stronger and sharper than that by excitation into the Is-lp band. This phenomenon is attributed to the size inhomogeneity and the strong electron-phonon interaction of the dusters. Copyright (C) 1996 Elsevier Science Ltd

Some new observation on the formation and optical properties of CdS clusters in zeolite-Y

CdS clusters in zeolite-Y have been prepared by the exchange of Cd2+ into the zeolite following by sulfurization with Na2S in solution. Blue-shifts from the bulk caused by quantum size effect and the change of absorption upon CdS loading are observed. Two absorption bands are detected for one of the sample and are assigned to the 1s-1s band and exciton transition, respectively. The exciton feature is more pronounced in the excitation spectrum than in the absorption spectrum, and the luminescence excited at the exciton band is stronger than that at the 1s-1s band. Copyright (C) 1996 Elsevier Science Ltd