Reaction of glucose catalyzed by framework and extraframework tin sites in zeolite beta

The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup, and is now being considered as an intermediate step in the possible route of biomass conversion into fuels and chemicals. Recently, it has been shown that a hydrophobic, large pore, silica molecular sieve having the zeolite beta structure and containing framework Sn⁴⁺ (Sn-Beta) is able to isomerize glucose into fructose in aqueous media. Here, I have investigated how this catalyst converts glucose to fructose and show that it is analogous to that achieved with metalloenzymes. Specifically, glucose partitions into the molecular sieve in the pyranose form, ring opens to the acyclic form in the presence of the Lewis acid center (framework Sn⁴⁺), isomerizes into the acyclic form of fructose and finally ring closes to yield the furanose product. Akin to the metalloenzyme, the isomerization step proceeds by intramolecular hydride transfer from C2 to C1. Extraframework tin oxides located within hydrophobic channels of the molecular sieve that exclude liquid water can also isomerize glucose to fructose in aqueous media, but do so through a base-catalyzed proton abstraction mechanism. Extraframework tin oxide particles located at the external surface of the molecular sieve crystals or on amorphous silica supports are not active in aqueous media but are able to perform the isomerization in methanol by a base-catalyzed proton abstraction mechanism. Post-synthetic exchange of Na⁺ with Sn-Beta alters the glucose reaction pathway from the 1,2 intramolecular hydrogen shift (isomerization) to produce fructose towards the 1,2 intramolecular carbon shift (epimerization) that forms mannose. Na⁺ remains exchanged onto silanol groups during reaction in methanol solvent, leading to a near complete shift in selectivity towards glucose epimerization to mannose. In contrast, decationation occurs during reaction in aqueous solutions and gradually increases the reaction selectivity to isomerization at the expense of epimerization. Decationation and concomitant changes in selectivity can be eliminated by addition of NaCl to the aqueous reaction solution. Thus, framework tin sites with a proximal silanol group are the active sites for the 1, 2 intramolecular hydride shift in the isomerization of glucose to fructose, while these sites with Na-exchanged silanol group are the active sites for the 1, 2 intramolecular carbon shift in epimerization of glucose to mannose.

1-mm gate periphery AlGaN/AIN/GaN HEMTs on SiC with output power of 9.39 W at 8 GHz

AlGaN/AlN/GaN high electron mobility transistor (HEMT) structures with high mobility GaN channel layer were grown on 50 min diameter semi-insulating (SI) 6H-SiC substrates by metalorganic chemical vapor deposition and large periphery HEMT devices were fabricated and characterized. High two-dimensional electron gas mobility of 2215 cm(2)/V s at room temperature with sheet electron concentration of 1.044 x 10(13)/cm(2) was achieved. The 50 mm diameter HEMT wafer exhibited a low average sheet resistance of 251.0 Omega/square, with the resistance uniformity of 2.02%. Atomic force microscopy measurements revealed a smooth AlGaN surface with a root-mean-square roughness of 0.27 nm for a scan area of 5 mu mi x 5 pm. The 1-mm gate width devices fabricated using the materials demonstrated a very high continuous wave output power of 9.39 W at 8 GHz, with a power added efficiency of 46.2% and power gain of 7.54 dB. A maximum drain current density of 1300 mA/mm, an extrinsic transconductance of 382 mS/mm, a current gain cutoff frequency of 31 GHz and a maximum frequency of oscillation 60 GHz were also achieved in the same devices. (C) 2007 Elsevier Ltd. 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].

Influence of A-type Zeolite on Methane Hydrate Formation

The porous medium has an important effect on hydrate formation. In this paper, the formation process and the gas storage capacity of the methane hydrate were investigated with A-type zeolite and Sodium Dodecyl Sulfate (SDS) existing in the system. The results show that A-type zeolite can influence methane hydrate formation. At the temperature of 273.5 K and pressure of 8.3 MPa, the distilled water with A-type zeolite can form methane hydrate with gaseous methane in 12 hours. The formation process of the system with A-type zeolite was quite steady and the amount of A-type zeolite can influence the gas storage capacity significantly. The adding of A-type zeolite with 0.067 g.(g water)(-1) into 2 x 10(-3) g.g(-1) SDS-water solution can increase the gas storage capacity, and the maximum increase rate was 31%. Simultaneously the promotion effect on hydrate formation of 3A-type zeolite is much more obvious than that of 5A-type zeolite when the water adding amounts are 0.033 g.g(-1) and 0.067 g.g(-1) at the experimental conditions.

Absorption spectra of Se-8-ring clusters in zeolite 5A

Samples with different weight ratio of Se to zeolite 5A (Se concentration) have been prepared by loading Se into the pores of zeolite 5A, and the measuerments of the absorption and Raman spectra have been carried out for the prepared samples. The measured absorption edges of the samples are close to the value for monoclinic Se containing Se-8-ring, suggesting the formation of Se-8-ring clusters(1) in the pores. The continuous and broadening features of the absorption spectra are interpreted by the strong electron-nucleus coupling in the Se-8-ring cluster. The absorption edges are red shifted with the increase of the Se concentration. It is tentatively attributed to two reasons. One is the existence of the double Se-8-ring cluster in the high Se concentration samples, and the other is that for the strong electron-nucleus coupling cluster, the absorption edge of the clusters system will be red shifted with the increase of the cluster concentration in the clusters system. A single broad band at about 262 cm(-1) is observed in the Raman spectra, which further supports the formation of Se-8-ring clusters. (C) 1997 Published by Elsevier Science S.A.

Absorption and Raman spectra of Se-8-ring clusters in zeolite 5A

Samples with different weight ratio of Se to zeolite 5A (Se composition) have been prepared by loading Se into the cages of zeolite 5A and the measurements of the absorption and Raman spectra have been carried out for the prepared samples. The measured absorption edges of the samples close and blue shifted to the value for monoclinic Se containing Se-8-ring, suggesting the formation of Se-8-ring clusters dagger in the cages. The continuous and broadening features of the absorption spectra are interpreted by the strong electron-phonon coupling in Se-8-ring clusters. The sample with high Se composition has a red shift of the absorption band edge relative to the samples with less Se composition. It is tentatively attributed to the reason that with different Se composition, single Se-8-ring clusters and double Se-8-ring clusters are formed in the cages of zeolite 5A. A single broad band at about 262 cm(-1) is observed in the Raman spectra, that gives the further support of the formation of Se-8-ring clusters. Copyright (C) 1996 Elsevier Science Ltd

Synthesis of NaA zeolite membrane on a ceramic hollow fiber

NaA zeolite membrane was successfully synthesized on a ceramic hollow fiber with an outer diameter of 400 mum, a thickness of 100 mum and an average pore radius of 0.1 mum. The as-synthesized membranes were characterized by XRD, SEM as well as gas permeation. A continuous C NaA zeolite membrane formed after a three-stage synthesis. The membrane thickness was similar to5 mum. Gas permeation data indicated that a relatively high quality NaA zeolite membrane formed on the ceramic hollow fiber support. (C) 2003 Elsevier B.V. All rights reserved.

Effect of acid strength distribution on conversion of FCC gasoline over a ZSM-5 zeolite catalyst

Acid strength distribution and the distribution of aromatics formed in the FCC gasoline conversion reaction on a ZSM-5 zeolite with different Na contents have been studied. With increasing Na content in the ZSM-5 zeolite, the acid sites determined by NH3-TPD technique, especially the strong acid sites, clearly decrease. When used as catalyst for the aromatization reaction, the transformation of olefins in the FCC gasoline into aromatics is governed directly by the strong acid sites on the ZSM-5 catalyst. Only under the conditions that a ZSM-5 catalyst possesses suitable strong acid sites is reaction temperature favorable for the aromatics formed.