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Effect of thermal treatment on surface and bulk properties of Fe/ZSM-5 zeolites prepared by different methods

Fe/ZSM-5 samples (5 wt.% Fe) prepared by in situ incorporation using TPABr template under hydrothermal conditions (Fe-ZSM-5in), chemical liquid deposition (Fe-ZSM-5imp) and solid-solid (Fe-ZSM-5ss) interaction were characterized by N2 physisorption, TG/DSC, X-ray diffraction, FTIR spectroscopy, UV-Vis diffuse reflectance spectroscopy and 57Fe Moessbauer spectroscopy techniques. Calcination at 550 C leads to almost complete removal of template that was associated with dislodgment of significant fraction of Fe to external positions as recognized for the in situ prepared sample (Fe-ZSM-5in). This sample showed an increase in lattice volume suggesting the presence of the majority of Fe ions in tetrahedral positions inside zeolite channels and offered as well the lowest crystallites size (75 nm) and maximum SBET (453 m2/g) between all samples. On the other hand, Fe-ZSM-5ssbef, resulting from solid-solid interaction and subjected to heat treatment in vacuum at 200 C, measured the lowest mean pore radius (r-; 23 A), and pore volume (Vp; 0.3887 cm3/g), giving a hint about the probability of finding neutral iron oxide nanoparticles (alpha-Fe 2O3) as a separate phase that has been validated by Moessbauer (IS = 0.3 mm/s, QS = -0.2 mm/s, Heff = 520 kOe) and UV-Vis (400 nm) investigations. This sample also demonstrated that the majority of Fe occupied framework positions beside a fraction identified as small oligonuclear oxo-iron ions (Fex3+-O; 290 nm). Interestingly, Fe-ZSM-5 ssaft, resulting from solid-solid interaction and subjected to air calcination at 550 C, measured maximum Vp (0.6380 cm 3/g) and r- (39 A) values, reflecting the enforced location of Fe in this sample leading to an effective pore widening and thus a pronounced mesoporosity is attained. IR bands due to nuasT-O in ZSM-5 (1105 cm-1) showed a shift to lower wave numbers (1059 cm -1) following Fe incorporation reflecting the extent of exchanging Fe in this sample (Fe-ZSM-5ssaft), unlike the rest of the samples which showed splitting, which accounted for the presence of residual Al3+ beside Fe3+ ions in the same site. Moessbauer data of this sample confirmed the latter result and indicated the maximum lattice imperfection and showed as well the lowest degree of crystallinity. The Fe-ZSM-5impaft sample, subjected to heat treatment at 550 C, showed alpha-Fe 2O3 species where that heated at 110 C presented the lowest SBET (361 m2/g). More correlations were evaluated and discussed on the effect of thermal treatment on the existence of various Fe species (either framework or non-framework), their electronic states and local structures.

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Particle size control and self-assembly processes in novel colloids of nanocrystalline manganese oxide

The synthesis of semiconducting nanocrystals of manganese oxide of controlled sizes and their manipulation to form ordered arrays is described. Nanocrystalline mixed-valent manganese oxides have been prepared as colloidal solutions via reduction of tetraalkylammonium (methyl, ethyl, propyl, and butyl) permanganate salts in aqueous solutions with 2-butanol and ethanol. Reduction with the poorly water miscible 2-butanol produces aqueous colloids for the methyl, ethyl, and propyl systems, whereas 2-butanol colloids are produced for the butyl system. The colloids are reddish-brown, have an average manganese oxidation state of 3.70-3.79, and have been prepared in manganese concentrations up to 0.57 M. The sols will gel upon aging, and the gel time depends on the cation, the amount of alcohol, the temperature, and the concentration of manganese. Small angle neutron scattering (SANS) data indicate that the particles are disklike in shape with radii in the range 20-80 A and are largely unassociated in solution. Thin films produced from evaporation of the colloid or spreading of the gel onto glass slides demonstrate long-range order, yielding an X-ray diffraction (XRD) pattern consistent with a structure of Cdl2-type layers of manganese oxide with tetraalkylammonium cations and water molecules interspersed between the layers. The SANS and XRD evidence are consistent with a mechanism of self-assembly of unassociated layers upon concentration and evaporation. Consistent with a mechanism of quantum confinement, UV/visible spectroscopy of the colloids reveals two absorbances, one near 220 nm and the other in the range 290-310 nm, blue-shifted from the maxima observed for bulk manganese oxide (400 nm). When the samples are aged, these bands shift to the red. The growth of particles in solution with aging, indicated by the shifts in absorbance, has been confirmed by SANS experiments. A 1999 American Chemical Society.

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Use of Concentration-Dependent Relaxation Rates for Carbon-13 Chemical Shift Assignment of Symmetric Tetraalkylammonium Salts in Acetonitrile.

The assignment of 13C chemical shifts of several symmetric tetraalkylammonim salts in acetonitrile is based on alkyl chain carbon spin-lattice relaxation rates (T-11), and on concentration-dependent changes in these rates.

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Metal catalyst and ligand design,
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Modification of pore size of MFI-type zeolite by catalytic cracking of silane and application to preparation of H2-separating zeolite membrane

Catalytic cracking of silane (CCS) is proposed as a new method for modifying the effective pore opening of a zeolite. In this method, first silane compounds which can penetrate into the pores of the zeolite are introduced and are pre-adsorbed on active sites within the zeolite, such as acid sites and metal cations. Next, the adsorbed species are cracked catalytically on the sites, leaving coke that contains Si atoms on the active sites. By the calcination of the coked material, mono SiO2 units are formed on active sites, thereby reducing the size of the pores. When this method is applied to powdery MFI-type zeolite, the adsorption capacity of benzene is markedly reduced, but that of CO2 is maintained constant. Furthermore, the proposed CCS method was applied to reduce the pore diameters of an MFI-type zeolite membrane. By use of the membrane, experiments of separating H2 from a mixture gas containing H2 and N2 or O2 were conducted in a flow system. The membrane showed a high H2 separation factor of about 90-140 (as compared with 1.4-4.5 for a non-treated MFI-type zeolite membrane).

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Metal catalyst and ligand design,
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Thermodynamic Characteristics of Solvation of Individual Ions in Ethanol at -50 to 55 deg C

Experimentally determined are the enthalpies of solution of 12 electrolytes (LiBr, LiI, NaBr, NaI, NaBPh4, Et4NCl, Et4NBr, Pr4Br, Bu4NBr, Am4NBr, Ph4PCl, Ph4PBr) in ethanol at -50 to 55 deg C. DeltasH0 values obtained on the basis of four different extrapolation equations are analyzed.The effect of temperature changes on the thermodynamic parameters of solvation of individual ions are calculated using thermodynamic data for the salt crystals (lattice) with the assumption that DeltasolvCp0(Ph4P+) = DeltasolvCp0(Ph4B-).

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Organic-templated silica membranes: I. Gas and vapor transport properties

A novel and efficient method for molecular engineering of the pore size and porosity of microporous sol-gel silica membranes is demonstrated in this communication. By adding a suitable organic template (e.g. tetraethyl- or tetrapropylammonium bromide) in polymeric silica sols, otherwise known to result in microporous membranes with pores in the range 3-4A, we can ‘shift’ the pore size to 5-6A, as judged by single-component gas and vapor permeation results with probe molecules of increasing kinetic diameter (dk). The templated membranes exhibit permeances as high as 10-7 to 10-6molm-2s-1Pa-1 for molecules with dk<4.0A (e.g. CO2, N2, CH4), coupled with single-component selectivities of 100-1800 for N2/SF6, 20-40 for n-butane/iso-butane, and 10-20 for para-xylene/ortho-xylene. The transport properties of the templated membranes are distinctly different from those of the respective silica membranes prepared without templating, and resemble somewhat the transport properties of polycrystalline zeolite MFI membranes prepared by the lengthy, batch hydrothermal synthesis approach, using tetrapropylammonium bromide as a structure directing agent. Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. Computed Properties of C12H28BrN, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 1941-30-6, in my other articles.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Protective dissolution: Generating secondary pores in zeolite by mechanochemical reaction

Introduction of meso-/macropores into the intrinsic microporous framework of zeolites has raised substantial interest in catalytic reactions with bulky reactants. Herein, we report the formation of secondary meso-/macropores in Silicalite-1 zeolite by a solvent-free mechanochemical grinding process. The strategy allows the preservation of high crystallinity and microporosity of the pristine zeolite, and the generation of mesopores at room temperature and marcopores at higher temperatures. The roles of the tetrapropylammonium bromide (TPABr) and ammonium fluoride (NH4F) have been proposed and demonstrated. A protective layer is formed by TPA+ ions bonded with the surficial defects to shield the outer surface from the direct attack by F-. Instead, F- diffuses into the micropore system in a local aqueous environment within zeolite formed by the mechanochemical reaction. As a result, freely diffused F- selectively dissolves zones with structural defects to form secondary pores inside the zeolite. Moreover, this strategy proves highly effective in encapsulation of nanoparticles (Pt, Co) in the meso-/macropores of Silicalite-1 zeolite, forming a yolk-shell composite catalyst for potential applications.

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Mesoporogen-free synthesis of hierarchically porous ZSM-5 below 100C

The molecular diffusion with zeolites is somewhat limited, particularly for bulky molecules because zeolites only have micropores, which, in turn, limit their use as catalysts. Generation of hierarchically porous ZSM-5 with micro and mesopores has been a rational solution for overcoming this problem. The conventional method for synthesizing hierarchically porous ZSM-5 generally requires high-temperature heating in the presence of an organic structure-directing agent (OSDA) and a mesopore-generating agent (mesoporogen). Herein, we report a new method for the synthesis of hierarchically porous ZSM-5, which leads to the synthesis at low temperature in the presence of a reduced amount of OSDA and in the absence of any mesoporogen. The OSDA seems to play an additional role as a scaffolding agent for mesopore generation. Our study also showed that the control of the molar composition is essential for the crystallization of hierarchically porous-ZSM-5.

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Metal catalyst and ligand design,
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Effect of support surface on methane dry-reforming catalyst preparation

Present investigation shows the different catalytic behavior of Ni-supported catalysts in the dry-reforming of methane. Highly ordered Silicalite-1, highly defective pure silica MCM-41 and pure silica delaminated zeolite ITQ-6 have been prepared and used as support for nickel deposition. The heterogeneity of the support surface strongly affects the nickel particles deposition. Delaminated surface of ITQ-6 material permits to obtain high nickel particles dispersion and high metal sintering resistance. The particles of Ni remain free from coke formation since they are very well dispersed and strongly linked to the support. Good overall catalytic performances was achieved by Ni-ITQ-6 catalyst, after 30 h of reaction: ?80% of CH4 conversion, ?90% of CO2 conversion, H2/CO molar ratio >1.3 and very low coke deposition, <4 wt.%. Note that a catalyst decreases the activation energy for both the forward and the reverse reactions and hence accelerates both the forward and the reverse reactions.Recommanded Product: Tetrapropylammonium bromide, you can also check out more blogs about1941-30-6

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Metal catalyst and ligand design,
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Synthesis and characterization of mesoporous ZSM-5 core-shell particles for improved catalytic properties

HZSM-5 is a unique catalyst for the conversion of methanol, dimethyl ether and other oxygenates into gasoline. During this process, catalyst deactivation by coking requires frequent regeneration and the improvement of catalyst life time is one of the challenges in catalyst development. In this study, a series of mesoporous samples consisting of a ZSM-5 core and a silicalite shell have been synthesized and characterized by XRD, N2-sorption, IR spectroscopy and electron microscopy techniques. Additionally, desilicated conventional and mesoporous ZSM-5-type samples were investigated. All samples were tested in the MTG reaction, and the results showed that both the shell-coated and the desilicated zeolites are significantly more resistant to coke formation. These results are ascribed to the effect of the removal of structural defects rather than to an improvement of the diffusion properties due to the formation of mesopores.

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Metal catalyst and ligand design,
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