5,192 research outputs found
Interaction between zeolites and cluster compounds. Part 2.—Thermal decomposition of iron pentacarbonyl on zeolites
Thermal decomposition in a thermobalance of Fe(CO)5 adsorbed on alkali-metal, hydrogen-Y, dealuminated Y, L and omega zeolites proceeds stepwise via slow decarbonylation at low and high temperatures, separated by a fast endothermic reaction. Average CO/Fe ratios have been determined after each step. From i.r. results the former intermediates are assigned to species bearing bridging CO, whereas reaction products with CO/Fe < 1 are associated with highly unsaturated carbonyl clusters in strong interaction with the zeolite.The thermal stability of zeolite/Fe(CO)5 adducts as well as of the intermediates increases with the electron-donor properties of the matrix and can be rationalized using the Sanderson electronegativity concept. Iron loadings ranging from 2.4 wt % in zeolite L up to 10 wt % with NaY and HY are obtained by decomposition in inert atmosphere. Under vacuum conditions loss of metal up to 50% is observed. Metallic iron clusters are the final decomposition products in alkali-metal zeolites, as probed by NO adsorption. In HY part of the metallic iron is oxidized to FeII ions, which are located at cation positions
Interaction between zeolites and cluster compounds. Part 1.—Adsorption of iron pentacarbonyl on zeolites
The adsorption isotherms of Fe(CO)5 on NaY, HY and Linde L zeolites obtained in McBain balances show micropore adsorption, whereas additional capillary condensation is found with zeolite omega and Na-mordenite. The pores and/or cages of the zeolites studied are completely filled with the complex upon saturation, with the exception of Na-mordenite. Their behaviour is explained, respectively, by pore blocking and the occurrence of channel openings that are too narrow. The silicalite channel system also is too narrow to accept Fe(CO)5 molecules.Infrared results show that an increasing interaction of the complex with faujasites exists in the sequence: dealuminated Y < CsY < HY < NaY. This is derived from the increasing band half-width of the adsorbed complex in the CO stretching region and from the increasing intensity of the v1 vibration, which upon adsorption becomes i.r. active. The interaction is assumed to be influenced mainly by electrostatic fields in the cages or pores, which can lead to a very restricted mobility for the encaged complex. The complex seems to remain intact upon adsorption at 293 K in all the zeolites studied
Photolytic and thermolytic decomposition products from iron pentacarbonyl adsorbed on Y zeolite
Zeolite supported iron systems obtained by photolysis and thermolysis of Fe(CO)5/Na---Y adducts are characterized via evaluation of the respective magnetic isotherms taken with a FONER magnetometer at T = 4.2 K. Thermolysis under fast heating in inert gas and under fluidized shallow bed conditions completes within a few minutes at not, vert, similar 500 K, and gives iron clusters of which at least 70 to 90 wt% is smaller than 1 nm. Prolonged photolysis at 290 K in the same fluidized bed conditions does not result in the formation of ‘naked’ iron(O) clusters, but gives a limited fraction of magnetically coupled Fex(CO)y entities. Photodimerization cannot be excluded to be the main reaction path
Characterization of a new iron-on-zeolite Y Fischer-Tropsch catalyst
Iron pentacarbonyl adsorbed on dry Na-Y zeolite can be oxidized at subambient temperatures into Fe203 located in the zeolite supercages (catalyst I). When catalyst I is hydrogen reduced at 575 K most of the iron has agglomerated externally to the zeolite (catalyst 11). When the iron carbonyl is thermally decomposed in vacuo at 525 K, an iron phase with a very low degree of dispersion is again obtained (catalyst 111). During a Fischer-Tropsch reaction most of the iron is transformed into a Hagg-type carbide phase, located externally to the zeolite. Catalysts I1 and 111 rapidly reach steady state and show a Schulz-Flory-type of product distribution, the Hagg carbide being the active phase. Catalyst I slowly moves to steady state and Schulz-Flory behavior. Product selectivity is only found on this catalyst during transient conditions. The physical information on the three catalysts before and after reaction was obtained with transmission electron microscopy and Mossbauer and EXAFS spectroscopies. These techniques supplied consistent and complementary evidenc
Inclusion Polymerization and Doping in Zeolite Channels. Polyaniline
Aniline has been polymerized in the three-dimensional channel system of zeolite Y. The monomer was diffused into zeolites with different levels of acidity from hexane solution. Subsequent admission of peroxydisulfate or iodate from aqueous solution yielded the intrazeolite polymers, as demonstrated by FT-IR, electronic absorption data and recovery of the included polymer. With S2O82-, the intrazeolite products are a function of the proton content of the zeolite. Polymer is only formed when a sufficient supply of protons is present in the zeolite host. When neutral iodate solution is used, no polymer is formed in NaY and acid zeolites, but at low pH aniline polymerizes in all zeolites. The open pore system of the zeolite host can be accessed by base such that the intrazeolite protonated polymer is transformed into the corresponding neutral polymer.
The polymer chains encapsulated in zeolite hosts represent a new class of low- dimensional electronic materials
Intrazeolite phototopotaxy. EXAFS analysis of precursor 8{W(CO)6}-Na56Y and photooxidation products 16(WO3)-Na56Y and 28(WO3)-Na56Y
The intrazeolite photooxidation chemistry of alpha-cage encapsulated hexacarbonyltungsten(0) in Na56Y with O2, denoted n{W(CO)6}-Na56Y/O2/hv, which has previously been shown to provide a novel synthetic pathway to alpha-cage located tungsten(VI) oxide, denoted n(WO3)-Na56Y, is now the subject of an extended X-ray absorption fine structure (EXAFS) analysis. The EXAFS data of a precursor 8{W(CO)6}Na56Y, which contains on average one W(CO)6 per alpha-cage shows that the W(CO)6 guest maintains its structural integrity with only minor observable perturbations of the skeletal WC and ligand CO bonds compared to those found for the same molecule in the free state. The EXAFS analysis results for the photoxidation products 16(WO3)-Na56Y and 28(WO3)-Na56Y are very similar and display the presence of two terminal tungsten-oxygen bonds (1.75-1.77 angstrom) and two bridging tungsten-oxide bonds (1.94-1.95 angstrom), together with a short distance to a second tungsten (3.24-3.30 angstrom). This bond length and coordination number information for n = 16 and 28 samples is best interpreted in terms of the formation of a single kind of tungsten trioxide dimer unit (WO3)2, most likely interacting with extraframework Na+ cations, denoted ZONa...O2W(mu-O)2WO2...NaOZ. In conjunction with earlier chemical and spectroscopic information on this system, the EXAFS data support the contention that 16(WO3)-Na56Y contains a uniform array of single size and shape tungsten (VI) oxide dimers (WO3)2 housed in the 13-angstrom supercages of the zeolite Y host. The sequential addition of WO3 units to the 16(WO3)-Na56Y sample appears to increase the (WO3)2 dimer population, causing a buildup of alpha-cage encapsulated dimers-of-dimers {(WO3)2}2 rather than further cluster growth to trimers (WO3)2 and/or tetramers (WO3)4
Intrazeolite metal carbonyl topotaxy. A comprehensive structural and spectroscopic study of intrazeolite Group VI metal hexacarbonyls and subcarbonyls
This paper focuses attention on the intrazeolite anchoring, thermal decarbonylation, ligand exchange, and addition chemistry of M(CO)6-M'56Y, where M = Cr, Mo, W; M' = H, Li, Na, K, Rb, Cs. The key points to emerge from this study include the following. (i) M(CO)6-M'56Y samples have the hexacarbonylmetal(O) molecule associated with two alpha-cage extraframework cations (or Bronsted protons), via the oxygen end of two trans bonded carbonyls with a saturation loading of 2M(CO)6/alpha-cage. (ii) M(CO)6-M'56Y samples have the hexacarbonylmetal(O) guest confined to the internal surface of the zeolite with a homogeneous distribution throughout the zeolite crystals. (iii) A Mo and Rb EXAFS structure analysis of 8{Mo(CO)6}-Rb56Y shows that the alpha-cage encapsulated Mo(CO)6 guest maintains its structural integrity, with some evidence for anchoring via extraframework Rb+ cations. (iv) A rapid C-13O intrazeolite ligand exchange occurs M(12CO)6-M '56Y to yield M(12CO)m(13CO)6-m-M'56Y, the extent of which depends on the 13CO loading. (v) M(CO)3-M'56Y can be cleanly generated via the mild vacuum thermal decarbonylation of M(CO)6-M56Y, the tricarbonyl stoichiometry of which is unequivocally established from its observed and calculated diagnostic M(12CO)n(13CO)3-n-M'56Y vibrational isotope pattern and from EXAFS structural data. (vi) Intrazeolite ractions of M(CO)3-M'56Y with large and small arenes, trienes, and phosphines cleanly yield the respective intrazeolite six-coordinate complexes (shown to be identical with the products of direct impregnation of the latter complexes), thereby supporting the tricarbonylmetal(0) assignment as well as pinpointing the location of the M(CO)3-M'56Y tricarbonylmetal(0) fragment on the internal surface of the zeolite. (vii) Cation effects in the mid/far-IR, EXAFS data, and optical reflectance spectra indicate that the supercage-confined M(CO)3-M'56Y moiety is anchored to an oxygen framework site rather than to an extrawork cation site via the metal or oxygens of the carbonyls. (viii) The tricarbonyl fragments show C(s) and C3-upsilon symmetry depending on the choice of M and M' which can be rationalized in terms of a second-order Jahn-Teller effect. (ix) EXAFS data for the mild thermal decomposition of Mo(CO)3-Rb56Y demonstrates the formation of molybdenum atoms statistically distributed in the zeolite lattice
Agglomeration mechanism during the preparation of nickel(0) and iron(0) zeolites
Magnetization measurements have been used to study the reduction process of Ni - zeolites and the thermal decomposition of
iron pentacarbonyl adsorbed on NaY zeolites . The Ni(0) particle size distribution in H2»reduced NiNaA, Ni NaX, Ni NaY and
NiNaM is bidisperse. The amount and the volume of particles
exceeding the cage dimensions increases in the sequence Μ,Υ,Χ,Α
zeolites. Particle fusion is found to be the rate determining
step. With decomposition of Fe(C0)5/NaY adducts, up to 97 wt.%
of the iron particles produced are smaller than 1.3 nm. Fluidized
sample bed, inert gas atmosphere and fast heating up to
440 Κ are essential to reach mononodal dispersion
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