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Title: Synthesis and Characterization of a New Microporous Material. 1. Structure of Aluminophosphate EMM-3

Abstract

Molecular sieves are extensively used in the chemical and petrochemical industry as catalysts, absorbents, and ion exchangers. New molecular sieve structures have the potential to improve the performance of these materials. We have discovered a new microporous material, EMM-3, prepared in both aluminophosphate and silicoaluminophosphate compositions by use of N,N,N,N{prime},N{prime},N{prime}-hexamethyl-1,6-hexanediammonium as a template at 160 C in 20 h. The structure of EMM-3 has been solved and refined from powder data by use of synchrotron X-ray radiation. The unit cell for the calcined AlPO form of EMM-3 has monoclinic space group symmetry, I2/m11, with cell dimensions a = 10.3132(2), b = 12.6975(3), and c = 21.8660(4) and {alpha}= 89.656(1). The microporous structure contains 12-ring, sinusoidal, unidimensional channels with pore openings of 6.1 x 6.5 Angstroms. This new framework contains two new building chains, not observed in other known framework structures. The {sup 31}P and {sup 27}Al NMR spectra of the calcined/dehydrated form are in agreement with a fully connected tetrahedral structure containing five unique phosphorus and five unique aluminum atoms. The material is stable upon calcination and absorbs 9-10 wt % hydrocarbons.

Authors:
; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
914184
Report Number(s):
BNL-78752-2007-JA
Journal ID: ISSN 0897-4756; CMATEX; TRN: US200804%%582
DOE Contract Number:
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chem. Mater.; Journal Volume: 18
Country of Publication:
United States
Language:
English
Subject:
02 PETROLEUM; ABSORBENTS; ALUMINIUM; ATOMS; CALCINATION; CATALYSTS; HYDROCARBONS; MOLECULAR SIEVES; NMR SPECTRA; OPENINGS; PERFORMANCE; PETROCHEMICALS; PHOSPHORUS; SPACE GROUPS; SYMMETRY; SYNTHESIS; national synchrotron light source

Citation Formats

Afeworki,M., Dorset, D., Kennedy, G., and Strohmaier, K.. Synthesis and Characterization of a New Microporous Material. 1. Structure of Aluminophosphate EMM-3. United States: N. p., 2006. Web. doi:10.1021/cm052174r.
Afeworki,M., Dorset, D., Kennedy, G., & Strohmaier, K.. Synthesis and Characterization of a New Microporous Material. 1. Structure of Aluminophosphate EMM-3. United States. doi:10.1021/cm052174r.
Afeworki,M., Dorset, D., Kennedy, G., and Strohmaier, K.. Sun . "Synthesis and Characterization of a New Microporous Material. 1. Structure of Aluminophosphate EMM-3". United States. doi:10.1021/cm052174r.
@article{osti_914184,
title = {Synthesis and Characterization of a New Microporous Material. 1. Structure of Aluminophosphate EMM-3},
author = {Afeworki,M. and Dorset, D. and Kennedy, G. and Strohmaier, K.},
abstractNote = {Molecular sieves are extensively used in the chemical and petrochemical industry as catalysts, absorbents, and ion exchangers. New molecular sieve structures have the potential to improve the performance of these materials. We have discovered a new microporous material, EMM-3, prepared in both aluminophosphate and silicoaluminophosphate compositions by use of N,N,N,N{prime},N{prime},N{prime}-hexamethyl-1,6-hexanediammonium as a template at 160 C in 20 h. The structure of EMM-3 has been solved and refined from powder data by use of synchrotron X-ray radiation. The unit cell for the calcined AlPO form of EMM-3 has monoclinic space group symmetry, I2/m11, with cell dimensions a = 10.3132(2), b = 12.6975(3), and c = 21.8660(4) and {alpha}= 89.656(1). The microporous structure contains 12-ring, sinusoidal, unidimensional channels with pore openings of 6.1 x 6.5 Angstroms. This new framework contains two new building chains, not observed in other known framework structures. The {sup 31}P and {sup 27}Al NMR spectra of the calcined/dehydrated form are in agreement with a fully connected tetrahedral structure containing five unique phosphorus and five unique aluminum atoms. The material is stable upon calcination and absorbs 9-10 wt % hydrocarbons.},
doi = {10.1021/cm052174r},
journal = {Chem. Mater.},
number = ,
volume = 18,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2006},
month = {Sun Jan 01 00:00:00 EST 2006}
}
  • Two isotypes of a new layered aluminophosphate, further denoted MDAP-3 and MDAE-1, have been synthesized under hydrothermal conditions using N-methyl-1,3-propanediamine and N-methyl-ethylenediamine, respectively. MDAP-3, with the empirical formula [Al{sub 2}(HPO{sub 4})(PO{sub 4}){sub 2}](C{sub 4}N{sub 2}H{sub 14})(H{sub 2}O), crystallizes in the orthorhombic space group Pna2(1) (No. 33) with a=9.602(16)A, b=9.26(2)A, c=16.03(3)A, Z=4, R{sub 1}=0.0498 and wR{sub 2}=0.1217. The second solid, MDAE-1, with the empirical formula [Al{sub 2}(HPO{sub 4})(PO{sub 4}){sub 2}](C{sub 3}N{sub 2}H{sub 12})(H{sub 2}O), crystallizes in the same space group with a=9.4250(19)A, b=9.3170(19)A, c=15.907(3)A, Z=4, R{sub 1}=0.0407 and wR{sub 2}=0.0954. The two compounds possess the same layer topology. Inorganic layers containmore » PO{sub 3}=O, PO{sub 3}OH, AlO{sub 4} and AlO{sub 6} polyhedra, linked together to generate a new 4x8 net. MDAP-3 and MDAE-1 represent the first examples of two-dimensional layered aluminophosphates with the Al{sub 2}P{sub 3}O{sub 12} stoichiometry, and containing AlO{sub 6} octahedra.« less
  • The crystal structure of an aluminophosphate, EMM-8 (ExxonMobil Material No. 8), was determined in its calcined, anhydrous form from synchrotron powder diffraction data using the computer program FOCUS. A linkage of double four-ring (D4R) building units forms a two-dimensional framework with 12-MR and 8-MR channels, and differs from a similar SAPO-40 (AFR) framework only by the relationship between paired D4R units. Rietveld refinement reveals a fit of the model to the observed synchrotron data by R{sub 2p} = 0.1118, R(F{sup 2}) = 0.1769. Local environments of the tetrahedral phosphorus and aluminium sites were established by solid-state NMR, which detects distinctmore » differences between as-synthesized and calcined materials. Distinct, reversible changes in the local symmetry of the P and Al atoms were observed by NMR upon calcination and subsequent hydration. These NMR data provided important constraints on the number of tetrahedral (T) atoms per unit cell and the connectivities of the T atoms. Detailed local structural information obtained by solid-state NMR thereby guided the ultimate determination of the structure of AlPO EMM-8 from the powder data. Comparisons are made to the recently published crystal structure of the fluoride-containing, as-synthesized SSZ-51, indicating that the unit-cell symmetry, axial dimensions and framework structure are preserved after calcination.« less
  • A novel layered aluminophosphate (TL-1) has been synthesized. Crystals grow as pseudo-hexagonal thin platelets and their whole morphology depends on the synthesis conditions. The structure was solved by single-crystal X-ray diffraction using charge flipping methods. The synthesized layered material, with composition [AlPO{sub 4}F(H{sub 2}O)]-(H{sub 10}C{sub 4}ON){sub 4}, crystallizes in the monoclinic space group P2{sub 1}/a with a=9.2282(5) Å, b=6.9152(4) Å, c=14.4615(9) Å, β=101.57(1)°. The novel compound has corner sharing AlO{sub 3}F{sub 2}(H{sub 2}O) octahedral chains running along [010], where fluorine atoms are at the shared apices, three oxygen atoms are shared with PO{sub 4} tetrahedra while the sixth oxygen pertainmore » to an H{sub 2}O molecule. The stability field of the novel material is enclosed in the HF/Al{sub 2}O{sub 3} ratio ranging between 1 and 4 and the HF/morpholine ratio lower than 3. At temperature lower than 190 °C, the synthesis results is a pure aluminophosphate sample (low alumina/morpholine ratio). A treatment with H{sub 2}CO{sub 3} leads to a complete morpholine removal, as shown by in situ Raman spectroscopy. Powder X-ray diffraction reveals that, after morpholine extraction, the material collapses. The collapse is irreversible. - Highlights: • A new layered aluminophosphate was obtained and characterized. • The crystal structure is a sequence of aluminophosphate and organic layers. • The stability field of the new phase was defined by changing chemistry and T. • The templating agent can be removed by using a CO{sub 2} aqueous solution. • The decomposition of the morpholine induce a collapse in the structure.« less
  • The first microporous solids incorporating two octahedrally coordinated transition elements, the phosphates (TMA)[sub 2](NH[sub 4])[sub 2][Fe[sub 2]Mo[sub 12]O[sub 30](H[sub 2]PO[sub 4])[sub 6](HOP[sub 4])[sub 2]][center dot]11H[sub 2]O (1) and (TMA)[sub 2]Na[sub 4][Fe[sub 3]Mo[sub 12]O[sub 30](H[sub x]PO[sub 4])[sub 8]][center dot]16H[sub 2]O (2) (TMA = (CH[sub 3])[sub 4]N[sup +]), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction and water absorption isotherms. Phosphate 1 is prepared in 94% yield from Na[sub 2]MoO[sub 4], Mo, FeCl[sub 3], (NH[sub 4])[sub 2]HPO[sub 4], (TMA)OH, H[sub 3]PO[sub 4], and H[sub 2]O in a mole ratio of 5:1:1:2:7:16:150 at 200[degrees]C for 64 h, while 2 is synthesizedmore » in 62% yield by the reaction of Na[sub 2]MoO[sub 4], Mo, FeCl[sub 3], (TMA)OH, H[sub 3]PO[sub 4] and H[sub 2]O in a mole ratio of 5:1:1:8:18:250 at 200[degrees]C for 3 days. Orange crystals of 1 are rhombohedral. Both structures are based on Fe[Mo[sub 6]O[sub 15](H[sub x]PO[sub 4])[sub 2]] units which are connected via their phosphate groups to additional Fe[sup 3+] ions to give three-dimensional frameworks. Both compounds display structures that can be rationalized on the basis of regions of hydrophobic and hydrophilic interactions. The interconnected voids and channels in the ferric molybdenum phosphate frameworks are filled with a mixture of charged-compensating cations and water of solvation. Reversible water absorption isotherms indicate that both compounds are microporous with internal void volumes of about 15 and 25 vol % for 1 and 2, respectively. 23 refs., 10 figs., 3 tabs.« less
  • A new 3D-layered inorganic-organic hybrid [D/L-C{sub 6}H{sub 13}O{sub 2}N-H]{sub 3}[(PO{sub 4})W{sub 12}O{sub 36}].4.5H{sub 2}O (1), as racemic material in the solid phase, has been synthesized and fully characterized by elemental microanalysis, single crystal X-ray diffraction, and infrared, Raman, and proton nuclear magnetic resonance spectroscopes. The most unique structural feature of 1 is its three-dimensional inorganic infinite tunnel-like framework that results in weak van der Waals interactions along the a-axis. A weak interlayer interaction between the titled layers provides a desirable condition to explore its potential as a host in a host-guest complex. The racemization has been observed in the crystalmore » structure with the centric space group (P2{sub 1}/c). The latter consists of {alpha}-[(PO{sub 4})W{sub 12}O{sub 36}]{sup 3-}and [D/L-C{sub 6}H{sub 13}O{sub 2}N-H]{sup +} moieties with water molecules linked together by a complex network of hydrogen bond interactions.« less