Hydrothermal synthesis, structure, and sorption properties of the new microporous ferric molybdenum phosphates [(CH[sub 3])[sub 4]N][sub 2](NH[sub 4])[sub 2][Fe[sub 2]Mo[sub 12]O[sub 30](H[sub 2]PO[sub 4])[sub 6](HPO[sub 4])[sub 2]][center dot]nH[sub 2]O and [(CH[sub 3])[sub 4]N][sub 2]Na[sub 4][Fe[sub 3]Mo[sub 12]O[sub 30](H[sub x]PO[sub 4])[sub 8]][center dot]nH[sub 2]O

Journal Article · Wed Apr 28 00:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00061a011· OSTI ID:6299079

Meyer, L A; Haushalter, R C ^[1]

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1. NEC Research Inst., Princeton, NJ (United States)

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 synthesized 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.

• OSTI ID: 6299079
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:9; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IRON OXIDES
HYDROTHERMAL SYNTHESIS
SORPTIVE PROPERTIES
IRON PHOSPHATES
MOLYBDENUM OXIDES
MOLYBDENUM PHOSPHATES
WATER
ADSORPTION
ACID PHOSPHATES
AMINES
CATIONS
CHEMICAL REACTION YIELD
CRYSTAL STRUCTURE
INTERACTIONS
IONS
ISOTHERMS
LATTICE PARAMETERS
POROSITY
TRANSITION ELEMENTS
TRICLINIC LATTICES
VOIDS
X-RAY DIFFRACTION
CHALCOGENIDES
CHARGED PARTICLES
COHERENT SCATTERING
CRYSTAL LATTICES
DIFFRACTION
ELEMENTS
HYDROGEN COMPOUNDS
IRON COMPOUNDS
METALS
MOLYBDENUM COMPOUNDS
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOSPHATES
PHOSPHORUS COMPOUNDS
REFRACTORY METAL COMPOUNDS
SCATTERING
SORPTION
SURFACE PROPERTIES
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
YIELDS
400201* - Chemical & Physicochemical Properties