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]

---

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

Related Subjects

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