Hydrothermal crystallization of porphyrin-containing layer silicates
- Argonne National Lab., IL (United States)
Porphyrins and metalloporphyrins have been demonstrated as organic templates in the hydrothermal crystallization of layered silicate smectite clays. Two water-soluble free-base porphyrins, tetrakis(N-methyl-4-pyridiniumyl)porphyrin (TMPyP) and tetrakis(N,N,N-trimethyl-4-aniliniumyl)porphyrin (TAP), along with metallo derivatives like Fe{sup III}TAP, were utilized as their chloride salts. Aqueous gels consisting of a 0.0166:0.20:1.00:1.52 porphyrin:LiF:Mg(OH){sub 2}:SiO{sub 2} molar ratio heated at reflux temperature crystallized synthetic porphyrin-containing hectorite clays in just 2 days. Results of x-ray powder diffraction indicated that the organic macrocycles are intercalated parallel between the clay layers. Microanalysis data and visible diffuse reflectance (DR) absorption spectra reveal that the porphyrin is incorporated intact. XRD and DR spectra also reveal that the free-base forms of the porphyrins dominate in hydrothermal crystallization products, while in ion-exchanged products the dication forms predominate. Small-angle neutron scattering (SANS) was used to follow the crystallization of these systems and to analyze interactions that exist when porphyrin is reacted with silica sol and magnesium hydroxide alone. Guinier analysis of the scattering curves yields structural information about the growth process of the clay system. Random network structures are observed for the porphyrin-silica system.
- DOE Contract Number:
- W-31109-ENG-38
- OSTI ID:
- 5955799
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:4; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
CARBOXYLIC ACIDS
CATALYTIC EFFECTS
CLAYS
COHERENT SCATTERING
CRYSTAL STRUCTURE
DATA
DIFFRACTION
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
LAYERS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PORPHYRINS
SCATTERING
X-RAY DIFFRACTION