Metal Substitution in Keggin-Type Tridecameric Aluminum−Oxo−Hydroxy Clusters

摘要: The species resulting from a typical preparation for metal-substituted hybrids of the Keggin tridecamer, Al13 or [AlO4Al12(OH)24(OH2)12]7+, were examined by performing 27Al NMR on solutions during aging and studying precipitated sulfate salts via solid state powder X-ray diffraction (XRD). Aqueous mixtures (0.25 mol L-1) AlCl3 another metal ion (M), in 12:1 mole ratio (Al:M), where M = Fe3+, Zn2+, Ga3+, In3+, Sn2+, La3+, Bi3+, subjected to forced hydrolysis addition NaOH (1.0 until OH/(Al + M) 2.25, kinetics formation disappearance with at 80 °C was monitored spectroscopy. units polymerize an apparent rate constant (k) 4.8(8) × 10-2 h-1 form referred as AlP2. Only containing Ga3+ Sn2+ exhibited faster conversion rates. GaAl12 forms quickly (k 0.54 h-1) is more stable than apparently promotes AlP2 0.38 h-1). XR...