A MAS NMR investigation of aluminosilicate, silicophosphate, and aluminosilicophosphate gels and the evolution of crystalline structures on heating the gels

Abstract

Gels of various composition containing SiO₂, Al₂O₃, and P₂O₅ have been investigated by employing high resolution magic-angle-spinning (MAS) ²⁷Al, ²⁹Si, and ³¹P NMR spectroscopy. Changes occurring in the NMR spectra as the gels are progressively heated have been examined to understand the nature of structural changes occurring during the crystallization of the gels. ²⁷Al resonance is sensitive to changes in the coordination number even when the Al concentration is as low as 1 mol%. As the percentage of Al increases, the hydroxyl groups tend to be located on the Al sites while Si remains as SiO_4/2 (Q₄). Mullite is the major phase formed at higher temperature in the aluminosilicate gels. In the case of the silicophosphate gels, Si is present in the form of Q₄ and Q₃ species. There is a change in the coordination of Si from four to six as the gel is heated. The formation of six-coordinated Si is facilitated even at lower temperatures (~673 K) when the P₂O₅ content is high. The phosphorus atoms present as orthophosphoric acid units in the xerogels change over to metaphosphate-like units as the gel is heated to higher temperatures. In aluminosilicophosphates, Si is present as Q₄ and Q₃ species while P is present as metaphosphate units; Al in these gels seems to be inducted into the tetrahedral network positions.