Insights of the Crystallization Process of Molecular Sieve AlPO<sub>4</sub>‑5 Prepared by Solvent-Free Synthesis

Crystallization of AlPO<sub>4</sub>-5 with AFI structure under solvent-free conditions has been investigated. Attention was mainly focused on the characterization of the intermediate phases formed at the early stages during the crystallization. The development in the long-range ordering of the solid phases as a function of crystallization time was monitored by XRD, SEM, IR, UV-Raman, and MAS NMR techniques. Particularly, the UV-Raman spectroscopy was employed to obtain the information on the formation process of the framework. <i>J</i>-HMQC <sup>27</sup>Al/<sup>31</sup>P double-resonance NMR experiments were used to identify the P–O–Al bonded species in the intermediate phases. For the first time the P–O–Al bonded species in the intermediate phases can be correctly described through using this advanced NMR technique. The crystallization under solvent-free conditions appears to follow the pathway: The initial amorphous raw material is converted to an intermediate phase which has four-/six-membered ring species, then gradually transformed into crystalline AlPO<sub>4</sub>-5. This observation is not consistent with the common idea that the intermediate phase is the semicrystalline intermediates with a three-dimensional structure.