Unraveling the non-classic crystallization of SAPO-34 in a dry gel system towards controlling meso-structure with the assistance of growth inhibitor: Growth mechanism, hierarchical structure control and catalytic properties

• Orientation attachment dominates the crystallization of SAPO-34 in dry gel synthesis.
• A route to prepare hierarchical SAPO-34 based on orientated attachment is proposed.
• Growth inhibitor 1,2,3-hexanetriol is used to generate hierarchical SAPO-34.
• Hierarchical SAPO-34 enhances catalytic lifetime in CH3Cl to olefin conversion.

Understanding silicoaluminophosphate formation mechanism lays the foundation for their structure manipulation via crystallization process control. Crystallization of SAPO-34 from a dry gel using tetraethyl ammonium hydroxide as structure-directing agent was monitored to unravel the formation mechanism. The initial gel was found to form a lamellar precursor first, which subsequently underwent phase transformation to discrete SAPO-34 nanocrystallites. The nanocrystallites thereafter mutually aligned with neighboring ones via a non-classic oriented attachment growth mechanism, affording large crystals as a result of grain boundary elimination. A new protocol to prepare hierarchical SAPO-34 was designed by hindering the aggregation of primary nanocrystallites with a growth inhibitor 1,2,3-hexanetriol. The structure of hierarchical SAPO-34 was characterized by XRD, N2 physisorption, mercury intrusion, SEM, TEM, as well as 27Al, 29Si, 31P MAS NMR spectra and compared with a conventional SAPO-34. More Si islands were formed via combined SM3 (Al+P pairs substitution by 2Si) and SM2 (P substitution by Si) mechanism for hierarchical SAPO-34 as Si was not fully incorporated into the precursor lamellar phase. NH3-TPD showed that hierarchical SAPO-34 has comparable acidic strength to conventional SAPO-34. The obtained hierarchical SAPO-34 is comprised of <100 nm crystallites and possesses well-connected mesopores, both factors are crucial to mass transfer in zeotype materials. Hierarchical SAPO-34 exhibited a 1.5 times lifetime increase in catalytic chloromethane to olefin conversion with respect to a conventional counterpart.

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