Understanding the structure directing action of copper-polyamine complexes in the direct synthesis of Cu-SAPO-34 and Cu-SAPO-18 catalysts for the selective catalytic reduction of NO with NH₃

Cu²⁺ cations complexed by linear polyamines have been studied as structure-directing agents (SDAs) for the direct synthesis of copper-containing microporous silicoaluminophosphate (SAPO) materials. The complexing ligands diethylenetriamine (DETA), N-(2-hydroxyethyl)ethylenediamine (HEEDA), triethylenetetramine (TETA), N,N′-bis(2-aminoethyl)-1,3-propanediamine (232), 1,2-bis(3-aminopropylamino)ethane (323), tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA) have been investigated. For comparison, syntheses have been performed using the analogous nickel-polyamine complexes. Cu²⁺ and Ni²⁺ forms of both SAPO-18 and SAPO-34 materials have been prepared. While most polyamine complexes direct crystallisation to SAPO-34, SAPO-18 has been prepared with Cu²⁺(232), Ni²⁺(232) and Ni²⁺(TETA). The coordination geometry of the included metal complexes was studied by UV-visible and EPR spectroscopy and computer simulation. SAPO-18 is favoured by the smaller square planar complexes or octahedral species (with 2 water molecules) of 232 and TETA. Calcination leaves extra-framework Cu²⁺ and Ni²⁺ cations within SAPO-18 and SAPO-34 frameworks. In situ synchrotron IR spectroscopy of Ni-SAPO-18 has shown thermal template degradation occurs via nitrile intermediates. Rietveld structural analysis located extra-framework Cu²⁺ and Ni²⁺ cations released by calcination. In SAPO-34, Cu²⁺ and Ni²⁺ were located in the 8R window of the cha cage. A second site was found for Ni²⁺ at the centre of the six-membered rings (6Rs) of the double-six-ring (D6R) sub-units. In SAPO-18 both Cu²⁺ and Ni²⁺ cations were located only in the 6Rs of the D6R sub-units. Selected copper SAPO-18 and SAPO-34 samples were tested in the selective catalytic reduction of NO with ammonia (NH₃-SCR); both showed high activity.