Synthesis and characterization of triclinic MeAPO-34 (Me=Zn, Fe) molecular sieves

Triclinic ZnAPO-34 and triclinic FAPO-34 were synthesized by hydrothermal crystallization from zinc(II)- and iron(II)-containing gels. The products are thermally stable up to 900 °C. XANES and EXAFS analyses were applied to study the local environment of zinc in the ZnAPO-34 samples, while XANES analysis and Mössbauer spectroscopy were performed on the iron-substituted samples. Zn(II) remains in the same oxidation state during synthesis and after thermal treatment, while iron exhibits Fe(II) and Fe(III) oxidation states. Analysis of the local structure showed that Zn(II) is located on tetrahedral sites of the framework, while Fe(II) and Fe(III) are present on octahedral sites. Infrared study of carbon monoxide adsorption at 100 K showed the presence of strong Brønsted acid sites on the Zn and Fe(II) samples, indicating the substitution of the metals in the framework. Rhombohedral FAPO-34 can be reversibly oxidized in the infrared cell, evidencing the disappearance of the Brønsted acid sites in the Fe(III) oxidation state.