From molecular fragments to crystals: a UV Raman spectroscopic study on the mechanism of Fe-ZSM-5 synthesis.
The nucleation process of iron-exchanged zeolite Fe-ZSM-5, from the assembly of distorted tetrahedrally coordinated iron species and silicate rings in the precursor to the final Fe-ZSM-5 crystals, as well as variations in the coordination environment of iron, were studied by UV resonance Raman spectroscopy and complementary techniques.The entire sequence of crystallization events of Fe-ZSM-5 was monitored by UV Raman spectroscopy in combination with HRTEM, UV/Vis spectroscopy, X-ray diffraction patterns, and periodic DFT calculations. Fe-ZSM-5 was synthesized by an organic-free method to avoid signal interference from the organic template in Raman spectra. Framework iron atoms with resonance Raman bands at 516, 1115, and 1165 cm(-1), and a Raman band at 1016 cm(-1) are detected for Fe-ZSM-5. In the early stage of Fe-ZSM-5 synthesis, the precursor contains iron atoms in distorted tetrahedral coordination and five- and six-membered silicate rings. Nucleation by aggregation of the precursor species was monitored by UV Raman spectroscopy based on the resonance Raman effect, and confirmed by periodic DFT calculations. Evolution of iron species on the surface and in the bulk phase was monitored by UV Raman spectroscopy with excitation at 244 and 325 nm, as well as HRTEM. Nucleation takes place first in the core of the amorphous particles, and crystalline nuclei with Fe-ZSM-5 structure are formed in the core by consuming the amorphous shell. Finally the amorphous particles are completely transformed into Fe-ZSM-5 crystals.
Fan
Fengtao
F
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, China.
Sun
Keju
K
Feng
Zhaochi
Z
Xia
Haian
H
Han
Bo
B
Lian
Yuxiang
Y
Ying
Pinliang
P
Li
Can
C