3 years ago

Electronic and Geometrical Structure of Zn+ Ions Stabilized in the Porous Structure of Zn-Loaded Zeolite H-ZSM-5: A Multifrequency CW and Pulse EPR Study

Electronic and Geometrical Structure of Zn+ Ions Stabilized in the Porous Structure of Zn-Loaded Zeolite H-ZSM-5: A Multifrequency CW and Pulse EPR Study
Mario Chiesa, Pablo Beato, Silvia Bordiga, Elisa Borfecchia, Gloria Berlier, Elena Morra
Electron spin resonance and hyperfine sublevel correlation (HYSCORE) spectroscopy at X- and Q-band frequencies have been employed, in conjunction with X-ray absorption spectroscopy (XAS), to determine the geometric and electronic structure of Zn+ ions in H-ZSM-5 zeolite. Zn+ ions were generated by the direct exposure of dehydrated acid H-ZSM-5 to Zn vapors. The number of Zn+ ions is found to increase substantially upon UV irradiation. A single EPR active species is detected, indicating a single site of adsorption, characterized by the presence of an Al3+ site, as revealed by superhyperfine interactions. The full g (gx = 1.9951, gy = 1.9984, gz = 2.0015) and 27Al |A| (Ax = 2.8, Ay = 2.7, Az = 4.6) MHz tensors were resolved, allowing for a detailed description of the geometric and electronic structure of Zn+ ions stabilized in the cages of H-ZSM-5 zeolite. The dispersion and nuclearity of Zn species formed during the sublimation/irradiation process was assessed by means of XAS spectroscopy, which indicates the absence of metal or metal oxide particles in a significant amount.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b04289

DOI: 10.1021/acs.jpcc.7b04289

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