Flexibility in zeolites: origin, limits, and evaluation.

Numerous pieces of evidence in the literature suggest that zeolitic materials exhibit significant intrinsic flexibility as a consequence of the spring-like behavior of Si-O and Al-O bonds and the distortion ability of Si-O-Si and Al-O-Si angles. Understanding the origin of flexibility and how it may be tuned to afford high adsorption selectivity in zeolites is a big challenge. Zeolite flexibility may be triggered by changes in temperature, pressure, or chemical composition of the framework and extra-framework compounds, as well as by the presence of guest molecules. Therefore, zeolite flexibility can be classified into three categories: (i) temperature and pressure-induced flexibility; (ii) guest-induced flexibility; and (iii) compositionally-induced flexibility. An outlook on zeolite flexibility and the challenges met during the precise experimental evaluations of zeolites will be discussed. Overcoming these challenges will provide an important tool for designing novel selective adsorbents.

Interplay between alkali-metal cations and silanol sites in nanosized CHA zeolite and implications for CO2 adsorption.

Silanols are key players in the application performance of zeolites, yet, their localization and hydrogen bonding strength need more studies. The effects of post-synthetic ion exchange on nanosized chabazite (CHA), focusing on the formation of silanols, were studied. The significant alteration of the silanols of the chabazite nanozeolite upon ion exchange and their effect on the CO2 adsorption capacity was revealed by solid-state nuclear magnetic resonance (NMR), Fourier-transform infrared (FTIR) spectroscopy, and periodic density functional theory (DFT) calculations. Both theoretical and experimental results revealed changing the ratio of extra-framework cations in CHA zeolites changes the population of silanols; decreasing the Cs+/K+ ratio creates more silanols. Upon adsorption of CO2, the distribution and strength of the silanols also changed with increased hydrogen bonding, thus revealing an interaction of silanols with CO2 molecules. To the best of our knowledge, this is the first evidence of the interplay between alkali-metal cations and silanols in nanosized CHA.

Internalization study of nanosized zeolite crystals in human glioblastoma cells.

While the use of nanozeolites for cancer treatment holds a great promise, it also requires a better understanding of the interaction between the zeolite nanoparticles and cancer cells and notably their internalization and biodistribution. It is particularly important in situation of hypoxia, a very common situations in aggressive cancers, which may change the energetic processes required for cellular uptake. Herein, we studied, in vitro, the kinetics of the internalization process and the intracellular localization of nanosized zeolite X (FAU-X) into glioblastoma cells. In normoxic conditions, scanning electron microscopy (SEM) showed a rapid cell membrane adhesion of zeolite nanoparticles (< 5 min following application in the cell medium), occurring before an energy-dependent uptake which appeared between 1 h and 4 h. Additionally, transmission electron microscopy (TEM) and flow cytometry analyzes, confirmed that the zeolite nanoparticles accumulate over time into the cytoplasm and were mostly located into vesicles visible at least up to 6 days. Interestingly, the uptake of zeolite nanoparticles was found to be dependent on oxygen concentration, i.e. an increase in internalization in severe hypoxia (0.2 % of O2) was observed. No toxicity of zeolite FAU-X nanoparticles was detected after 24 h and 72 h. The results clearly showed that the nanosized zeolites crystals were rapidly internalized via energy-requiring mechanism by cancer cells and even more in the hypoxic conditions. Once the zeolite nanoparticles were internalized into cells, they appeared to be safe and stable and therefore, they are envisioned to be used as carrier of various compounds to target cancer cells.

The role of mixed alkali metal cations on the formation of nanosized CHA zeolite from colloidal precursor suspension.

A clear understanding of the crystal formation pathways of zeolites remains one of the most challenging issues to date. Here we investigate the synthesis of nanosized chabazite (CHA) zeolites using organic template-free colloidal suspensions by varying the time of aging at room temperature and the time of hydrothermal treatment at 90 °C. The role of mixed alkali metal cations (Na+, K+, Cs+) on the formation of CHA in the colloidal suspensions was studied. Increasing the aging time of the precursor colloidal suspension from 4 to 17 days resulted in faster crystallization of CHA nanocrystals (3 h instead of 7 h at 90 °C) to afford significantly smaller particles (60 nm vs 600 nm). During the crystallization a considerable change in the content of inorganic cations in the recovered solid material was observed to coincide with the formation of the CHA nanocrystals. The Na+ cations were found to direct the formation of condensed and pre-shaped aluminosilicate particles in the colloidal precursor suspensions, while K+ cations facilitated the formation of secondary building units (SBUs) of the CHA type framework structure such as d6r and cha cages, and the Cs+ cations promoted the long-range crystalline order facilitating the crystallization of stable zeolite nanocrystals.