Synthesis of Discrete CHA Zeolite Nanocrystals without Organic Templates for Selective CO2 Capture.

Small-pore zeolites such as chabazite (CHA) are excellent candidates for the selective separation of CO2 ; however, the current synthesis involves several steps and the use of organic structure-directing agent (OSDA), increasing their cost and energy requirements. We report the synthesis of small-pore zeolite crystals (aluminosilicate) with CHA-type framework structure by direct synthesis in a colloidal suspension containing a mixture of inorganic cations only (Na+ , K+ , and Cs+ ). The location of CO2 molecules in the host structure was revealed by 3D electron diffraction (3D ED). The high sorption capacity for CO2 (3.8 mmol g-1 at 121 kPa), structural stability and regenerability of the discreate CHA zeolite nanocrystals is maintained for 10 consecutive cycles without any visible degradation. The CHA zeolite (Si:Al=2) reaches an almost perfect CO2 storage capacity (8 CO2 per unit cell) and high selectivity (no CH4 was adsorbed).

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.

Interzeolite conversion of a micronsized FAU to a nanosized CHA zeolite free of organic structure directing agent with a high CO2 capacity.

The interzeolite transformation of a micronsized FAU zeolite to a nanosized CHA zeolite via alkali treatment is presented. The impact of the selection of the FAU zeolite starting material on the properties of the produced CHA zeolite was analyzed by XRD, ICP, SEM, TEM, N2 and CO2 adsorption, and in situ FT-IR. The analysis showed that the choice of starting FAU zeolite had a large impact on the chemical composition, size, morphology, and porosity of the produced CHA zeolite. The as prepared CHA samples show high capacity toward CO2 (4.26 mmol g-1) and it was demonstrated that the chemisorbed vs. physisorbed CO2 was controlled by varying the amount of alkali cations in the CHA zeolite.