Cation Control of Cooperative CO₂ Adsorption in Li-Containing Mixed Cation Forms of the Flexible Zeolite Merlinoite

Abstract

The lithium-exchanged form of a merlinoite zeolite (MER) with Si/Al = 4.2 (unit cell composition Li6.2Al6.2Si25.8O64) possesses a strongly contracted framework when dehydrated (the unit cell volume decreases by 12.9% from the hydrated 'wide-pore' form to the dehydrated 'narrow-pore' form). It shows cooperative adsorption behaviour for CO2, leading to two-step isotherms with the second step at elevated pressure (>2.5 bar at 298 K). Partially exchanging Na and K cations to give single phase Li,Na-and Li,K-MER materials reduces the pressure of this second adsorption step because the transition from narrow-to wide-pore forms upon CO2 adsorption occurs at lower partial pressures compared to that in Li-MER: partial exchange with Cs does not reduce the pressure of this transition. Exsolution effects are also seen at K cation contents >2.2 per unit cell. The phase transitions proceed via intermediate structures, by complex phase behaviour rarely seen for zeolitic materials. The strongly distorted narrow-pore structures adopted upon dehydration give one dimensional channel structures in which the 2 percolation of CO2 through the material requires cation migration from their locations in ste sites. This is slow in Li3.4Cs2.8-MER where Cs cations occupy these critical ste cavities in the channels, causing very slow adsorption kinetics. As the partial pressure of CO2 increases, a threshold pressure is reached where cooperative adsorption and Cs cation migration occur and the wide-pore form results, with a three dimensionally connected pore system, leading to a sharp increase in uptake. This is far in excess of the increase of unit cell volume because more of the pore space becomes accessible. Strong hysteretic effects occur upon desorption, leading to CO2 encapsulation. CO2 remaining within the material after repeated adsorption/desorption cycles without heated activation improves sorption kinetics and modifies the stepped isotherms.

Gating effect for gas adsorption in microporous materials—mechanisms and applications

“…The MER zeolites (Si/Al = 2.3/3.8/4.2) exhibited cation (Na + , K + , Rb + , Cs + , and Li + ) relocation upon CO 2 adsorption, accompanied with an expansion of the framework, showing an unusual cooperative gating-breathing effect. 87,88 In the gismondine (GIS) zeolite (xNa 2 OÁ1.0Al 2 O 3 Á10SiO 2 Á220H 2 O), the number of Na + is key to governing the CO 2 adsorption. Too much Na + occupying the 8MR will sterically hinder the CO 2 adsorption, while too little Na + will allow the CO 2 freely to pass through the 8MR.…”

Cation Ordering and Exsolution in Copper‐Containing Forms of the Flexible Zeolite Rho (Cu,M‐Rho; M=H, Na) and Their Consequences for CO2 Adsorption

“…Exsolution commonly occurs upon cooling of solid solutions [39,40] but is rarely seen in zeolites. In zeolitic materials that have been reported, such as those of zeolite P, amicite and merlinoite, it is, as in this case, observed upon dehydration of a zeolite with a flexible framework [25,41,42] . During dehydration, cations must be able to diffuse through the structure on a micron length scale to achieve thermodynamically favourable locations.…”

“…In zeolitic materials that have been reported, such as those of zeolite P, amicite and merlinoite, it is, as in this case, observed upon dehydration of a zeolite with a flexible framework. [ 25 , 41 , 42 ] During dehydration, cations must be able to diffuse through the structure on a micron length scale to achieve thermodynamically favourable locations. Since phase separation is associated with an entropy loss, this process must result in a reduction in enthalpy, as the zeolite distorts to coordinate cations more closely.…”

“…Some zeolites possess flexible frameworks, which, when dehydrated, adapt to achieve optimal coordination with the extra‐framework cations. Zeolite Rho is the archetypal flexible zeolite, but other zeolites have been found to exhibit similar types of behaviour [9,22–28] . Varying the cations can change the framework configuration of the ‘activated’ adsorbent and thereby the effective pore size, particularly for molecules that interact weakly with cations, such as O 2 and N 2 .…”

“…Zeolite Rho is the archetypal flexible zeolite, but other zeolites have been found to exhibit similar types of behaviour. [ 9 , 22 , 23 , 24 , 25 , 26 , 27 , 28 ] Varying the cations can change the framework configuration of the ‘activated’ adsorbent and thereby the effective pore size, particularly for molecules that interact weakly with cations, such as O 2 and N 2 . Additionally, as the framework distorts, the geometry of cation sites changes, so that cation coordination with framework O atoms, and therefore cation site preferences, are likely to change.…”