CO2 Desorbs Water from K-MER Zeolite under Equilibrium Control.

Competitive adsorption by water in zeolites is so strongly prevalent that established gravimetric techniques for quantification have assumed that humid CO2 has no effect on preadsorbed water at the same relative humidity. Here, we demonstrate sites in small-pore zeolite K-MER, in which CO2 adsorption causes 20% of preabsorbed water to desorb under equilibrium control at 30 °C and 5% relative humidity. Diffuse reflectance IR spectroscopic data demonstrate that dimeric water species that are coordinated to cationic sites in K-MER zeolite are selectively displaced by CO2 under these humid conditions. Though Cs-RHO contains more weakly bound water than K-MER, we observe a lack of dimeric water species and no evidence of CO2 outcompeting water in Cs-RHO. We conclude that the desorption of water by CO2 in K-MER is driven by a highly desired site for CO2 adsorption as opposed to an intrinsically weak binding of water to the zeolite. Our demonstration that CO2 can outcompete water in a zeolite under wet conditions introduces new opportunities for the design of selective sites for humid CO2 adsorption and stresses the importance of independently characterizing adsorbed water and CO2 in these systems.

Exploring the Impact of Active Site Structure on the Conversion of Methane to Methanol in Cu-Exchanged Zeolites.

In the past, Cu-oxo or -hydroxy clusters hosted in zeolites have been suggested to enable the selective conversion of methane to methanol, but the impact of the active site's stoichiometry and structure on methanol production is still poorly understood. Herein, we apply theoretical modeling in conjunction with experiments to study the impact of these two factors on partial methane oxidation in the Cu-exchanged zeolite SSZ-13. Phase diagrams developed from first-principles suggest that Cu-hydroxy or Cu-oxo dimers are stabilized when O2 or N2O are used to activate the catalyst, respectively. We confirm these predictions experimentally and determine that in a stepwise conversion process, Cu-oxo dimers can convert twice as much methane to methanol compared to Cu-hydroxyl dimers. Our theoretical models rationalize how Cu-di-oxo dimers can convert up to two methane molecules to methanol, while Cu-di-hydroxyl dimers can convert only one methane molecule to methanol per catalytic cycle. These findings imply that in Cu clusters, at least one oxo group or two hydroxyl groups are needed to convert one methane molecule to methanol per cycle. This simple structure-activity relationship allows to intuitively understand the potential of small oxygenated or hydroxylated transition metal clusters to convert methane to methanol.