Cooperative and Competitive Occlusion of Organic and Inorganic Structure-Directing Agents within Chabazite Zeolites Influences Their Aluminum Arrangement

We combine experiment and theory to investigate the cooperation or competition between organic and inorganic structure-directing agents (SDAs) for occupancy within microporous voids of chabazite (CHA) zeolites and to rationalize the effects of SDA siting on biasing the framework Al arrangement (Al-O(-Si-O)_x-Al, x = 1-3) among CHA zeolites of essentially fixed composition (Si/Al = 15). CHA zeolites crystallized using mixtures of TMAda⁺ and Na⁺ contain one TMAda⁺ occluded per cage and Na⁺ co-occluded in an amount linearly proportional to the number of 6-MR paired Al sites, quantified by Co²⁺ titration. In contrast, CHA zeolites crystallized using mixtures of TMAda⁺ and K⁺ provide evidence that three K⁺ cations, on average, displace one TMAda⁺ from occupying a cage and contain predominantly 6-MR isolated Al sites. Moreover, CHA crystallizes from synthesis media containing more than 10-fold higher inorganic-to-organic ratios with K⁺ than with Na⁺ before competing crystalline phases form, providing a route to decrease the amount of organic SDA needed to crystallize high-silica CHA. Density functional theory calculations show that differences in the ionic radii of Na⁺ and K⁺ determine their preferences for siting in different CHA rings, which influences their energy to co-occlude with TMAda⁺ and stabilize different Al configurations. Monte Carlo models confirm that energy differences resulting from Na⁺ or K⁺ co-occlusion promote the formation of 6-MR and 8-MR paired Al arrangements, respectively. These results highlight opportunities to exploit using mixtures of organic and inorganic SDAs during zeolite crystallization in order to more efficiently use organic SDAs and influence framework Al arrangements.