Synthetic Placement of Active Sites in MFI Zeolites for Selective Toluene Methylation to para-Xylene.

Brønsted acidic zeolites are ubiquitous catalysts in fuel and chemical production. Broadening the catalytic diversity of a given zeolite requires strategies to manipulate the acid site placement at framework positions within distinct microporous locations. Here, we combine experiment and theory to elucidate how intermolecular interactions between organic structure-directing agents (OSDAs) and framework Al centers influence the placement of H+ sites in distinct void environments of MFI zeolites and demonstrate the catalytic consequences of active site location on kinetically controlled (403 K) toluene methylation to xylene regioisomers. Kinetic measurements, interpreted using mechanism-derived rate expressions and transition state theory, alongside density functional theory (DFT) calculations show that larger intersection environments similarly stabilize all three xylene isomer transition states without altering well-established aromatic substitution patterns (ortho/para/meta ∼ 60%:30%:10%), while smaller channel environments preferentially destabilize transition states that form bulkier ortho- and meta-isomers, thereby resulting in high intrinsic para-xylene selectivity (∼80%). DFT calculations reveal that the flexibility of nonconventional OSDAs (e.g., 1,4-diazabicyclo[2.2.2]octane) to reorient within MFI intersections and their ability to hydrogen-bond to form protonated complexes favor the placement of Al in smaller channel environments compared to conventional quaternary OSDAs (e.g., tetra-n-propylammonium). These molecular-level insights establish a mechanistic link between OSDA structure, active site placement, and transition state stability in MFI zeolites and provide active site design strategies that are orthogonal to crystallite design approaches harnessing complex reaction-diffusion phenomena to enhance regioisomer selectivity in the industrial production of valuable polymer precursors.

Advances and challenges in designing active site environments in zeolites for Brønsted acid catalysis.

Zeolites contain proton active sites in diverse void environments that stabilize the reactive intermediates and transition states formed in converting hydrocarbons and oxygenates to chemicals and energy carriers. The catalytic diversity that exists among active sites in voids of varying sizes and shapes, even within a given zeolite topology, has motivated research efforts to position and quantify active sites within distinct voids (synthesis-structure) and to link active site environment to catalytic behavior (structure-reactivity). This Feature Article describes advances and challenges in controlling the position of framework Al centers and associated protons within distinct voids during zeolite synthesis or post-synthetic modification, in identifying and quantifying distinct active site environments using characterization techniques, and in determining the influence of active site environments on catalysis. During zeolite synthesis, organic structure directing agents (SDAs) influence Al substitution at distinct lattice positions via intermolecular interactions (e.g., electrostatics, hydrogen bonding) that depend on the size, structure, and charge distribution of organic SDAs and their mobility when confined within zeolitic voids. Complementary post-synthetic strategies to alter intrapore active site distributions include the selective removal of protons by differently-sized titrants or unreactive organic residues and the selective exchange of framework heteroatoms of different reactivities, but remain limited to certain zeolite frameworks. The ability to identify and quantify active sites within distinct intrapore environments depends on the resolution with which a given characterization technique can distinguish Al T-site positions or proton environments in a given zeolite framework. For proton sites in external unconfined environments, various (post-)synthetic strategies exist to control their amounts, with quantitative methods to distinguish them from internal sites that largely depend on using stoichiometric or catalytic probes that only interact with external sites. Protons in different environments influence reactivity by preferentially stabilizing larger transition states over smaller precursor states and influence selectivity by preferentially stabilizing or destabilizing competing transition states of varying sizes that share a common precursor state. We highlight opportunities to address challenges encountered in the design of active site environments in zeolites by closely integrating precise (post-)synthetic methods, validated characterization techniques, well-defined kinetic probes, and properly calibrated theoretical models. Further advances in understanding the molecular details that underlie synthesis-structure-reactivity relationships for active site environments in zeolite catalysis can accelerate the predictive design of tailored zeolites for desired catalytic transformations.