Authors: Sopuruchukwu Ezenwa | Rajamani Gounder
Source: Chemical Communications (review, 2024-01-01)
Field: Chemistry — Inorganic Chemistry

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 <i>via</i> intermolecular interactions (<i>e.g.</i>, 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. Catalysis ; Brønsted–Lowry acid–base theory ; Chemistry ; Combinatorial chemistry ; Nanotechnology ; Organic chemistry ; Materials science Zeolite Catalysis and Synthesis ; Catalytic Processes in Materials Science ; Catalysis and Hydrodesulfurization Studies