Challenges and Opportunities for Exploiting the Role of Zeolite Confinements for the Selective Hydrogenation of Acetylene.

Zeolites, with their ordered crystalline porous structure, provide a unique opportunity to confine metal catalysts, whether single atoms (e.g., transition metal ions (TMIs)) or metal clusters, when used as a catalyst support. The confined environment has been shown to provide rate and selectivity enhancement across a variety of reactions via both steric and electronic effects, such as size exclusion and transition state stabilization. In this review, we provide a survey of various zeolite confined catalysts used for the semihydrogenation of acetylene highlighting their performance, defined by ethylene selectivity at full acetylene conversion, in relationship to the synthesis technique employed. Synthesis methods that ensure confinement with the catalyst transition metal location in the extra-framework positions are reported to have the highest selectivity to ethylene. However, the underlying molecular factors responsible for selective catalysis within confinement remain elusive due to the difficulty in deconvoluting individual effects. Through the careful use of a combination of characterization and spectroscopic methods, insights into the relationship between the properties of zeolite confined catalysts and their performance have been explored in other works for a variety of reactions. More specifically, operando spectroscopy studies have revealed the dynamic behavior of zeolite confined catalysts under various conditions implying that the structure and properties observed ex situ do not always match those of the active catalyst under reaction conditions. Applying this type of analysis to acetylene semihydrogenation, a simple gas phase reaction, can help elucidate the structure-function relationship of zeolite confined catalysts allowing for more informed design choices and consequently their application to a wider variety of more complex reactions such as the liquid phase hydrogenation of alkynols where solvent effects must also be considered in addition to those of confinement.