Surface Fingerprinting of Faceted Metal Oxides and Porous Zeolite Catalysts by Probe-Assisted Solid-State NMR Approaches

Acid catalysis in heterogeneous systems such as metal oxides and porous zeolites has been widely involved in various catalytic processes for chemical and petrochemical industries. In acid-catalyzed reactions, the performance (e.g., activity and selectivity) is closely associated with the acidic features of the catalysts, viz., type (Lewis vs Brønsted acidity), distribution (external vs internal surface), strength (strong vs weak), concentration (amount), and spatial interactions of acidic sites. The characterization of local structure and acidic properties of these active sites has important implications for understanding the reaction mechanism and the practical catalytic applications of acidic catalysts. Among diverse acidity characterization approaches, the solid-state nuclear magnetic resonance (SSNMR) technique with suitable probe molecules has been recognized as a reliable and versatile tool. Such a probe-assisted SSNMR approach could provide qualitative (type, distribution, and spatial interactions) and quantitative (strength and concentration) information on each acidic site. This Account aims to integrate our recent important findings in determining the structures and acidic characteristics of some typical metal oxide and zeolite catalysts by using the probe-assisted SSNMR technique, as well as clarifying the continuously evolving process of each discrete acidic site under hydrothermal or chemical treatments even at the molecular level with multiscale theoretical simulations.More specifically, we will describe herein the development and applications of the probe-assisted SSNMR methods, such as trimethylphosphine (TMP) and acetonitrile-d₃ (CD₃CN) in conjunction with advanced two-dimensional (2D) homo- and heteronuclear correlation spectroscopy, for characterizing the structures and properties of acidic sites in varied solid catalysts. Moreover, relevant information regarding the surface fingerprinting of various facets on crystalline metal oxide nanoparticles and active centers inside porous zeolites, the mapping of relevant spatial interactions, and the verification of structure-activity correlation were investigated as well. Relevant discussions are mainly based on the recent NMR experiments of our collaborating research groups, including (i) determining the acidic characterization with probe-assisted SSNMR approaches, (ii) mapping various active centers (or crystalline facets), and (iii) revealing their influence on catalytic performance of solid acid catalyst systems. It is anticipated that this information may provide more in-depth insights toward our fundamental understanding of solid acid catalysis.