Multiscale spatiotemporal heterogeneity of zeolite-catalyzed methanol-to-hydrocarbons reaction.

The methanol-to-hydrocarbons (MTH) process provides a sustainable route to light olefins, aromatics, and gasoline-range products with methanol synthesized via syngas platform molecules obtained from nonpetroleum alternative feedstocks, such as coal, biomass, and natural gas. Zeolite-catalyzed MTH reactions inherently exhibit multiscale heterogeneity, which is intrinsically linked to the rational design of high-efficiency industrial catalysts and the regulation of product selectivity. Despite extensive research on zeolite-based MTH catalysis, most studies focused on a single scale and a multiscale understanding that connects molecular-scale, crystal-scale, particle-scale, and reactor-scale performance remains elusive. This review integrates recent advances in spectroscopic characterization, molecular imaging, and spatially resolved techniques to dissect the heterogeneity of the MTH reaction (i.e. from molecular diffusion to acidity, temperature distribution, and coke deposition) across four levels and to clarify how these nonuniform microenvironments emerge, interact, and propagate. By integrating insights across these four scales, we aim to bridge micro- (molecule) and macro-processes (reactor), summarize both the adverse and favorable effects of multiscale heterogeneity in zeolite‑catalyzed processes, reveal spatiotemporal heterogeneity as the intrinsic and crucial principle of MTH reaction over zeolites, and expect this knowledge to provide theoretical support for the rational design of new-generation high-efficiency catalysts, enabling a more effective and selective MTH process.