Recent Advances in Zn/ZSM‐5 Catalysts for Propane Dehydroaromatization: Active Sites, Co‐Aromatization, and Morphological Engineering

ABSTRACT

Propane dehydroaromatization (PDA) represents a promising route for the value‐added utilization of shale gas resources, where Zn/ZSM‐5 zeolite is one of the most commonly employed catalysts. In this case, the rate of C–H bond cleavage at Zn sites is frequently much faster than the subsequent oligomerization and cyclization steps at Brønsted acid sites (BAS), which normally leads to the accumulation of reactive intermediates, triggering rapid catalyst deactivation and limiting aromatic selectivity. Overcoming this kinetic mismatch in PDA requires the comprehensive integration of atomic‐level site engineering, mesoscale transport optimization, and macroscopic reaction environment control. This review summarizes recent advances in Zn/ZSM‐5 catalysts for PDA, with a focus on active site engineering, small‐molecule aromatization systems, and ZSM‐5 morphological regulation. Notably, isolated Zn ²⁺ and hydroxylated ZnOH ⁺ species function as primary dehydrogenation centers, whereas oxygen‐bridged [Zn–O–Zn] ²⁺ dimers exhibit superior stability under harsh reducing atmospheres. In addition, the co‐feeding of small molecules such as CO ₂ , CH ₄ , or methanol effectively shifts the thermodynamic equilibrium and promotes aromatic production via hydrogen scavenging or synergistic carbon incorporation. Furthermore, constructing hierarchical porosity and reducing b ‐axis crystal length significantly alleviates diffusion limitations and inhibiting carbon deposition. Finally, future data‐driven paradigms are discussed, particularly the integration of high‐throughput operando characterization with machine learning (ML), which offers a promising pathway to overcome current stability challenges and accelerate commercialization.