Selectivity Descriptors of Methanol‐to‐Aromatics Process over 3‐Dimensional Zeolites

• Published in: Angewandte Chemie International Edition Vol. 63; no. 43; pp. e202411197 - n/a
• Main Authors: Zhang, Xin, Gong, Xuan, Abou‐Hamad, Edy, Zhou, Hexun, You, Xinyu, Gascon, Jorge, Dutta Chowdhury, Abhishek
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 21.10.2024
• Edition: International ed. in English
• Subjects: Aromatic compounds; Carbonyls; Catalysis; Decarbonization; Dual-cycle Mechanism; Heterogeneous Catalysis; Intermediates; Magnetic resonance spectroscopy; Methanol; Methanol-to-hydrocarbons; NMR spectroscopy; Physicochemical properties; Reaction Mechanism; Technology assessment; Zeolite; Zeolites; Zeolite; Dual-cycle Mechanism; Reaction Mechanism; Heterogeneous Catalysis; Methanol-to-hydrocarbons
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202411197

The zeolite‐catalyzed methanol‐to‐aromatics (MTA) process is a promising avenue for industrial decarbonization. This process predominantly utilizes 3‐dimensional 10‐member ring (10‐MR) zeolites like ZSM‐5 and ZSM‐11, chosen for their confinement effect essential for aromatization. Current research mainly focuses on enhancing selectivity and mitigating catalyst deactivation by modulating zeolites′ physicochemical properties. Despite the potential, the MTA technology is at a low Technology Readiness Level, hindered by mechanistic complexities in achieving the desired selectivity towards liquid aromatics. To bridge this knowledge gap, this study proposes a roadmap for MTA catalysis by strategically combining controlled catalytic experiments with advanced characterization methods (including operando conditions and “mobility‐dependent” solid‐state NMR spectroscopy). It identifies the descriptor‐role of Koch‐carbonylated intermediates, longer‐chain hydrocarbons, and the zeolites′ intersectional cavities in yielding preferential liquid aromatics selectivity. Understanding these selectivity descriptors and architectural impacts is vital, potentially advancing other zeolite‐catalyzed emerging technologies. The selectivity descriptors and architectural impacts were established in methanol‐to‐aromatics reaction over ZSM‐5 and ZSM‐11 zeolites via strategically integrating operando UV/Visible spectroscopy, solid‐state NMR spectroscopy, and controlled catalytic experiments. This work emphasizes the significance of the descriptor‐role of Koch‐carbonylated intermediates, longer‐chain hydrocarbons, and the zeolites′ intersectional cavities in yielding preferential liquid aromatics selectivity.