Mechanistic insights into methanol conversion and methanol-mediated tandem catalysis toward hydrocarbons

Abstract

Methanol, a crucial C1 intermediate, bridges traditional fossil-based chemical processes with emerging sustainable catalytic technologies by serving as both a versatile hydrogenation product from CO/CO₂ and an active intermediate for hydrocarbon synthesis. Despite significant progress in methanol-to-hydrocarbon (MTH) conversion, a comprehensive understanding of reaction mechanisms remains essential to enhance catalyst design and industrial applicability. This review critically synthesizes recent advances in mechanistic insights related to methanol conversion and methanol-mediated catalytic processes. Firstly, we systematically outline key reaction pathways involved in initial carbon–carbon (C–C) bond formation through direct and indirect mechanisms, emphasizing significant breakthroughs from spectroscopic analyses and theoretical calculations. Subsequently, we highlight the autocatalytic characteristics and dual-cycle mechanisms underlying MTH processes, critically evaluating the roles of zeolite structures, pore sizes, topology, and acidity in governing product selectivity and catalyst stability. Additionally, we discuss cutting-edge developments in tandem catalytic systems employing methanol as a pivotal intermediate for CO_x hydrogenation, emphasizing the transferable mechanistic principles and catalytic insights. Finally, we identify future research directions, including elucidating precise hydrocarbon pool (HCP) intermediates, optimizing zeolite structures through computational-guided design, and developing robust catalytic systems leveraging advanced characterization methods and artificial intelligence. By integrating multidisciplinary approaches from catalytic science, materials engineering, and reaction engineering, this review provides actionable guidance towards rational design and optimization of advanced catalytic systems for efficient methanol conversion processes.