Architecting Metal–Organic Framework-Based/Derived Catalysts for Methane Functionalization

Methane, Earth’s most abundant hydrocarbon, represents a critical dual challenge: an essential chemical feedstock amid resource constraints and a potent greenhouse gas. Traditional catalytic approaches face significant limitations due to methane’s chemical inertness and harsh reaction conditions. Methane functionalization through selective C–H bond activation remains a challenging yet strategically important transformation in catalysis. In response to these pressing concerns, researchers have increasingly focused on metal–organic frameworks (MOFs), a class of highly porous, tunable, and structurally versatile materials, to convert methane into value-added products efficiently. MOFs offer distinct advantages such as isolated active sites, high surface area, structural tunability through isoreticular design, and the ease of postsynthetic modification, all of which contribute to improved catalytic efficiency and selectivity. This review systematically summarizes MOF-based catalytic strategies for methane activation, covering all reported functionalization pathways from inception to present, including selective oxidation, reforming, coupling, and borylation. It highlights design principles, mechanistic insights, and the potential of MOFs for efficient methane functionalization, offering a comprehensive perspective on current progress, emerging trends, and future directions in MOF-catalyzed methane valorization.