Decoupling Activation and Preservation: Architectural Design Principles of Organic Frameworks for Selective Photocatalytic Methane Oxidation

Abstract

ABSTRACT Photocatalytic methane (CH 4 ) conversion faces a dilemma, where C─H bond activation requires a substantial oxidative driving force, whereas partially oxidized C 1 products are intrinsically more susceptible to further oxidation. As a result, strengthening photocatalytic throughput while avoiding overoxidation remains challenging in the field of highly valuable CH 4 conversion. Organic semiconductor platforms, including polymeric carbon nitrides (PCN), metal–organic frameworks (MOFs), and covalent organic frameworks (COFs), exhibit structural features that fundamentally differ from those of conventional inorganic counterparts. Their electronic states originate from molecular building units, and their frameworks allow controlled positioning of redox centers, modulation of charge‐transfer pathways, and definition of pore environments, enabling systematic regulation of band energetics, carrier distribution, oxygen activation modes, and proton management of photocatalysts. This review examines how electronic structure engineering, interfacial charge routing, reactive species control, and microenvironment design influence pathway selection in CH 4 photooxidation. Particular attention is given to mechanisms that favor associative multi‐electron oxygen reduction or energy‐transfer processes while suppressing hydroxyl radical ( • OH)‐dominated chemistry. Although CH 4 ‐specific systems remain limited, mechanistic insights from related photocatalytic reactions provide transferable design principles. Establishing quantitative relationships between architectural parameters and reactive‐species identity is essential for advancing selective solar‐driven C 1 oxidation.