Rethinking Graphene-Based Advanced Oxidation Processes through Catalytic Interface Engineering

Abstract

Advanced oxidation processes (AOPs) have evolved from radical-centered oxidation schemes into a broader family of interfacial reaction platforms, yet the role of graphene-based catalysts is still often discussed in terms of material identity rather than catalytic function. Here, we provide a critical short review of graphene-enabled AOPs from the perspective of catalytic interface engineering. We argue that the relevance of graphene, graphene oxide, reduced graphene oxide, and their hybrids lies not in graphene being an intrinsically superior catalyst, but in their ability to create tunable solid–liquid interfaces that couple pollutant enrichment, oxidant adsorption, charge redistribution, short-range electron transfer, and confined oxidation. Moving beyond conventional categories such as defect engineering, heteroatom doping, heterojunction construction, and membrane-level nanoconfinement, we further discuss emerging interface-engineering concepts, including interfacial microenvironment regulation, built-in electric-field effects, molecular/ionic functionalization, dynamic interfacial reconstruction, and coordination-environment tuning. These strategies are important because they directly influence adsorption geometry, local reaction environment, oxidant utilization, and the competition between radical and nonradical pathways. This interface-centered view is particularly relevant to catalytic and electrified membrane systems, where transport, confinement, and electron flow become inseparable from mechanism. We also highlight persistent limitations, including ambiguous active-site identification, overassignment of reactive oxygen species, overreliance on simplified model pollutants, insufficient durability and regeneration assessment, and the scarcity of continuous-flow and real-water validation. Looking forward, progress will depend on moving from composition-driven catalyst screening toward mechanism-resolved, process-relevant interface design, supported by operando characterization, multiscale descriptors, stability-aware evaluation, and integrated reactor architectures. This perspective positions graphene-based AOPs not as a mature catalyst class, but as a rapidly evolving framework for constructing selective, efficient, durable, and practically relevant oxidation interfaces.