Spatially Decoupled yet Synergistic Oxygen and Substrate Activation on Carbon-Cloth-like 1D/2D C3N4/K-MnO2 for Sustainable Biomass Conversion

Aerobic catalytic oxidation is indispensable for sustainable chemistry, enabling the conversion of renewable resources into valuable chemicals and fuels by leveraging lattice oxygen (O L ) and molecular oxygen (O 2 ). However, these reactions typically follow the Mars-van Krevelen (MvK) mechanism, posing a significant challenge in meeting three often-competing requirements. These include sufficiently weakening metal-oxygen bonds to boost O L reactivity for substrate oxidation, maintaining structural integrity to facilitate efficient O 2 dissociation for O L regeneration, and preserving substrate accessibility to active sites. To navigate this complexity, we introduce a spatial decoupled synergy strategy, embodied in the hierarchical carbon-cloth-like C 3 N 4 /K-MnO 2 (CKM) catalyst. Here, lattice distortion caused by metal intercalation within elongated 1D MnO 2 nanowires, which activates O L for biomass conversion. Concurrently, the 2D C 3 N 4 nanosheets create a distinct heterointerface that both boosts O 2 dissociation for O L regeneration and optimizes substrate activation. This design features electronically coupled yet spatially separated functionalities, each tailored for O L activation, O 2 dissociation, and substrate activation. Our findings also reveal a critical insight that O 2 activation, rather than O L reactivity, serves as the kinetic bottleneck governing performance. The CKM catalyst demonstrates superior performance in biomass valorization, with a 2,5-furandicarboxylic acid (FDCA) production rate of 1621 μmol·g -1 ·h -1 and 97.3% selectivity, outperforming many other state-of-the-art systems. This work establishes spatial decoupling as a fundamental design principle, with broad potential for advancing sustainable catalysis and energy applications.