Dual‐Single‐Atom Catalyst with Aptamer‐Engineered Confined Reactive Milieu for Spatiotemporally Controlled Selective Conversion

ABSTRACT Spatiotemporal control of short‐lived reactive intermediates remains a central challenge in heterogeneous catalysis, as non‐selective diffusion fundamentally limits efficiency in complex media. Inspired by enzymatic compartmentalization, we report an aptamer‐functionalized Au‐Fe dual‐single‐atom catalyst (Apt‐Au 1 ‐Fe 1 /NC) that mimics nature's precision by integrating atomically dispersed Au‐Fe sites with a genetically engineered recognition element. This material design creates a “smart reactive pocket” featuring two synergistic interfaces: the Au‐Fe heteronuclear pair electronically modulates the d ‐band center to lock the oxygen reduction reaction (ORR) into a highly selective 3‐electron pathway with a lowered energy barrier (0.424 eV), while the grafted aptamer acts as a molecular gatekeeper for substrate pre‐enrichment. The resulting architecture achieves exceptional selectivity (87.0%–92.6%) for specific targets while suppressing non‐specific mineralization to below 5.3%—a stark contrast to conventional systems where selectivity is negligible and mineralization exceeds 90%. Mechanistically, the synergistic electronic interaction ensures localized ·OH generation, while the aptamer enforces a strict “proximity effect,” confining these radicals within the nanoscale space for instantaneous consumption by captured substrates. By imposing biological recognition‐based spatial constraints on inorganic active centers, this work establishes a universal paradigm for decoupling activity from selectivity, enabling precision chemical conversion in complex matrices.