Reactive Glass–Metal Interaction under Ambient Conditions Enables Surface Modification of Gold Nano‐Islands

Abstract Stabilizing gold nanoparticles with tunable surface composition via reactive metal–support interactions under ambient conditions remains a formidable challenge. Here, reactive glass–metal interaction (RGMI) is demonstrated as an effective strategy for engineering gold nano‐islands (GNIs) with enhanced stability and tailored surface chemistry. By manipulating sodium aluminophosphosilicate (NAPS) glass composition, it is shown that glass chemistry directly modulates interfacial phenomena, enabling gold nanostructure stability at moderate temperatures (550 °C) in ambient conditions. Comprehensive characterization reveals that adsorption and intercalation of Na and P at GNI surfaces induce lattice distortions in the Au(111) planes and create new electronic states near the Fermi level. This approach bypasses requirements for chemical precursors, reducing agents, extreme temperatures, and extended reaction times, offering an environmentally sustainable fabrication pathway. The resulting GNI–glass interface significantly influences hot carrier dynamics, extending electron lifetimes essential for enhanced catalytic performance. RGMI provides a versatile strategy for engineering stable, multi‐element nanostructures with broad applications in heterogeneous catalysis, sensing, and optoelectronics.