摘要
Atomic layer deposition (ALD) is a promising approach to stabilizing supported metal nanoparticles; however, conventional oxide overcoating often forms continuous layers that obstruct active sites and compromise catalytic performance. Here, we present a synthesis-integrated strategy for inherent area-selective ALD, in which the interfacial reactivity established during nanoparticle synthesis directs subsequent oxide nucleation. Using Ag/ZnO as a model system, we demonstrate that synthesis-programmed surface chemistry governs the nucleation and spatial distribution of ALD-grown ZnO. Microwave-assisted polyol synthesis generates oxygen-containing Ag surface species that serve as favorable nucleation sites, creating an intrinsic reactivity contrast between the Ag nanoparticles and carbon support. This promotes preferential ZnO nucleation on Ag without additional surface pretreatment or blocking agents. The resulting nucleation-dominated ZnO nanodomains help stabilize the electrochemical response of Ag and mitigate surface changes during repeated cycling in alkaline media while preserving catalytic accessibility. In H2/O2 anion exchange membrane fuel cells, the selectively modified Ag/C cathode delivers improved performance and stability compared with its conventionally prepared counterpart. More broadly, this work demonstrates that synthesis-programmed surface chemistry provides a practical and versatile approach for controlling ALD nucleation and engineering metal–oxide interfaces, with broader applicability to other supported catalyst systems for electrochemical energy conversion.
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•Synthesis-programmed strategy for inherent area-selective ALD.•Engineered surface chemistry directs ALD nucleation behavior.•Selective ZnO growth on Ag without additional blocking agents.•Improved stability while retaining catalytic accessibility.•Versatile strategy for robust PGM-free electrocatalysts.