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In this study, by in situ reduction of Pd2+ ions attached on the surface of the sulfonated polystyrene (PS‐SO3H) spheres, complete and dense palladium (Pd) nanoparticles (NPs) layer were deposited around PS‐SO3H spheres. The PS@Pd spheres were wrapped by polypyrrole (PPy) shell, which could avoid escaping of Pd NPs. After selectively etching the PS core, the hollow structures with Pd NPs embedded...