Solvent‐Driven Dissolution‐Regrowth‐Migration Synthesis of Asymmetric Carbon Nanoparticles for Electrocatalytic Semihydrogenation

ABSTRACT Asymmetric nanostructured materials are of significant interest due to their unique physicochemical properties and promising applications. However, the one‐step synthesis of hierarchical asymmetric architectures with precisely controlled morphology and high‐curvature interfaces remains challenging. Here, we propose a solvent‐driven dissolution‐regrowth‐migration (SDM) strategy that directs the growth of phenolic resin and regulates the water‐oil interface, enabling the one‐pot fabrication of asymmetric polymeric and carbon nanoparticles consisting of a mesoporous nanosphere “head” and highly curved lamellar nanosheet “tail”. This SDM process integrates bottom‐up self‐assembly with top‐down selective etching and repolymerization, achieving an “internal‐external synergy” that precisely tailors the surface migration process and asymmetric nanoarchitecture by simply tuning the ethanol content. The asymmetric carbon electrocatalyst, ACN‐PdCu, possesses a higher specific surface area, uniformly dispersed PdCu alloy phases, and an elevated Cu 0 /Cu δ + ratio compared with conventional symmetric nanoparticles. Finite‐element simulations and theoretical calculations uncover that this asymmetric architecture enhances local mass diffusion, strengthens substrate adsorption and activation, as well as facilitates charge transfer, thereby improving overall catalytic performance toward the electrocatalytic semihydrogenation of 3‐butyne‐1‐ol, achieving >92% conversion and >98% selectivity to 3‐butene‐1‐ol, along with excellent cycling stability. The SDM strategy opens a new avenue for designing asymmetric architectures and advanced functional materials with enhanced catalytic activities.