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Abstract The synthesis of cone‐shaped Pt nanoparticles featuring compressively‐strained {111} facets by depositing Pt atoms on the vertices of Pd icosahedral nanocrystals, followed by selective removal of the Pd template via wet etching, is reported. By controlling the lateral dimensions down to ca. 3 nm, together with a thickness of ca. 2 nm, the Pt cones show greatly enhanced specific and mass activities toward oxygen reduction, with values being 2.8 and 6.4 times those of commercial Pt/C, respectively. Both the strain field and the observed activity trend are rationalized using density functional theory calculations. With the formation of ultrathin linkers among the Pt cones derived from the same Pd icosahedral seed, the interconnected Pt cones acquire stronger interactions with the carbon support, preventing them from detachment and aggregation during the catalytic reaction. Even after 20 000 cycles of accelerated durability test, the Pt cones still show a mass activity 5.3 times higher than the initial value of the Pt/C. 

Abstract Surface ligands play an important role in shape‐controlled growth and stabilization of colloidal nanocrystals. Their quick removal tends to cause structural deformation and/or aggregation to the nanocrystals. Herein, we demonstrate that the surface ligand based on poly(vinylpyrrolidone) (PVP) can be slowly removed from Pd nanosheets (NSs, 0.93±0.17 nm in thickness) by simply aging the colloidal suspension. The aged Pd NSs show well‐preserved morphology, together with significantly enhanced stability toward both e‐beam irradiation and electrocatalysis (e.g., ethanol oxidation). It is revealed that the slow desorption of PVP during aging forces the re‐exposed Pd atoms to reorganize, facilitating the surface to transform from being nearly perfect to defect‐rich. The resultant Pd NSs with abundant defects no longer rely on surface ligand to stabilize the atomic arrangement and thus show excellent structural and electrochemical stability. This work provides a facile and effective method to maintain the integrity of colloidal nanocrystals by slowly removing the surface ligand. 

Manganese dioxide (MnO 2 ) with different crystal structures has been widely investigated as the cathode material for Zn-ion batteries, among which spinel λ -MnO 2 is yet rarely reported because Zn-ion intercalation in spinel lattice is speculated to be limited by the narrow three-dimensional tunnels. In this work, we demonstrate that Zn-ion insertion in spinel lattice can be enhanced by reducing particle size and elucidate an intriguing electrochemical reaction mechanism dependent on particle size. Specifically, λ -MnO 2 nanoparticles (NPs, ~80 nm) deliver a high capacity of 250 mAh/g at 20 mA/g due to large surface area and solid-solution type phase transition pathway. Meanwhile, severe water-induced Mn dissolution leads to the poor cycling stability of NPs. In contrast, micron-sized λ -MnO 2 particles (MPs, ~0.9  μ m) unexpectedly undergo an activation process with the capacity continuously increasing over the first 50 cycles, which can be attributed to the formation of amorphous MnO x nanosheets in the open interstitial space of the MP electrode. By adding MnSO 4 to the electrolyte, Mn dissolution can be suppressed, leading to significant improvement in the cycling performance of NPs, with a capacity of 115 mAh/g retained at 1 A/g for over 500 cycles. This work pinpoints the distinctive impacts of the particle size on the reaction mechanism and cathode performance in aqueous Zn-ion batteries.