Self‐assembled nanocrystal superlattices represent an emergent class of designer materials with potentially programmable functionalities. The ability to construct hierarchically structured nanocrystal superlattices with tailored geometry and porosity is critical for extending their applications. Here, 2D superlattices comprising monolayer FeP nanoframes are synthesized through a space‐confined topochemical transformation approach induced by the Kirkendall effect, using carbon‐coated Fe3O4 nanocube superlattices as a precursor. The particle shape and the close‐packed nature of Fe3O4 nanocubes as well as the interconnected carbon layer network contribute to the topochemical transformation process. The resulting 2D FeP nanoframe superlattices possess several unique and advantageous structural features that are unavailable in conventional 3D nanocrystal superlattices, which make them particularly attractive for catalytic applications. As a proof of concept, such 2D FeP nanoframe superlattices are harnessed as highly efficient and durable electrocatalysts for the hydrogen evolution reaction, the performance of which is superior to that of most FeP‐based catalysts reported previously. This topochemical transformation approach is scalable and general, representing a new route of designing hierarchical superlattices with highly open features that cannot be accessible by traditional self‐assembly methods.
This contribution describes the self-assembly of colloidal nanodumbbells (NDs) with tunable shapes within cylindrical channels. We present that the intrinsic concave geometry of NDs endows them with peculiar packing and interlocking behaviors, which, in conjunction with the adjustable confinement constraint, leads to a variety of superstructures such as tilted-ladder chains and crossed-chain superlattices. A mechanistic investigation, corroborated by geometric calculations, reveals that the phase behavior of NDs under strong confinement can be rationalized by the entropy-driven maximization of the packing efficiency. Based on the experimental results, an empirical phase diagram is generated, which could provide general guidance in the design of intended superstructures from NDs. This study provides essential insight into how the interplay between the particle shape and confinement conditions can be exploited to direct the orientationally ordered assembly of concave nanoparticles into unusual superlattices.
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