Flattening bent Janus nanodiscs expands lattice parameters

• Published in: Chem Vol. 9; no. 4; pp. 948 - 962
• Main Authors: Park, Jongsik, Kim, Hong Ki, Park, Jisol, Kim, Byeongyoon, Baik, Hionsuck, Baik, Mu-Hyun, Lee, Kwangyeol
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 13.04.2023
• Subjects: cation exchange; Janus structure; lattice parameter engineering; morphological transformation; nanocrystal; quantum chemical calculations; surface chemistry; nanocrystal; Janus structure; surface chemistry; lattice parameter engineering; morphological transformation; quantum chemical calculations; SDG7: Affordable and clean energy; cation exchange; Other
• ISSN: 2451-9294; 2451-9294
• DOI: 10.1016/j.chempr.2022.12.004

Nanoscale lattice parameter engineering is a potentially powerful tool for tailoring the electronic properties of nanomaterials. The nascent strain in juxtaposed hetero-interfaces of nanocrystals was recently shown to substantially affect the energy states of the exposed surfaces and improve catalytic activity; however, practical implementations of this design strategy are rare. Herein, we report that Rh3S4 and Cu31S16 can be combined to produce a bent Janus-type nanodisc in which the surface strain can be controlled precisely by modulating the curvature. These nanodiscs are conveniently prepared by replacing copper with rhodium in Cu31S16 via anisotropic cation exchange, which induces lattice strain and bends the nanodiscs. Flattening the Rh3S4/Cu31S16 nanodisc leads to a unique surface lattice structure and affords superior electrocatalytic performance in the hydrogen evolution reaction. We demonstrate a general and straightforward strategy for controlling the lattice strains in hetero-nanostructures and for systematically improving their catalytic performance. [Display omitted] •Rh3S4/Cu31S16 bent nanodiscs can be achieved via regiospecific cation exchange•Quantum chemical computations demonstrate the morphological transformation mechanism•Nanoscale lattice engineering of nanocrystals manipulates hydrogen adsorption energy Manipulating lattice parameters has emerged as a promising approach to creating new crystalline materials with novel physical and chemical properties, achieving the fabrication of targeted, tailored substances in various research fields. Despite its critical importance, lattice engineering of nanoscale crystalline solids remains elusive due to the complex interdependence between the structural lattices and energetic parameters of particles. Herein, we demonstrated the concept of nanoscale lattice engineering in tensile-strained bent Janus nanocrystals via regiospecific cation exchange, which synergistically optimizes the adsorption energy, surface electronic structure, and catalytic performance. The strategy described here allows for manipulating lattice parameters of nanoscale crystalline materials, pointing to a novel direction toward tailor-made substances for specific application targets. Lattice engineering of nanoscale crystalline solids has emerged as a promising strategy for creating unconventional nanomaterials with novel physicochemical properties. Herein, we materialized the bent Janus nanocrystals where the surface strain can be controlled precisely by partially reconstructing the anion sublattice of primary templates via regiospecific cation exchange. Modulating the curvature creates an optimal surface electronic structure in the hydrogen evolution reaction, affording superior electrocatalytic performance. This strategy could pave the way for floating a novel direction toward tailor-made substances.