High-Entropy Metal-Organic Frameworks (HEMOFs): A New Frontier in Materials Design for CO 2 Utilization.

Autor: Sikma RE; Sandia National Laboratories, 1515 Eubank Blvd. SE, Albuquerque, NM, 87123, USA., Vogel DJ; Sandia National Laboratories, 1515 Eubank Blvd. SE, Albuquerque, NM, 87123, USA., Reyes RA; Sandia National Laboratories, 1515 Eubank Blvd. SE, Albuquerque, NM, 87123, USA., Meyerson ML; Sandia National Laboratories, 1515 Eubank Blvd. SE, Albuquerque, NM, 87123, USA., Kotula PG; Sandia National Laboratories, 1515 Eubank Blvd. SE, Albuquerque, NM, 87123, USA., Gallis DFS; Sandia National Laboratories, 1515 Eubank Blvd. SE, Albuquerque, NM, 87123, USA.
Jazyk: angličtina
Zdroj: Advanced materials (Deerfield Beach, Fla.) [Adv Mater] 2024 Nov; Vol. 36 (45), pp. e2407435. Date of Electronic Publication: 2024 Sep 09.
DOI: 10.1002/adma.202407435
Abstrakt: High-entropy materials (HEMs) emerged as promising candidates for a diverse array of chemical transformations, including CO 2 utilization. However, traditional HEMs catalysts are nonporous, limiting their activity to surface sites. Designing HEMs with intrinsic porosity can open the door toward enhanced reactivity while maintaining the many benefits of high configurational entropy. Here, a synergistic experimental, analytical, and theoretical approach to design the first high-entropy metal-organic frameworks (HEMOFs) derived from polynuclear metal clusters is implemented, a novel class of porous HEMs that is highly active for CO 2 fixation under mild conditions and short reaction times, outperforming existing heterogeneous catalysts. HEMOFs with up to 15 distinct metals are synthesized (the highest number of metals ever incorporated into a single MOF) and, for the first time, homogenous metal mixing within individual clusters is directly observed via high-resolution scanning transmission electron microscopy. Importantly, density functional theory studies provide unprecedented insight into the electronic structures of HEMOFs, demonstrating that the density of states in heterometallic clusters is highly sensitive to metal composition. This work dramatically advances HEMOF materials design, paving the way for further exploration of HEMs and offers new avenues for the development of multifunctional materials with tailored properties for a wide range of applications.
(© 2024 Wiley‐VCH GmbH.)
Databáze: MEDLINE
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