Trends in Siting of Metals in Heterometallic Nd–Yb Metal–Organic Frameworks and Molecular Crystals

Ibikunle, Ifayoyinsola A.; Yang, Yuhan; Valdez, Nichole R.; Rodriguez, Mark A.; Harvey, Jacob A.; Sava Gallis, Dorina F.; Sholl, David S.

doi:10.1021/acsami.2c15638

Trends in Siting of Metals in Heterometallic Nd–Yb Metal–Organic Frameworks and Molecular Crystals

Journal Article · Fri Nov 18 00:00:00 EST 2022 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.2c15638· OSTI ID:1906607

Ibikunle, Ifayoyinsola A. ^[1]; Yang, Yuhan ^[1]; Valdez, Nichole R. ^[2]; Rodriguez, Mark A. ^[2]; ^[2]; ^[2]; ^[3]

Georgia Institute of Technology, Atlanta, GA (United States)
Sandia National Laboratory (SNL-NM), Albuquerque, NM (United States)
Georgia Institute of Technology, Atlanta, GA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Several studies suggest that metal ordering within metal–organic frameworks (MOFs) is important for understanding how MOFs behave in relevant applications; however, these siting trends can be difficult to determine experimentally. To garner insight into the energetic driving forces that may lead to nonrandom ordering within heterometallic MOFs, we employ density functional theory (DFT) calculations on several bimetallic metal–organic crystals composed of Nd and Yb metal atoms. We also investigate the metal siting trends for a newly synthesized MOF. Our DFT-based energy of mixing results suggest that Nd will likely occupy sites with greater access to electronegative atoms and that local homometallic domains within a mixed-metal Nd–Yb system are favored. We also explore the use of less computationally extensive methods such as classical force fields and cluster expansion models to understand their feasibility for large system sizes. Here, this study highlights the impact of metal ordering on the energetic stability of heterometallic MOFs and crystal structures.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC05-00OR22725; NA0003525

OSTI ID:: 1906607

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 48 Vol. 14; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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