Computational Analysis of the Energetic Stability of High-Entropy Structures of a Prototypical Lanthanide-Based Metal–Organic Framework

Kumar, Surbhi K. A.; Sava Gallis, Dorina F.; Sholl, David S.

doi:10.1021/acs.jpcc.5c04892

Computational Analysis of the Energetic Stability of High-Entropy Structures of a Prototypical Lanthanide-Based Metal–Organic Framework

Journal Article · Thu Oct 09 00:00:00 EDT 2025 · The Journal of Physical Chemistry C

DOI:https://doi.org/10.1021/acs.jpcc.5c04892· OSTI ID:3000381

Kumar, Surbhi K. A. ^[1]; ^[2]; ^[3]

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

High-entropy materials are characterized by their complex compositions, typically comprising five or more elements in near-equiatomic proportions. Applying this concept to metal ions in metal−organic frameworks (MOFs) has paved the way for exploring a new class of high-entropy MOFs. While the compositional strategy of high-entropy materials leverages configurational entropy to aid thermodynamic stability, it also poses significant analytical challenges due to the vast compositional landscape and diverse phases that these materials can adopt. We present a computational study of several complexities associated with selecting potential high-entropy versions of a prototype lanthanidebased MOF. We compute the energetics of metal mixing of these heterometallic MOFs using density functional theory (DFT) and machine learning interatomic potential (MLIP) methods. The use of MLIP methods allows a systematic exploration of the convex hull of thermodynamically stable MOF structures containing up to 5 distinct metals.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE

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

OSTI ID:: 3000381

Journal Information:: The Journal of Physical Chemistry C, Journal Name: The Journal of Physical Chemistry C Journal Issue: 42 Vol. 129; ISSN 1932-7455; ISSN 1932-7447

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (58)

Nanostructured High-Entropy Alloys with Multiple Principal Elements: Novel Alloy Design Concepts and Outcomes Yeh, J.-W.; Chen, S.-K.; Lin, S.-J. Advanced Engineering Materials, Vol. 6, Issue 5, p. 299-303 https://doi.org/10.1002/adem.200300567	journal	May 2004
High‐Entropy Metal–Organic Frameworks for Highly Reversible Sodium Storage Ma, Yanjiao; Ma, Yuan; Dreyer, Sören Lukas Advanced Materials, Vol. 33, Issue 34 https://doi.org/10.1002/adma.202101342	journal	July 2021
High‐Entropy Metal‐Organic Frameworks (HEMOFs): A New Frontier in Materials Design for CO₂ Utilization Sikma, R. Eric; Vogel, Dayton J.; Reyes, Raphael A. Advanced Materials, Vol. 36, Issue 45 https://doi.org/10.1002/adma.202407435	journal	September 2024
Synthesis Strategies for High Entropy Nanoparticles Yang, Linlin; He, Ren; Chai, Jiali Advanced Materials, Vol. 37, Issue 1 https://doi.org/10.1002/adma.202412337	journal	October 2024
Mixed‐Metal MOFs: Unique Opportunities in Metal–Organic Framework (MOF) Functionality and Design Masoomi, Mohammad Yaser; Morsali, Ali; Dhakshinamoorthy, Amarajothi Angewandte Chemie, Vol. 131, Issue 43 https://doi.org/10.1002/ange.201902229	journal	October 2019
Functional Mixed Metal-Organic Frameworks with Metalloligands Das, Madhab C.; Xiang, Shengchang; Zhang, Zhangjing Angewandte Chemie International Edition, Vol. 50, Issue 45 https://doi.org/10.1002/anie.201101534	journal	September 2011
Assembly and Upconversion Properties of Lanthanide Coordination Polymers Based on Hexanuclear Building Blocks with (μ ₃ ‐OH) Bridges Weng, Danfeng; Zheng, Xiangjun; Jin, Linpei European Journal of Inorganic Chemistry, Vol. 2006, Issue 20 https://doi.org/10.1002/ejic.200600491	journal	October 2006
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Relative effects of enthalpy and entropy on the phase stability of equiatomic high-entropy alloys Otto, F.; Yang, Y.; Bei, H. Acta Materialia, Vol. 61, Issue 7 https://doi.org/10.1016/j.actamat.2013.01.042	journal	April 2013
Short-range ordering and its impact on thermodynamic property of high-entropy alloys Chen, Shuai; Wang, Tian; Li, Xiaoyan Acta Materialia, Vol. 238 https://doi.org/10.1016/j.actamat.2022.118201	journal	October 2022
Deciphering chemical ordering in High Entropy Materials: A machine learning-accelerated high-throughput cluster expansion approach Vazquez, Guillermo; Sauceda, Daniel; Arróyave, Raymundo Acta Materialia, Vol. 276 https://doi.org/10.1016/j.actamat.2024.120137	journal	September 2024
Multicomponent isoreticular metal-organic frameworks: Principles, current status and challenges Dutta, Archisman; Pan, Ying; Liu, Jian-Qiang Coordination Chemistry Reviews, Vol. 445 https://doi.org/10.1016/j.ccr.2021.214074	journal	October 2021
Mixed metal-metal organic frameworks (MM-MOFs) and their use as efficient photocatalysts for hydrogen evolution from water splitting reactions Jaryal, Ritika; Kumar, Rakesh; Khullar, Sadhika Coordination Chemistry Reviews, Vol. 464 https://doi.org/10.1016/j.ccr.2022.214542	journal	August 2022
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav Computational Materials Science, Vol. 68 https://doi.org/10.1016/j.commatsci.2012.10.028	journal	February 2013
Development of high entropy alloys (HEAs): Current trends V., Balaji; M., Anthony Xavior Heliyon, Vol. 10, Issue 7 https://doi.org/10.1016/j.heliyon.2024.e26464	journal	April 2024
From high entropy alloys to diluted multi-component alloys: Range of existence of a solid-solution Laurent-Brocq, Mathilde; Perrière, Loïc; Pirès, Rémy Materials & Design, Vol. 103 https://doi.org/10.1016/j.matdes.2016.04.046	journal	August 2016
Microstructural development in equiatomic multicomponent alloys Cantor, B.; Chang, I. T. H.; Knight, P. Materials Science and Engineering: A, Vol. 375-377 https://doi.org/10.1016/j.msea.2003.10.257	journal	July 2004
Thermodynamic and Kinetic Effects in the Crystallization of Metal–Organic Frameworks Cheetham, Anthony K.; Kieslich, G.; Yeung, H. H. -M. Accounts of Chemical Research, Vol. 51, Issue 3 https://doi.org/10.1021/acs.accounts.7b00497	journal	February 2018
High-Entropy Metal–Organic Framework Arrays Boost Oxygen Evolution Electrocatalysis Xu, Shuaishuai; Li, Ming; Wang, Haiming The Journal of Physical Chemistry C, Vol. 126, Issue 33 https://doi.org/10.1021/acs.jpcc.2c05083	journal	August 2022
Heterometallic Metal–Organic Frameworks of MOF-5 and UiO-66 Families: Insight from Computational Chemistry Trousselet, Fabien; Archereau, Aurélien; Boutin, Anne The Journal of Physical Chemistry C, Vol. 120, Issue 43 https://doi.org/10.1021/acs.jpcc.6b08594	journal	October 2016
Curated Collection of More than 20,000 Experimentally Reported One-Dimensional Metal–Organic Frameworks Gharagheizi, Farhad; Yu, Zhenzi; Sholl, David S. ACS Applied Materials & Interfaces, Vol. 14, Issue 37 https://doi.org/10.1021/acsami.2c12485	journal	September 2022
Trends in Siting of Metals in Heterometallic Nd–Yb Metal–Organic Frameworks and Molecular Crystals Ibikunle, Ifayoyinsola A.; Yang, Yuhan; Valdez, Nichole R. ACS Applied Materials & Interfaces, Vol. 14, Issue 48 https://doi.org/10.1021/acsami.2c15638	journal	November 2022
Adapting UFF4MOF for Heterometallic Rare-Earth Metal–Organic Frameworks Yang, Yuhan; Ibikunle, Ifayoyinsola A.; Sava Gallis, Dorina F. ACS Applied Materials & Interfaces, Vol. 14, Issue 48 https://doi.org/10.1021/acsami.2c16726	journal	November 2022
The inorganic crystal structure data base Bergerhoff, G.; Hundt, R.; Sievers, R. Journal of Chemical Information and Modeling, Vol. 23, Issue 2 https://doi.org/10.1021/ci00038a003	journal	May 1983
Li−Fe−P−O ₂ Phase Diagram from First Principles Calculations Ong, Shyue Ping; Wang, Lei; Kang, Byoungwoo Chemistry of Materials, Vol. 20, Issue 5 https://doi.org/10.1021/cm702327g	journal	February 2008
Introduction to Metal–Organic Frameworks Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M. Chemical Reviews, Vol. 112, Issue 2, p. 673-674 https://doi.org/10.1021/cr300014x	journal	September 2011
Quest for Multifunctionality: Current Progress in the Characterization of Heterometallic Metal–Organic Frameworks Sikma, R. Eric; Butler, Kimberly S.; Vogel, Dayton J. Journal of the American Chemical Society, Vol. 146, Issue 9 https://doi.org/10.1021/jacs.3c05425	journal	February 2024
Towards universal neural network potential for material discovery applicable to arbitrary combination of 45 elements Takamoto, So; Shinagawa, Chikashi; Motoki, Daisuke Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-30687-9	journal	May 2022
Orthogonal luminescence lifetime encoding by intermetallic energy transfer in heterometallic rare-earth MOFs Deneff, Jacob I.; Rohwer, Lauren E. S.; Butler, Kimberly S. Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-36576-z	journal	February 2023
A map of single-phase high-entropy alloys Chen, Wei; Hilhorst, Antoine; Bokas, Georgios Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-38423-7	journal	May 2023
CHGNet as a pretrained universal neural network potential for charge-informed atomistic modelling Deng, Bowen; Zhong, Peichen; Jun, KyuJung Nature Machine Intelligence, Vol. 5, Issue 9 https://doi.org/10.1038/s42256-023-00716-3	journal	September 2023
A universal graph deep learning interatomic potential for the periodic table Chen, Chi; Ong, Shyue Ping Nature Computational Science, Vol. 2, Issue 11 https://doi.org/10.1038/s43588-022-00349-3	journal	November 2022
Benchmarking density functional theory predictions of framework structures and properties in a chemically diverse test set of metal–organic frameworks Nazarian, Dalar; Ganesh, P.; Sholl, David S. Journal of Materials Chemistry A, Vol. 3, Issue 44 https://doi.org/10.1039/C5TA03864B	journal	January 2015
Kinetic trapping – a strategy for directing the self-assembly of unique functional nanostructures Yan, Yun; Huang, Jianbin; Tang, Ben Zhong Chemical Communications, Vol. 52, Issue 80 https://doi.org/10.1039/C6CC03620A	journal	January 2016
Modelling photophysical properties of metal–organic frameworks: a density functional theory based approach Wilbraham, Liam; Coudert, François-Xavier; Ciofini, Ilaria Physical Chemistry Chemical Physics, Vol. 18, Issue 36 https://doi.org/10.1039/C6CP04056J	journal	January 2016
Assessing Hubbard-corrected AM05+U and PBEsol+U density functionals for strongly correlated oxides CeO ₂ and Ce ₂ O ₃ Weck, Philippe F.; Kim, Eunja Physical Chemistry Chemical Physics, Vol. 18, Issue 38 https://doi.org/10.1039/C6CP05479J	journal	January 2016
Structure and electronic properties of rare earth DOBDC metal–organic-frameworks Vogel, Dayton J.; Sava Gallis, Dorina F.; Nenoff, Tina M. Physical Chemistry Chemical Physics, Vol. 21, Issue 41 https://doi.org/10.1039/C9CP04038B	journal	January 2019
Ambient fast, large-scale synthesis of entropy-stabilized metal–organic framework nanosheets for electrocatalytic oxygen evolution Zhao, Xinhui; Xue, Zhimin; Chen, Wenjun Journal of Materials Chemistry A, Vol. 7, Issue 46 https://doi.org/10.1039/C9TA09975A	journal	January 2019
Probabilistic prediction of material stability: integrating convex hulls into active learning Novick, Andrew; Cai, Diana; Nguyen, Quan Materials Horizons, Vol. 11, Issue 21 https://doi.org/10.1039/D4MH00432A	journal	January 2024
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
Benchmarking of GGA density functionals for modeling structures of nanoporous, rigid and flexible MOFs Formalik, Filip; Fischer, Michael; Rogacka, Justyna The Journal of Chemical Physics, Vol. 149, Issue 6 https://doi.org/10.1063/1.5030493	journal	August 2018
The atomic simulation environment—a Python library for working with atoms Hjorth Larsen, Ask; Jørgen Mortensen, Jens; Blomqvist, Jakob Journal of Physics: Condensed Matter, Vol. 29, Issue 27 https://doi.org/10.1088/1361-648X/aa680e	journal	June 2017
Band theory and Mott insulators: Hubbard U instead of Stoner I Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K. Physical Review B, Vol. 44, Issue 3, p. 943-954 https://doi.org/10.1103/PhysRevB.44.943	journal	July 1991
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Atomic short-range order and incipient long-range order in high-entropy alloys Singh, Prashant; Smirnov, A. V.; Johnson, D. D. Physical Review B, Vol. 91, Issue 22 https://doi.org/10.1103/PhysRevB.91.224204	journal	June 2015
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
Local Structure and Short-Range Order in a NiCoCr Solid Solution Alloy Zhang, F. X.; Zhao, Shijun; Jin, Ke Physical Review Letters, Vol. 118, Issue 20 https://doi.org/10.1103/PhysRevLett.118.205501	journal	May 2017
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Generalized convex hull construction for materials discovery Anelli, Andrea; Engel, Edgar A.; Pickard, Chris J. Physical Review Materials, Vol. 2, Issue 10 https://doi.org/10.1103/PhysRevMaterials.2.103804	journal	October 2018
Recent developments in the Inorganic Crystal Structure Database: theoretical crystal structure data and related features Zagorac, D.; Müller, H.; Ruehl, S. Journal of Applied Crystallography, Vol. 52, Issue 5 https://doi.org/10.1107/S160057671900997X	journal	September 2019
The Cambridge Structural Database Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P. Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179 https://doi.org/10.1107/S2052520616003954	journal	April 2016
The thermodynamic scale of inorganic crystalline metastability Sun, Wenhao; Dacek, Stephen T.; Ong, Shyue Ping Science Advances, Vol. 2, Issue 11 https://doi.org/10.1126/sciadv.1600225	journal	November 2016
High-entropy materials for catalysis: A new frontier Sun, Yifan; Dai, Sheng Science Advances, Vol. 7, Issue 20 https://doi.org/10.1126/sciadv.abg1600	journal	May 2021
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013

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