Entropy-Driven Structural Evolution in Ceramic Oxides

Liu, Shuo; Dun, Chaochao; Xiong, Lin; Das, Shaon; Ghose, Sanjit; Wierzbicki, Dominik; Chen, Kaiwen; Xuan, Zhengxi; Wang, Kun; Yang, Feipeng; Mazumder, Baishakhi; Wang, Xinyi; Chen, Wei; Lin, Zhou; Urban, Jeffrey J.; Swihart, Mark T.

doi:10.1021/jacs.5c06254

Entropy-Driven Structural Evolution in Ceramic Oxides

Journal Article · Thu Jul 24 00:00:00 EDT 2025 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5c06254· OSTI ID:2574503

Liu, Shuo ^[1]; ^[2]; ^[3]; Das, Shaon ^[4]; Ghose, Sanjit ^[5]; Wierzbicki, Dominik ^[6]; Chen, Kaiwen ^[4]; Xuan, Zhengxi ^[4]; Wang, Kun ^[7]; Yang, Feipeng ^[5]; ^[4]; Wang, Xinyi ^[8]; ^[4]; ^[3]; ^[2]; ^[4]

State Univ. of New York at Buffalo, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
Univ. of Massachusetts, Amherst, MA (United States)
State Univ. of New York at Buffalo, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); AGH Univ. of Science and Technology, Krakow, Poland
Alfred Univ., NY (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

High-entropy ceramics, with five or more elements randomly occupying the same cation crystallographic sites, offer vast compositional diversity and unique properties for material design and applications. However, for many dissimilar elements, entropic stabilization cannot overcome the enthalpic barrier to cation substitution. As a result, most high-entropy ceramics incorporate only a few similar elements, limiting the in-depth exploration of the effect of entropy on ceramic properties. Here, in this study, we first use density functional theory to model fluorite crystal structures composed of 1-10 elements and then experimentally present practical fluorite oxide nanostructures containing 1, 3, 8, and 15 metals, as well as a record-breaking 25-element high-entropy ceramic incorporating a diverse palette of rare-earth, transition, alkaline, p-block, and noble metals. As entropy increases, structural and configurational disorder in the solid solution rises, altering structural features such as lattice distortion, crystallinity, homogeneity, defect density, and thermal stability. This research provides new insights and understanding of the role of entropy in stabilizing compositionally complex ceramics.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: American Chemical Society Petroleum Research Fund (ACS PRF); National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Building Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; EE0008675; FE0032209; SC0012704

OSTI ID:: 2574503

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 31 Vol. 147; ISSN 1520-5126; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (66)

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
Selenic Acid Etching Assisted Vacancy Engineering for Designing Highly Active Electrocatalysts toward the Oxygen Evolution Reaction Zhang, Lin; Lu, Chengjie; Ye, Fei Advanced Materials, Vol. 33, Issue 14 https://doi.org/10.1002/adma.202007523	journal	March 2021
Enhanced Mechanical Properties and Oxidation Resistance of Zirconium Diboride Ceramics via Grain‐Refining and Dislocation Regulation Xu, Haiyue; Ji, Wei; Guo, Weiming Advanced Science, Vol. 9, Issue 6 https://doi.org/10.1002/advs.202104532	journal	January 2022
Controlling the Oxidation State of Pt Single Atoms for Maximizing Catalytic Activity Jeong, Hojin; Shin, Dongjae; Kim, Beom‐Sik Angewandte Chemie, Vol. 132, Issue 46 https://doi.org/10.1002/ange.202009776	journal	September 2020
Dual‐Atomic‐Site Catalysts for Molecular Oxygen Activation in Heterogeneous Thermo‐/Electro‐catalysis Wang, Zhongsen; Cheng, Ming; Liu, Yi Angewandte Chemie, Vol. 135, Issue 22 https://doi.org/10.1002/ange.202301483	journal	March 2023
A General Route to Flame Aerosol Synthesis and In Situ Functionalization of Mesoporous Silica Liu, Shuo; Dun, Chaochao; Chen, Junjie Angewandte Chemie International Edition, Vol. 61, Issue 35 https://doi.org/10.1002/anie.202206870	journal	July 2022
Influence of Grain Size on the Electrochemical Performance of Li_7‐3xLa₃Zr₂Al_xO₁₂ Solid Electrolyte Botros, Miriam; Gonzalez‐Julian, Jesus; Scherer, Torsten Batteries & Supercaps, Vol. 7, Issue 11 https://doi.org/10.1002/batt.202300370	journal	June 2024
Structure of Nano-sized CeO ₂ Materials: Combined Scattering and Spectroscopic Investigations Marchbank, Huw R.; Clark, Adam H.; Hyde, Timothy I. ChemPhysChem, Vol. 17, Issue 21 https://doi.org/10.1002/cphc.201600697	journal	September 2016
Plasma‐Induced Oxygen Defect Engineering in Perovskite Oxide for Boosting Oxygen Evolution Reaction Wang, Kaiteng; Zhou, Jun; Fu, Lei Small, Vol. 20, Issue 48 https://doi.org/10.1002/smll.202404239	journal	September 2024
The thermodynamics of cation distributions in simple spinels Navrotsky, A.; Kleppa, O. J. Journal of Inorganic and Nuclear Chemistry, Vol. 29, Issue 11 https://doi.org/10.1016/0022-1902(67)80008-3	journal	November 1967
Thermodynamics of formation of simple spinels Navrotsky, A.; Kleppa, O. J. Journal of Inorganic and Nuclear Chemistry, Vol. 30, Issue 2 https://doi.org/10.1016/0022-1902(68)80475-0	journal	February 1968
Thermodynamics of A3O4-B3O4 spinel solid solutions Navrotsky, A. Journal of Inorganic and Nuclear Chemistry, Vol. 31, Issue 1 https://doi.org/10.1016/0022-1902(69)80054-0	journal	January 1969
Wear-resistant ultra-fine-grained ceramics Wang, Xiaotong; Padture, Nitin P.; Tanaka, Hidehiko Acta Materialia, Vol. 53, Issue 2 https://doi.org/10.1016/j.actamat.2004.09.020	journal	January 2005
An assessment of the lattice strain in the CrMnFeCoNi high-entropy alloy Owen, L. R.; Pickering, E. J.; Playford, H. Y. Acta Materialia, Vol. 122 https://doi.org/10.1016/j.actamat.2016.09.032	journal	January 2017
Phase stability and distortion in high-entropy oxides Anand, G.; Wynn, Alex P.; Handley, Christopher M. Acta Materialia, Vol. 146 https://doi.org/10.1016/j.actamat.2017.12.037	journal	March 2018
Thermodynamics of high entropy oxides McCormack, Scott J.; Navrotsky, Alexandra Acta Materialia, Vol. 202 https://doi.org/10.1016/j.actamat.2020.10.043	journal	January 2021
Low-temperature water–gas shift: Strategy to lower Pt loading by doping ceria with Ca2+ improves formate mobility/WGS rate by increasing surface O-mobility Linganiso, Linda Z.; Jacobs, Gary; Azzam, Khalid G. Applied Catalysis A: General, Vol. 394, Issue 1-2 https://doi.org/10.1016/j.apcata.2010.12.043	journal	February 2011
Insight into the effects of the oxygen species over Ni/ZrO2 catalyst surface on methane reforming with carbon dioxide Zhang, Meng; Zhang, Junfeng; Wu, Yingquan Applied Catalysis B: Environmental, Vol. 244 https://doi.org/10.1016/j.apcatb.2018.11.068	journal	May 2019
Enhanced energy storage density of Sr0.7BixTiO3 lead-free relaxor ceramics via A-site defect and grain size tuning Zhu, Xiaopei; Shi, Peng; Kang, Ruirui Chemical Engineering Journal, Vol. 420 https://doi.org/10.1016/j.cej.2021.129808	journal	September 2021
Flame aerosol synthesis of hollow alumina nanoshells for application in thermal insulation Liu, Shuo; Shah, Mihir; Rao, Satyarit Chemical Engineering Journal, Vol. 428 https://doi.org/10.1016/j.cej.2021.131273	journal	January 2022
Creation of hollow silica-fiberglass soft ceramics for thermal insulation Liu, Shuo; Dun, Chaochao; Wei, Jilun Chemical Engineering Journal, Vol. 454 https://doi.org/10.1016/j.cej.2022.140134	journal	February 2023
Highly efficient CeO2-supported noble-metal catalysts: From single atoms to nanoclusters Yan, Han; Zhang, Ningqiang; Wang, Dingsheng Chem Catalysis, Vol. 2, Issue 7 https://doi.org/10.1016/j.checat.2022.05.001	journal	July 2022
Recent status and challenging perspective of high entropy oxides for chemical catalysis Wang, Yi; Mi, Jinxing; Wu, Zhong-Shuai Chem Catalysis, Vol. 2, Issue 7 https://doi.org/10.1016/j.checat.2022.05.003	journal	July 2022
Producing ultrastable Ni-ZrO2 nanoshell catalysts for dry reforming of methane by flame synthesis and Ni exsolution Liu, Shuo; Dun, Chaochao; Shah, Mihir Chem Catalysis, Vol. 2, Issue 9 https://doi.org/10.1016/j.checat.2022.05.013	journal	September 2022
Atom probe tomography analysis of the reference zircon gj-1: An interlaboratory study Exertier, F.; La Fontaine, A.; Corcoran, C. Chemical Geology, Vol. 495 https://doi.org/10.1016/j.chemgeo.2018.07.031	journal	September 2018
Effect of particle/grain size on the optical properties of Y2O3:Er,Yb Eilers, Hergen Journal of Alloys and Compounds, Vol. 474, Issue 1-2 https://doi.org/10.1016/j.jallcom.2008.07.001	journal	April 2009
New entropy-stabilized oxide with pyrochlore structure: Dy2(Ti0.2Zr0.2Hf0.2Ge0.2Sn0.2)2O7 Vayer, Florianne; Decorse, Claudia; Bérardan, David Journal of Alloys and Compounds, Vol. 883 https://doi.org/10.1016/j.jallcom.2021.160773	journal	November 2021
Prediction of lattice distortion and mechanical behavior of tetragonal phase (Bi0.2Na0.2Ba0.2Sr0.2Ca0.2)TiO3 high-entropy perovskite with A-site disorder from first-principles calculations Shao, Lin; Jiang, Huang-Hui; Xu, Chao-Ren Journal of Alloys and Compounds, Vol. 954 https://doi.org/10.1016/j.jallcom.2023.170205	journal	September 2023
A five-component entropy-stabilized fluorite oxide Chen, Kepi; Pei, Xintong; Tang, Lei Journal of the European Ceramic Society, Vol. 38, Issue 11 https://doi.org/10.1016/j.jeurceramsoc.2018.04.063	journal	September 2018
High porosity and low thermal conductivity high entropy (Zr0.2Hf0.2Ti0.2Nb0.2Ta0.2)C Chen, Heng; Xiang, Huimin; Dai, Fu-Zhi Journal of Materials Science & Technology, Vol. 35, Issue 8 https://doi.org/10.1016/j.jmst.2019.04.006	journal	August 2019
Anomalous decrease in X-ray diffraction intensities of Cu–Ni–Al–Co–Cr–Fe–Si alloy systems with multi-principal elements Yeh, Jien-Wei; Chang, Shou-Yi; Hong, Yu-Der Materials Chemistry and Physics, Vol. 103, Issue 1 https://doi.org/10.1016/j.matchemphys.2007.01.003	journal	May 2007
Extreme mixing in nanoscale transition metal alloys Yao, Yonggang; Huang, Zhennan; Hughes, Lauren A. Matter, Vol. 4, Issue 7 https://doi.org/10.1016/j.matt.2021.04.014	journal	July 2021
A general flame aerosol route to high-entropy nanoceramics Liu, Shuo; Pao, Chih-Wen; Chen, Jeng-Lung Matter, Vol. 7, Issue 11 https://doi.org/10.1016/j.matt.2024.07.019	journal	November 2024
Overview of high-entropy oxide ceramics Jiao, Yitao; Dai, Jian; Fan, Zhenhao Materials Today, Vol. 77 https://doi.org/10.1016/j.mattod.2024.06.005	journal	August 2024
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
High-entropy ceramics: Review of principles, production and applications Akrami, Saeid; Edalati, Parisa; Fuji, Masayoshi Materials Science and Engineering: R: Reports, Vol. 146 https://doi.org/10.1016/j.mser.2021.100644	journal	October 2021
Inhibition of grain coarsening up to 1000°C in (AlCrNbSiTiV)N superhard coatings Huang, Ping-Kang; Yeh, Jien-Wei Scripta Materialia, Vol. 62, Issue 2 https://doi.org/10.1016/j.scriptamat.2009.09.015	journal	January 2010
On the homogeneity of high entropy oxides: An investigation at the atomic scale Chellali, Mohammed Reda; Sarkar, Abhishek; Nandam, Sree Harsha Scripta Materialia, Vol. 166 https://doi.org/10.1016/j.scriptamat.2019.02.039	journal	June 2019
Tuning Oxygen Vacancies in Oxides by Configurational Entropy Zhang, Mengyuan; Duan, Xiaolan; Gao, Ying ACS Applied Materials & Interfaces, Vol. 15, Issue 39 https://doi.org/10.1021/acsami.3c07268	journal	September 2023
Raman Analysis of Mode Softening in Nanoparticle CeO _2−δ and Au-CeO _2−δ during CO Oxidation Lee, Youjin; He, Guanghui; Akey, Austin J. Journal of the American Chemical Society, Vol. 133, Issue 33 https://doi.org/10.1021/ja204479j	journal	August 2011
Probing the Local Site Disorder and Distortion in Pyrochlore High-Entropy Oxides Jiang, Bo; Bridges, Craig A.; Unocic, Raymond R. Journal of the American Chemical Society, Vol. 143, Issue 11 https://doi.org/10.1021/jacs.0c10739	journal	December 2020
Understanding the Role of Entropy in High Entropy Oxides Aamlid, Solveig S.; Oudah, Mohamed; Rottler, Jörg Journal of the American Chemical Society, Vol. 145, Issue 11 https://doi.org/10.1021/jacs.2c11608	journal	March 2023
Entropy-stabilized oxides Rost, Christina M.; Sachet, Edward; Borman, Trent Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9485	journal	September 2015
Entropy-stabilized single-atom Pd catalysts via high-entropy fluorite oxide supports Xu, Haidi; Zhang, Zihao; Liu, Jixing Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17738-9	journal	August 2020
Challenging thermodynamics: combining immiscible elements in a single-phase nano-ceramic Liu, Shuo; Dun, Chaochao; Jiang, Qike Nature Communications, Vol. 15, Issue 1 https://doi.org/10.1038/s41467-024-45413-w	journal	February 2024
Engineering relaxors by entropy for high energy storage performance Yang, Bingbing; Zhang, Qinghua; Huang, Houbing Nature Energy, Vol. 8, Issue 9 https://doi.org/10.1038/s41560-023-01300-0	journal	July 2023
A single-atom library for guided monometallic and concentration-complex multimetallic designs Han, Lili; Cheng, Hao; Liu, Wei Nature Materials, Vol. 21, Issue 6 https://doi.org/10.1038/s41563-022-01252-y	journal	May 2022
Scalable two-step annealing method for preparing ultra-high-density single-atom catalyst libraries Hai, Xiao; Xi, Shibo; Mitchell, Sharon Nature Nanotechnology, Vol. 17, Issue 2 https://doi.org/10.1038/s41565-021-01022-y	journal	November 2021
Designing disorder into crystalline materials Simonov, Arkadiy; Goodwin, Andrew L. Nature Reviews Chemistry, Vol. 4, Issue 12 https://doi.org/10.1038/s41570-020-00228-3	journal	October 2020
Clarifying the four core effects of high-entropy materials Hsu, Wei-Lin; Tsai, Che-Wei; Yeh, An-Chou Nature Reviews Chemistry, Vol. 8, Issue 6 https://doi.org/10.1038/s41570-024-00602-5	journal	May 2024
High-entropy ceramics Oses, Corey; Toher, Cormac; Curtarolo, Stefano Nature Reviews Materials, Vol. 5, Issue 4 https://doi.org/10.1038/s41578-019-0170-8	journal	February 2020
A mobile robotic chemist Burger, Benjamin; Maffettone, Phillip M.; Gusev, Vladimir V. Nature, Vol. 583, Issue 7815 https://doi.org/10.1038/s41586-020-2442-2	journal	July 2020
A stable atmospheric-pressure plasma for extreme-temperature synthesis Xie, Hua; Liu, Ning; Zhang, Qian Nature, Vol. 623, Issue 7989 https://doi.org/10.1038/s41586-023-06694-1	journal	November 2023
An autonomous laboratory for the accelerated synthesis of novel materials Szymanski, Nathan J.; Rendy, Bernardus; Fei, Yuxing Nature, Vol. 624, Issue 7990 https://doi.org/10.1038/s41586-023-06734-w	journal	November 2023
Scaling deep learning for materials discovery Merchant, Amil; Batzner, Simon; Schoenholz, Samuel S. Nature, Vol. 624, Issue 7990 https://doi.org/10.1038/s41586-023-06735-9	journal	November 2023
Denary oxide nanoparticles as highly stable catalysts for methane combustion Li, Tangyuan; Yao, Yonggang; Huang, Zhennan Nature Catalysis, Vol. 4, Issue 1 https://doi.org/10.1038/s41929-020-00554-1	journal	January 2021
High-entropy grain boundaries Luo, Jian; Zhou, Naixie Communications Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s43246-023-00335-w	journal	February 2023
General synthesis of high-entropy alloy and ceramic nanoparticles in nanoseconds Wang, Bing; Wang, Cheng; Yu, Xiwen Nature Synthesis, Vol. 1, Issue 2 https://doi.org/10.1038/s44160-021-00004-1	journal	February 2022
A High-Temperature Reducing Jet Reactor for Flame-Based Metal Nanoparticle Production Scharmach, William J.; Buchner, Raymond D.; Papavassiliou, Vasilis Aerosol Science and Technology, Vol. 44, Issue 12 https://doi.org/10.1080/02786826.2010.511320	journal	November 2010
Modeling of Solution Droplet Evaporation and Particle Evolution in Droplet-to-Particle Spray Methods Eslamian, Morteza; Ahmed, Mahmoud; Ashgriz, Nasser Drying Technology, Vol. 27, Issue 1 https://doi.org/10.1080/07373930802565665	journal	January 2009
Entropy-driven phase transitions in complex ceramic oxides Spurling, R. Jackson; Lass, Eric A.; Wang, Xin Physical Review Materials, Vol. 6, Issue 9 https://doi.org/10.1103/PhysRevMaterials.6.090301	journal	September 2022
Carbothermal shock synthesis of high-entropy-alloy nanoparticles Yao, Yonggang; Huang, Zhennan; Xie, Pengfei Science, Vol. 359, Issue 6383 https://doi.org/10.1126/science.aan5412	journal	March 2018
High-entropy-stabilized chalcogenides with high thermoelectric performance Jiang, Binbin; Yu, Yong; Cui, Juan Science, Vol. 371, Issue 6531 https://doi.org/10.1126/science.abe1292	journal	February 2021
High-entropy nanoparticles: Synthesis-structure-property relationships and data-driven discovery Yao, Yonggang; Dong, Qi; Brozena, Alexandra Science, Vol. 376, Issue 6589 https://doi.org/10.1126/science.abn3103	journal	April 2022
High-entropy mechanism to boost ionic conductivity Zeng, Yan; Ouyang, Bin; Liu, Jue Science, Vol. 378, Issue 6626 https://doi.org/10.1126/science.abq1346	journal	December 2022
High figure-of-merit and power generation in high-entropy GeTe-based thermoelectrics Jiang, Binbin; Wang, Wu; Liu, Shixuan Science, Vol. 377, Issue 6602 https://doi.org/10.1126/science.abq5815	journal	July 2022

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