An Unexpected Decrease in Vibrational Entropy of Multicomponent Rutile Oxides

Wang, Yaowen1; Li, Xinbo1; Luo, Jipeng2; Woodfield, Brian F.3; Wang, Xiyang4; Feng, Tao5; Yin, Nan2; Shi, Quan2; Li, Guangshe1; Li, Liping1

2024-05-14

10.1021/jacs.3c14801

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

High-entropy oxides (HEOs), featuring infinite chemical composition and exceptional physicochemical properties, are attracting much attention. The configurational entropy caused by a component disorder of HEOs is popularly believed to be the main driving force for thermal stability, while the role of vibrational entropy in the thermodynamic landscape has been neglected. In this study, we systematically investigated the vibrational entropy of multicomponent rutile oxides (including Fe0.5Ta0.5O2, Fe0.333Ti0.333Ta0.333O2, Fe0.25Ti0.25Ta0.25Sn0.25O2, and Fe0.21Ti0.21Ta0.21Sn0.21Ge0.16O2) by precise heat capacity measurements. It is found that vibrational entropy gradually decreases with increasing component disorder, beyond what one could expect from an equilibrium thermodynamics perspective. Moreover, all multicomponent rutile oxides exhibit a positive excess vibrational entropy at 298.15 K. Upon examinations of configuration disorder, size mismatch, phase transition, and polyhedral distortions, we demonstrate that the excess vibrational entropy plays a pivotal role in lowering the crystallization temperature of multicomponent rutile oxides. These findings represent the first experimental confirmation of the role of lattice vibrations in the thermodynamic landscape of rutile HEOs. In particular, vibrational entropy could serve as a novel descriptor to guide the predictive design of multicomponent oxide materials.

SCI ; EI

英语

其他

National Natural Science Foundation of China["22293041","22175070"] ; National Natural Science Foundation of China[SKL202302018] ; Jilin Provincial Science and Technology Department[2020HSC-UE002]

Chemistry

Chemistry, Multidisciplinary

WOS:001225295900001

AMER CHEMICAL SOC

Web of Science

1.Jilin Univ, Coll Chem, State Key Lab Inorgan Synth & Preparat Chem, Changchun 130012, Peoples R China
2.Chinese Acad Sci, Dalian Inst Chem Phys, Thermochemistry Lab, Dalian 116023, Peoples R China
3.Brigham Young Univ, Dept Chem & Biochem, Provo, UT 84602 USA
4.Univ Waterloo, Dept Mech & Mechatron Engn, Waterloo, ON N2L 3G1, Canada
5.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China

Wang, Yaowen,Li, Xinbo,Luo, Jipeng,et al. An Unexpected Decrease in Vibrational Entropy of Multicomponent Rutile Oxides[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024,146(21).

Wang, Yaowen.,Li, Xinbo.,Luo, Jipeng.,Woodfield, Brian F..,Wang, Xiyang.,...&Li, Liping.(2024).An Unexpected Decrease in Vibrational Entropy of Multicomponent Rutile Oxides.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,146(21).

Wang, Yaowen,et al."An Unexpected Decrease in Vibrational Entropy of Multicomponent Rutile Oxides".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146.21(2024).