Designing water resistant high entropy oxide materials

Mengyuan Zhang; Ying Gao; Chengmin Xie; Xiaolan Duan; Xiaoyan Lu; Kongliang Luo; Jian Ye; Xiaopeng Wang; Xinhua Gao; Qiang Niu; Pengfei Zhang; Sheng Dai

doi:10.1038/s41467-024-52531-y

Designing water resistant high entropy oxide materials

Mengyuan Zhang, Ying Gao, Chengmin Xie, Xiaolan Duan, Xiaoyan Lu, Kongliang Luo, Jian Ye, Xiaopeng Wang, Xinhua Gao, Qiang Niu, Pengfei Zhang, Sheng Dai

Chemical Sciences Division

Research output: Contribution to journal › Article › peer-review

Abstract

The ubiquitous presence of moisture usually shows adverse effects on industrial catalysis. Herein, a concept of engineering entropy to design water-resistant oxide catalysts is proposed. The C₃H₆ oxidation by spinel ACr₂O₄ (A=Ni, Mg, Cu, Zn, Co) catalysts is selected as a model. Through DFT calculation, the adsorption energy of C₃H₆, the dissociation energy of molecular H₂O on the oxide surface, and the formation energy of oxygen vacancy all suggest better performance induced by higher configurational entropy. Indeed, (Ni_0.2Mg_0.2Cu_0.2Zn_0.2Co_0.2)Cr₂O₄ experimentally show excellent water resistance (>100 h) in C₃H₆ oxidation, while in sharp contrast binary oxides (e.g., NiCr₂O₄, CoCr₂O₄) are deactivated in 20 h. H₂O-TPD, in-situ Raman, and in-situ FTIR all confirm the low H₂O adsorption energy and strong hydrothermal stability of high entropy oxide, which is attributed to their lower Gibbs free energy. This work may inspire the rational design of water-resistant catalysts.

Original language	English
Article number	8306
Journal	Nature Communications
Volume	15
Issue number	1
DOIs	https://doi.org/10.1038/s41467-024-52531-y
State	Published - Dec 2024

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title = "Designing water resistant high entropy oxide materials",

abstract = "The ubiquitous presence of moisture usually shows adverse effects on industrial catalysis. Herein, a concept of engineering entropy to design water-resistant oxide catalysts is proposed. The C3H6 oxidation by spinel ACr2O4 (A=Ni, Mg, Cu, Zn, Co) catalysts is selected as a model. Through DFT calculation, the adsorption energy of C3H6, the dissociation energy of molecular H2O on the oxide surface, and the formation energy of oxygen vacancy all suggest better performance induced by higher configurational entropy. Indeed, (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Cr2O4 experimentally show excellent water resistance (>100 h) in C3H6 oxidation, while in sharp contrast binary oxides (e.g., NiCr2O4, CoCr2O4) are deactivated in 20 h. H2O-TPD, in-situ Raman, and in-situ FTIR all confirm the low H2O adsorption energy and strong hydrothermal stability of high entropy oxide, which is attributed to their lower Gibbs free energy. This work may inspire the rational design of water-resistant catalysts.",

author = "Mengyuan Zhang and Ying Gao and Chengmin Xie and Xiaolan Duan and Xiaoyan Lu and Kongliang Luo and Jian Ye and Xiaopeng Wang and Xinhua Gao and Qiang Niu and Pengfei Zhang and Sheng Dai",

note = "Publisher Copyright: {\textcopyright} The Author(s) 2024.",

year = "2024",

month = dec,

doi = "10.1038/s41467-024-52531-y",

language = "English",

volume = "15",

journal = "Nature Communications",

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TY - JOUR

T1 - Designing water resistant high entropy oxide materials

AU - Zhang, Mengyuan

AU - Gao, Ying

AU - Xie, Chengmin

AU - Duan, Xiaolan

AU - Lu, Xiaoyan

AU - Luo, Kongliang

AU - Ye, Jian

AU - Wang, Xiaopeng

AU - Gao, Xinhua

AU - Niu, Qiang

AU - Zhang, Pengfei

AU - Dai, Sheng

PY - 2024/12

Y1 - 2024/12

N2 - The ubiquitous presence of moisture usually shows adverse effects on industrial catalysis. Herein, a concept of engineering entropy to design water-resistant oxide catalysts is proposed. The C3H6 oxidation by spinel ACr2O4 (A=Ni, Mg, Cu, Zn, Co) catalysts is selected as a model. Through DFT calculation, the adsorption energy of C3H6, the dissociation energy of molecular H2O on the oxide surface, and the formation energy of oxygen vacancy all suggest better performance induced by higher configurational entropy. Indeed, (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Cr2O4 experimentally show excellent water resistance (>100 h) in C3H6 oxidation, while in sharp contrast binary oxides (e.g., NiCr2O4, CoCr2O4) are deactivated in 20 h. H2O-TPD, in-situ Raman, and in-situ FTIR all confirm the low H2O adsorption energy and strong hydrothermal stability of high entropy oxide, which is attributed to their lower Gibbs free energy. This work may inspire the rational design of water-resistant catalysts.

AB - The ubiquitous presence of moisture usually shows adverse effects on industrial catalysis. Herein, a concept of engineering entropy to design water-resistant oxide catalysts is proposed. The C3H6 oxidation by spinel ACr2O4 (A=Ni, Mg, Cu, Zn, Co) catalysts is selected as a model. Through DFT calculation, the adsorption energy of C3H6, the dissociation energy of molecular H2O on the oxide surface, and the formation energy of oxygen vacancy all suggest better performance induced by higher configurational entropy. Indeed, (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Cr2O4 experimentally show excellent water resistance (>100 h) in C3H6 oxidation, while in sharp contrast binary oxides (e.g., NiCr2O4, CoCr2O4) are deactivated in 20 h. H2O-TPD, in-situ Raman, and in-situ FTIR all confirm the low H2O adsorption energy and strong hydrothermal stability of high entropy oxide, which is attributed to their lower Gibbs free energy. This work may inspire the rational design of water-resistant catalysts.

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DO - 10.1038/s41467-024-52531-y

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SN - 2041-1723

VL - 15

JO - Nature Communications

JF - Nature Communications

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Designing water resistant high entropy oxide materials

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