Designing water resistant high entropy oxide materials

IF 14.7 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES

Nature Communications Pub Date : 2024-09-27 DOI:10.1038/s41467-024-52531-y

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

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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.

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设计防水高熵氧化物材料

无处不在的湿气通常会对工业催化产生不利影响。本文提出了一种设计防水氧化物催化剂的工程熵概念。以尖晶石 ACr2O4（A=Ni、Mg、Cu、Zn、Co）催化剂氧化 C3H6 为模型。通过 DFT 计算，C3H6 的吸附能、分子 H2O 在氧化物表面的解离能以及氧空位的形成能都表明，较高的构型熵会诱导催化剂发挥更好的性能。事实上，(Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Cr2O4 在 C3H6 氧化实验中表现出卓越的耐水性（100 小时），而与此形成鲜明对比的是二元氧化物（如H2O-TPD、原位拉曼和原位傅立叶变换红外光谱都证实了高熵氧化物具有较低的 H2O 吸附能和较强的水热稳定性，这归功于它们较低的吉布斯自由能。这项工作可能会对合理设计防水催化剂有所启发。

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来源期刊

Nature Communications Biological Science Disciplines-

CiteScore

24.90

自引率

2.40%

发文量

6928

审稿时长

3.7 months

期刊介绍： Nature Communications, an open-access journal, publishes high-quality research spanning all areas of the natural sciences. Papers featured in the journal showcase significant advances relevant to specialists in each respective field. With a 2-year impact factor of 16.6 (2022) and a median time of 8 days from submission to the first editorial decision, Nature Communications is committed to rapid dissemination of research findings. As a multidisciplinary journal, it welcomes contributions from biological, health, physical, chemical, Earth, social, mathematical, applied, and engineering sciences, aiming to highlight important breakthroughs within each domain.