General Synthesis of High-Entropy Oxide Nanofibers

Mengyuan Zhang; Jian Ye; Ying Gao; Xiaolan Duan; Jiahua Zhao; Shuangshuang Zhang; Xiaoyan Lu; Kongliang Luo; Qiongqiong Wang; Qiang Niu; Pengfei Zhang; Sheng Dai

doi:10.1021/acsnano.3c07506

General Synthesis of High-Entropy Oxide Nanofibers

Mengyuan Zhang, Jian Ye, Ying Gao, Xiaolan Duan, Jiahua Zhao, Shuangshuang Zhang, Xiaoyan Lu, Kongliang Luo, Qiongqiong Wang, Qiang Niu, Pengfei Zhang, Sheng Dai

Chemical Sciences Division

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

8 Scopus citations

Abstract

The discovery of high-entropy oxides (HEOs) in 2015 has provided a family of potential solid catalysts, due to their tunable components, abundant defects or lattice distorts, excellent thermal stability (ΔG↓ = ΔH - TΔS↑), and so on. When facing the heterogeneous catalysis by HEOs, the micrometer bulky morphology and low surface areas (e.g., <10 m² g^-1) by traditional synthesis methods obstructed their way. In this work, an electrospinning method to fabricate HEO nanofibers with diameters of 50-100 nm was demonstrated. The key point lay in the formation of one-dimensional filamentous precursors, during which the uniform dispersion of five metal species with disordered configuration would help to crystallize into single-phase HEOs at lower temperatures: inverse spinel (Cr_0.2Mn_0.2Co_0.2Ni_0.2Fe_0.2)₃O₄ (400 °C), perovskite La(Mn_0.2Cu_0.2Co_0.2Ni_0.2Fe_0.2)O₃ (500 °C), spinel Ni_0.2Mg_0.2Cu_0.2Mn_0.2Co_0.2)Al₂O₄ (550 °C), and cubic Ni_0.2Mg_0.2Cu_0.2Zn_0.2Co_0.2O (750 °C). As a proof-of-concept, (Ni₃MoCoZn)Al₁₂O₂₄ nanofiber exhibited good activity (CH₄ Conv. > 96%, CO₂ Conv. > 99%, H₂/CO ≈ 0.98), long-time stability (>100 h) for the dry reforming of methane (DRM) at 700 °C without coke deposition, better than control samples (Ni₃MoCoZn)Al₁₂O₂₄-Coprecipitation-700 (CH₄ Conv. < 3%, CO₂ Conv. < 7%). The reaction mechanism of DRM was studied by in situ infrared spectroscopy, CO₂-TPD, and CO₂/CH₄-TPSR. This electrospinning method provides a synthetic route for HEO nanofibers for target applications.

Original language	English
Pages (from-to)	1449-1463
Number of pages	15
Journal	ACS Nano
Volume	18
Issue number	2
DOIs	https://doi.org/10.1021/acsnano.3c07506
State	Published - Jan 16 2024

Funding

This research was supported by R & D Program Plan (2022YFA1504803 and 2020YFB0606400), National Natural Science Foundation of China (grant no. 22178219), Project funded by China Postdoctoral Science Foundation (2022M722075), Inner Mongolia R & D Program Plan (2021ZD0042, 2021EEDSCXSFQZD006, 2021GG0350), Ordos R&D Program (2121HZ231-8).

Funders	Funder number
Inner Mongolia R & D Program Plan	2021ZD0042, 2121HZ231-8, 2021GG0350, 2021EEDSCXSFQZD006
R & D Program Plan	2022YFA1504803, 2020YFB0606400
National Natural Science Foundation of China	22178219
China Postdoctoral Science Foundation	2022M722075

Keywords

dry reforming of methane
electrospinning
high entropy catalysts
high entropy oxide
nanofibers

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/acsnano.3c07506

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title = "General Synthesis of High-Entropy Oxide Nanofibers",

abstract = "The discovery of high-entropy oxides (HEOs) in 2015 has provided a family of potential solid catalysts, due to their tunable components, abundant defects or lattice distorts, excellent thermal stability (ΔG↓ = ΔH - TΔS↑), and so on. When facing the heterogeneous catalysis by HEOs, the micrometer bulky morphology and low surface areas (e.g., <10 m2 g-1) by traditional synthesis methods obstructed their way. In this work, an electrospinning method to fabricate HEO nanofibers with diameters of 50-100 nm was demonstrated. The key point lay in the formation of one-dimensional filamentous precursors, during which the uniform dispersion of five metal species with disordered configuration would help to crystallize into single-phase HEOs at lower temperatures: inverse spinel (Cr0.2Mn0.2Co0.2Ni0.2Fe0.2)3O4 (400 °C), perovskite La(Mn0.2Cu0.2Co0.2Ni0.2Fe0.2)O3 (500 °C), spinel Ni0.2Mg0.2Cu0.2Mn0.2Co0.2)Al2O4 (550 °C), and cubic Ni0.2Mg0.2Cu0.2Zn0.2Co0.2O (750 °C). As a proof-of-concept, (Ni3MoCoZn)Al12O24 nanofiber exhibited good activity (CH4 Conv. > 96%, CO2 Conv. > 99%, H2/CO ≈ 0.98), long-time stability (>100 h) for the dry reforming of methane (DRM) at 700 °C without coke deposition, better than control samples (Ni3MoCoZn)Al12O24-Coprecipitation-700 (CH4 Conv. < 3%, CO2 Conv. < 7%). The reaction mechanism of DRM was studied by in situ infrared spectroscopy, CO2-TPD, and CO2/CH4-TPSR. This electrospinning method provides a synthetic route for HEO nanofibers for target applications.",

keywords = "dry reforming of methane, electrospinning, high entropy catalysts, high entropy oxide, nanofibers",

author = "Mengyuan Zhang and Jian Ye and Ying Gao and Xiaolan Duan and Jiahua Zhao and Shuangshuang Zhang and Xiaoyan Lu and Kongliang Luo and Qiongqiong Wang and Qiang Niu and Pengfei Zhang and Sheng Dai",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society",

year = "2024",

month = jan,

day = "16",

doi = "10.1021/acsnano.3c07506",

language = "English",

volume = "18",

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TY - JOUR

T1 - General Synthesis of High-Entropy Oxide Nanofibers

AU - Zhang, Mengyuan

AU - Ye, Jian

AU - Gao, Ying

AU - Duan, Xiaolan

AU - Zhao, Jiahua

AU - Zhang, Shuangshuang

AU - Lu, Xiaoyan

AU - Luo, Kongliang

AU - Wang, Qiongqiong

AU - Niu, Qiang

AU - Zhang, Pengfei

AU - Dai, Sheng

PY - 2024/1/16

Y1 - 2024/1/16

N2 - The discovery of high-entropy oxides (HEOs) in 2015 has provided a family of potential solid catalysts, due to their tunable components, abundant defects or lattice distorts, excellent thermal stability (ΔG↓ = ΔH - TΔS↑), and so on. When facing the heterogeneous catalysis by HEOs, the micrometer bulky morphology and low surface areas (e.g., <10 m2 g-1) by traditional synthesis methods obstructed their way. In this work, an electrospinning method to fabricate HEO nanofibers with diameters of 50-100 nm was demonstrated. The key point lay in the formation of one-dimensional filamentous precursors, during which the uniform dispersion of five metal species with disordered configuration would help to crystallize into single-phase HEOs at lower temperatures: inverse spinel (Cr0.2Mn0.2Co0.2Ni0.2Fe0.2)3O4 (400 °C), perovskite La(Mn0.2Cu0.2Co0.2Ni0.2Fe0.2)O3 (500 °C), spinel Ni0.2Mg0.2Cu0.2Mn0.2Co0.2)Al2O4 (550 °C), and cubic Ni0.2Mg0.2Cu0.2Zn0.2Co0.2O (750 °C). As a proof-of-concept, (Ni3MoCoZn)Al12O24 nanofiber exhibited good activity (CH4 Conv. > 96%, CO2 Conv. > 99%, H2/CO ≈ 0.98), long-time stability (>100 h) for the dry reforming of methane (DRM) at 700 °C without coke deposition, better than control samples (Ni3MoCoZn)Al12O24-Coprecipitation-700 (CH4 Conv. < 3%, CO2 Conv. < 7%). The reaction mechanism of DRM was studied by in situ infrared spectroscopy, CO2-TPD, and CO2/CH4-TPSR. This electrospinning method provides a synthetic route for HEO nanofibers for target applications.

AB - The discovery of high-entropy oxides (HEOs) in 2015 has provided a family of potential solid catalysts, due to their tunable components, abundant defects or lattice distorts, excellent thermal stability (ΔG↓ = ΔH - TΔS↑), and so on. When facing the heterogeneous catalysis by HEOs, the micrometer bulky morphology and low surface areas (e.g., <10 m2 g-1) by traditional synthesis methods obstructed their way. In this work, an electrospinning method to fabricate HEO nanofibers with diameters of 50-100 nm was demonstrated. The key point lay in the formation of one-dimensional filamentous precursors, during which the uniform dispersion of five metal species with disordered configuration would help to crystallize into single-phase HEOs at lower temperatures: inverse spinel (Cr0.2Mn0.2Co0.2Ni0.2Fe0.2)3O4 (400 °C), perovskite La(Mn0.2Cu0.2Co0.2Ni0.2Fe0.2)O3 (500 °C), spinel Ni0.2Mg0.2Cu0.2Mn0.2Co0.2)Al2O4 (550 °C), and cubic Ni0.2Mg0.2Cu0.2Zn0.2Co0.2O (750 °C). As a proof-of-concept, (Ni3MoCoZn)Al12O24 nanofiber exhibited good activity (CH4 Conv. > 96%, CO2 Conv. > 99%, H2/CO ≈ 0.98), long-time stability (>100 h) for the dry reforming of methane (DRM) at 700 °C without coke deposition, better than control samples (Ni3MoCoZn)Al12O24-Coprecipitation-700 (CH4 Conv. < 3%, CO2 Conv. < 7%). The reaction mechanism of DRM was studied by in situ infrared spectroscopy, CO2-TPD, and CO2/CH4-TPSR. This electrospinning method provides a synthetic route for HEO nanofibers for target applications.

KW - dry reforming of methane

KW - electrospinning

KW - high entropy catalysts

KW - high entropy oxide

KW - nanofibers

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General Synthesis of High-Entropy Oxide Nanofibers

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