Heteropolyacid hosted to nano-silica catalyst for the oxidation of methacrolein

doi:10.1016/j.cjche.2024.10.027

中国化学工程学报 ›› 2025, Vol. 78 ›› Issue (2): 150-162.DOI: 10.1016/j.cjche.2024.10.027

Heteropolyacid hosted to nano-silica catalyst for the oxidation of methacrolein

Gang Hu¹, Qinqin Wang¹, Mingyuan Zhu², Lihua Kang¹

1. School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China;
2. College of Chemistry & Chemical Engineering, Yantai University, Yantai 264010, China

收稿日期:2024-07-19 修回日期:2024-09-30 接受日期:2024-10-07 出版日期:2025-02-08 发布日期:2024-12-26
通讯作者: Mingyuan Zhu,E-mail:zhuminyuan@shzu.edu.cn;Lihua Kang,E-mail:kanglihua@shzu.edu.cn
基金资助:
This work was financially supported by the Taishan Scholars Program of Shandong Province (tsqn202103051), Tianshan Talents Training Program of Xinjiang (Science and Technology Innovation Team, 2022TSYCTD0021), the Science and Technology Project of Xinjiang Bingtuan Supported by Central Government (2022BC001), the project of scientific research in Shihezi University (CXFZ202205), and special funds for over provincial level leading talent of Yantai City.

Heteropolyacid hosted to nano-silica catalyst for the oxidation of methacrolein

Gang Hu¹, Qinqin Wang¹, Mingyuan Zhu², Lihua Kang¹

1. School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China;
2. College of Chemistry & Chemical Engineering, Yantai University, Yantai 264010, China

Received:2024-07-19 Revised:2024-09-30 Accepted:2024-10-07 Online:2025-02-08 Published:2024-12-26
Supported by:
This work was financially supported by the Taishan Scholars Program of Shandong Province (tsqn202103051), Tianshan Talents Training Program of Xinjiang (Science and Technology Innovation Team, 2022TSYCTD0021), the Science and Technology Project of Xinjiang Bingtuan Supported by Central Government (2022BC001), the project of scientific research in Shihezi University (CXFZ202205), and special funds for over provincial level leading talent of Yantai City.

摘要/Abstract

摘要： In this study, a catalyst was synthesized using a two-step in-situ molecular beam epitaxy method to grow H₄PMo₁₁VO₄₀ (HPAV) on amination-treated SiO₂ nanoparticles, which served as both dopant and host agents. SiO₂ dopant was modified with (3-aminopropyl)triethoxysilane (APTS), facilitating the formation of ammonium ions that enhanced the overall positive charge. This modification enabled the effective dispersion and exposure of HPAV's active species and induced a structural transformation of HPAV from a triclinic to a cubic crystal phase. The two-step hosting growth process optimized the proportions of Cs⁺, H⁺ and NH₄⁺ antinuclear ions, thereby fine-tuning the synergistic catalysis of oxidation and acidity, as well as the oxidative sensitivity at HPAV catalytic interface. The resultant 8(HPAV)&4(Cs₃PAV)-NH₂-SiO₂ catalyst achieved a methacrolein (MAL) conversion rate of 84% and a methacrylic acid (MAA) selectivity of 71%. Even after 10.5 h of reaction time, the catalyst retained its high dispersion, cubic crystal structure, and Keggin configuration, demonstrating stable catalytic performance over a continuous 200-h reaction period.

关键词: Catalyst, Nanomaterial, Composite, Heteropoly acid, Dopant, Synthesis

Abstract: In this study, a catalyst was synthesized using a two-step in-situ molecular beam epitaxy method to grow H₄PMo₁₁VO₄₀ (HPAV) on amination-treated SiO₂ nanoparticles, which served as both dopant and host agents. SiO₂ dopant was modified with (3-aminopropyl)triethoxysilane (APTS), facilitating the formation of ammonium ions that enhanced the overall positive charge. This modification enabled the effective dispersion and exposure of HPAV's active species and induced a structural transformation of HPAV from a triclinic to a cubic crystal phase. The two-step hosting growth process optimized the proportions of Cs⁺, H⁺ and NH₄⁺ antinuclear ions, thereby fine-tuning the synergistic catalysis of oxidation and acidity, as well as the oxidative sensitivity at HPAV catalytic interface. The resultant 8(HPAV)&4(Cs₃PAV)-NH₂-SiO₂ catalyst achieved a methacrolein (MAL) conversion rate of 84% and a methacrylic acid (MAA) selectivity of 71%. Even after 10.5 h of reaction time, the catalyst retained its high dispersion, cubic crystal structure, and Keggin configuration, demonstrating stable catalytic performance over a continuous 200-h reaction period.

Key words: Catalyst, Nanomaterial, Composite, Heteropoly acid, Dopant, Synthesis

Gang Hu, Qinqin Wang, Mingyuan Zhu, Lihua Kang. Heteropolyacid hosted to nano-silica catalyst for the oxidation of methacrolein[J]. 中国化学工程学报, 2025, 78(2): 150-162.

Gang Hu, Qinqin Wang, Mingyuan Zhu, Lihua Kang. Heteropolyacid hosted to nano-silica catalyst for the oxidation of methacrolein[J]. Chinese Journal of Chemical Engineering, 2025, 78(2): 150-162.

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Heteropolyacid hosted to nano-silica catalyst for the oxidation of methacrolein

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