Regulation of metal-support interaction by pentacoordinate Al3+ content on CeO2/γ-Al2O3 catalyst for oxidative dehydrogenation of cyclohexane

doi:10.1016/j.cjche.2025.08.011

中国化学工程学报 ›› 2025, Vol. 86 ›› Issue (10): 64-71.DOI: 10.1016/j.cjche.2025.08.011

• Special Issue on Celebrating the 100th Anniversary of the School of Chemical Engineering and Technology of Tianjin University • 上一篇下一篇

Regulation of metal-support interaction by pentacoordinate Al³⁺ content on CeO₂/γ-Al₂O₃ catalyst for oxidative dehydrogenation of cyclohexane

Jinyao Wang¹, Bowen Liu¹, Xiaoling Liu², Mingben Chong², Dangguo Cheng^1,2, Fengqiu Chen^1,2

1. College of Chemical and Biological Engineering, Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, Zhejiang University, Hangzhou 310027, China;
2. Institute of Zhejiang University-Quzhou, Quzhou 324000, China

收稿日期:2025-04-24 修回日期:2025-08-17 接受日期:2025-08-18 出版日期:2025-10-28 发布日期:2025-09-08
通讯作者: Dangguo Cheng,E-mail:dgcheng@zju.edu.cn
基金资助:
The support from Zhejiang Provincial Natural Science Foundation of China (LZ23B060001) is greatly appreciated.

Regulation of metal-support interaction by pentacoordinate Al³⁺ content on CeO₂/γ-Al₂O₃ catalyst for oxidative dehydrogenation of cyclohexane

Jinyao Wang¹, Bowen Liu¹, Xiaoling Liu², Mingben Chong², Dangguo Cheng^1,2, Fengqiu Chen^1,2

1. College of Chemical and Biological Engineering, Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, Zhejiang University, Hangzhou 310027, China;
2. Institute of Zhejiang University-Quzhou, Quzhou 324000, China

Received:2025-04-24 Revised:2025-08-17 Accepted:2025-08-18 Online:2025-10-28 Published:2025-09-08
Contact: Dangguo Cheng,E-mail:dgcheng@zju.edu.cn
Supported by:
The support from Zhejiang Provincial Natural Science Foundation of China (LZ23B060001) is greatly appreciated.

摘要/Abstract

摘要： Supported metal oxide catalysts have garnered significant attention in oxidative dehydrogenation (ODH) due to their tunable metal-support interactions. The pentacoordinate Al³⁺ (Al_V³⁺) in γ-Al₂O₃ supports plays a pivotal role in modulating metal-support interaction. This study investigates oxalic acid (OA) pretreatment as a defect engineering strategy to enhance the catalytic performance of CeO₂/γ-Al₂O₃ in cyclohexane ODH. Through integrated characterization (XRD, ²⁷Al MAS NMR, H₂-TPR, TPRO, MS, XPS) and catalytic testing, we demonstrate that optimal OA treatment (1:10 ratio) eliminates 100% of surface Al_V³⁺ defects while enhancing CeO₂ crystallinity and interfacial oxygen mobility. The removal of Al_V³⁺ species restructures metal-support interaction, accelerating interfacial oxygen mobility. In oxidation dehydrogenation of cyclohexane, the modified CeO₂/γ-Al₂O₃ achieves 29% of cyclohexane conversion with stable selectivity of 49% cyclohexene. These findings provide an initial framework for designing redox-active catalysts via targeted support modification in CeO₂/γ-Al₂O₃ systems, emphasizing the relationship between metal-support interaction and oxygen mobility.

关键词: Cyclohexane, Oxidative dehydrogenation, Ceria, Pentacoordinate Al³⁺, Metal-support interaction

Abstract: Supported metal oxide catalysts have garnered significant attention in oxidative dehydrogenation (ODH) due to their tunable metal-support interactions. The pentacoordinate Al³⁺ (Al_V³⁺) in γ-Al₂O₃ supports plays a pivotal role in modulating metal-support interaction. This study investigates oxalic acid (OA) pretreatment as a defect engineering strategy to enhance the catalytic performance of CeO₂/γ-Al₂O₃ in cyclohexane ODH. Through integrated characterization (XRD, ²⁷Al MAS NMR, H₂-TPR, TPRO, MS, XPS) and catalytic testing, we demonstrate that optimal OA treatment (1:10 ratio) eliminates 100% of surface Al_V³⁺ defects while enhancing CeO₂ crystallinity and interfacial oxygen mobility. The removal of Al_V³⁺ species restructures metal-support interaction, accelerating interfacial oxygen mobility. In oxidation dehydrogenation of cyclohexane, the modified CeO₂/γ-Al₂O₃ achieves 29% of cyclohexane conversion with stable selectivity of 49% cyclohexene. These findings provide an initial framework for designing redox-active catalysts via targeted support modification in CeO₂/γ-Al₂O₃ systems, emphasizing the relationship between metal-support interaction and oxygen mobility.

Key words: Cyclohexane, Oxidative dehydrogenation, Ceria, Pentacoordinate Al³⁺, Metal-support interaction

Jinyao Wang, Bowen Liu, Xiaoling Liu, Mingben Chong, Dangguo Cheng, Fengqiu Chen. Regulation of metal-support interaction by pentacoordinate Al³⁺ content on CeO₂/γ-Al₂O₃ catalyst for oxidative dehydrogenation of cyclohexane[J]. 中国化学工程学报, 2025, 86(10): 64-71.

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Regulation of metal-support interaction by pentacoordinate Al³⁺ content on CeO₂/γ-Al₂O₃ catalyst for oxidative dehydrogenation of cyclohexane

Regulation of metal-support interaction by pentacoordinate Al³⁺ content on CeO₂/γ-Al₂O₃ catalyst for oxidative dehydrogenation of cyclohexane

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