Revisiting the origin of the superior performance of defective zirconium oxide catalysts in propane dehydrogenation: Double-edged oxygen vacancy

doi:10.1016/S1872-2067(24)60163-4

IMR OpenIR

	Revisiting the origin of the superior performance of defective zirconium oxide catalysts in propane dehydrogenation: Double-edged oxygen vacancy
	Tang, Yuqing 1; Chen, Yanjun 2; Abid, Aqsa 3; Meng, Zichun 1; Sun, Xiaoying 1; Li, Bo 1; Zhao, Zhen 1,2
通讯作者	Li, Bo(boli@synu.edu.cn) ; Zhao, Zhen(zhenzhao@cup.edu.cn)
	2025
发表期刊	CHINESE JOURNAL OF CATALYSIS
ISSN	0253-9837
卷号	68 页码:272-281
摘要	Recent studies have revealed the extraordinary performance of zirconium oxide in propane dehydrogenation, which is attributed to the excellent reactivity of the coordinatively unsaturated zirconium sites (Zrcus) around the oxygen vacancies. The origin of the enhanced catalytic activity of ZrO2 with defective tetrahedral Zr sites was examined by direct comparison with its pristine counterpart in the current study. Electronic-structure analysis revealed that electrons from oxygen removal were localized within vacancies on the defective surface, which directly attacked the C-H bond in propane. The involvement of localized electrons activates the C-H bond via back-donation to the antibonding orbital on the defective surface; conversely, charge is transferred from propane to the pristine surfaces. The barrier for the first C-H bond activation is clearly significantly reduced on the defective surfaces compared to that on the pristine surfaces, which verifies the superior activity of Zrcus. Notably, however, the desorption of both propene and hydrogen molecules from Zrcusis more difficult due to strong binding. The calculated turnover frequency (TOF) for propene formation demonstrates that the pristine surfaces exhibit better catalytic performance at lower temperatures, whereas the defective surfaces have a larger TOF at high temperatures. However, the rate-determining step and reaction order on the defective surface differ from those on the pristine surface, which corroborates that the catalysts follow different mechanisms. A further optimization strategy was proposed to address the remaining bottlenecks in propane dehydrogenation on zirconium oxide. (c) 2025, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
关键词	Propane dehydrogenation Zirconium oxide Oxygen vacancy Density functional theory Microkinetic
资助者	National Natural Science Foundation of China ; Basic Research Project of Education Office of Liaoning Province ; Fundamental Research Funds for the Liaoning Universities ; Shenyang Normal
DOI	10.1016/S1872-2067(24)60163-4
收录类别	SCI
语种	英语
资助项目	National Natural Science Foundation of China[22372105] ; National Natural Science Foundation of China[22172100] ; Basic Research Project of Education Office of Liaoning Province[JYTZD2023183] ; Fundamental Research Funds for the Liaoning Universities[LJ212410166043] ; Shenyang Normal
WOS研究方向	Chemistry ; Engineering
WOS类目	Chemistry, Applied ; Chemistry, Physical ; Engineering, Chemical
WOS记录号	WOS:001411290600001
出版者	ELSEVIER
引用统计
文献类型	期刊论文
条目标识符	http://ir.imr.ac.cn/handle/321006/180504
专题	中国科学院金属研究所
通讯作者	Li, Bo; Zhao, Zhen
作者单位	1.Shenyang Normal Univ, Inst Catalysis Energy & Environm, Coll Chem & Chem Engn, Shenyang 110034, Liaoning, Peoples R China 2.China Univ Petr, State Key Lab Heavy Oil Proc, Beijing 102249, Peoples R China 3.Chinese Acad Sci, Inst Met Res, Shenyang 110016, Liaoning, Peoples R China
推荐引用方式 GB/T 7714	Tang, Yuqing,Chen, Yanjun,Abid, Aqsa,et al. Revisiting the origin of the superior performance of defective zirconium oxide catalysts in propane dehydrogenation: Double-edged oxygen vacancy[J]. CHINESE JOURNAL OF CATALYSIS,2025,68:272-281.
APA	Tang, Yuqing.,Chen, Yanjun.,Abid, Aqsa.,Meng, Zichun.,Sun, Xiaoying.,...&Zhao, Zhen.(2025).Revisiting the origin of the superior performance of defective zirconium oxide catalysts in propane dehydrogenation: Double-edged oxygen vacancy.CHINESE JOURNAL OF CATALYSIS,68,272-281.
MLA	Tang, Yuqing,et al."Revisiting the origin of the superior performance of defective zirconium oxide catalysts in propane dehydrogenation: Double-edged oxygen vacancy".CHINESE JOURNAL OF CATALYSIS 68(2025):272-281.