Enhancing catalytic activity of Cr2O3 in CO2-assisted propane dehydrogenation with effective dopant engineering: a DFT-based microkinetic simulation

doi:10.1039/d3cp05548e

IMR OpenIR

	Enhancing catalytic activity of Cr₂O₃ in CO₂-assisted propane dehydrogenation with effective dopant engineering: a DFT-based microkinetic simulation
	Jan, Faheem 1,2; Zhi, Shuaike 1,2; Sun, XiaoYing 3; Li, Bo 3
通讯作者	Sun, XiaoYing(sunxiaoying78@163.com) ; Li, Bo(boli@synu.edu.cn)
	2024-03-20
发表期刊	PHYSICAL CHEMISTRY CHEMICAL PHYSICS
ISSN	1463-9076
卷号	26 期号:12 页码:9708-9721
摘要	Using CO2 as a mild oxidizing agent in propane dehydrogenation (PDH) presents an attractive pathway for the generation of propene while maintaining high selectivity. Cr2O3 is one of the most important catalysts used for the CO2-assisted PDH process. In this study, the doping of Cr2O3 with single atoms such as Ge, Ir, Ni, Sn, Zn, and Zr was used for the PDH process. The introduction of dopants significantly modifies the electronic structure of pristine Cr2O3, leading to substantial alterations in its catalytic capabilities. The dehydrogenation reactions were explored both in the absence and presence of CO2. The addition of CO2 introduces two distinct pathways for PDH. On physisorbed CO2 surfaces, Ge and Ni-Cr2O3 enhance dehydrogenation. On the dissociated surface, the CO* and O* species actively participate in the reaction. All doped surfaces exhibit low energy barriers for dehydrogenation, except undoped Cr2O3 on dissociated CO2 surfaces. The Ni-Cr2O3 surface emerges as the most active surface for dehydrogenation of propane in all scenarios. Additionally, the catalytic surface is re-oxidized through H-2 release, and doped surfaces facilitate coke removal via the reverse Boudouard reaction more efficiently than undoped Cr2O3. Microkinetics simulations identify the removal of the first H-atom as the rate-determining step. CO2 reduces the apparent activation energy, directly impacting C3H8 conversion and C3H6 formation. This study offers a decisive description of Cr2O3 modification for the CO2-assisted PDH process.
资助者	National Natural Science Foundation of China ; Education department of LiaoNing Province ; ShenYang Normal University ; Program for Excellent Talents in Shenyang Normal University
DOI	10.1039/d3cp05548e
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] ; Education department of LiaoNing Province[JYTZD2023183] ; ShenYang Normal University[BS202208] ; Program for Excellent Talents in Shenyang Normal University
WOS研究方向	Chemistry ; Physics
WOS类目	Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
WOS记录号	WOS:001183144900001
出版者	ROYAL SOC CHEMISTRY
引用统计	被引频次：4[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.imr.ac.cn/handle/321006/184649
专题	中国科学院金属研究所
通讯作者	Sun, XiaoYing; Li, Bo
作者单位	1.Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang, Liaoning, Peoples R China 2.Univ Sci & Technol China, Sch Mat Sci & Engn, Shenyang, Liaoning, Peoples R China 3.Shenyang Normal Univ, Inst Catalysis Energy & Environm, Coll Chem & Chem Engn, Shenyang, Peoples R China
推荐引用方式 GB/T 7714	Jan, Faheem,Zhi, Shuaike,Sun, XiaoYing,et al. Enhancing catalytic activity of Cr₂O₃ in CO₂-assisted propane dehydrogenation with effective dopant engineering: a DFT-based microkinetic simulation[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2024,26(12):9708-9721.
APA	Jan, Faheem,Zhi, Shuaike,Sun, XiaoYing,&Li, Bo.(2024).Enhancing catalytic activity of Cr₂O₃ in CO₂-assisted propane dehydrogenation with effective dopant engineering: a DFT-based microkinetic simulation.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,26(12),9708-9721.
MLA	Jan, Faheem,et al."Enhancing catalytic activity of Cr₂O₃ in CO₂-assisted propane dehydrogenation with effective dopant engineering: a DFT-based microkinetic simulation".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 26.12(2024):9708-9721.