| Resolving the Mechanism Complexity of Oxidative Dehydrogenation of Hydrocarbons on Nanocarbon by Microkinetic Modeling | |
| Lian, Zan1,2; Si, Chaowei1,2; Jan, Faheem1,2; Yang, Min1,2; Li, Bo1 | |
| Corresponding Author | Li, Bo(boli@imr.ac.cn) |
| 2020-12-04 | |
| Source Publication | ACS CATALYSIS
 |
| ISSN | 2155-5435 |
| Volume | 10Issue:23Pages:14006-14014 |
| Abstract | As metal-free catalysts with great potential for widespread application, nanostructured carbon materials have excellent performance comparable to traditional metal oxide catalysts in the oxidative dehydrogenation (ODH) of alkanes. Unlike the mature narrations of the mechanism on the metal catalyst, the mechanism of ODH on the nanocarbon catalyst is still disputable and inconclusive. In this work, density functional theory (DFT) calculation and microkinetic modeling (MKM) are combined to provide unique insights into the mechanism. Four possible mechanisms were studied, which are Eley-Rideal (ER), Langmuir-Hinshelwood (LH), and Mars-van Krevelen (MvK), together with the reactions between weakly adsorbed species and radicals. The simulation clearly identified the mechanism of the reaction that the ER pathway is more likely than both LH and MvK pathways under various conditions. Carbonyl groups are the main active sites for the first hydrogen abstraction of ethylbenzene. On the other hand, the hydrogen abstraction from intermediate hydrocarbons (such as C6H5CHCH3 center dot) by O-2* and HO2 center dot yields a significant contribution to the total reaction rate under certain conditions. The reaction is first-order in ethylbenzene and zero-order in O-2 when the ratio of reactants nears stoichiometry. Moreover, the defective site does not affect the intrinsic catalytic performance. The defective site is subsequently transformed into the carbonyl group at the steady state and thus increases the number of active sites. This study provides a decisive description of the mechanism of ODH on nanocarbon catalysts under various reaction conditions and sheds light on design of the catalyst and optimization of reaction conditions. |
| Keyword | oxidative dehydrogenation carbon catalysis microkinetic modeling radical reaction reaction mechanism density functional theory |
| Funding Organization | National Natural Science Foundation of China ; Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science ; State Key Laboratory of Catalytic Materials and Reaction Engineering (RIPP, SINOPEC) ; Special Program for Applied Research on Super Computation of the NSFC Guangdong Joint Fund |
| DOI | 10.1021/acscatal.0c02952 |
| Indexed By | SCI |
| Language | 英语 |
| Funding Project | National Natural Science Foundation of China[21573255] ; Joint Research Fund Liaoning-Shenyang National Laboratory for Materials Science ; State Key Laboratory of Catalytic Materials and Reaction Engineering (RIPP, SINOPEC) ; Special Program for Applied Research on Super Computation of the NSFC Guangdong Joint Fund[U1501501] |
| WOS Research Area | Chemistry |
| WOS Subject | Chemistry, Physical |
| WOS ID | WOS:000598140200024 |
| Publisher | AMER CHEMICAL SOC |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.imr.ac.cn/handle/321006/158946 |
| Collection | 中国科学院金属研究所 |
| Corresponding Author | Li, Bo |
| Affiliation | 1.Chinese Acad Sci, Inst Met Res, Shenyang Natl Lab Mat Sci, Shenyang 110016, Liaoning, Peoples R China 2.Univ Sci & Technol China, Sch Mat Sci & Engn, Shenyang 110016, Peoples R China |
| Recommended Citation GB/T 7714 | Lian, Zan,Si, Chaowei,Jan, Faheem,et al. Resolving the Mechanism Complexity of Oxidative Dehydrogenation of Hydrocarbons on Nanocarbon by Microkinetic Modeling[J]. ACS CATALYSIS,2020,10(23):14006-14014. |
| APA | Lian, Zan,Si, Chaowei,Jan, Faheem,Yang, Min,&Li, Bo.(2020).Resolving the Mechanism Complexity of Oxidative Dehydrogenation of Hydrocarbons on Nanocarbon by Microkinetic Modeling.ACS CATALYSIS,10(23),14006-14014. |
| MLA | Lian, Zan,et al."Resolving the Mechanism Complexity of Oxidative Dehydrogenation of Hydrocarbons on Nanocarbon by Microkinetic Modeling".ACS CATALYSIS 10.23(2020):14006-14014. |
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