Theoretical DFT Study on the Mechanisms of CO/CO2 Conversion in Chemical Looping Catalyzed by Calcium Ferrite

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2021-09, Vol.125 (37), p.8159-8167
• Main Authors: Wang, Jing, Gu, Jiande, Rony, Asif, Fan, Maohong, Leszczynski, Jerzy
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.1c04431

The CO/CO2 conversion mechanism on the calcium ferrite (CFO) surface in chemical looping was explored by a computational study using the density functional theory approach. The CFO catalytic reaction pathway of 2CO + O2 → 2CO2 conversion has been elucidated. Our results show that the Fe center in CFO plays the key role as a catalyst in the CO/CO2 conversion. Two energetically stable spin states of CFO, quintet and septet, serve as the effective catalysts. The presence of the triplet O2 molecule caused the conversion of these two spin-state structures into each other along the catalytic reaction pathway. A double release of CO2 was predicted following this reaction mechanism. The rate-determining step is the formation of the 2CO2–CFO complex (P4) in the quintet state (19.0 kcal/mol). The predicted energy barriers for all the steps suggest that the proposed pathway is plausible.