Density Functional Theory Study of Mechanism of Reduction of N2O by CO over Fe-ZSM-5 Zeolites

Abstract

Nitrous oxide (N2O) is an industrial waste gas (e.g., from the production of adipic acid), which damages the ozone layer and causes the greenhouse effect. Density functional theory calculations were employed to investigate the mechanism of direct catalytic decomposition of N2O and selective catalytic reduction (SCR) of N2O by CO over Fe-ZSM-5 zeolites. Two stable Fe-active sites with six-membered ring structures on Fe-ZSM-5 were considered. The calculations indicate that the decomposition of N2O is affected by the coordination environment around Fe and can occur through two reaction pathways. However, there is invariably a more considerable energy hurdle for the initiation of the second stage of N2O decomposition. When CO participated in the reaction, it showed good reactivity and stability, the reaction energy barriers of the rate-limiting step were reduced by roughly 20.57 kcal/mol compared to the direct catalytic decomposition of N2O. CO exhibited a superior electron-donating ability and orbital hybridization performance during the reaction, which enhanced the cyclicity of the N2O reduction catalytic process. Our calculations confirmed the significant role of CO in N2O reduction over Fe-ZSM-5 observed in previous studies. This study provides a valuable theoretical reference for exploring CO-SCR methods for N2O reduction over Fe-based zeolite catalysts.

Rational Design of Fe Single Sites Supported on Hierarchical Zeolites via Atomic Layer Deposition for Few-Walled Carbon Nanotube Production

“…Identifying the precise location of isolated Fe species within the zeolite framework is crucial for comprehending the formation of single-site Fe; however, it remains a challenge. It also highlights previous attempts using density functional theory (DFT) calculations to analyze the preferred sites of Fe species within the zeolite extra-framework . Li and coworkers investigated the localization of isolated [Fe III O] + species stabilized within the ZSM-5 framework.…”

“…It also highlights previous attempts using density functional theory (DFT) calculations to analyze the preferred sites of Fe species within the zeolite extra-framework. 43 Li and coworkers investigated the localization of isolated [Fe III O] + species stabilized within the ZSM-5 framework. Their findings revealed that, at the high spin state, the most stable configuration of isolated [Fe III O] + occurs at the δ site with the [AlO 2 ] − unit at the T-11 position due to the lowest free energy.…”