Microwave-Induced Deep Catalytic Oxidation of NO Using Molecular-Sieve-Supported Oxygen-Vacancy-Enriched Fe–Mn Bimetal Oxides

• Published in: Environmental science & technology 2022-07, Vol.56 (14), p.10423-10432
• Main Authors: Yuan, Bo, Qian, Zhen, Yang, Xiaojie, Luo, Mengchao, Feng, Xiaohe, Fu, Le, Yang, Weijie, Yang, Lijuan, Zhang, Jinghong, Zhao, Yi, Hao, Runlong
• Format: Article
• Language: English
• Subjects: Bimetals; Catalysts; Catalytic oxidation; Denitrification; Density functional theory; Electron paramagnetic resonance; Electron spin resonance; Ferric oxide; Irradiation; Low temperature; Manganese dioxide; Molecular sieves; Nitrates; Nitrites; Nitrogen dioxide; Oxidation; Oxygen; Oxygen enrichment; Physicochemical properties; Resonance testing; Sulfur dioxide; Treatment and Resource Recovery; Vacancies
• ISSN: 0013-936X; 1520-5851
• DOI: 10.1021/acs.est.2c02851

A novel microwave (MW) catalytic oxidation denitrification method was developed, which can deeply oxidize NO into nitrate/nitrite with little NO2 yield. A molecular-sieve-supported oxygen-vacancy-enriched Fe2O3–MnO2 catalyst (Ov–Fe–Mn@MOS) was fabricated. Physicochemical properties of the catalyst were revealed by various characterization methods. MW irradiation was superior to the conventional heating method in NO oxidation (90.5 vs 70.6%), and MW empowered the catalyst with excellent low-temperature activity (100–200 °C) and good resistance to H2O and SO2. Ion chromatography analysis demonstrated that the amount of nitrate/nitrite accounted for over 90.0% of the N products, but the main product gradually varied from nitrate to nitrite as the reaction proceeded because of the switching of the main reaction path of NO removal. Mechanism analyses clarified that NO oxidation was a non-radical catalytic reaction: (i) the chemisorbed NO on Mn­(IV) reacted with O2* to produce nitrate and (ii) the excited NO* due to MW irradiation reacted with the active O* generated from Ov···O2 to form nitrite. Density functional theory calculations combined with electron paramagnetic resonance tests revealed the promotional effects of Fe2O3 in (i) boosting the Ov’s quantity; (ii) facilitating O2 adsorption; (iii) increasing the nitrite formation; and (iv) alleviating the suppression of SO2.