Catalytic performance and reaction mechanisms of NO removal with NH₃ at low and medium temperatures on Mn-W-Sb modified siderite catalysts

Iron-based catalysts have been explored for selective catalytic reduction (SCR) of NO due to environmentally benign characters and good SCR activity. Mn-W-Sb modified siderite catalysts were prepared by impregnation method based on siderite ore, and SCR performance of the catalysts was investigated. The catalysts were analyzed by X-ray diffraction, H₂-temperature-programmed reduction, Brunauer-Emmett-Teller, Thermogravimetry-derivative thermogravimetry and in-situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS). The modified siderite catalysts calcined at 450°C mainly consist of Fe₂O₃, and added Mn, W and Sb species are amorphous. 3Mn-5W-1.5Sb-siderite catalyst has a wide temperature window of 180-360°C and good N₂ selectivity at low temperatures. In-situ DRIFTS results show NH₄⁺, coordinated NH₃, NH₂, NO₃⁻ species (bidentate), NO₂⁻ species (nitro, nitro-nitrito, monodentate), and adsorbed NO₂ can be discovered on the surface of Mn-W-Sb modified siderite catalysts, and doping of Mn will enhance adsorbed NO₂ formation by synergistic catalysis with Fe³⁺. In addition, the addition of Sb can inhibit sulfates formation on the surface of the catalyst in the presence of SO₂ and H₂O. Time-dependent in-situ DRIFTS studies also indicate that both of Lewis and Brønsted acid sites play a role in SCR of NO by ammonia at low temperatures. The mechanism of NO removal on the 3Mn-5W-1.5Sb-siderite catalyst can be discovered as a combination of Eley-Rideal and Langmuir-Hinshelwood mechanisms with three reaction pathways. The mechanism of NO, oxidized by synergistic catalysis of Fe³⁺ and Mn^4+/3+ to form NO₂ among three pathways, reveals the reason of high NO_x conversion of the catalyst at medium and low temperatures.