Synthesis of W-modified CeO2/ZrO2 catalysts for selective catalytic reduction of NO with NH3

Abstract

In this paper, a series of tungsten–zirconium mixed binary oxides (denoted as W_mZrO_x) were synthesized via co-precipitation as supports to prepare Ce_0.4/W_mZrO_x catalysts through an impregnation method. The promoting effect of W doping in ZrO₂ on selective catalytic reduction (SCR) performance of Ce_0.4/ZrO₂ catalysts was investigated. The results demonstrated that addition of W in ZrO₂ could remarkably enhance the catalytic performance of Ce_0.4/ZrO₂ catalysts in a broad temperature range. Especially when the W/Zr molar ratio was 0.1, the Ce_0.4/W_0.1ZrO_x catalyst exhibited the widest active temperature window of 226–446 °C (NO_x conversion rate > 80%) and its N₂ selectivity was almost 100% in the temperature of 150–450 °C. Moreover, the Ce_0.4/W_0.1ZrO_x catalyst also exhibited good SO₂ tolerance, which could maintain more than 94% of NO_x conversion efficiency after being exposed to a 100 ppm SO₂ atmosphere for 18 h. Various characterization results manifested that a proper amount of W doping in ZrO₂ was not only beneficial to enlarge the specific surface area of the catalyst, but also inhibited the growth of fluorite structure CeO₂, which were in favor of CeO₂ dispersion on the support. The presence of W was conducive to the growth of a stable tetragonal phase crystal of ZrO₂ support, and a part of W and Zr combined to form W–Zr–O_x solid super acid. Both of them resulted in abundant Lewis acid sites and Brønsted acid sites, enhancing the total surface acidity, thus significantly improving NH₃ species adsorption on the surface of the Ce_0.4/W_0.1ZrO_x catalyst. Furthermore, the promoting effect of adding W on SCR performance was also related to the improved redox capability, higher Ce³⁺/(Ce³⁺ + Ce⁴⁺) ratio and abundant surface chemisorbed oxygen species. The in situ DRIFTS results indicated that nitrate species adsorbed on the surface of the Ce_0.4/W_0.1ZrO_x catalyst could react with NH₃ due to the activation of W. Therefore, the reaction pathway over the Ce_0.4/W_0.1ZrO_x catalyst followed both Eley–Rideal (E–R) and Langmuir–Hinshelwood (L–H) mechanisms at 250 °C.