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

In this paper, a series of tungsten-zirconium mixed binary oxides (denoted as WmZrOx) were synthesized via co-precipitation as supports to prepare Ce-0.4/WmZrOx 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/W0.1ZrOx catalyst exhibited the widest active temperature window of 226-446 degrees C (NOx conversion rate > 80%) and its N-2 selectivity was almost 100% in the temperature of 150-450 degrees C. Moreover, the Ce-0.4/W0.1ZrOx catalyst also exhibited good SO2 tolerance, which could maintain more than 94% of NOx 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 Bronsted acid sites, enhancing the total surface acidity, thus significantly improving NH3 species adsorption on the surface of the Ce-0.4/W0.1ZrOx 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/W0.1ZrOx catalyst could react with NH3 due to the activation of W. Therefore, the reaction pathway over the Ce-0.4/W0.1ZrOx catalyst followed both Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) mechanisms at 250 degrees C.