V2O5–WO3/TiO2 Catalyst for Efficient Synergistic Control of NO x and Chlorinated Organics: Insights into the Arsenic Effect

Municipal solid waste incineration and the iron and steel smelting industry can simultaneously discharge NO x and chlorinated organics, particularly polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). Synergistic control of these pollutants has been considered among the most cost-effective methods. This work combined experimental and computational methods to investigate the reaction characteristics of a catalytically synergistic approach and gives the first insight into the effect of arsenic (As) on the multipollutant conversion efficiency, synergistic reaction mechanism, and toxic byproduct distribution over a commercial V2O5–WO3/TiO2 catalyst. The loaded As2O3 species were shown to distinctly decrease the formation energy of an oxygen vacancy at the V–O–V site, which likely contributed to the extensive formation of more toxic polychlorinated byproducts in the synergistic reaction. The As2O5 species strongly attacked neighboring VO sites forming the As–O–V bands. Such an interaction deactivated the deNO x reaction, but led to excessive NO being oxidized into NO2 that greatly promoted the V5+–V4+ redox cycle and in turn facilitated chlorobenzene (CB) oxidation. Subsequent density functional theory (DFT) calculation further reveals that both the As2O3 and As2O5 loadings can facilitate H2O adsorption on the V2O5–WO3/TiO2 catalyst, leading to competitive adsorption between H2O and CB, and thereby deactivate the CB oxidation with water stream.