Insights into the promotion role of phosphorus doping on carbon as a metal-free catalyst for low-temperature selective catalytic reduction of NO with NH3

Abstract

The catalytic reduction of NO with NH₃ (NH₃-SCR) on phosphorus-doped carbon aerogels (P-CAs) was studied in the temperature range of 100–200 °C. The P-CAs were prepared by a one-pot sol–gel method by using phosphoric acid as a phosphorus source followed by carbonization at 600–900 °C. A correlation between catalytic activity and surface P content is observed. The P-CA-800_vac sample obtained via carbonization at 800 °C and vacuum treatment at 380 °C shows the highest NO conversion of 45.6–76.8% at 100–200 °C under a gas hourly space velocity of 500 h⁻¹ for the inlet gas mixture of 500 ppm NO, 500 ppm NH₃ and 5.0 vol% O₂. The coexistence of NH₃ and O₂ is essential for the high conversion of NO on the P-CA carbon catalysts, which can decrease the spillover of NO₂ and N₂O. The main Brønsted acid sites derived from P-doping and contributed by the C–OH group at edges of carbon sheets are beneficial for NH₃ adsorption. In addition, the C₃–PO configuration seems to have the most active sites for favorable adsorption and dissociation of O₂ and facilitates the formation of NO₂. Therefore, the simultaneous presence of acidic groups for NH₃ adsorption and the C₃–PO active sites for NO₂ generation due to the activation of O₂ molecules is likely responsible for the significant increase in the NH₃-SCR activity over the P–CAs. The transformation of C₃–PO to C–O–P functional groups after the reaction is found, which could be assigned to the oxidation of C₃–PO by the dissociated O*, resulting in an apparent decrease of catalytic activity for P-CAs. The C–O–P based functional groups are also active in the NH₃-SCR reaction.