HCl-Tolerant HxPO4/RuOx–CeO2 Catalysts for Extremely Efficient Catalytic Elimination of Chlorinated VOCs

Bulk metal doping and surface phosphate modification were synergically adopted in a rational design to upgrade the CeO2 catalyst, which is highly active but easily deactivated for the catalytic oxidation of chlorinated volatile organic compounds (Cl-VOCs). The metal doping increased the redox ability and defect sites of CeO2, which mostly promoted catalytic activity and inhibited the formation of dechlorinated byproducts but generated polychlorinated byproducts. The subsequent surface modification of the metal-doped CeO2 catalysts with nonmetallic phosphate completely suppressed the formation of polychlorinated byproducts and, more importantly, enhanced the stability of the surface structure by forming a chainmail layer. A highly active, durable, and selective catalyst of phosphate-functionalized RuOx–CeO2 was the most promising among all the metal-doped (Ru, Pd, Pt, Cr, Mn, Fe, Co, and Cu) CeO2 catalysts investigated owing to the prominent chemical stability of RuOx and its superior versatility in the catalytic oxidation of different kinds of Cl-VOCs and other typical pollutants, including dimethyl sulfide, CO, and C3H8. Moreover, the chemical stability of the catalyst, including its bulk and surface structural stability, was investigated by combining intensive treatment with HCl/H2O or HCl with subsequent ex situ ultraviolet–visible light Raman spectroscopy and confirmed the superior resistance to Cl poisoning of the phosphate-functionalized RuOx–CeO2. This work exemplifies a promising strategy for developing ideal catalysts for the removal of Cl-VOCs and provides a catalyst with the superior catalytic performance in Cl-VOC oxidation to date.