Boosting Catalytic and Anti-fluorination Performance of the Ru/Vanadia–Titania Catalyst for the Oxidative Destruction of Freon by Sulfuric Acid Modification

Chlorofluorocarbons (CFCs) exert a strong greenhouse effect and constitute the largest contributor to ozone depletion. Catalytic removal is considered an effective pathway for eliminating low-concentration CFCs under mild conditions. The key issue is the easy deactivation of the catalysts due to their surface fluorination. We herein report a comparative investigation on catalytic dichlorodifluoromethane (CFC-12) removal in the absence or presence of water over the sulfuric-acid-modified three-dimensionally ordered macroporous vanadia–titania-supported Ru (S-Ru/3DOM VTO) catalysts. The S-Ru/3DOM VTO catalyst exhibited high activity (T_90% = 278 °C at space velocity = 40 000 mL g^–1 h^–1) and good stability within 60 h of on-stream reaction in the presence of 1800 ppm of water due to the improvements in acid site amount and redox ability that promoted the adsorption of CFC-12 and the activation of C–F bonds. Compared with the case under dry conditions, catalytic performance for CFC-12 removal was better over the S-Ru/3DOM VTO catalyst in the presence of water. Water introduction mitigated surface fluorination by the replenishment of hydroxyl groups, inhibited the formation of halogenated byproducts via the surface fluorine species cleaning effect, and promoted the reaction pathway of COX₂ (X = Cl/F) → carboxylic acid → CO₂.