A Radiocatalytic Conversion Platform Enables Upcycling of CHF ₃ Waste to Fluorochemical

Comprehensive Summary Fluoroform (CHF 3 ), a potent greenhouse gas produced by fluorochemicals production, has garnered attention as a valuable feedstock for synthesizing fluorochemicals, benefiting from its high‐value trifluoromethyl group. A common approach to activating CHF 3 is C–H heterolysis using a base to deprotonate CHF 3 , followed by a combination with a Lewis acid (LA) to form (LA)‐CF 3 adduct. However, restricted by the poor compatibility of the reaction mixture, only elaborately designed pairs of LAs and bases can meet the requirement of promoting the formation of a Lewis acid (LA)‐CF 3 adduct. Herein, we report a C–H homolysis strategy that utilizes the ·OH generated by water radiolysis to activate CHF 3 , forming ·CF 3 . Notably, as a proof‐of‐concept, an ideal route to produce trifluoroacetic acid (CF 3 COOH, TFA) using CHF 3 and CO 2 as the starting materials was conducted via the ·CF 3 radical pathway. A radiation‐synthesized Cu/ZnO with bifunctional properties was used as a catalyst, enhancing reaction efficiency and product selectivity by improving water radiolysis efficiency and regulating radical selectivity. This study proposes a novel strategy for upcycling CHF 3 through water radiolysis‐mediated C–H homolysis, supported by an alternative pathway that converts CHF 3 into valuable fluorinated compounds using CHF 3 and CO 2 as feedstocks.