Stable dechlorination of Trichloroacetic Acid (TCAA) to acetic acid catalyzed by palladium nanoparticles deposited on H₂-transfer membranes

Trichloroacetic acid (TCAA) is a common disinfection byproduct (DBP) produced during chlorine disinfection. With the outbreak of the Coronavirus Disease 2019 (COVID-19) pandemic, the use of chlorine disinfection has increased, raising the already substantial risks of DBP exposure. While a number of methods are able to remove TCAA, their application for continuous treatment is limited due to their complexity and expensive or hazardous inputs. We investigated a novel system that employs palladium (Pd⁰) nanoparticles (PdNPs) for catalytic reductive dechlorination of TCAA. H₂ was delivered directly to PdNPs in situ coated on the surface of bubble-free hollow-fiber gas-transfer membranes. The H₂-based membrane Pd film reactor (H₂−MPfR) achieved a high catalyst-specific TCAA reduction rate, 32 L/g-Pd/min, a value similar to the rate of using homogeneously suspended PdNP, but orders of magnitude higher than with other immobilized PdNP systems. In batch tests, over 99% removal of 1 mM TCAA was achieved in 180 min with strong product selectivity (≥ 93%) to acetic acid. During 50 days of continuous operation, over 99% of 1 mg/L influent TCAA was removed, again with acetic acid as the major product (≥ 94%). We identified the reaction pathways and their kinetics for TCAA reductive dechlorination with PdNPs using direct delivery of H₂. Sustained continuous TCAA removal, high selectivity to acetic acid, and minimal loss of PdNPs support that the H₂−MPfR is a promising catalytic reactor to remove chlorinated DBPs in practice.