Degradation and dechlorination of trichloroacetic acid induced by an in situ 222 nm KrCl* excimer radiation.

Since the coronavirus disease 2019 (COVID-19) pandemic epidemic, the excessive usage of chlorinated disinfectants raised the substantial risks of disinfection by-products (DBPs) exposure. While several technologies may remove the typical carcinogenic DBPs, trichloroacetic acid (TCAA), their application for continuous treatment is limited due to their complexity and expensive or hazardous inputs. In this study, degradation and dechlorination of TCAA induced by an in situ 222 nm KrCl* excimer radiation as well as role of oxygen in the reaction pathway were investigated. Quantum chemical calculation methods were used to help predict the reaction mechanism. Experimental results showed that UV irradiance increased with increasing input power and decreased when the input power exceeded 60 W. Decomposition and dechlorination were simultaneously achieved, where around 78% of TCAA (0.62 mM) can be eliminated and 78% dechlorination within 200 min. Dissolved oxygen showed little effect on the TCAA degradation but greatly boosted the dechlorination as it can additionally generate hydroxyl radical (•OH) in the reaction process. Computational results showed that under 222 nm irradiation, TCAA was excited from S0 to S1 state and then decayed by internal crossing process to T1 state, and a reaction without potential energy barrier followed, resulting in the breaking of C-Cl bond and finally returning to S0 state. Subsequent C-Cl bond cleavage occurred by a barrierless •OH insertion and HCl elimination (27.9 kcal/mol). Finally, the •OH attacked (14.6 kcal/mol) the intermediate byproducts, leading to complete dechlorination and decomposition. The KrCl* excimer radiation has obvious advantages in terms of energy efficiency compared to other competitive methods. These results provide insight into the mechanisms of TCAA dechlorination and decomposition under KrCl* excimer radiation, as well as important information for guiding research toward direct and indirect photolysis of halogenated DBPs.

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.