Effects of anions on the kinetics and reactivity of nanoscale Pd/Fe in trichlorobenzene dechlorination

Influences of anionic co-solutes on dechlorination of 1,2,4-trichlorobenzene (124TCB) by the nanoscale Pd/Fe particles were investigated in batch experiments in the presence of an anionic solute such as nitrate, nitrite, perchlorate, phosphate, carbonate, silica, sulfate, sulfite, or sulfide. Based on the extent of inhibitory effects on the 124TCB dechlorination, the anions can be ranked in the order of: control ≈ sulfate ≈ silica < perchlorate < carbonate < nitrate < phosphate < nitrite < sulfite < sulfide. Mineralogical analysis with XRD, morphological study with SEM-EDX, and spectroscopic analysis with FTIR spectrometer of the fresh and reacted Pd/Fe samples were conducted to examine the influences of the various anions on the Pd/Fe surface. Silica and sulfate did not show any significant short-term effect on reactivity of the nanoscale Pd/Fe, because the 124TCB dechlorination reaction was only dependent on the reactivity of the Pd site that was apparently not passivated by the anions. However, sulfide and sulfite could immediately terminate the 124TCB dechlorination process. Based on the natures of their inhibitory effects on 124TCB dechlorination by the Pd/Fe, the anions can be classified as: (1) adsorption-precipitation passivating species (e.g., phosphate and carbonate), (2) redox-active species (e.g., nitrate, nitrite, and perchlorate), and (3) catalyst poisons (e.g., sulfide and sulfite).