Nano‐scale zero‐valent iron (nZVI) attached to Fe3O4 nanoparticles (Fe0@Fe3O4), which has better dispersibility and a larger specific surface area than the nanoparticles alone, were prepared and applied to the reductive dechlorination of carbon tetrachloride (CT). CT removal efficiencies by Fe0@Fe3O4 composites with different ratios of the two components were compared. Under optimum conditions, when the Fe0/Fe3O4 ratio was 1:2, almost no CT was detected after 50 min and it took only about 30 min to reach a removal efficiency of 90%, compared with 120 min for an Fe0/Fe3O4 ratio of 1:4. An increase in the amount of nZVI in the catalyst effectively improved the removal of CT and accelerated the reaction rate. Chloroform was the main product. Compared with Fe3O4 alone, a significant increase in the solution concentrations of ferrous and ferric ions occurred in the Fe0@Fe3O4 system: both Fe2+ and Fe3+ reached their maximum concentrations at 60 min and then tended to decline over the next 60 min. The increase in Fe2+ concentration was attributed to the reaction between nZVI and CT, which produces ferrous ions when electrons transfer from Fe0 to organic chlorides. Synergistic effects between the composite constituents promoted the relative rates of mass transfer to reactive sites and Fe2+ generated in solution facilitated the reduction of chlorinated organic pollutants by magnetite. Thus, Fe0@Fe3O4 nanoparticles effectively achieved reductive dechlorination of CT and provide an improved nZVI catalyst for the remediation of chlorinated organic compounds.
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