Chlorophenols are extremely toxic to the environment and recalcitrant to biological degradation. Herein chemical degradation of 4-chlorophenol (4-CP) from aqueous solutions by zero-valent aluminum (Al), zero-valent iron (Fe), Al and Fe mixtures (Al/Fe mass ratio 90/10, labeled as Al/Fe10) and Al-Fe alloy (Al/Fe mass ratio 90/10, labeled as Al-Fe10) were investigated. No removal was found for 50 mg·L−1 4-CP under anoxic conditions at initial pH 2.5 during a period of 10 hrs while 56%, 83%, 78% and 99% of 4-CP were removed by Fe, Al, Al/Fe10 and Al-Fe10, respectively under aeration conditions. The removal of 4-CP by Al/Fe10 mixtures was primarily in the Fe mode in the beginning 4 h and then transitioned to the Al mode. The removal of 4-CP by Al-Fe10 alloy was accomplished via two intermediate products, hydroquinone (HQ) and 4-chlorocatechol (4-CC), and it was speculated that reactive oxygen species and hydroxyl radicals (·OH) play an important role in the degradation of 4-CP and that Al-Fe intermetallic compounds might catalyze the reactions. This study demonstrates that alloying Al with Fe offers a promising strategy for developing new materials for water and wastewater remediation.

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