"In-situ synthesized" iron-based bimetal promotes efficient removal of Cr(VI) in by zero-valent iron-loaded hydroxyapatite

Anionic Cr(VI) and cationic heavy metals generally co-exist in industrial effluents and threaten the public health. Zero-valent iron (ZVI) particles tent to passivate rapidly, which results in a gradual drop in its reactivity. In this work, a strategy of "in-situ synthesized" iron-based bimetal was first developed to stimulate the self-activation of passivated ZVI. During this process, ZVI-loaded hydroxyapatite (ZVI/HAP) was prepared to enhance the affinity for co-existing Cu2+, which promoted the in-situ Cu-0 deposition on ZVI/HAP to form a Fe-Cu bimetal. The deposited Cu-0 significantly decreased the activation energy (Ea) of Cr(VI) reduction by 24.9%, and its corresponding Cr(VI) removal (96.53%) was much higher that of single Cr(VI) system (68.67%) within 9 h. More importantly, the removal of Cr(VI) and Cu2+ were synchronously achieved. Systematical electrochemical characterizations were first introduced to explore the galvanic behaviors of iron-based bimetal. The charge transfer resistance and the negative open circuit potential of ZVI/HAP significantly decreased with the Cu-0 deposition, thereby accelerating the electron transfer from Fe-0 to Cu2+. The enhanced electron transfer further facilitated the Fe(II) release to promote Cr(VI) reduction. This "in-situ synthesized" iron-based bimetal strategy provides a novel pattern for ZVI activation and exhibits practical application in remediation of combined contaminant.