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Mechanical ball-milled fulvic acid-modified zero-valent iron: Enhanced electron transport for Fe(III)/Fe(II) cycling
Guohua Wu1, Ying Sun1, Yinuo Xiao1
1State Key Laboratory of Green and Efficient Development of Phosphorus Resources, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, People's Republic of China.
Abstract:
This study synthesized fulvic acid-modified zero-valent iron (ZVI/FA) via mechanical ball-milling to efficiently remove Cr(VI) from wastewater. Characterizations confirmed FA was successfully anchored on ZVI surface without altering its crystalline structure. ZVI/FA-5 (with 5.0% FA) achieved 96.2% Cr(VI) removal efficiency, far exceeding the 17.0% of ball-milled ZVI. Tafel polarization and open circuit potential (OCP) measurements showed ZVI/FA-5 had superior electron transport capability and reductive activity compared to ball-milled ZVI. 1,10-phenanthroline (Phen) quenching resulted in 70.3% inhibition of Cr(VI) removal, highlighting synergistic contributions of Fe0 and Fe(II). Iron species analysis revealed FA promoted Fe0 exposure and Fe(III)/Fe(II) redox cycling, thereby enhancing Cr(VI) reduction. Moreover, lower solution pH improved Cr(VI) removal due to favorable surface corrosion under acidic conditions. Remarkably, ZVI/FA-5 sustained an 85% removal efficiency for Cr(VI) even in the presence of typical coexisting cations and anions, and its Cr(VI) removal performance could be regained through re-ball milling following three cycles. This study offers new insights into enhancing ZVI reducibility for Cr(VI) removal through natural organic matter modification.
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