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Mechanochemically synthesized Fe-Mn binary oxides for efficient As(III) removal: Insight into the origin of synergy action from mutual Fe and Mn doping

Huimin Hu,Qiwu Zhang,Chao Wang,Min Chen,Mengfei Chen

Iron manganese oxide resources are widely derived from the geological structure , and their combinations play an important role in the migration and transformation of arsenic. Iron oxide and manganese oxide exist generally in a mixed state in Fe-Mn oxides synthesized via the well studied co-precipitation methods using potassium permanganate and manganese/iron sulfates. Herein, a newly designed Fe-Mn-O compositing oxide with Fe-MnO 2 , Mn-Fe 2 O 3 , (Fe 0.67 Mn 0.33 )OOH solid solution and FeOOH as the main components, simply through solvent-free mechanical ball milling pyrolusite (MnO 2 ) and ferrihydrite (FeOOH) together has been reported. Atomic-scale integrations by doping Fe and Mn with each other were detected and an adsorption-oxidation bifunctionality was achieved, where Fe-doped MnO 2 served as oxidizer for As(III) and amorphous/ground FeOOH acted as adsorbent first for As(III) and then As(V) from the oxidization. The maximal adsorption for As(III) could reach 44.99 mg/g and over 82.5% of As(III) was converted to As(V). More importantly, high removal ability of arsenic worked in a wide pH range of 2–10.5%, and 87.2% of its initial adsorption-oxidation capacity could be kept even after 5-cycles reuse for treating 20 mg/L As(III) with a dosage at 1 g/L. Together with the enhanced adsorption capacity by the milled FeOOH, surface electron transfer efficiency of the developed Fe-MnO 2 surrounded with Mn-Fe 2 O 3 has been studied for the first time to understand the oxidization effect to As(V). Besides the environment-friendliness of ball milling method, the prepared sample is quite stable without noticeable metal release into solution. Mechanism studies of arsenic removal by the as-prepared Fe-Mn-O oxide provide a new direction for improving the oxidation efficiency of MnO 2 to As(III) based on the widely available cheap Mn and Fe oxides, contributing to the development of advanced oxidization process in the treatment of waste water.