Synergistic effect triggered by Fe2O3 and oxygen-induced hydroxyl radical enhances formation of amino-phenolic humic-like substance

Metal oxides play a promising role in the transformation of polyphenols and amino acids involved in naturally occurring humification. The objective of this study was to explore the synergistic interactions between Fe2O3 and O2 in the formation of humic substances under a controlled O2 atmosphere (0%, 21% and 40% O2 levels). The results indicate that an O2 level of 21% with Fe2O3 was optimal for humic acid (HA) production. Hydroxyl radicals (∙OH) formed and promoted the formation of HA in the presence of O2, and O2 improved the enhancing capacity of Fe2O3 by oxidizing Fe(II) to Fe(III). Moreover, the combination of these processes resulted in a synergistic improvement in humification. The evolution of functional groups in HA suggested that O2 promoted the formation of oxygen-containing groups such as lipids, and Fe2O3 was conducive to the formation of dark-coloured polymers during the darkening process of humification. Furthermore, the O2 level of 40% inhibited the formation of HA by reducing the transformation from Fe(III) to Fe(II). The XRD results showed few changes in the composition of Fe2O3 before and after humification, which indicated that Fe2O3 was a catalyst and an oxidant. The heterospectral UV-Vis/FTIR results suggested that ∙OH attacked phenolic rings to form the aromatic ring skeleton of HA and benefit the ring-opening copolymerization of humic precursors. In addition, structural equation modelling demonstrated that dissolved Fe was the key parameter affecting the HA yield. These findings provide new insights into the synergism of O2-mediated ∙OH production associated with metal oxide-facilitated humification.