Using CuMgFe layered double oxide to replace laccase as a catalyst for abiotic humification

Humification offers a promising avenue for sequestering dissolved organic carbon while facilitating environmental cleanup. In this study, CuMgFe layered double oxides (LDO) were applied as a catalyst to replace conventional enzymes, such as laccase, thereby enhancing the in vitro polyphenol-Maillard humification reaction. CuMgFe LDO was synthesized through calcination of CuMgFe layered double hydroxides (LDH) at 500 °C for 5 h. A suite of characterization methods confirmed the successful formation into mixed oxides (Cu₂O, CuO, MgO, FeO, and Fe₂O₃) after thermal treatment. A rapid humification reaction was observed with CuMgFe LDO, occurring within a two-week span, likely due to a distinct synergy between copper and iron elements. Subsequent analyses identified that MgO in CuMgFe LDO also played a pivotal role in humification by stabilizing the pH of the reaction. In the absence of magnesium, LDO's humification activity was more pronounced in the early stages of the reaction, but it rapidly diminished as the reaction progressed. The efficiency of CuMgFe LDO was heightened at elevated temperatures (35 °C), while light conditions manifested a discernible effect, with a modest decrease in humification efficacy under indoor light exposure. CuMgFe LDO surpassed both laccase and MgFe LDH in performance, boasting a superior humification efficiency relative to its precursor, CuMgFe LDH. The catalysts' humification activity was modulated by their crystallinity and valence dynamics. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) results suggested that introducing the amino acid, glycine, expedited the CuMgFe LDO-fueled humification, enhancing the formation of C-N and C-C bonds in the resultant products. The humic-like substances derived from the catalyst-enhanced reaction displayed an elevated presence of aromatic configurations and a richer array of oxygen functional groups in comparison to a typical commercial humic material.