Hydrothermal carbonization (HTC) has been regarded as a promising technique for turning wet biomass into hydrochar due to its low energy consumption, low exhaust gas emissions, etc. In addition, hydrochar is an important source of dissolved organic matter (DOM), which plays a crucial part in the migration and destiny of pollutants in the environmental medium. However, there are limited studies that focus on the factors that influence the formation of DOM in hydrochar, such as hydrothermal temperature. Therefore, the current study comprehensively characterized the optical properties of DOM within hydrochar derived from sawdust (HDOM) under different hydrothermal temperatures (150–300 °C) by Ultraviolet–visible (UV–Vis) and fluorescence spectroscopy, as well as its complexation characteristic with Cu(II). The findings revealed that the organic carbon content of HDOM reached a peak of 37.3 mg L⁻¹ when the temperature rose to 240 °C and then decreased as the temperature increased. UV–Vis spectroscopy analysis showed that the absorption capacity of HDOM at 275 nm increases with temperature and reaches a maximum value at 240 °C, indicating that high temperature promotes the formation of monocyclic aromatic compounds. High temperature enhances the aromaticity, hydrophobicity, and humification degree of HDOM, thus improving its stability and aromaticity. The E3/E4 ratios are all greater than 3.5, confirming that the main component of HDOM is fulvic acid, which corresponds to 3D-EEM and Pearson's correlation coefficient analysis. The humification index (HIX) of HDOM increased with the rise in hydrothermal temperature (150–240 °C), as observed by the three-dimensional excitation-emission matrix spectroscopy (3D-EEMs). After reaching its peak at 240 °C, the HIX value gradually dropped in line with the trend of the DOC change. Moreover, the bioavailability (BIX) value of DOM was all high and greater than 1, indicating all the HDOM are readily bioavailable. Two microbial humic substances (C1 and C4), a humic-like substance (C2), and a protein-like substance (C3) were discovered in DOM by integrating 3D-EEMs with parallel factor analysis (PARAFAC). Their fluorescence intensity decreases as the Cu(II) concentration increases, indicating the formation of complexes with Cu(II). As the temperature rises, the binding ability of DOM and Cu(II) changes significantly, reaching the optimum at 300 °C. Meanwhile, the substance C2 has the strongest binding ability with Cu(II). This research emphasizes the significance of spectroscopy analysis in determining the evolution of hydrochar-derived DOM, the potential for heavy metal binding and migration, and its characteristics and features. Graphical Abstract

The hydrofluoric acid modified biochar (HF-BC) was obtained, aiming to improve its performance for activating persulfate (PS) to make acid orange 7 (AO7) degraded in water solution. Results showed that the surface area, micropore volume, carboxyl and phenolic hydroxyl group content of HF-BC increased by 171%, 172%, 23.8% and 50%, respectively, compared to unmodified biochar (BC). The decolorization of AO7 in HF-BC/PS and BC/PS systemwas much more rapid and efficient than that in HF-BC, BC and PS alone system. For the HF-BC/PS system, the AO7 was removal of 99.8%, much higher than that of BC/PS system, probably because of its better surface characteristics. Moreover, for the HF-BC/PS system, it was the higher PS concentration and HF-BC dosage that caused greater AO7 degradation rates, and lower pH was favorable for the degradation. Our results provided a novel method to design biochar as an activator for persulfate-based remediation of dye wastewater. Abbreviations: HF-BC, hydrofluoric acid modified biochar; BC, unmodified biochar; AO7, Acid orange 7; PS, persulfate