Abstract Engineered biochar with enhanced photochemical properties holds great potential for environmental remediation. However, natural humic substances, crucial players in environmental redox processes, are structurally complex and slow-forming, hindering mechanistic insights and practical applications. Here, we propose a co-engineering strategy that combines biochar with artificial humic substances synthesized from pine sawdust via controlled hydrothermal humification (180–340 °C). Modulating the hydrothermal temperature can yield artificial humic substances with diverse degradation degrees of lignin, yielding tailored phenolic architectures and electron-donating capacities (EDC). Using Ag⁺ photoreduction as a model reaction, we demonstrate that artificial humic substances produced at 340 °C exhibit optimal phenol content and the strongest reducing capacity (19.2-fold greater than that of substances synthesized at 180 °C). Notably, higher molecular weight fractions (> 5 kDa) of artificial humic substances were found to dominate Ag⁺ photoreduction due to their enriched phenolic content and superior EDC. Mechanistic investigations reveal that photo-excited phenolic groups generate superoxide radical (O 2 •− ), initiating Ag⁺ reduction via a ligand-to-metal charge transfer (LMCT) pathway. Moreover, we discovered a previously overlooked phenomenon: hydrochar undergoes photo-induced dissolution, further enhancing photoreduction. This work provides new insights into the temperature-dependent lignin transformation into redox-active artificial humic substances and highlights the dynamic photochemical behavior of engineered biochar (hydrochar) under solar irradiation. Graphical Abstract
Sun et al. (Thu,) studied this question.