Co-engineering biochar and artificial humic substances: advancing photoreduction performance through structure design

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