Synergistic enhancement of microbes-to-pollutants and inter-microbes electron transfer by Fe, N modified ordered mesoporous biochar in anaerobic digestion

Extracellular electron transfer was essential for degrading recalcitrant pollutants by anaerobic digestion (AD). Therefore, existing studies improved AD efficiency by enhancing the electron transfer from microbes-to-pollutants or inter-microbes. This study synthesized a novel Fe, N co-doped biochar (Fe, N-BC), which could enhance both the microbes-to-pollutants and inter-microbes electron transfer in AD. Detailed characterization data indicated that Fe, N-BC has an ordered mesoporous structure, high specific surface area (463.46 m²/g), and abundant redox functional groups (Fe²⁺/Fe³⁺, pyrrolic-N), which translate into excellent biocompatibility and electrochemical properties of Fe, N-BC. By adding Fe, N-BC, the stability and efficiency of the medium-temperature AD system in the treatment of methyl orange (MO) wastewater were improved: obtained a high degradation efficiency of MO (96.8 %) and enhanced the methane (CH₄) production by 65 % compared to the control group. Meanwhile, Fe, N-BC reduced the accumulation of volatile fatty acids in the AD system, and the activity of anaerobic granular sludge electron transport system and coenzyme F₄₂₀ was enhanced. In addition, Fe, N-BC showed positive enrichment of azo dyes decolorization bacteria (Georgenia) and direct interspecies electron transfer (DIET) synergistic partners (Syntrophobacter, Methanosarcina). Overall, the rapid degradation of MO and enhanced CH₄ production in AD systems by Fe, N-BC is associated with enhancing two electronic pathways, i.e., microbes to MO and DIET between syntrophic bacteria and methanogenic archaea. This study introduced an enhanced "two-pathways of electron transfer" theory, realized by Fe, N-BC. These findings provided new insights into the interactions within AD systems and offer strategies for enhancing their performance with recalcitrant pollutants.