Evaporation-driven interfacial restructuring induces highly efficient methanogenesis of waste biomass

Methanogenesis of waste biomass (WB) is a promising method for global sustainable development, reduction of pollution and carbon emission levels, and recovering bioenergy. Unlike in the methanogenesis of organic wastewater, in which microbial cells come into direct contact with the dissolved substrate, the ‘solid–liquid–solid’ modes in WB and between WB and microbial cells, which involve numerous solid–liquid interfaces, greatly hinder the methanogenesis efficiency of WB. Amongst all WB, waste activated sludge is the most complex, poorly biodegradable and representative. Herein, we highlight the role of water evaporation-driven solid-liquid interfacial restructuring of sludge in determining its methanogenesis efficiency. Non-free water evaporation increased surface roughness and adhesion, and compressed pore structure with numerous capillaries in sludge, resulting in a new solid-liquid interface of sludge with great capillary force and highly ordered interfacial water molecules, which provides an extremely favourable condition for high mass transfer and proton-coupled electron transfer (PCET) in sludge. This restructuring was confirmed to induce the enhancement of solid–liquid interfacial noncovalent interactions and electron transfer efficiency in the subsequent methanogenesis process (P < 0.05), promoting the effective contact between the sludge substrate and microbial cells, thereby enriching the methanogenic consortia (i.e., Clostridia and Methanosarcina were increased by 290.0% and 239.7%, respectively) and improving the activities of key enzymes. Stable isotope tracing and metagenomic analysis further reveal that this restructuring promoted the participation of water molecules in the methane formation by PCET-driven release of protons from water, and enhanced main methanogenesis metabolic pathways, especially the metabolic pathway of CO2-reduction methanogenesis (+65.2%), thereby resulting in a great advance in methane generation (+147%, P < 0.001). The findings can provide a reference for regulating directional anaerobic biotransformation of water-rich multiphase complex substrates by interfacial restructuring inducement.