Carbon quantum dots in-situ relieve humic acids inhibition on methanogens while significantly increasing the abundance of Methanosarcinaceae

Monophenols form humic acids (HA) through polycondensation reaction in the anaerobic digestion (AD) process, which will inhibit AD process. Currently, metal ions are the option for in-situ relieving HA inhibition during AD, but excess metal ions are harmful to microorganisms. In this study, carbon quantum dots (CQDs, a non-metallic materials) were proposed to relieve HA inhibition in-situ. We investigated the effect of HA on AD acidification and methanation stage, and synthesized CQDs using sodium citrate (s-CQDs) and p-phenylenediamine (p-CQDs) as precursors to relieve the HA inhibition in-situ. Results showed that s-CQDs (3.0 g/L) significantly increased the cumulative CH4 yield from AD of ethanol with 1.0 g/L HA (1.9 times higher than that without s-CQDs). Microbiological analysis indicated the most dominant methanogen was Methanosarcinaceae, with richness of 89.7%. Compared to the HA inhibition system, the relative abundance of Methanosarcinaceae increased by 87.5%. The analysis of interaction mechanism between CQDs and HA indicated that s-CQDs has an in-situ binding effect to HA by reacting with-OH, C--C, and-COOH. This study provided a novel means for in-situ relieving HA in-hibition, and illustrated the interaction mechanism between CQDs and HA, which will guide the application in production of bioenergy.