Aggregation of biochar nanoparticles and the impact on bisphenol A sorption: Experiments and molecular dynamics simulations

The unique properties and environmental implications of biochar nanoparticles (BNPs) have attracted increasing attention. The abundant functional groups and aromatic structures in BNPs may promote the aggregation of BNPs, but the mechanism and implications of this aggregation process remain unclear. Thus, this study investigated the aggregation of BNPs and the sorption of bisphenol A (BPA) on BNPs by combining experimental investigations with molecular dynamics simulations. As the concentration of BNP increased from 100 mg/L to 500 mg/L, the particle size increased from approximately 200 nm to 500 nm, and the exposed surface area ratio in the aqueous phase decreased from 0.46 to 0.05, which confirmed the aggregation of BNPs. The sorption of BPA on BNPs decreased with increasing BNP concentration in both the experiments and molecular dynamics simulations because of BNP aggregation. According to a detailed analysis of the BPA molecules adsorbed on BNP aggregates, the sorption mechanisms were hydrogen bonding, hydrophobic effect, and pi-pi interactions, which were driven by aromatic rings and O- and N-containing functional groups. The aggregation of BNPs embedded some functional groups in the aggregates and thus inhibited sorption. Interestingly, the steady configuration of the BNP aggregates in the molecular dynamics simulations (2000 ps relaxation) also determined the apparent BPA sorption. BPA molecules were adsorbed in the V-shaped interlayers of the BNP aggregates that acted as semi-closed pores, but could not be adsorbed in the parallel interlayers because of their small layer spacing. This study can provide theoretical guidance for the application of BNPs in pollution control and remediation.