Reduction of silver ions to silver nanoparticles by biomass and biochar: Mechanisms and critical factors

The reduction of metal ions by biomasses (BMs) and biochars (BCs) is often neglected when evaluating the environmental behavior and risk of heavy metals. In this study, the formation mechanisms of silver nanoparticles (AgNPs) when Ag⁺ coexists with BMs/BCs were investigated. Four types of BMs (pine sawdust, bagasse, lignin, and cellulose) as well as their BCs were investigated for their roles in transforming Ag⁺ to AgNPs. The electron donating capacity (EDC) of all the BMs/BCs was larger than zero. The UV-Vis spectrometer and scanning electron microscopy-energy dispersive X-ray spectrometer (SEM-EDX) analysis confirmed the formation of AgNPs. The quantities of AgNPs formed by BM systems were higher than that by their corresponding BCs. The quantities of formed AgNPs by bagasse and its BCs were the highest when compared with other BMs/BCs, which may be due to their highest EDC values. We found that hydroxyl group (-OH) was the important redox-active functional group in BMs and BCs that contributed to Ag⁺ reduction according to the results from X-ray photoelectron spectrometric (XPS) and Fourier transform infrared spectroscopic (FTIR) analyses. AgNPs formation was enhanced at elevated pH, probably because of the deprotonated functional groups with high EDC values and electron density. The higher temperature could enhance the formation of AgNPs, suggesting that the reduction of Ag⁺ by BMs/BC was a thermodynamically favored process. This study illustrated that Ag⁺ was transformed to AgNPs by BMs and BCs through the redox reactive -OH of BMs/BCs, which further improved our understanding on the formation of AgNPs in the environment.