Stability of Functionally Modified Biochar: The Role of Surface Charges and Surface Homogeneity

Abstract

Biochar modification has received significant research attention due to its attractive and fruitful rewards in improving biochar performances. However, the determinants of modified biochars’ stability and the ability of aged modified biochars to remove heavy metals have not been comprehensively evaluated. Therefore, three commonly used functional groups of modified biochars (5% and 10% H2O2-modified (BCH5 and BCH20); 25% and 65% HNO3-modified (BCA25 and BCA65); and amino-modified (BCN), were prepared in this study to explore their stability and the Cd(II) removal performance of aged functional groups modified biochars was studied. The results showed that the O/C ratio is not sensitive enough to predict the stability of functional groups modified biochars, which was commonly used to evaluate pristine biochar (BC0); instead, -COOH content is crucial for modified biochar stability (r = −0.99, r = −0.91, p < 0.05). BCA65 displayed the highest less prone to oxidation property, which indicated that the high surface charges and uniform surface determined the less prone to oxidation ability of the functionally modified biochars. The order of the stability of functionally modified biochars was HNO3-modified > H2O2-modified > amino-modified. After oxidation, the surface charges and pores were significantly reduced, and the Cd2+ adsorption mechanism of modified biochar changed from multilayer adsorption to monolayer adsorption, which led to a reduction in overall Cd(II) removal. The maximum adsorption capacities of BCA65 were reduced from 18.15 mg·g−1 to 4.86 mg·g−1 after oxidation, particularly. In the design and preparation of modified biochar, the long-term stability of the structure and function of modified biochar and its sustainable application in the environment should be considered while improving the heavy metal removal performance of biochars.