Role of Functional Groups in Selective Adsorption of Gold over Copper Cyano complexes by Activated Carbon: A DFT Study

The adsorption of gold and copper cyanide complexes on the activated carbon is investigated using the Density Functional Theory (DFT). In order to represent the activated carbon, two fullerene-like model (presenting structural defect sites) and a simple graphene layer containing different functional groups (presenting chemical active sites) are employed. The structural defect sites show a much lower adsorption tendency toward all the cyano complexes comparing to the chemical active sites. The interaction energy for all of the complexes with structural defect sites (concave) is very low. However, the graphene layer with unsaturated active sites displays the highest level of interaction almost for all the complexes except Cu(CN)4-3. The effect of oxygen functional groups on the graphite edges shows a crucial role in the selectivity of gold adsorption over copper complexes. It has increased adsorption energy for Cu(CN)2- in the presence of OH and COOH, and has decreased adsorption energy for Au(CN)2- by OH and increased by COOH. The study results elucidate the lower selectivity for adsorption of gold over copper cyanides by high oxygen content activated carbon. The energy levels of the HOMO and LUMO orbitals show adsorption of unpaired cyanide anions on the activated carbon surface occurs by electron transfer from the complex to the adsorbent and adsorption onto the activated carbon edges by transferring electrons from the absorbent to the complex. The result has clearly demonstrated that the functional groups increase the adsorption tendency for both the gold (only COOH) and copper complexes (OH and COOH) but deteriorate the selectivity of gold over copper cyanides.