The Activated Carbons Adsorption of Cyanide Complexes of Transition Metals from Solutions and Pulps: Cause and Effect

Cyanidation of gold ore results in formation not only of Na[Au(CN)2], but also cyanometallate complexes of some transition metals. During subsequent gold extraction from such solutions and pulps, using activated carbons (??), a number of problems arise. An effective solution of the problem is not possible without detailed knowledge of the interaction mechanism of transition metals cyanide complexes with AC particles. The chemical properties of AC particles and graphene, saturated with [?u(CN)n](n-1)- (n=2, 3), were studied by XPS, ESR, SQUID, and DFT. The obtained results were compared with the data on AC adsorption of anionic form of Ag(I), Au(I), Cd(II), Hg(II), Cr(III), Fe(II), Fe(III), Co(III), Rh(III), Ni(II), Pd(II), Pt(II) and Pt(IV) cyanide complexes. The adsorption of [?u(CN)n](n-1)- (n=2, 3) on AC from aqueous solutions in air is accompanied with oxidation of ?u(I) atoms. Besides, Cu(II) and Cu(III) compounds were found on AC surface. Quantum-chemical calculations confirmed the possibility of formation of Cu(I) complex with carbene-like sites of AC. The reactions of [?u(CN)n](n-1)- (n=2, 3) complexes and aromatic carbenes and their cation-radical were theoretically studied at DFT PBE level to obtain the information on adsorption of cyanometallate complexes on AC. Carbenes with different fragments were regarded as a model of activated carbons, which have free edge sites with paired o and n electrons. It was shown that [Cu(CN)2]- bounds firmly with triplet carbene, if one Cu-CN bond breaks. The dissociation process occurs through a multi-step spin-crossing mechanism to reduce total spin multiplicity of the metal-carbene complex. The behavior of transition element complexes in contact with AC in aqueous solutions is determined by the following characteristics: geometrical structure of ionic complexes; nature of ligands bonded to the central atom; concentration of reactive oxygen species in solution and its pH; nature of binding sites of AC.