Selective Pd recovery from acidic leachates by 3-mercaptopropylphosphonic acid grafted TiO2: does surface coverage correlate to performance?

Abstract

Modification of metal oxides with organophosphonic acids (PAs) provides the ability to control and tailor the surface properties. The metal oxide phosphonic acid bond (M–O–P) is known to be stable under harsh conditions, making PAs a promising candidate for the recovery of metals from complex acidic leachates. The thiol functional group is an excellent regenerable scavenging group for these applications. However, the research on organophosphonic acid grafting with thiol groups is very limited. In this study, four different metal sorbent materials were designed with different thiol surface coverages. An aqueous-based grafting of 3-mercaptopropylphosphonic acid (3MPPA) on mesoporous TiO₂ was employed. Surface grafted thiol groups could be obtained in the range from 0.9 to 1.9 groups per nm². The different obtained surface properties were studied and correlated to the Pd adsorption performance. High Pd/S adsorption efficiencies were achieved, indicating the presence of readily available sorption sites. A large difference in their selectivity towards Pd removal from a spend automotive catalyst leachate was observed due to the co-adsorption of Fe on the titania support. The highest surface coverage showed the highest selectivity (K_d: 530 mL g⁻¹) and adsorption capacity (Q_max: 0.32 mmol g⁻¹) towards Pd, while strongly reducing the co-adsorption of Fe on remaining TiO₂ sites.