Zr4+-mercaptosuccinate MOF for the uptake and recovery of gold nanoparticles and gold ions under batch and continuous flow conditions

The increasing use of nanomaterials in commercial products has raised concerns regarding their potential effects on water quality and living organisms. So far, most sorbents available for removing nanosized inorganic pollutants from water rely on electrostatic interactions or entrapment in the sorbent pores. However, this limits their applicability in real wastewater samples containing nanomaterials with variable surface properties and sizes, along with high concentrations of competitive species such as inorganic salts and organics. Little attention has also been paid to the recovery of nanoparticles after sorption. In this work, a Zr4+-mercaptosuccinate metal organic framework (MOF) with free thiol groups was investigated as a sorbent for the removal of Au nanoparticles and Au3+ ions from water. Sorption occurs on the surface of the MOF via the formation of strong metal-thiolate chemical bonds enabling the fast uptake of noble metal nanoparticles and noble metal ions from water (within <1 h). The maximum sorption capacity was found to depend on the size of the Au nanoparticles and ranged from 8 - 41.5 mg/g. The surface functionalization of nanoparticles did not influence sorption performance, which was also maintained in natural waters of variable matrix complexity. The material was also efficient in fixed bed columns with an estimated maximum Au sorption capacity of approximately 7 mg/g, which is significantly higher than the environmental concentrations of Au nanoparticles and adequate for their removal from industrial wastewater. Importantly, the sorbed nanoparticles could be quantitatively recovered (>90 %), at the expense of material degradation, enabling their potential reuse.