Aqueous biphasic systems (ABSs) that are based on deep
eutectic
solvents (DESs) are environmentally benign systems to use for metal
ion separation. In this work, a series of DESs was synthesized for
the first time with PEG 400 as hydrogen bond donors and tetrabutylphonium
bromide (P4Br), tetrabutylammonium bromide (N4Br), or tetrabutylammonium chloride (N4Cl) as hydrogen
bond acceptors, and then they were combined with citrate (Na3C6H5O7), which is eco-friendly,
to construct an ABS for use in the separation of Au(I) from an aurocyanide
solution. Phase diagrams of DESs + Na3C6H5O7 + H2O systems were constructed using
the experimentally measured data. Multiple factors that affect the
efficiency of the gold extraction were studied; these factors were
the species of salt or DES and their content, the equilibrium pH,
the oscillation time, and the initial gold concentration. Gold(I)
is preferentially retained in the DES-rich phase, and the P4Br:PEG 1:2 + Na3C6H5O7 + H2O system has a high extraction efficiency of 100.0%
under optimized conditions. FT-IR, NMR, and TEM characterizations
and DFT calculations show that the migration of Au(I) from the salt-rich
to the DES-rich phase follows an ion exchange mechanism. Specifically,
Au(CN)2
– replaces Br– in the original P4Br and generates a stable ion pair
with the quaternary phosphonium salt cation, P+, and this
replacement is driven by electrostatic attractions. A new strong hydrogen
bond network simultaneously forms between the anionic Au(CN)2
– and the −OH group in the PEG 400 component.
Finally, the gold of Au(I)-loaded P4Br:PEG 1:2 can be successfully
reduced by sodium borohydride with an efficiency of 100.0%. The strategy
to extract gold(I) from alkaline cyanide solutions using an ABS based
on DESs as proposed in this work provides a potential platform for
developing green technology for recovering gold.