The recovery of precious metals from waste has garnered significant attention owing to their non-renewable nature and essential role in the burgeoning information industry. However, enhancing the extraction efficiency of microemulsions remains a significant challenge. In this study, three water-in-oil microemulsions were formulated using gemini surfactants with different spacers (14-OH-14, 14-SO4-14, and 14-3-14) as emulsifiers, supplemented with n-butanol as a cosurfactant, n-heptane as the oil phase, and NaCl aqueous solution as the internal aqueous phase. These microemulsions were employed for the extraction of gold(III) from hydrochloric acid solutions. The results illustrate that all three microemulsions effectively extracted gold(III) through a spontaneous, exothermic, enthalpy-driven anion-exchange mechanism, achieving notable extraction efficiency. In contrast to 14-3-14, incorporating -OH into the spacer significantly augments the positive electrostatic potential through the cationization of -OH in an HCl solution, resulting in a higher binding constant (2.43) and thereby improving the extraction efficiency. However, the presence of -SO4 diminishes the positive electrostatic potential through partial neutralization, resulting in a lower binding constant (1.17), which is detrimental to the extraction process. Response surface optimization revealed that concentrations of C(14-OH-14) and V(1-butanol) significantly influence extraction efficiency and exhibit pronounced interaction. At optimal conditions (C(14-OH14) = 0.09 mol & sdot;L- 1, V(1-butanol) = 47.41 %, R=20, and C(NaCl) = 1.57 mol & sdot;L- 1), over 95.54 % of gold(III) can be extracted from actual e-waste solutions. This study offers an alternative approach for designing or selecting surfactants in microemulsion-based extraction of gold(III) from e-waste.
