Colorimetric sensing of copper(II) based on catalytic etching of gold nanoparticles

Based on the catalytic etching of gold nanoparticles (AuNPs), a label-free colorimetric probe was developed for the detection of Cu(2+) in aqueous solutions. AuNPs were first stabilized by hexadecyltrimethylammonium bromide in NH3-NH4Cl (0.6M/0.1M) solutions. Then thiosulfate (S2O3(2-)) ions were introduced and AuNPs were gradually dissolved by dissolved oxygen. With the further addition of Cu(2+), Cu(NH3)4(2+) oxidized AuNPs to produce Au(S2O3)2(3-) and Cu(S2O3)3(5-), while the later was oxid-ized to Cu(NH3)4(2+) again by dissolved oxygen. The dissolving rate of AuNPs was thereby remarkably promoted and Cu(2+) acted as the catalyst. The process went on due to the sufficient supply of dissolved oxygen and AuNPs were rapidly etched. Meanwhile, a visible color change from red to colorless was observed. Subsequent tests confirmed such a non-aggregation-based method as a sensitive (LOD=5.0 nM or 0.32 ppb) and selective (at least 100-fold over other metal ions except for Pb(2+) and Mn(2+)) way for the detection of Cu(2+) (linear range, 10-80 nM). Moreover, our results show that the color change induced by 40 nM Cu(2+) can be easily observed by naked eyes, which is particularly applicable to fast on-site investigations.