Core-shell Cu@Au nanoparticles as an optical probe for ultrasensitive detection of chromium(VI) via an etching effect

Under normal circumstances, chromate ions cannot oxidize core-shell Cu-Au nanoparticles (NPs) because the standard redox potential of the Cr(VI)/Cr(III) system is lower than that of Au(I)/Au. However, in the presence of a certain concentration of hydrogen bromide, the Nernst potential becomes higher than that of Au(I)/Au and Cu(II)/Cu (as calculated by the Nernst equation). Based on this finding, a colorimetric method was developed that is based on oxidative etching of Cu@Au NPs by chromate. The Cu-Au NPs have a light red color in the presence of 5 mM HBr. On addition of Cr(VI), the gold shell is rapidly etched from the surface of the Cu-Au NPs, and this is accompanied by a color change to blue. The color changes were characterized by UV-vis spectroscopy. The absorbance at 526 nm changes in the 0.4 nM to 1 μM chromate concentration range, and the detection limit is 0.21 nM. Schematic of a highly sensitive and selective colorimetric method for detection of chromate based on the redox etching of Cu@Au nanoparticles induced by Cr(VI). The presence of HBr enables Cu@Au NPs to be oxidized by Cr 6+ .