Effect of Nobel Metal Ions on the Synthesis of Metal Nanoclusters for Selective Detetction of Various Heavy Metals

Abstract

In this study, effect of noble metal ion (Au, Ag and Cu) on the synthesis of metal nanoclusters (MNCs) has been investigated. Through heating at 70ºC, TSA/BSA-Au, -Ag and -Cu NCs were separately prepared from Au3+, Ag+and Cu2+in the presence of bovine serum albumin (BSA) and thiosalicylic acid (TSA). They exhibit photoluminescence (PL) at 700, 624 and 430 nm,with average life times of 1500, 100 and 11.71 ns,respectively, when excited at 350 nm. X–ray photoelectronspectroscopy (XPS) data support the presence of metal core (M0) and metal–thiolate shell (Mn–SRm), each in the TSA/BSA-MNCs. Spectroscopic measurements reveal the formation of Au32–SR, Ag9–SR and (Cu4–Cu13)–SR species separately in the TSA/BSA-Au, -Ag and -Cu NCs. Through PL quenching of the TSA/BSA-Au, -Ag and -Cu NCs, they have been used separately for quantitation of Hg2+, As3+and Cr6+ , with linear rangesof 10-400, 4-18, and 40-400 nM and limits of detection (LODs) of 0.25, 2.34 and 3.54 nM, respectively. The PL quenching is mainly due to aggregationof the MNCs through metallophilic or metal–thiol complexation.The stable TSA/BSA–Au, -Ag and -Cu NCs have been employed separately for the determination of the concentrations of Hg2+, As3+and Cr6+ions in the spiked sea water samples, showing advantages of simplicity, rapidity, high selectivity, and sensitivity.