Facile and Rapid Synthesis of a Dithiol-Protected Ag7 Quantum Cluster for Selective Adsorption of Cationic Dyes

Abstract

We report a facile and rapid (less than 15 min) synthesis of atomically precise, dithiol-protected, silver quantum cluster, Ag7(DMSA)4 (DMSA: meso-2,3-dimercaptosuccinic acid), through a modified solid state route. The as-synthesized cluster exhibits molecular optical absorption features with a prominent λmax at ~500 nm. Composition of the cluster was confirmed using various spectroscopic and microscopic techniques such as electrospray ionization mass spectrometry (ESI MS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive analysis of X-rays (EDAX). Clusters supported on neutral alumina have been shown as better adsorbents for selective adsorption of cationic dyes (over anionic dyes) from water. This selectivity for cationic dyes was evaluated by zeta potential (ζ) measurements. The efficiency of clusters for removal of dyes is very high when compared to nanoparticles (NPs) protected with ligands (citrate and mercaptosuccinic acid (MSA)) possessing similar chemical structures as that of DMSA. The higher efficiency of clusters for the removal of dyes is attributed to their smaller size and large surface area compared to the NPs in addition to favorable electrostatic interactions between the clusters and cationic dyes. Adsorption of dyes (cationic and anionic) was enhanced when dye molecules contain hydrogen bond forming functional groups. Supported clusters have been reused up to five cycles without the loss of activity once the adsorbed dye is extracted using suitable solvents.