Reversing Ostwald Ripening

The phenomenon of Ostwald Ripening is generally considered a limiting factor in the monodisperse production of nanoparticles. However, by analysing the free energy of a binary AB solution with precipitated A particles we show that there is a region in the parameter space of component concentrations and interaction energies where smaller particles are more stable than bigger ones. The strong binding of B species to surfaces of A particles significantly decreases the particle effective surface energy, making it negative. The global minimum of free energy in such a system is thus reached when mass is transferred from bigger particles to the smaller ones, such that all particles become identical in size. The process of mass transfer is opposite to Ostwald ripening, and can be used for generating monodisperse arrays of nanoparticles.Comment: 11 pages and 4 figures of the main text plus 4 pages and 1 figure supporting materia

Uptake of Toxic Metal Ions from Water by Naked and Monolayer Protected Silver Nanoparticles: An X-ray Photoelectron Spectroscopic Investigation

where MSA is mercaptosuccinic acid). The particles were of 30 and 8 nm diameter, respectively. We observed that the metal ions interact with both the core of the nanoparticles and the functional groups of the capping agents. We study the effects of interaction using spectroscopic and microscopic techniques such as ultraviolet-visible spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FTIR), X-ray diffractio

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

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 λ_max 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

Understanding the Degradation Pathway of the Pesticide, Chlorpyrifos by Noble Metal Nanoparticles

Application of nanoparticles (NPs) in environmental remediation such as water purification requires a detailed understanding of the mechanistic aspects of the interaction between the species involved. Here, an attempt was made to understand the chemistry of noble metal nanoparticle–pesticide interaction, as these nanosystems are being used extensively for water purification. Our model pesticide, chlorpyrifos (CP), belonging to the organophosphorothioate group, is shown to decompose to 3,5,6-trichloro-2-pyridinol (TCP) and diethyl thiophosphate at room temperature over Ag and Au NPs, in supported and unsupported forms. The degradation products were characterized by absorption spectroscopy and electrospray ionization mass spectrometry (ESI MS). These were further confirmed by ESI tandem mass spectrometry. The interaction of CP with NP surfaces was investigated using transmission electron microscopy, energy dispersive analysis of X-rays, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). XPS reveals no change in the oxidation state of silver after the degradation of CP. It is proposed that the degradation of CP proceeds through the formation of AgNP–S surface complex, which is confirmed by Raman spectroscopy. In this complex, the P–O bond cleaves to yield a stable aromatic species, TCP. The rate of degradation of CP increases with increase of temperature and pH. Complete degradation of 10 mL of 2 ppm CP solution is achieved in 3 h using 100 mg of supported Ag@citrate NPs on neutral alumina at room temperature at a loading of ∼0.5 wt %. The effect of alumina and monolayer protection of NPs on the degradation of CP is also investigated. The rate of degradation of CP by Ag NPs is greater than that of Au NPs. The results have implications to the application of noble metal NPs for drinking water purification, as pesticide contamination is prevalent in many parts of the world. Study shows that supported Ag and Au NPs may be employed in sustainable environmental remediation, as they can be used at room temperature in aqueous solutions without the use of additional stimulus such as UV light