Tarasankar Pal

Photochemical green synthesis of calcium-alginate-stabilized Ag and Au nanoparticles and their catalytic application to 4-nitrophenol reduction.

Silver and gold nanoparticles have been grown on calcium alginate gel beads using a green photochemical approach. The gel served as both a reductant and a stabilizer. The nanoparticles were characterized using UV-visible spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), energy dispersive X-ray (EDS), and selected area electron diffraction (SAED) analyses. The particles are spherical, crystalline, and the size ranges for both Ag and Au nanoparticles are <10 nm. It is noticed from the sorption experiment that the loading of gold on calcium alginate beads is much more compared to that of Ag. The effectiveness of the as-prepared dried alginate-stabilized Ag and Au nanoparticles as a solid phase heterogeneous catalyst has been evaluated, for the first time, on the well-known 4-nitrophenol (4-NP) reduction to 4-aminophenol (4-AP) in the presence of excess borohydride. The reduction was very efficient and followed zero-order kinetics for both Ag and Au nanocomposites. The effects of borohydride, initial 4-NP concentration, and catalyst dose were evaluated. The catalyst efficiency was examined on the basis of turnover frequency (TOF) and recyclability. The catalytic efficiency of alginate-based Ag catalyst was much more compared to that of the Au catalyst. The as-prepared new solid-phase biopolymer-based catalysts are very efficient, stable, easy to prepare, eco-friendly, and cost-effective, and they have the potential for industrial applications.

Silver nanoparticle catalyzed reduction of aromatic nitro compounds

The combination of catalytic quantities of silver metal nanoparticles with NaBH4 smoothly reduces aromatic nitro compounds to amines in aqueous medium. Silver nanoparticles formed in situ are the active catalyst. The kinetic parameters of the reaction with still growing microelectrode (GME) and full grown microelectrode (FGME) silver metal particles in aqueous solution have been compared taking the plasmon band of the silver metal nanoparticles into consideration. In aqueous solution the reaction follows a first order kinetics with the full-grown (FGME) particles and zero order kinetics with the still growing particles (GME). The metal surface remains active and the activity remains unaltered throughout the course of the reduction. Catalysis was due to the efficient nanoparticle mediated electron transfer from BH4− ion to the nitro compounds. Nitro compounds like 2-nitrophenol (2-NP), 4-nitrophenol (4-NP) and 4-nitroaniline (4-NA) were tested with NaBH4 using both GME and FGME as catalyst and their rate of reduction has been observed to follow the sequence, 4-NP>2-NP>4-NA.

Size controlled synthesis of gold nanoparticles using photochemically prepared seed particles

Gold nanoparticles having prechosen size ranging from 5 to 110 nm have been prepared in two steps. Firstly, small spherical particles (seed) of average diameters between 5 and 20 nm were prepared by varying the ratio of gold ion concentration to stabilizer/reductant, TX-100 concentration and using UV irradiation. Secondly, 20–110 nm particles were formed by a non-iterative seed-mediated growth where small particles produced by the above irradiation technique were exploited as seeds and fresh Au(III) ions were reduced onto the surface on the seed particles by ascorbic acid. The kinetics of particle formation has also been reported. These methods were fast and showed improved monodispersity sphericity and excellent reproducibility.

Silver Nanoparticle Decorated Reduced Graphene Oxide (rGO) Nanosheet: A Platform for SERS Based Low-Level Detection of Uranyl Ion

Herein, a simple wet-chemical pathway has been demonstrated for the synthesis of silver nanoparticle conjugated reduced graphene oxide nanosheets where dimethylformamide (DMF) is judiciously employed as an efficient reducing agent. Altogether, DMF reduces both silver nitrate (AgNO3) and graphene oxide (GO) in the reaction mixture. Additionally, the presence of polyvinylpyrolidone (PVP) assists the nanophasic growth and homogeneous distribution of the plasmonic nanoparticle Ag(0). Reduction of graphene oxide and the presence of aggregated Ag NPs on reduced graphene oxide (rGO) nanosheets are confirmed from various spectroscopic techniques. Finally, the composite material has been exploited as an intriguing platform for surface enhanced Raman scattering (SERS) based selective detection of uranyl (UO2(2+)) ion. The limit of detection has been achieved to be as low as 10 nM. Here the normal Raman spectral (NRS) band of uranyl acetate (UAc) at 838 cm(-1) shifts to 714 and 730 cm(-1) as SERS bands for pH 5.0 and 12.0, respectively. This distinguished Raman shift of the symmetric stretching mode for UO2(2+) ion is indicative of pronounced charge transfer (CT) effect. This CT effect even supports the higher sensitivity of the protocol toward UO2(2+) over other tested oxo-ions. It is anticipated that rGO nanosheets furnish a convenient compartment to favor the interaction between Ag NPs and UO2(2+) ion through proximity induced adsorption even at low concentration.

Fabrication of porous β-Co(OH)2 architecture at room temperature: a high performance supercapacitor.

A facile, cost-effective, surfactant-free chemical route has been demonstrated for the fabrication of porous β-Co(OH)2 hierarchical nanostructure in gram level simply by adopting cobalt acetate as a precursor salt and ethanolamine as a hydrolyzing agent at room temperature. A couple of different morphologies of β-Co(OH)2 have been distinctly identified by varying the mole ratio of the precursor and hydrolyzing agent. The cyclic voltammetry measurements on β-Co(OH)2 displayed significantly high capacitance. The specific capacitance obtained from charge-discharge measurements made at a discharge current of 1 A/g is 416 F/g for the Co(OH)2 sample obtained at room temperature. The charge-discharge stability measurements indicate retention of specific capacitance about 93% after 500 continuous charge-discharge cycles at a current density of 1 A g(-1). The capacitive behavior of the other synthesized morphology was also accounted. The nanoflower-shaped porous β-Co(OH)2 with a characteristic three-dimensional architecture accompanied highest pore volume which made it promising electrode material for supercapacitor application. The porous nanostructures accompanied by high surface area facilitates the contact and transport of electrolyte, providing longer electron pathways and therefore giving rise to highest capacitance in nanoflower morphology. From a broad view, this study reveals a low-temperature synthetic route of β-Co(OH)2 of various morphologies, qualifying it as supercapacitor electrode material.

Seed-mediated successive growth of gold particles accomplished by UV irradiation: a photochemical approach for size-controlled synthesis

Preparation of monodispersed metal nanoparticles of different size has enormous importance in nanotechnology. Currently, the size controlled synthesis of nanoparticles is carried out either by using the capping property of a stabilizer that restrict the particle growth at the intermediate stage or by exploiting the variable size of the water pool of a reverse micelle as template. We have reported here a powerful and general method to prepare gold nanoparticles of controlled size by through UV irradiation technique. First small particles are prepared and then they are used as seed to prepare bigger particles by photoactivation technique. Metal particles of gold of different size ( 20‐80 nm) have been synthesized by this method.

Interaction of DNA bases with silver nanoparticles: Assembly quantified through SPRS and SERS

Colloidal silver nanoparticles were prepared by reducing silver nitrate with sodium borohydride. The synthesized silver particles show an intense surface plasmon band in the visible region. The work reported here describes the interaction between nanoscale silver particles and various DNA bases (adenine, guanine, cytosine, and thymine), which are used as molecular linkers because of their biological significance. In colloidal solutions, the color of silver nanoparticles may range from red to purple to orange to blue, depending on the degree of aggregation as well as the orientation of the individual particles within the aggregates. Transmission electron microscopy (TEM), X-ray diffraction (XRD), and absorption spectroscopy were used to characterize the assemblies. DNA base-induced differential silver nanoparticle aggregation was quantified from the peak separation (relates to color) of surface plasmon resonance spectroscopy (SPRS) and the signal intensity of surface-enhanced Raman scattering (SERS), which rationalize the extent of silver-nucleobase interactions.

Morphology Controlled Synthesis of SnS2 Nanomaterial for Promoting Photocatalytic Reduction of Aqueous Cr(VI) under Visible Light

A mild, template free protocol has been demonstrated for SnS2 nanoflake formation at the gram level from SnCl2 and thioacetamide (TAA). The SnS2 nanoflakes congregate to nanoflowers and nanoyarns with variable TAA concentrations. BET measurements reveal that the synthesized nanomaterials are highly porous having very high surface area, and the nanoflower has higher surface area than the nanoyarn. The synthesized nanomaterial finds application for promoting photoreduction of extremely toxic and lethal Cr(VI) under visible light irradiation due to their porous nature. The nanoflowers photocatalyst is proved to be superior to nanoyarn due to the increased surface area and higher pore volume. It was also inferred that increased pH decreased the reaction rate. The present result suggests that the morphology-dependent photoreduction of Cr(VI) by SnS2 nanomaterial under visible light exposure will endorse a new technique for harvesting energy and purification of wastewater.

Redox-Switchable Copper(I) Metallogel: A Metal–Organic Material for Selective and Naked-Eye Sensing of Picric Acid

Thiourea (TU), a commercially available laboratory chemical, has been discovered to introduce metallogelation when reacted with copper(II) chloride in aqueous medium. The chemistry involves the reduction of Cu(II) to Cu(I) with concomitant oxidation of thiourea to dithiobisformamidinium dichloride. The gel formation is triggered through metal-ligand complexation, i.e., Cu(I)-TU coordination and extensive hydrogen bonding interactions involving thiourea, the disulfide product, water, and chloride ions. Entangled network morphology of the gel selectively develops in water, maybe for its superior hydrogen-bonding ability, as accounted from Kamlet-Taft solvent parameters. Complete and systematic chemical analyses demonstrate the importance of both Cu(I) and chloride ions as the key ingredients in the metal-organic coordination gel framework. The gel is highly fluorescent. Again, exclusive presence of Cu(I) metal centers in the gel structure makes the gel redox-responsive and therefore it shows reversible gel-sol phase transition. However, the reversibility does not cause any morphological change in the gel phase. The gel practically exhibits its multiresponsive nature and therefore the influences of different probable interfering parameters (pH, selective metal ions and anions, selective complexing agents, etc.) have been studied mechanistically and the results might be promising for different applications. Finally, the gel material shows a highly selective visual response to a commonly used nitroexplosive, picric acid among a set of 19 congeners and the preferred selectivity has been mechanistically interpreted with density functional theory-based calculations.

Controlled interparticle spacing for surface-modified gold nanoparticle aggregates

Aggregation of gold nanoparticles of increasing size has been studied as a consequence of adsorption of 2-aminothiophenol (ATP) on gold nanoparticle surfaces. The capping property of ATP in the acidic pH range has been accounted from UV-vis absorption spectroscopy and surface-enhanced Raman scattering (SERS) studies. The effect of nanoparticle size (8-55 nm) on the nature of aggregation as well as the variation in the optical response due to variable degree of interparticle coupling effects among the gold particles have been critically examined. Various techniques such as transmission electron microscopy, X-ray diffraction, zeta-potential, and average particle size measurement were undertaken to characterize the nanoparticle aggregates. The aggregate size, interparticle distances, and absorption band wavelengths were found to be highly dependent on the pH of the medium and the concentration of the capping agent, ATP. The acquired SERS spectra of ATP relate the interparticle spacing. It has been observed that the SERS signal intensities are different for different sized gold nanoparticles.