Experimental and DFT calculation study of interaction between silver nanoparticle and 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid.

The mechanism of stabilization of silver nanoparticles (Ag NPs) by 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid (IL) is elucidated from experimental spectroscopic investigations and density functional theory (DFT) calculations. FTIR spectrum of the synthesized IL stabilized silver nanoparticles reveals small red shift in B-F stretching frequency while C-H stretching remains unshifted. There is no shift in NMR peaks of IL before and after the synthesis of IL stabilized Ag NPs. This suggests that Ag NPs are surrounded by anions of ILs. The optimized structure obtained from density functional theory (DFT) calculations also shows the anionic part of the IL surrounding the Ag nanocluster. This is supported by the IR frequency data calculated using DFT. The calculated binding energy and interaction energy obtained between cluster and IL is considerably attractive. Density of State (DOS) calculation shows that the HOMO-LUMO gap of the Ag cluster-IL composite is significantly lesser than that of the IL alone.

Mechanism of visible light enhanced catalysis over curcumin functionalized Ag nanocatalysts.

There is little research on the visible light photocatalytic properties of the hybrids of plasmonic metals and organic molecules (OM) with the HOMO-LUMO gap in the visible range. Here, we investigate the mechanism of the visible light enhanced reduction of p-nitrophenol (PNP) by glycerol (a green reductant) at ambient temperature over curcumin functionalized Ag nanoparticles (c-AgNPs). The catalytic activity got significantly boosted under visible light irradiation. Reaction kinetics indicated that the catalytic mechanism followed under visible light and in the dark were different. DFT calculations showed that in the ground state, the HOMO resides on Ag while the LUMO is on the curcumin part of the composite. TD-DFT calculations demonstrated the transfer of charge from Ag to curcumin on photo-excitation. Based on this information, we propose a mechanism for understanding the role of curcumin in this photocatalytic phenomenon.

Ag-Cu Bimetallic Nanoparticles as Efficient Oxygen Reduction Reaction Electrocatalysts in Alkaline Media.

The alkaline medium oxygen reduction reaction (ORR) activities of Ag-Cu bimetallic nanoparticles (BNPs), consisting of neighboring Ag and Cu domains, were studied and compared with those of pure Ag and Cu nanoparticles prepared by the same polyol route. Three variations of Ag-Cu BNPs viz. Ag-Cu (4:1), Ag-Cu (2:1), Ag-Cu (1:1) BNPs were considered. The electrocatalytic performances of these nanoparticles were investigated by using different techniques, such as cyclic voltammetry (CV) and linear sweep voltammograms (LSV). The Ag-Cu bimetallics demonstrated synergistic ORR electrocatalytic activity compared to pure Ag or Cu. Optimum values of these parameters were observed for Ag-Cu (4:1) BNPs. According to LSV, the reduction peak position is at lower applied potential and showed higher intensity for the Ag-Cu (4:1) as compared to Ag-Cu (2:1) and Ag-Cu (1:1) BNPs. Density Functional Theory (DFT) calculations show that charge transfer from Cu to Ag (in the bimetallic nanoparticles) results in their stronger oxygen interaction and water activation properties relative to that of pure Ag nanoparticles.