Mass-spectrometric study of the formation of silver nanoclusters in polyether media: 2. Fast atom bombardment and modeling

Within the problem of the synthesis of silver nanoclusters and nanoparticles in polyether media, systems containing silver nitrate AgNO3 and low-molecular-weight polyethers, poly(ethylene glycol) PEG-400 or oxyethylated glycerol OEG-5, were studied by fast atom bombardment (FAB) mass spectrometry. The formation of stable clusters of polyether oligomers (Mm) with silver cations Mm · Ag+ was shown, in agreement with the previous data of laser desorption/ionization. Quantum-chemical DFT calculations have shown that the Mm · Ag+ clusters are stabilized by wrapping of the polyether chain around the silver cation with the cation coordinating ether oxygen atoms. Silver nanoclusters were not found in the FAB mass spectra of liquid systems, but Agn+ clusters were detected for silver nanoparticles separated from the reaction medium. No products of chemical transformations of PEG-400 or OEG-5 were observed by FAB. A plausible mechanism of the reduction of silver cations involving nitrate anions is discussed.