Surface-enhanced infrared spectroscopic studies of the catalytic behavior of silver nanoparticles on a germanium substrate.

The catalytic activity of silver nanoparticles (AgNPs) on a germanium substrate is reported. Para-nitrothiophenol (pNTP) that had been adsorbed on this substrate is converted to p-aminothiophenol (pATP) under very mild reaction conditions, such as simply soaking in water. The AgNPs may be formed either by physical vapor deposition or by electroless deposition from a solution of silver nitrate. Analogous reactions were not observed on copper nanoparticles on germanium or AgNPs on silicon or zinc selenide even though very slow conversion of pNTP to pATP was observed with Au nanoparticles (AuNPs) on Ge under controlled reaction conditions. The effects of factors that could influence the catalytic reaction were examined; these included the particle size of the AgNPs, reaction temperature, concentration and chemical nature of other ions present in the solution, the pH of the water, and the nature of the substrate. The reaction rate was approximately independent of the particle size for AgNPs between 50 and 150 nm in diameter. Increasing the temperature accelerates the reaction significantly; at temperatures above 40 °C, the adsorbed pNTP is completely converted by water within five minutes. Not surprisingly, the reaction rate was increased as the pH of the solution was decreased, as the reduction of each nitro group to an amino group requires six protons. The presence of Br(-) and I(-) ions accelerated the reaction to the point that even at 4 °C, the conversion of the nitro group was still observable, while solutions containing chloride ions had to be heated to 40 °C before their effect became apparent. Apparently, Br(-) and I(-) ions remove the oxide layer from the surface of the germanium substrate, facilitating transfer of electrons from the germanium to the nitro group of the pNTP.