Annealing-induced reversible change in optical absorption of Ag nanoparticles

Optical absorption of silver nanoparticles dispersed within pores of monolithic mesoporous silica was investigated after annealing in different atmospheres. It has been found that treatment in H2 or N2 induces a strong surface plasmon resonance (SPR) as usually expected, but air annealing results in the disappearance of the SPR, which is contrary to the fact that bulk metal silver is stable and not oxidized in air at above 200 °C. The absence and appearance of the SPR absorption can be controlled through alternate annealing in air and H2 (or N2). Thermodynamic analysis for oxidation of Ag nanoparticles, by additionally considering the surface and curvature effects of a particle, shows the existence of critical particle size. Only when a Ag particle size is smaller than the critical value is the oxidation possible in air at above 200 °C. The optical changes are attributed to the occurrence of the redox of the Ag particles in different atmospheres at a high temperature.