Synthesis and kinetics of growth of metal nanoparticles inside ion-exchange polymers

Copper and silver nanoparticles have been obtained by means of saturation of a sulfostyrene-divinylbenzene cation-exchange polymer with metal ions and their subsequent chemical reduction. This procedure was repeated several times up to formation of a long-range conducting network (percolating cluster). Another system under study was an ensemble of Ag nanoparticles of various sizes on the silver electrode surface obtained by reduction of anodically formed layers of silver oxide. Recrystallization of deposited metal crystals inside the polymer matrix in contact with metal-ion containing solution is very slow for electrically separated particles. Formation of the electric network results in an enormous acceleration of this process via electron-ion mechanism, with growth of the average particle size, so that their potential will approach that of the compact metal with time. The initial period of the particle growth is well described by the parabolic law (Burke and Turnbull). The values of the particle-growth coefficient in this law, k, are drastically different for particles inside the matrix and on the electrode surface. Particle-to-particle electron transfer is impeded by insulating areas inside the polymer matrix. Besides, ionogenic centers of the matrix restrict the mobility of metal cations, thus slowing down the ion transfer within the recrystallization circuit. These observations have allowed us to establish the conditions resulting in long-term stabilization of metal nanoparticles inside the ion-exchange matrix with respect to their recrystallization.