Surface Structure of Silver Nanoparticles as a Model for Understanding the Oxidative Dissolution of Silver Ions

Bastiaan Molleman, Tjisse Hiemstra*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

56 Citations (Scopus)

Abstract

The toxicity of silver nanoparticles (AgNPs) has been related to the release of ionic silver. This process is influenced by a large variety of factors and is poorly understood. The key to understanding Ag+ release by AgNPs is its subvalency. This is a fundamental property of Ag that can be elucidated by analyzing the crystal structures of a specific class of Ag materials as well as MO/DFT (molecular orbital/density functional theory)-optimized Ag13(OH)4 clusters, being precursors of AgNPs. Semimetallic silver at the (111) faces of AgNPs has a subvalency of +1/3 v.u., forming ≡ Ag3OH0 surface groups with a maximum site density of 4.7 sites/nm2. Oxidative dissolution may remove these groups with the simultaneous formation of oxygen radicals that may further interact with the surface via different pathways. Reactive oxygen species (ROS) can create a circular process with the dissolution of ≡ Ag3OH0, exposure of new metallic sites at the underlying lattice, and subsequent oxidation to ≡ Ag3OH0. This regeneration process is interrupted by the penetration of O radicals into the lattice, forming highly stable Ag6O octahedra with subvalent silver that protects the AgNP from further oxidation. A thermodynamic model has been developed that quantitatively describes the equilibrium condition between ≡ Ag3OH0 and ≡ Ag6O0 and explains a large variety of collectively observed phenomena.

Original languageEnglish
Pages (from-to)13361-13372
JournalLangmuir
Volume31
Issue number49
DOIs
Publication statusPublished - 2015

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