On the Mechanism of Metal Nanoparticle Synthesis in the Brust–Schiffrin Method

• Published in: Langmuir 2013-08, Vol.29 (31), p.9863-9873
• Main Authors: Perala, Siva Rama Krishna, Kumar, Sanjeev
• Format: Article
• Language: English
• Subjects: Chemistry; Colloidal state and disperse state; Exact sciences and technology; General and physical chemistry; Gold - chemistry; Metal Nanoparticles - chemistry; Particle Size; Physical and chemical studies. Granulometry. Electrokinetic phenomena; Surface Properties
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la401604q

Brust–Schiffrin synthesis (BSS) of metal nanoparticles has emerged as a major breakthrough in the field for its ability to produce highly stable thiol functionalized nanoparticles. In this work, we use a detailed population balance model to conclude that particle formation in BSS is controlled by a new synthesis route: continuous nucleation, growth, and capping of particles throughout the synthesis process. The new mechanism, quite different from the others known in the literature (classical LaMer mechanism, sequential nucleation–growth-capping, and thermodynamic mechanism), successfully explains key features of BSS, including size tuning by varying the amount of capping agent instead of the widely used approach of varying the amount of reducing agent. The new mechanism captures a large body of experimental observations quantitatively, including size tuning and only a marginal effect of the parameters otherwise known to affect particle synthesis sensitively. The new mechanism predicts that, in a constant synthesis environment, continuous nucleation–growth-capping mechanism leads to complete capping of particles (no more growth) at the same size, while the new ones are born continuously, in principle leading to synthesis of more monodisperse particles. This prediction is validated through new experimental measurements.