Evaluating the mechanism of nucleation and growth of silver nanoparticles in a polymer membrane under continuous precursor supply: tuning of multiple to single nucleation pathway

被引:29
作者
Naik, Apurva N. [1 ]
Patra, Sabyasachi [1 ]
Sen, Debasis [1 ,2 ]
Goswami, Asok [3 ]
机构
[1] Bhabha Atom Res Ctr, Radiochem Div, Mumbai 400085, Maharashtra, India
[2] Homi Bhabha Natl Inst, Mumbai 400094, Maharashtra, India
[3] Bhabha Atom Res Ctr, Solid State Phys Div, Mumbai 400085, Maharashtra, India
关键词
XANES; ANGLE; SIZE;
D O I
10.1039/c8cp06202a
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Size controlled synthesis of nanoparticles in a structured media, such as a membrane, has not yet been achieved successfully in comparison to that in solution due to the lack of mechanistic investigations on the nucleation and growth of nanoparticles in these media. Slower diffusion of precursor and monomer species inside these structured media complicates the nanoparticle formation mechanism. We herein report a novel experimental approach to reveal the mechanism of nucleation and growth during the synthesis of silver nanoparticles in a Nafion-117 membrane using radiolabeling and small angle X-ray scattering (SAXS). The study has been conducted under the conditions of continuous supply of precursor (silver citrate). Repetitive LaMer type nucleations have been found to occur in the membrane leading to the formation of polydispersed spherical nanoparticles as evident from time resolved small angle X-ray scattering. These repetitive nucleations have been shown to be responsible for continuous birth of new seeds, which grow to larger particles, mainly by random coagulation introducing non-uniformity in the growth profile of nanoparticles. The additional nucleation events have been successfully ceased by careful tuning of reaction temperature and precursor concentration, thereby eliminating the nanoparticle growth by random coagulation. This has led to the formation of silver nanoparticles with improved morphology and size distributions, which has been manifested in remarkable improvement in the optical quality of the silver nanoparticles. The present study is the first of its kind showing the crucial role of the membrane host in retarding the reaction kinetics which allowed successful probing of temporal variation of monomer concentration during nucleation and growth using a radiotracer. This was hitherto difficult to probe in solution due to its ultrafast kinetics. Additionally, using the experimental monomer concentrations during nucleation, the free energy of activation (G(crit)) and the critical radius (r(crit)) for nucleation have been estimated and found to be 73 kJ mol(-1) and 6.6 angstrom, respectively. The present work validates the well known theoretical model by La Mer for the synthesis of nanoparticles in a membrane under continuous precursor supply.
引用
收藏
页码:4193 / 4199
页数:7
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