Submicrometer intermediates in the citrate synthesis of gold nanoparticles: New insights into the nucleation and crystal growth mechanisms

Mikhlin, Yu. L.; Karacharov, Anton; Likhatski, Maxim; Podlipskaya, T. Yu.; Zubavichus, Yan V.; Велигжанин, А. А.; Zaikovski, Vladimir

doi:10.1016/j.jcis.2011.06.077

Cited by 65 publications

(73 citation statements)

References 41 publications

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“…Citrate ions are widely utilized in the wet chemical synthesis of silver [3][4][5][6][7][8][9][10][11][12][13][14], gold [15][16][17][18][19][20][21], platinum [22] and other nanoparticles, acting as reducing (direct reduction of aqueous Ag + ions by citrate occurs under boiling or hydrothermal conditions [9][10][11][12][13]), complexing, and stabilizing agent, although the precise mechanisms are far from being fully understood. Сitrate is a key reagent for the preparation of silver nanoplates, cubes, disks, etc., as the selective adsorption of citrate on Ag (111) facets impedes their growth and promotes the yield of anisotropic particles [12,[23][24][25].…”

Section: Introductionmentioning

confidence: 99%

On the nature of citrate-derived surface species on Ag nanoparticles: Insights from X-ray photoelectron spectroscopy

Mikhlin

Vorobyev

Сайкова

et al. 2018

Applied Surface Science

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Citrate is an important stabilizing, reducing, and complexing reagent in the wet chemical synthesis of nanoparticles of silver and other metals, however, the exact nature of adsorbates, and its mechanism of action are still uncertain. Here, we applied X-ray photoelectron spectroscopy, soft X-ray absorption near-edge spectroscopy, and other techniques in order to determine the surface composition and to specify the citrate-related species at Ag nanoparticles 3 immobilized from the dense hydrosol prepared using room-temperature reduction of aqueous Ag + ions with ferrous ions and citrate as stabilizer (Carey Lea method). It was found that, contrary to the common view, the species adsorbed on the Ag nanoparticles are, in large part, products of citrate decomposition comprising an alcohol group and one or two carboxylate bound to the surface Ag, and minor unbound carboxylate group; these may also be mixtures of citrate with lower molecular weight anions. No ketone groups were specified, and very minor surface Ag(I) and Fe (mainly, ferric oxyhydroxides) species were detected. Moreover, the adsorbates were different at AgNPs having various size and shape. The relation between the capping and the particle growth, colloidal stability of the high-concentration sol and properties of AgNPs is briefly considered.

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Section: Introductionmentioning

confidence: 99%

On the nature of citrate-derived surface species on Ag nanoparticles: Insights from X-ray photoelectron spectroscopy

Mikhlin

Vorobyev

Сайкова

et al. 2018

Applied Surface Science

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“…In situ microscopic methods such as atomic force microscopy (AFM) or liquid-phase TEM can be utilised to follow the growth process [15][16][17][18]. The drawback of studying nucleation and growth through electrochemistry on a solid electrode is the presence of defects on the electrode surface which act as preferential nucleation sites causing heterogeneity within the reaction [19].…”

Section: Introductionmentioning

confidence: 99%

In situ XAFS Study of Palladium Electrodeposition at the Liquid/Liquid Interface

Booth

Chang

Uehara

et al. 2017

Electrochimica Acta

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We report the use of XAFS (X-ray absorption fine structure) as an in situ method to follow the electrochemically driven deposition of palladium nanoparticles at a liquid/liquid interface.A novel glass/plastic hybrid electrochemical cell was used to enable control of the potential applied to the liquid/liquid interface. In situ measurements indicate that the nucleation of metallic nanoparticles can be triggered through chronoamperometry or cyclic voltammetry.Page 2 of 37 A c c e p t e d M a n u s c r i p tIn contrast to spontaneous nucleation at the liquid/liquid interface, whereby fluctuations in Pd oxidation state and concentration are observed, under a fixed interfacial potential the growth process occurs at a steady rate leading to a build-up of palladium at the interface. Raman spectroscopy of the deposit suggests that the organic electrolyte binds directly to the surface of the deposited nanoparticles. It was found that the introduction of citric acid results in the formation of spherical nanoparticles at the interface.

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“…[13,15,[21][22][23] The presence of these intermediate aggregates could be understood by considering that several nuclei could be generated by the same Au I /DCA complex. As the reaction proceeds the size of the constituent particles seems to increase until a certain stage at which the aggregates decompose into individual rather monodisperse particles with a typical average diameter of about 15 nm.…”

Section: Introductionmentioning

confidence: 99%

Shape-Tailored Colloidal Molecules Obtained by Self-Assembly of Model Gold Nanoparticles with Flexible Polyelectrolyte

Shi

Carn

2015

Langmuir

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ABSTRACT.We study the effect of citrate to gold molar ratio (X) on the size of citrated gold nanoparticles (AuNPs). This dependence is still a matter of debate for X  3 where the polydispersity is yet minimized. Indeed, there is no consensus between experiments proposed so far for comparable experimental conditions. Nonetheless, the sole available theoretical prediction has never been validated experimentally in this range of X. We show unambiguously using 3 techniques (UV-Vis spectroscopy, dynamic light scattering and transmission electronic microscopy), 2 different synthetic approaches (Direct, Inverse) and 10 X values for each approach that AuNPs' size decay as a monoexponential with X. This result is, for the first time, in agreement with the sole available theoretical prediction by Kumar et al. on the whole studied range of X.2

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Submicrometer intermediates in the citrate synthesis of gold nanoparticles: New insights into the nucleation and crystal growth mechanisms

Cited by 65 publications

References 41 publications

On the nature of citrate-derived surface species on Ag nanoparticles: Insights from X-ray photoelectron spectroscopy

On the nature of citrate-derived surface species on Ag nanoparticles: Insights from X-ray photoelectron spectroscopy

In situ XAFS Study of Palladium Electrodeposition at the Liquid/Liquid Interface

Shape-Tailored Colloidal Molecules Obtained by Self-Assembly of Model Gold Nanoparticles with Flexible Polyelectrolyte

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