Name: Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles (Video) | JoVE Journal
Uploaded: 2018-06-25T13:00:00.000+00:00
Duration: 11 min 54 s
Description: Discover ligand-mediated nucleation and growth of palladium nanoparticles using in situ SAXS and kinetic modeling. This method enables predictive synthesis of size-controlled colloidal metal nanoparticles for catalysis applications.

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The work was primarily funded by the National Science Foundation (NSF), Chemistry Division (award number CHE-1507370) is acknowledged. Ayman M. Karim and Wenhui Li acknowledge partial financial support by 3M Non-Tenured Faculty Award. This research used resources of the Advanced Photon Source (beamline 12-ID-C, user proposal GUP-45774), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The authors would like to thank Yubing Lu, a Ph.D. candidate in the Chemical Engineering Department at Virginia Tech for his kind help with the SAXS measurements. The presented work was partly executed at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. Los Alamos National Laboratory, an affirmative action equal opportunity employer, is operated by Los Alamos National Security, LLC, for the National Nuclear Security Administration of the U.S. Department of Energy under contract DE-AC52-06NA25396.

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</ol>

There is no conflict of interest to report.

In this study, we presented a powerful methodology to examine the effect of capping ligands on the nucleation and growth of metal nanoparticles. We synthesized Pd nanoparticles in different solvents (toluene and pyridine) using Pd acetate as the metal precursor and TOP as the ligand.We used in situ SAXS to extract the concentration of reduced atoms (nucleation and growth events) as well as the concentration of nanoparticles (nucleation event), where both experimental observables were used as the model inputs. In...

Controlled synthesis of metallic nanoparticles is of great importance due to the large applications of nanostructured materials in catalysis, photovoltaic, photonics, sensors, and drug delivery1,2,3,4,5. To synthesize the nanoparticles with specific sizes and size distribution, it is vital to understand the underlying mechanism for the particle nucleation and growth. Nevertheless, obtaining nanoparticles with such criteria has challenged the nano-synthesis community due to the slow progress in understanding the synthesis mechanisms and the lack of robust kinetic models available in the literature. In 1950s, LaMer proposed a model for the nucleation and growth of sulfur sols, where there is a burst of nucleation followed by a diffusion-controlled growth of nuclei6,7. In this proposed model, it is postulated that the monomer concentration increases (due to the reduction or decomposition of the precursor) and once the level is above the critical supersaturation, the energy barrier for particle nucleation can be overcome, resulting in a burst nucleation (homogeneous nucleation). Owing to the proposed burst nucleation, the monomer concentration drops and when it falls below the critical supersaturation level, the nucleation stops. Next, the formed nuclei are postulated to grow via the diffusion of monomers towards the nanoparticles surface, while no additional nucleation events occur. This results in effectively separating the nucleation and growth in time and controlling the size distribution during the growth process8. This model was used to describe the formation of different nanoparticles including Ag9, Au10, CdSe11, and Fe3O412. However, several studies illustrated that the classical nucleation theory (CNT) cannot describe the formation of colloidal nanoparticles, in particular for metallic nanoparticles where the overlap of the nucleation and growth is observed1,13,14,15,16,17. In one of those studies, Watzky and Finke established a two-step mechanism for the formation of iridium nanoparticles13, in which a slow continuous nucleation overlaps with a fast nanoparticle surface growth (where growth is autocatalytic). The slow nucleation and fast autocatalytic growth were also observed for different types of metal nanoparticles, such as Pd14,15,18, Pt19,20, and Rh21,22. Despite recent advances in developing nucleation and growth models1,23,24,25, the role of the ligands is often ignored in the proposed models. Nevertheless, ligands are shown to affect the nanoparticles size14,15,26 and morphology19,27 as well as the catalytic activity and selectivity28,29. For example, Yang et al.30 controlled the Pd nanoparticle size ranging from 9.5 and 15 nm by varying the concentration of trioctylphosphine (TOP). In the synthesis of magnetic nanoparticles (Fe3O4), the size noticeably decreased from 11 to 5 nm when the ligand (octadecylamine) to metal precursor ratio increased from 1 to 60. Interestingly, the size of Pt nanoparticles was shown to be sensitive to the chain length of amine ligands (e.g., n-hexylamine and octadecylamine), where smaller nanoparticle size could be obtained using longer chain (i.e., octadecylamine)31.
The size alteration caused by different concentration and different types of the ligands is a clear evidence for the contribution of ligands in the nucleation and growth kinetics. Unfortunately, few studies accounted for the role of ligands, and in these studies, several assumptions were often made for the sake of simplicity, which in turn make these models applicable only for specific conditions32,33. More specifically, Rempel and co-workers developed a kinetic model to describe the formation of quantum dots (CdSe) in the presence of capping ligands. However, in their study, the binding of the ligand with nanoparticle surface is assumed to be at equilibrium at any given time32. This assumption might hold true when the ligands are in large excess. Our group recently developed a new ligand-based model14 which accounted for the binding of capping ligands with both the precursor (metal complex) and the surface of nanoparticle as reversible reactions14. In addition, our ligand-based model could potentially be used in other metal nanoparticle systems, where the synthesis kinetics seem to be affected by the presence of the ligands.
In the current study, we use our newly developed ligand-based model to predict the formation and growth of Pd nanoparticles in different solvents including toluene and pyridine. For our model input, in situ SAXS was utilized to obtain the concentration of nanoparticles and size distribution during the synthesis. Measuring both the size and concentration of particles, complemented by kinetic modeling, allows us to extract more precise information on the nucleation and growth rates. We further demonstrate that our ligand-based model, which explicitly accounts for the ligand-metal binding, is highly predictive and can be used to design the synthesis procedures to obtain nanoparticles with desired sizes.

<table><tbody><tr><td>palladium acetate (Pd(OAc)2)</td><td>ALDRICH</td><td>520764</td><td></td></tr><tr><td>anhydrous acetic acid</td><td>SIAL</td><td>338826</td><td></td></tr><tr><td>trioctylphosphine</td><td>ALDRICH</td><td>718165</td><td></td></tr><tr><td>pyridine</td><td>MilliporeSigma</td><td>PX2012-7</td><td></td></tr><tr><td>toluene</td><td>SIAL</td><td>244511</td><td></td></tr><tr><td>1-hexanol</td><td>SIAL</td><td>471402</td><td></td></tr><tr><td>N8 Horizon SAXS</td><td>Bruker</td><td>A32-X1</td><td></td></tr><tr><td>glovebox</td><td>Vaccum Atmospheres Co.</td><td>109035</td><td></td></tr><tr><td>MR HEI-TEC 115V Hotplate</td><td>Heidolph</td><td>5053000000</td><td></td></tr><tr><td>hotplate Monoblock insert</td><td>Heidolph</td><td>5058000800</td><td></td></tr><tr><td>heat-On 25-ml insert</td><td>Heidolph</td><td>5058006200</td><td></td></tr><tr><td>7 mL vials</td><td>SUPELCO</td><td>27518</td><td></td></tr><tr><td>micro stir bar PTFE&amp;nbsp;</td><td>VWR</td><td>58948-353</td><td></td></tr><tr><td>egg-Shaped Bars&amp;nbsp;</td><td>Fisherbrand&amp;trade;&amp;nbsp;</td><td>14-512-121</td><td></td></tr><tr><td>25 mL round bottom flasks</td><td>ALDRICH</td><td>Z167495</td><td></td></tr><tr><td>quartz capillary</td><td>Hampton Research</td><td>HR6-148</td><td></td></tr><tr><td>MATLAB R2016b</td><td>MathWorks</td><td></td><td></td></tr><tr><td>Bruker SAXS 1.0v</td><td>Bruker</td><td></td><td></td></tr><tr><td>Diffrac Measurement Center 4.0v</td><td>Bruker</td><td></td><td></td></tr></tbody></table>

ligand-mediated nucleation and growth of palladium metal nanoparticles

Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles

The size, size distribution and stability of colloidal nanoparticles are greatly affected by the presence of capping ligands. Despite the key contribution of capping ligands during the synthesis reaction, their role in regulating the nucleation and growth rates of colloidal nanoparticles is not well understood. In this work, we demonstrate a mechanistic investigation of the role of trioctylphosphine (TOP) in Pd nanoparticles in different solvents (toluene and pyridine) using in situ SAXS and ligand-based kinetic modeling. Our results under different synthetic conditions reveal the overlap of nucleation and growth of Pd nanoparticles during the reaction, which contradicts the LaMer-type nucleation and growth model. The model accounts for the kinetics of Pd-TOP binding for both, the precursor and the particle surface, which is essential to capture the size evolution as well as the concentration of particles in situ. In addition, we illustrate the predictive power of our ligand-based model through designing the synthetic conditions to obtain nanoparticles with desired sizes. The proposed methodology can be applied to other synthesis systems and therefore serves as an effective strategy for predictive synthesis of colloidal nanoparticles.

To systematically examine whether the capping ligands alter the kinetics of nucleation and growth, we took the two following approaches: (i) the binding of the ligand with the metal was not considered in the kinetic model similar to previous studies (i.e., the nucleation and autocatalytic growth) (ii) the reversible binding of capping ligand with the precursor and surface of the nanoparticle was taken into account in the model (i.e., ligand-based model described in Proto...

The main goal of this work is to elucidate the role of capping agents in regulating the size of palladium nanoparticles by combining in situ small angle x-ray scattering (SAXS) and ligand-based kinetic modeling.

The size, size distribution and stability of colloidal nanoparticles are greatly affected by the presence of capping ligands. Despite the key contribution ...

ligand-mediated-nucleation-and-growth-of-palladium-metal-nanoparticles

Research

JoVE Journal

Chemistry

Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1) is an easy accessible, cheap, and air stable, but highly active Heck catalyst with an excellent functional group tolerance that efficiently operates under mild reaction conditions to give the coupling products in very high yields.

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions

Because of the importance and extensive use of palladium, gold and cobalt metals in high-technology equipment, their recovery and recycling constitute an important industrial challenge. The metal recovery system described herein is a simple, low-cost means for the effective detection, removal, and recovery of these metals from the urban mine.

Detection and Recovery of Palladium, Gold and Cobalt Metals from the Urban Mine Using Novel Sensors/Adsorbents Designated with Nanoscale Wagon-wheel-shaped Pores

A novel method for metal core nanoparticle synthesis using a water stable silanol is described.

Generation of Zerovalent Metal Core Nanoparticles Using n-(2-aminoethyl)-3-aminosilanetriol

A protocol for the synthesis of bimetallic nanoparticles in ionic liquids and the procedure of their catalytic testing in the selective hydrogenation of unsaturated aldehydes are described.

Synthesis of Bimetallic Pt/Sn-based Nanoparticles in Ionic Liquids

For a continuous and scalable synthesis of noble-metal-based nanocomposites, a novel photocatalytic reactor is developed and its structure, operation principles, and product quality optimization strategies are described.

A Continuous-flow Photocatalytic Reactor for the Precisely Controlled Deposition of Metallic Nanoparticles

A synthesis method for cellulose nanofiber biotemplated palladium composite aerogels is presented.The resulting composite aerogel materials offer potential for catalysis, sensing, and hydrogen gas storage applications.

Synthesis Method for Cellulose Nanofiber Biotemplated Palladium Composite Aerogels

A protocol for anisotropic photodeposition of Pd onto aqueously-suspended Au nanorods via localized surface plasmon excitation is presented.

Photodeposition of Pd onto Colloidal Au Nanorods by Surface Plasmon Excitation

Presented here is a protocol for the synthesis of silver-palladium (Ag-Pd) alloy nanoparticles (NPs) supported on ZrO2 (Ag-Pd/ZrO2). This system allows for harvesting energy from visible light irradiation to accelerate and control molecular transformations. This is illustrated by nitrobenzene reduction under light irradiation catalyzed by Ag-Pd/ZrO2 NPs.

Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination

Temperature control during liquid-phase electron microscopy experiments opens up new perspectives of studying the dynamic of nanoparticles in liquid environments mimicking their formation or application media. Using recently developed heating liquid cells, we directly observed the influence of temperature on the nucleation and growth processes of gold nanoparticles in water.

Studying the Effects of Temperature on the Nucleation and Growth of Nanoparticles by Liquid-Cell Transmission Electron Microscopy

This protocol shows a convenient method for comparing the catalytic properties of supported platinum catalysts, synthesized by deposition of nanosized colloids or by impregnation. The hydrogenation of cyclohexene serves as a model reaction to determine the catalytic activity of the catalysts.

Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes

Discover ligand-mediated nucleation and growth of palladium nanoparticles using in situ SAXS and kinetic modeling. This method enables predictive synthesis of size-controlled colloidal metal nanoparticles for catalysis applications.

Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles

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