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.

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

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...

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Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles

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 ...

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10.3K Views.  Virginia Polytechnic Institute and State University. 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.

Video: Ligand-Mediated Nucleation and Growth of Palladium Metal Nanoparticles

A Technique to Functionalize and Self-assemble Macroscopic Nanoparticle-ligand Monolayer Films onto Template-free Substrates

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and scalable technique efficiently functionalizes metallic nanoparticles with thiol-ligands in a miscible water/organic solvent mixture allowing for rapid grafting of thiol groups onto the gold nanoparticle surface. The hydrophobic ligands on the nanoparticles then quickly phase separate the nanoparticles from the aqueous based suspension and confine them to the air-fluid interface. This drives the ligand-capped nanoparticles to form monolayer domains at the air-fluid interface.&#160; The use of water-miscible organic solvents is important as it enables the transport of the nanoparticles from the interface onto template-free substrates.&#160; The flow is mediated by a surface tension gradient3,4 and creates macroscopic, high-density, monolayer nanoparticle-ligand films.&#160; This self-assembly technique may be generalized to include the use of particles of different compositions, size, and shape and may lead to an efficient assembly method to produce low-cost, macroscopic, high-density, monolayer nanoparticle films for wide-spread applications.

A simple, robust and scalable technique to functionalize and self-assemble macroscopic nanoparticle-ligand monolayer films onto template-free substrates is described in this protocol.

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and ...

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

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family of easy accessible, very cheap, and air stable, but highly active and universally applicable C-C cross-coupling catalysts with an excellent functional group tolerance. Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1), the least stable complex within this series towards protons; e.g. in the form of water, allows an eased nanoparticle formation and hence, proved to be the most active Heck catalyst within this series at 100 &#176;C and is a very rare example of an effective and versatile catalyst system that efficiently operates under mild reaction conditions. Rapid and complete catalyst degradation under work-up conditions into phosphonates, piperidinium salts and other, palladium-containing decomposition products assure an easy separation of the coupling products from catalyst and ligands. The facile, cheap, and rapid synthesis of 1,1',1"-(phosphinetriyl)tripiperidine and 1 respectively, the simple and convenient use as well as its excellent catalytic performance in the Heck reaction at 100 &#176;C make 1 to one of the most attractive and greenest Heck catalysts available.
We provide here the visualized protocols for the ligand and catalyst syntheses as well as the reaction protocol for Heck reactions performed at 10 mmol scale at 100 &#176;C and show that this catalyst is suitable for its use in organic syntheses.

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

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.

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family ...

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

In this work, a facile one-pot reaction for the formation of metal nanoparticles in a water solution through the use of n-(2-aminoethyl)-3-aminosilanetriol is presented. This compound can be used to effectively reduce and complex metal salts into metal core nanoparticles coated with the compound. By controlling the concentrations of salt and silane one is able to control reaction rates, particle size, and nanoparticle coating. The effects of these changes were characterized through transmission electron microscopy (TEM), UV-Vis spectrometry (UV-Vis), Nuclear Magnetic Resonance spectroscopy (NMR) and Fourier Transform Infrared spectroscopy (FTIR). A unique aspect to this reaction is that usually silanes hydrolyze and cross-link in water; however, in this system the silane is water-soluble and stable. It is known that silicon and amino moieties can form complexes with metal salts. The silicon is known to extend its coordination sphere to form penta- or hexa-coordinated species. Furthermore, the silanol group can undergo hydrolysis to form a Si-O-Si silica network, thereby transforming the metal nanoparticles into a functionalized nanocomposites.

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

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

In this work, a facile one-pot reaction for the formation of metal nanoparticles in a water solution through the use of ...

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

We demonstrate a method for the synthesis of bimetallic nanoparticles consisting of Pt and Sn. A synthesis strategy is used in which the particular physico-chemical properties of ionic liquids (ILs) are exploited to control both nucleation and growth processes. The nanoparticles form colloidal sols of very high colloidal stability in the IL, which is particularly interesting in view of their use as quasi-homogeneous catalysts. Procedures for both nanoparticle extraction in conventional solvents and for nanoparticle precipitation are presented. The size, structure and composition of the synthesized nanocrystals are confirmed using inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM) with energy-dispersive X-ray spectroscopy (EDX). By this, we show that the nanocrystals are random-type alloy and of small (2-3 nm) size. The catalytic activity and selectivity in the hydrogenation of &#945;,&#946;-unsaturated aldehydes is tested in a semi-continuous batch-type reactor. In this context, the bimetallic Pt/Sn-based nanoparticles reveal a high selectivity towards the unsaturated alcohol.

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.

We demonstrate a method for the synthesis of bimetallic nanoparticles consisting of Pt and Sn. A synthesis strategy is used in which the particular ...

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

In this work, a novel photocatalytic reactor for the pulsed and controlled excitation of the photocatalyst and the precise deposition of metallic nanoparticles is developed. Guidelines for the replication of the reactor and its operation are provided in detail. Three different composite systems (Pt/graphene, Pt/TiO2, and Au/TiO2) with monodisperse and uniformly distributed particles are produced by this reactor, and the photodeposition mechanism, as well as the synthesis optimization strategy, are discussed. The synthesis methods and their technical aspects are described comprehensively. The role of the ultraviolet (UV) dose (in each excitation pulse) on the photodeposition process is investigated and the optimum values for each composite system are provided.

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.

In this work, a novel photocatalytic reactor for the pulsed and controlled excitation of the photocatalyst and the precise deposition of metallic ...

Synthesis Method for Cellulose Nanofiber Biotemplated Palladium Composite Aerogels

Here, a method to synthesize cellulose nanofiber biotemplated palladium composite aerogels is presented. Noble metal aerogel synthesis methods often result in fragile aerogels with poor shape control. The use of carboxymethylated cellulose nanofibers (CNFs) to form a covalently bonded hydrogel allows for the reduction of metal ions such as palladium on the CNFs with control over both nanostructure and macroscopic aerogel monolith shape after supercritical drying. Crosslinking the carboxymethylated cellulose nanofibers is achieved using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) in the presence of ethylenediamine. The CNF hydrogels maintain their shape throughout synthesis steps including covalent crosslinking, equilibration with precursor ions, metal reduction with high concentration reducing agent, rinsing in water, ethanol solvent exchange, and CO2 supercritical drying. Varying the precursor palladium ion concentration allows for control over the metal content in the final aerogel composite through a direct ion chemical reduction rather than relying on the relatively slow coalescence of pre-formed nanoparticles used in other sol-gel techniques. With diffusion as the basis to introduce and remove chemical species into and out of the hydrogel, this method is suitable for smaller bulk geometries and thin films. Characterization of the cellulose nanofiber-palladium composite aerogels with scanning electron microscopy, X-ray diffractometry, thermal gravimetric analysis, nitrogen gas adsorption, electrochemical impedance spectroscopy, and cyclic voltammetry indicates a high surface area, metallized palladium porous structure.

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.

Here, a method to synthesize cellulose nanofiber biotemplated palladium composite aerogels is presented. Noble metal aerogel synthesis methods often ...

Photodeposition of Pd onto Colloidal Au Nanorods by Surface Plasmon Excitation

A protocol is described to photocatalytically guide Pd deposition onto Au nanorods (AuNR) using surface plasmon resonance (SPR). Excited plasmonic hot electrons upon SPR irradiation drive reductive deposition of Pd on colloidal AuNR in the presence of [PdCl4]2-. Plasmon-driven reduction of secondary metals potentiates covalent, sub-wavelength deposition at targeted locations coinciding with electric field &#8220;hot-spots&#8221; of the plasmonic substrate using an external field (e.g., laser). The process described herein details a solution-phase deposition of a catalytically-active noble metal (Pd) from a transition metal halide salt (H2PdCl4) onto aqueously-suspended, anisotropic plasmonic structures (AuNR). The solution-phase process is amenable to making other bimetallic architectures. Transmission UV-vis monitoring of the photochemical reaction, coupled with ex situ XPS and statistical TEM analysis, provide immediate experimental feedback to evaluate properties of the bimetallic structures as they evolve during the photocatalytic reaction. Resonant plasmon irradiation of AuNR in the presence of [PdCl4]2- creates a thin, covalently-bound Pd0 shell without any significant dampening effect on its plasmonic behavior in this representative experiment/batch. Overall, plasmonic photodeposition offers an alternative route for high-volume, economical synthesis of optoelectronic materials with sub-5 nm features (e.g., heterometallic photocatalysts or optoelectronic interconnects).

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

A protocol is described to photocatalytically guide Pd deposition onto Au nanorods (AuNR) using surface plasmon resonance (SPR). Excited plasmonic hot ...

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

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles (NPs) can accelerate and control the selectivity of a variety of molecular transformations. This opens possibilities for the use of visible or near-IR light as a sustainable input to drive and control reactions when plasmonic nanoparticles supporting LSPR excitation in these ranges are employed as catalysts. Unfortunately, this is not the case for several catalytic metals such as palladium (Pd). One strategy to overcome this limitation is to employ bimetallic NPs containing plasmonic and catalytic metals. In this case, the LSPR excitation in the plasmonic metal can contribute to accelerate and control transformations driven by the catalytic component. The method reported herein focuses on the synthesis of bimetallic silver-palladium (Ag-Pd) NPs supported on ZrO2 (Ag-Pd/ZrO2) that acts as a plasmonic-catalytic system. The NPs were prepared by co-impregnation of corresponding metal precursors on the ZrO2 support followed by simultaneous reduction leading to the formation of bimetallic NPs directly on the ZrO2 support. The Ag-Pd/ZrO2 NPs were then used as plasmonic catalysts for the reduction of nitrobenzene under 425 nm illumination by LED lamps. Using gas chromatography (GC), the conversion and selectivity of the reduction reaction under the dark and light irradiation conditions can be monitored, demonstrating the enhanced catalytic performance and control over selectivity under LSPR excitation after alloying non-plasmonic Pd with plasmonic metal Ag. This technique can be adapted to a wide range of molecular transformations and NPs compositions, making it useful for the characterization of the plasmonic catalytic activity of different types of catalysis in terms of conversion and selectivity.

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.

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles (NPs) can accelerate and control the selectivity of a variety of molecular ...

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

Temperature control is a recent development that provides an additional degree of freedom to study nanochemistry by liquid cell transmission electron microscopy. In this paper, we describe how to prepare an in situ heating experiment for studying the effect of temperature on the formation of gold nanoparticles driven by radiolysis in water. The protocol of the experiment is fairly simple involving a special liquid cell with uniform heating capabilities up to 100 &#176;C, a liquid-cell TEM holder with flow capabilities and an integrated interface for controlling the temperature. We show that the nucleation and growth mechanisms of gold nanoparticles are drastically impacted by the temperature in liquid cell. Using STEM imaging and nanodiffraction, the evolution of the density, size, shape and atomic structure of the growing nanoparticles are revealed in real time. Automated image processing algorithms are exploited to extract useful quantitative data from video sequences, such as the nucleation and growth rates of nanoparticles. This approach provides new inputs for understanding the complex physico-chemical processes at play during the liquid-phase synthesis of nanomaterials.

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.

Temperature control is a recent development that provides an additional degree of freedom to study nanochemistry by liquid cell transmission electron ...

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

Ligands like amines are used in the colloidal synthesis approach to protect platinum nanoparticles (Pt NP&#39;s) from agglomeration. Normally, ligands like amines are removed by diverse pre-treatment procedures before use in heterogeneous catalysis as amines are considered as a catalyst poison. However, a possible beneficial influence of these surface modifiers on hydrogenation reactions, which is known from spectator species on metal surfaces, is often neglected.
Therefore, amine-stabilized Pt nanoparticles supported by titania (P25) were used without any pre-treatment in order to elucidate a possible influence of the ligand in liquid phase hydrogenation reactions. The catalytic activity of amine-stabilized Pt nanoparticles of two different sizes was investigated in a double-walled stirring tank reactor at 69 &#176;C to 130 &#176;C and 1 atm hydrogen pressure. The conversion of cyclohexene to cyclohexane was determined by gas chromatography (GC) and was compared to ligand-free Pt particles. All catalysts were checked before and after reaction by transmission electron spectroscopy (TEM) and X-ray photoelectron spectroscopy (XPS) for possible changes in size, shape, and ligand shell. The hydrogenation of cyclohexene in liquid phase revealed a higher conversion for amine-stabilized Pt nanoparticles on titania than the ligand-free particles. The hydrogenation of 5-methylfurfural (5-MF) was chosen for a further test reaction, since the hydrogenation of &#945;, &#946;-unsaturated aldehydes is more complex and exhibits various reaction paths. However, XPS and infrared spectroscopy (IR) proved that 5-MF acts as catalyst poison at the given reaction conditions.

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.

Ligands like amines are used in the colloidal synthesis approach to protect platinum nanoparticles (Pt NP&#39;s) from agglomeration. Normally, ligands ...