A Versatile Approach to the Synthesis of Functionalized Thiol-Protected Palladium Nanoparticles

Cargnello, Matteo; Wieder, Noah L.; Canton, Patrizia; Montini, Tiziano; Giambastiani, Giuliano; Benedetti, Alvise; Gorte, Raymond J.; Fornasiero, Paolo

doi:10.1021/cm2014658

Cited by 96 publications

(97 citation statements)

References 37 publications

(72 reference statements)

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“…[39] In a typical synthesis, Pd(OAC) 2 (0.2 mmol) and TOAB (0.4 mmol) were mixed and dissolved in THF (15 mL). After stirring for 20 mins, 4-tert-butylbenzenethiol (0.2 mmol) was added to the above orange solution and the mixture was stirred for another 30 min.…”

Section: Synthesis Of Ultrasmall Thiolate-protected Palladium Nanoclumentioning

confidence: 99%

Ultrasmall Palladium Nanoclusters as Effective Catalyst for Oxygen Reduction Reaction

et al. 2016

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The recent prosperity of ultrasmall gold nanoclusters makes it desirable to expand the family of clusters to other metals. Here, we present a one‐phase approach for synthesizing thiolate‐protected palladium nanoclusters with a mass of approximately 5 kDa. Such nanoclusters are further evaluated for the oxygen reduction reaction in alkaline solutions. Ligand‐on palladium nanoclusters exhibit an onset potential of −0.09 V (vs. Ag/AgCl) and superior durability in open air. With ligands removed, the palladium nanoclusters display an onset potential of −0.02 V and a higher mass activity (272.4 A g−1 at the potential of −0.15 V) than that of Pt/C (166.6 A g−1). Kinetic investigation indicates a direct four‐electron reduction pathway over palladium nanoclusters, which is preferred in oxygen reduction, owing to enhanced power generation. The efficient catalytic performance of palladium nanoclusters makes them an excellent candidate as electrocatalysts in fuel cell technology.

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Section: Synthesis Of Ultrasmall Thiolate-protected Palladium Nanoclumentioning

confidence: 99%

Ultrasmall Palladium Nanoclusters as Effective Catalyst for Oxygen Reduction Reaction

et al. 2016

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“…Finally, in a study of 11-mercaptoundecanoic acid-protected palladium nanoparticles by HRTEM, Cargnello et al 24 found that the crystallinity of the nanoparticles strongly depends on the temperature during the synthesis. It was observed that the lower the temperature used, the greater the crystallinity of the nanoparticles.…”

Section: ■ Introductionmentioning

confidence: 99%

Influence of Capping on the Atomistic Arrangement in Palladium Nanoparticles at Room Temperature

et al. 2014

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The role that protecting molecules have on the way that palladium atoms arrange themselves in nanoparticles prepared at room temperature was studied by the analysis of aberration-corrected scanning transmission electron microscopy images and atomistic Langevin dynamics simulations. It was found that the arrangement of Pd atoms is less ordered in thiolate-protected nanoparticles than in amine-protected ones. The experimental and theoretical data showed that the disorder in ∼3 nm thiolate-protected particles is promoted by the strong S−Pd bond in the sulfide layer that surrounds the nanoparticles. ■ INTRODUCTIONThe unique properties of thiolate self-assembled monolayers (SAMs) have provoked great interest in these assemblies, especially for their role in the stability and interfacial properties of thiolate-protected noble-metal nanoparticles (NPs).1,2 Gold nanoparticles are among the most studied metal nanoparticles, to the point of being considered the de facto model system in this field of research.3,4 However, some properties of other metals can be very different from those of gold, and the case of palladium is an example that fulfills this statement. For instance, the adsorption of alkanethiols on planar palladium surfaces produces a sulfide layer (with submonolayer coverage) lying at the interface between palladium and thiolate moieties. 5−7Density functional theory (DFT) calculations show that the sulfide layer comes from the S−C bond scission caused by a charge transfer from the palladium d band to antibonding thiolate orbitals. 7 In addition, it was recently shown that the chemical composition of the surface of alkanethiolate-protected palladium nanoparticles is very similar to that of alkanethiolatemodified bulk palladium: Pd(0) cores are surrounded by a submonolayer of sulfide species, which are protected by alkanethiolates. 8−10 Despite the fact that these particles have very interesting properties that can be exploited in catalysis 11 and sensing, 12 their detailed structure has been barely studied. Indeed, even in recent studies, the already known 5,8 chemical nature of the Pd−thiolate interface is ignored. 11−14It is well-known that thiolate species produce a reconstruction of the gold surface both in planar substrates 15 and in nanoparticles. 16 Results from molecular simulations suggest that the influence of the capping molecule can also reach deeper atomic layers in gold nanoparticles smaller than 2 nm. 17,18 In the case of planar palladium, DFT calculations show that when only thiolates are adsorbed on the surface, there is no reordering of the metal atoms in the first layers; 7,13 however, when sulfide is incorporated as an adsorbate, a considerable surface reconstruction takes place. This behavior is attributed to

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“…[28][29][30]41 Most of these studies were oriented toward catalytic applications [42][43][44] and sensor devices. 45,46 The direct reduction route that was developed in this study makes use of biocompatible molecules (AA DMSA), enabling the synthesis of Pd and Pd@Au NPs.…”

Section: Resultsmentioning

confidence: 99%

Rapid, one-pot procedure to synthesise¹⁰³Pd:Pd@Au nanoparticles en route for radiosensitisation and radiotherapeutic applications

et al. 2015

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ARTICLEThis journal is © The Royal Society of Chemistry 2013 J. Name., 2013, 00, 1--3 | 1 The radioisotope palladium ( 103 Pd), encapsulated in millimetre-size seed implants, is widely used in prostate cancer brachytherapy. Gold nanoparticles (Au NPs) distributed in the vicinity of 103 Pd radioactive implants, strongly enhance the therapeutic dose of radioactive implants (radiosensitisation effect). A new strategy under development to replace millimetre-size implants, consist in injecting radioactive NPs in the affected tissues. The development of 103 Pd@Au NPs distributed in the diseased tissue, could increase the uniformity of treatment (compared with massive seeds), while enhancing the radiotherapeutic dose to the cancer cells (through Au-mediated radiosensitisation effect). To achieve this goal, it is necessary to develop a rapid, efficient, one-pot and easy-to-automatise procedure, allowing the synthesis of coreshell Pd@Au NPs. The novel synthesis route proposed here enables the production of Pd@Au NPs in not more than 4h, in aqueous media, with minimal manipulations, and relying on biocompatible and non-toxic molecules. This rapid multi-step process consists of the preparation of ultra-small Pd NPs by chemical reduction of an aqueous solution of H 2 PdCl 4 supplemented with ascorbic acid (AA) as reducing agent and 2, 3-meso-dimercaptosuccinic acid (DMSA) as a capping agent. Pd conversion yields close to 87% were found, indicating the efficiency of the reaction process. Then Pd NPs were used as seeds for the growth of a gold shell (Pd@Au), followed by grafting with polyethylene glycol (PEG) to ensure colloidal stability. Pd@Au-PEG (TEM: 20.2 ± 12.1 nm) formed very stable colloids in saline solution as well as in cell culture medium. The physico-chemical properties of the particles were characterised by FTIR, XPS, and UV-vis. spectroscopies. The viability of PC3 human prostate cancer cells was not affected after a 24-h incubation cycle with Pd@Au-PEG NPs to concentrations up to 4.22 mM Au. Finally, suspensions of Pd@Au-PEG NPs measured in computed tomography (CT) are found to attenuate X-rays more efficiently than commercial Au NPs CT contrast media. A proof-of-concept was performed to demonstrate the possibility synthesise radioactive 103 Pd:Pd@Au-PEG NPs. This study reveals the possibility to synthesise Pd@Au NPs rapidly (including radioactive 103 Pd:Pd@Au-PEG NPs), and following a methodology that respects all the strict requirements underlying the production of NPs for radiotherapeutic use (rapidity, reaction yield, colloidal stability, NPs concentration, purification). Journal of Materials Chemistry B RSCPublishing ARTICLEThis journal is

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A Versatile Approach to the Synthesis of Functionalized Thiol-Protected Palladium Nanoparticles

Cited by 96 publications

References 37 publications

Ultrasmall Palladium Nanoclusters as Effective Catalyst for Oxygen Reduction Reaction

Ultrasmall Palladium Nanoclusters as Effective Catalyst for Oxygen Reduction Reaction

Influence of Capping on the Atomistic Arrangement in Palladium Nanoparticles at Room Temperature

Rapid, one-pot procedure to synthesise¹⁰³Pd:Pd@Au nanoparticles en route for radiosensitisation and radiotherapeutic applications

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A Versatile Approach to the Synthesis of Functionalized Thiol-Protected Palladium Nanoparticles

Cited by 96 publications

References 37 publications

Ultrasmall Palladium Nanoclusters as Effective Catalyst for Oxygen Reduction Reaction

Ultrasmall Palladium Nanoclusters as Effective Catalyst for Oxygen Reduction Reaction

Influence of Capping on the Atomistic Arrangement in Palladium Nanoparticles at Room Temperature

Rapid, one-pot procedure to synthesise103Pd:Pd@Au nanoparticles en route for radiosensitisation and radiotherapeutic applications

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Rapid, one-pot procedure to synthesise¹⁰³Pd:Pd@Au nanoparticles en route for radiosensitisation and radiotherapeutic applications