Polychromatic neutron phase-contrast imaging of weakly absorbing samples enabled by phase retrieval.

The use of a phase-retrieval technique for propagation-based phase-contrast neutron imaging with a polychromatic beam is demonstrated. This enables imaging of samples with low absorption contrast and/or improving the signal-to-noise ratio to facilitate e.g. time-resolved measurements. A metal sample, designed to be close to a phase pure object, and a bone sample with canals partially filled with D2O were used for demonstrating the technique. These samples were imaged with a polychromatic neutron beam followed by phase retrieval. For both samples the signal-to-noise ratios were significantly improved and, in the case of the bone sample, the phase retrieval allowed for separation of bone and D2O, which is important for example for in situ flow experiments. The use of deuteration contrast avoids the use of chemical contrast enhancement and makes neutron imaging an interesting complementary method to X-ray imaging of bone.

Surfactant-Free Colloidal Syntheses of Gold-Based Nanomaterials in Alkaline Water and Mono-alcohol Mixtures.

Gold nanoparticles (Au NPs) and gold-based nanomaterials combine unique properties relevant for medicine, imaging, optics, sensing, catalysis, and energy conversion. While the Turkevich-Frens and Brust-Schiffrin methods remain the state-of-the-art colloidal syntheses of Au NPs, there is a need for more sustainable and tractable synthetic strategies leading to new model systems. In particular, stabilizers are almost systematically used in colloidal syntheses, but they can be detrimental for fundamental and applied studies. Here, a surfactant-free synthesis of size-controlled colloidal Au NPs stable for months is achieved by the simple reduction of HAuCl4 at room temperature in alkaline solutions of low-viscosity mono-alcohols such as ethanol or methanol and water, without the need for any other additives. Palladium (Pd) and bimetallic Au x Pd y NPs, nanocomposites and multimetallic samples, are also obtained and are readily active (electro)catalysts. The multiple benefits over the state-of-the-art syntheses that this simple synthesis bears for fundamental and applied research are highlighted.

Chemical Insights into the Formation of Colloidal Iridium Nanoparticles from In Situ X-ray Total Scattering: Influence of Precursors and Cations on the Reaction Pathway.

Iridium nanoparticles are important catalysts for several chemical and energy conversion reactions. Studies of iridium nanoparticles have also been a key for the development of kinetic models of nanomaterial formation. However, compared to other metals such as gold or platinum, knowledge on the nature of prenucleation species and structural insights into the resultant nanoparticles are missing, especially for nanoparticles obtained from IrxCly precursors investigated here. We use in situ X-ray total scattering (TS) experiments with pair distribution function (PDF) analysis to study a simple, surfactant-free synthesis of colloidal iridium nanoparticles. The reaction is performed in methanol at 50 °C with only a base and an iridium salt as precursor. From different precursor salts─IrCl3, IrCl4, H2IrCl6, or Na2IrCl6─colloidal nanoparticles as small as Ir∼55 are obtained as the final product. The nanoparticles do not show the bulk iridium face-centered cubic (fcc) structure but show decahedral and icosahedral structures. The formation route is highly dependent on the precursor salt used. Using IrCl3 or IrCl4, metallic iridium nanoparticles form rapidly from IrxClyn- complexes, whereas using H2IrCl6 or Na2IrCl6, the iridium nanoparticle formation follows a sudden growth after an induction period and the brief appearance of a crystalline phase. With H2IrCl6, the formation of different Irn (n = 55, 55, 85, and 116) nanoparticles depends on the nature of the cation in the base (LiOH, NaOH, KOH, or CsOH, respectively) and larger particles are obtained with larger cations. As the particles grow, the nanoparticle structure changes from partly icosahedral to decahedral. The results show that the synthesis of iridium nanoparticles from IrxCly is a valuable iridium nanoparticle model system, which can provide new compositional and structural insights into iridium nanoparticle formation and growth.

Surfactant-free syntheses and pair distribution function analysis of osmium nanoparticles.

A surfactant-free synthesis of precious metal nanoparticles (NPs) performed in alkaline low-boiling-point solvents has been recently reported. Monoalcohols are here investigated as solvents and reducing agents to obtain colloidal Os nanoparticles by using low-temperature (<100 °C) surfactant-free syntheses. The effect of the precursor (OsCl3 or H2OsCl6), precursor concentration (up to 100 mM), solvent (methanol or ethanol), presence or absence of a base (NaOH), and addition of water (0 to 100 vol %) on the resulting nanomaterials is discussed. It is found that no base is required to obtain Os nanoparticles as opposed to the case of Pt or Ir NPs. The robustness of the synthesis for a precursor concentration up to 100 mM allows for the performance of X-ray total scattering with pair distribution function (PDF) analysis, which shows that 1-2 nm hexagonal close packed (hcp) NPs are formed from chain-like [OsO x Cl y ] complexes.

Solvent-Dependent Growth and Stabilization Mechanisms of Surfactant-Free Colloidal Pt Nanoparticles.

Understanding the formation of nanoparticles (NPs) is key to develop materials by sustainable routes. The Co4CatTM process is a new synthesis of precious metal NPs in alkaline mono-alcohols well-suited to develop active nanocatalysts. The synthesis is 'facile', surfactant-free and performed under mild conditions like low temperature. The reducing properties of the solvent are here shown to strongly influence the formation of Pt NPs. Based on the in situ formation of CO adsorbed on the NP surface by solvent oxidation, a model is proposed that accounts for the different growth and stabilization mechanisms as well as re-dispersion properties of the surfactant-free NPs in different solvents. Using in situ and ex situ characterizations, it is established that in methanol, a slow nucleation with a limited NP growth is achieved. In ethanol, a fast nucleation followed by continuous and pronounced particle sintering occurs.

UV-induced syntheses of surfactant-free precious metal nanoparticles in alkaline methanol and ethanol.

Surfactant-free UV-induced syntheses of Pt and Ir nanoparticles in alkaline methanol and ethanol are presented. Small size nanoparticles ca. 2 nm in diameter are obtained without surfactants in a wide range of base concentration.

Controlled Synthesis of Surfactant-Free Water-Dispersible Colloidal Platinum Nanoparticles by the Co4Cat Process.

The recently reported Co4Cat process is a synthesis method bearing ecological and economic benefits to prepare precious-metal nanoparticles (NPs) with optimized catalytic properties. In the Co4Cat process, a metal precursor (e.g., H2 PtCl6 ) is dissolved in an alkaline solution of a low-boiling-point solvent (methanol) and reduced to NPs at low temperature (<80 °C) without the use of surfactants. Here, the Co4Cat process to prepare Pt NPs is described in detail. The advantages of this new synthesis method for research and development but also industrial production are highlighted in a comparison with the popular "polyol" synthesis. The reduction of H2 PtCl6 from PtIV to PtII and further to Pt0 is followed by UV/Vis and XANES/EXAFS measurements. It is demonstrated how the synthesis can be accelerated, how size control is achieved, and how the colloidal dispersions can be stabilized without the use of surfactants. Despite being surfactant-free, the Pt NPs exhibit surprisingly long-term (up to 16 months) stability in water over a wide pH range (4-12) and in aqueous buffer solutions. The Co4Cat process is thus relevant to produce NPs for heterogeneous catalysis, electro-catalysis, or bio/medical applications.

Colloids for Catalysts: A Concept for the Preparation of Superior Catalysts of Industrial Relevance.

Compared to conventional preparation methods for supported heterogeneous catalysts, the use of colloidal nanoparticles (NPs) allows for a precise control over size, size distribution, and distribution/location of the NPs on the support. However, common colloidal syntheses have restrictions that limit their applicability for industrial catalyst preparation. We present a simple, surfactant-free, and scalable preparation method for colloidal NPs to overcome these restrictions. We demonstrate how precious-metal NPs are prepared in alkaline methanol, how the particle size can be tuned, and how supported catalysts are obtained. The potential of these colloids in the preparation of improved catalysts is demonstrated by two examples from heterogeneous catalysis and electrocatalysis.

Flexible sample environment for high resolution neutron imaging at high temperatures in controlled atmosphere.

High material penetration by neutrons allows for experiments using sophisticated sample environments providing complex conditions. Thus, neutron imaging holds potential for performing in situ nondestructive measurements on large samples or even full technological systems, which are not possible with any other technique. This paper presents a new sample environment for in situ high resolution neutron imaging experiments at temperatures from room temperature up to 1100 °C and/or using controllable flow of reactive atmospheres. The design also offers the possibility to directly combine imaging with diffraction measurements. Design, special features, and specification of the furnace are described. In addition, examples of experiments successfully performed at various neutron facilities with the furnace, as well as examples of possible applications are presented. This covers a broad field of research from fundamental to technological investigations of various types of materials and components.