Sub-millisecond microfluidic mixers coupled to time-resolved in situ photonics to study ultra-fast reaction kinetics: the case of ultra-small gold nanoparticle synthesis.

We report a continuous microreactor platform achieving sub-millisecond homogeneous reagent mixing (∼300 µs) for a time-resolved study on the synthesis of ultra-small gold nanoparticles (NPs). The microreactor (coupled with small angle X-ray scattering, UV-vis, and X-ray absorption spectroscopy for in situ and in operando characterizations), operates within mixing time frames below system characteristic times, providing a unique opportunity to deepen the comprehension of reaction and phase transition pathways with unprecedented details. The microreactor channel length can be approximated to a given reaction time when operated in continuous mode and steady state. As a result, the system can be statically investigated, eliminating technique-dependent probing time constraints and local inhomogeneities caused by mixing issues. We have studied Au(0) NP formation kinetics from Au(III) precursors complexed with oleylamine in organic media, using triisopropylsilane as a reducing agent. The existence of Au(III)/Au(I) prenucleation clusters and the formation of a transient Au(I) lamellar phase under certain conditions, before the onset of Au(0) formation, have been observed. Taking advantage of the high frequency time-resolved information, we propose and model two different reaction pathways associated with the presence or absence of the Au(I) lamellar phase. In both cases, non-classical pathways leading to the formation of NPs are discussed.

Magnetically Induced CO2 Methanation In Continuous Flow Over Supported Nickel Catalysts with Improved Energy Efficiency.

A new selective and efficient catalytic system for magnetically induced catalytic CO2 methanation was developed, composed of an abundant iron-based heating agent, namely a commercial iron wool, combined with supported Nickel nanoparticles (Ni NPs) as catalysts. The effect of metal oxide support was evaluated by preparing different 10 wt % Ni catalyst (TiO2 , ZrO2 , CeO2 , and CeZrO2 ) via organometallic decomposition route. As-prepared catalysts were thoroughly characterized using powder X-ray diffraction, electron microscopy, elemental analysis, vibrating sample magnetometer, and X-ray photoelectron spectroscopy techniques. High conversion and selectivity toward methane were observed at mid-temperature range, hence improving energy efficiency of the process with respect to the previous results under magnetic heating conditions. To gain further insight into the catalytic system, the effects of the synthesis method and of 0.5 wt % Ru doping were evaluated. Finally, the dynamic nature of magnetically induced heating was demonstrated through fast stop-and-go experiments, proving the suitability of this technology for the storage of intermittent renewable energy through P2G process.

Growth and analysis of the tetragonal (ST12) germanium nanowires.

New semiconducting materials, such as state-of-the-art alloys, engineered composites and allotropes of well-established materials can demonstrate unique physical properties and generate wide possibilities for a vast range of applications. Here we demonstrate, for the first time, the fabrication of a metastable allotrope of Ge, tetragonal germanium (ST12-Ge), in nanowire form. Nanowires were grown in a solvothermal-like single-pot method using supercritical toluene as a solvent, at moderate temperatures (290-330 °C) and a pressure of ∼48 bar. One-dimensional (1D) nanostructures of ST12-Ge were achieved via a self-seeded vapour-liquid-solid (VLS)-like paradigm, with the aid of an in situ formed amorphous carbonaceous layer. The ST12 phase of Ge nanowires is governed by the formation of this carbonaceous structure on the surface of the nanowires and the creation of Ge-C bonds. The crystalline phase and structure of the ST12-Ge nanowires were confirmed by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and Raman spectroscopy. The nanowires produced displayed a high aspect ratio, with a very narrow mean diameter of 9.0 ± 1.4 nm, and lengths beyond 4 µm. The ST12-Ge nanowire allotrope was found to have a profound effect on the intensity of the light emission and the directness of the bandgap, as confirmed by a temperature-dependent photoluminescence study.

Single-Crystalline Body Centered FeCo Nano-Octopods: From One-Pot Chemical Growth to a Complex 3D Magnetic Configuration.

Single crystalline magnetic FeCo nanostars were prepared using an organometallic approach under mild conditions. The fine-tuning of the experimental conditions allowed the direct synthesis of these nano-octopods with body-centered cubic (bcc) structure through a one-pot reaction, contrarily to the seed-mediated growth classically used. The FeCo nanostars consist of 8 tetrahedrons exposing {311} facets, as revealed by high resolution transmission electron microscopy (HRTEM) imaging and electron tomography (ET), and exhibit a high magnetization comparable with the bulk one (Ms = 235 A·m2·kg-1). Complex 3D spin configurations resulting from the competition between dipolar and exchange interactions are revealed by electron holography. This spin structures are stabilized by the high aspect ratio tetrahedral branches of the nanostars, as confirmed by micromagnetic simulations. This illustrates how magnetic properties can be significantly tuned by nanoscale shape control.

Magnetophoresis-Assisted Capillary Assembly: A Versatile Approach for Fabricating Tailored 3D Magnetic Supercrystals.

The fabrication and integration of sub-millimeter magnetic materials into predefined circuits is of major importance for the realization of portable devices designed for telecommunications, automotive, biomedical, and space applications but remains highly challenging. We report here a versatile approach for the fabrication and direct integration of nanostructured magnetic materials of controlled shaped at specific locations onto silicon substrates. The magnetophoresis-assisted capillary assembly of magnetic nanoparticles, either spherical or anisotropic, leads to the fabrication of high-performance Co-based permanent magnets and Fe-based supercrystals. Integrated sub-millimeter magnets as well as millimeter self-standing magnets exhibiting magnetic properties competing with NdFeB-based composites were obtained through this cost- and time-efficient process. The proof-of-concept of electromagnetic actuation of a micro-electromechanical system cantilever by means of these supercrystals highlights their potentiality as efficient integrated magnetic materials within nomadic devices.

The role of pre-nucleation clusters in the crystallization of gold nanoparticles.

The syntheses of metal nanoparticles by reduction in apolar solvents in the presence of long chain surfactants have proven to be extremely effective in the control of the particle size and shape. Nevertheless, the elucidation of the nucleation/growth mechanism is not straightforward because of the multiple roles played by surfactants. The nucleation stage, in particular, is very difficult to describe precisely and requires in situ and time-resolved techniques. Here, relying on in situ small angle X-ray scattering (SAXS), X-ray absorption spectroscopy (XAS) and high-energy X-ray diffraction (HE-XRD), we propose that ultra-small gold particles prepared by reduction of gold chloride in a solution of oleylamine (OY) in hexane with triisopropylsilane do not follow a classical nucleation process but result from pre-nucleation clusters (PNCs). These PNCs contain Au(iii) and Au(i) precursors; they are almost stable in size during the induction stage, as shown by SAXS, prior to undergoing a very fast shrinkage during the nucleation stage. The gold speciation as a function of time deduced from the XAS spectra has been analyzed through multi-step reaction pathways comprising both highly reactive species, involved in the nucleation and growth stages, and poorly reactive species acting as a reservoir for the reactive species. The duration of the induction period is related to the reactivity of the gold precursors, which is tuned by the coordination of OY to the gold complexes, while the nucleation stage was found to depend on the size and reactivity of the PNCs. The role of the PNCs in determining the final particle size and structure is also discussed in relation to previous studies. The multiple roles of OY, as the solubilizing agent of the gold salt, the ligand of the gold complexes determining both the size of the PNCs and the reactivity of the gold precursors, and finally the capping agent of the final gold particles as oleylammonium chloride, have been clearly established. This work opens new perspectives to synthesize metal NPs via metal-organic PNCs and to define new synthesis routes for nanoparticles that may present structure and morphologies different from those obtained by the classical nucleation routes.

Engineering Iron-Nickel Nanoparticles for Magnetically Induced CO2 Methanation in Continuous Flow.

Induction heating of magnetic nanoparticles (NPs) is a method to activate heterogeneous catalytic reactions. It requires nano-objects displaying high heating power and excellent catalytic activity. Here, using a surface engineering approach, bimetallic NPs are used for magnetically induced CO2 methanation, acting both as heating agent and catalyst. The organometallic synthesis of Fe30 Ni70 NPs displaying high heating powers at low magnetic field amplitudes is described. The NPs are active but only slightly selective for CH4 after deposition on SiRAlOx owing to an iron-rich shell (25 mL min-1 , 25 mT, 300 kHz, conversion 71 %, methane selectivity 65 %). Proper surface engineering consisting of depositing a thin Ni layer leads to Fe30 Ni70 @Ni NPs displaying a very high activity for CO2 hydrogenation and a full selectivity. A quantitative yield in methane is obtained at low magnetic field and mild conditions (25 mL min-1 , 19 mT, 300 kHz, conversion 100 %, methane selectivity 100 %).

To heat or not to heat: a study of the performances of iron carbide nanoparticles in magnetic heating.

Heating magnetic nanoparticles with high frequency magnetic fields is a topic of interest for biological applications (magnetic hyperthermia) as well as for heterogeneous catalysis. This study shows why FeC NPs of similar structures and static magnetic properties display radically different heating power (SAR from 0 to 2 kW g-1). By combining results from Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS) and static and time-dependent high-frequency magnetic measurements, we propose a model describing the heating mechanism in FeC nanoparticles. Using, for the first time, time-dependent high-frequency hysteresis loop measurements, it is shown that in the samples displaying the larger heating powers, the hysteresis is strongly time dependent. More precisely, the hysteresis area increases by a factor 10 on a timescale of a few tens of seconds. This effect is directly related to the ability of the nanoparticles to form chains under magnetic excitation, which depends on the presence or not of strong dipolar couplings. These differences are due to different ligand concentrations on the surface of the particles. As a result, this study allows the design of a scalable synthesis of nanomaterials displaying a controllable and reproducible SAR.

Chemical Ordering in Bimetallic FeCo Nanoparticles: From a Direct Chemical Synthesis to Application As Efficient High-Frequency Magnetic Material.

Single-crystalline FeCo nanoparticles with tunable size and shape were prepared by co-decomposing two metal-amide precursors under mild conditions. The nature of the ligands introduced in this organometallic synthesis drastically affects the reactivity of the precursors and, thus, the chemical distribution within the nanoparticles. The presence of the B2 short-range order was evidenced in FeCo nanoparticles prepared in the presence of HDAHCl ligands, combining 57Fe Mössbauer, zero-field 59Co ferromagnetic nuclear resonance (FNR), and X-ray diffraction studies. This is the first time that the B2 structure is directly formed during synthesis without the need of any annealing step. The as-prepared nanoparticles exhibit magnetic properties comparable with the ones for the bulk ( Ms = 226 Am2·kg-1). Composite magnetic materials prepared from these FeCo nanoparticles led to a successful proof-of-concept of the integration on inductor-based filters (27% enhancement of the inductance value at 100 MHz).

Nanoparticle Ripening : A Versatile Approach for the Size and Shape Control of Metallic Iron Nanoparticles.

A novel approach for the synthesis of Fe(0) nanoparticles (NPs) with tunable sizes and shapes is reported. Ultrasmall Fe(0) NPs were reacted under mild conditions in the presence of a mixture of palmitic acid and amine ligands. These NPs acted not only as preformed seeds but also as an internal iron(II) source that was produced by the partial dissolution of the NPs by the acid. This fairly simple approach allows the strict separation of the nucleation and the growth steps. By changing the acid concentration, a fine tuning of the relative ratio between the remaining Fe(0) seeds and the iron(II) reservoir was achieved, giving access to both size (from 7 to 20 nm) and shape (spheres, cubes or stars) control. The partial dissolution of the ultrasmall Fe(0) NPs into iron(II) source and the successive growth was further studied by using combined TEM and Mössbauer spectroscopy. The successive corrosion, coalescence, and ripening observed could be understood in the framework of an environment-dependent growth model.

Shape selection through epitaxy of supported platinum nanocrystals.

Supported nanocrystals of original shapes are highly desirable for the development of optimized catalysts; however, conventional methods for the preparation of supported catalysts do not allow shape control. In this work, we have synthesized concave platinum nanocubes exposing {110} crystallographic facets at 20 °C. In the presence of a crystallographically oriented Pt(111) support in the reaction medium, the concave nanocubes grow epitaxially on the support, producing macroscopic nanostructured surfaces. Higher reaction temperature produces a mixture of different nanostructures in solution; however, only the nanostructures growing along the 111 direction are obtained on the Pt(111) support. Therefore, the oriented surface acts as a template for a selective immobilization of specific nanostructures out of a mixture, which can be regarded as an "epitaxial resolution" of an inhomogeneous mixture of nanocrystals. Thus, a judicious choice of the support crystallographic orientation may allow the isolation of original nanostructures that cannot be obtained in a pure form.

Ultrathin Gold Nanowires with the Polytetrahedral Structure of Bulk Manganese.

Despite the intensive interest in thin gold nanowires for a variety of technologically important applications, key details of the mechanism of their formation and atomic-scale structure remain unknown. Here we synthesize highly uniform, very long, and ultrathin gold nanowires in a liquid-phase environment and study their nucleation and growth using in situ high-energy synchrotron X-ray diffraction. By controlling the type of solvents, reducing agents, and gold precursor concentration, it is shown that the nucleation and growth of gold nanowires involve the emergence and self-assembly of transient linear gold complexes, respectively. In sharp contrast with the face-centered-cubic bulk gold, the evolved nanowires are found to possess a tetrahedrally close packed structure incorporating distorted icosahedra and larger size coordination polyhedra of the type observed with the room-temperature phase of bulk manganese. We relate the complexes to synergistic effects between the selected precursor and reducing agents that become appreciable over a narrow range of their molar ratios. We attribute the unusual structural state of gold nanowires to geometrical frustration effects arising from the conflicting tendencies of assemblies of metal atoms to evolve toward attaining high atomic packing density while keeping the atomic-level stresses low, ultimately favoring the growth of cylindrical nanowires with a well-defined diameter and atomically smooth surface. Our work provides a roadmap for comprehensive characterization and, hence, better understanding of 1D metallic nanostructures with an unusual atomic arrangement and may have important implications for their synthesis and performance in practical applications.

Synergism of Au and Ru Nanoparticles in Low-Temperature Photoassisted CO2 Methanation.

Au and Ru nanoparticles (NPs) have been deposited on Siralox® substrate by impregnation and chemical reduction, respectively (Au-Ru-S). The as-prepared material is very active in the selective CO2 methanation to CH4 at temperatures below 250 °C. In addition, Au-Ru-S shows enhanced CH4 production upon irradiation with UV/Vis light starting at temperatures higher than 200 °C, although the contribution of the photoassisted pathway of CH4 production decreases as the temperature increases. Thus, a maximum CH4 production of 204 mmol gRu -1 at 250 °C upon 100 mW cm-2 irradiation was achieved. Control experiments, in which Ru-S and Au-S materials were used, revealed that Ru NPs are the CO2 methanation active sites, while Au NPs contribute by harvesting light, mainly visible as a consequence of the strong Au plasmon band centered at 529 nm. The visible light absorbed by the plasmonic band of Au NPs could make them act ass local heaters of the neighboring Ru NPs, increasing their temperature and enhancing CH4 production.

Three-Dimensional Branched and Faceted Gold-Ruthenium Nanoparticles: Using Nanostructure to Improve Stability in Oxygen Evolution Electrocatalysis.

Achieving stability with highly active Ru nanoparticles for electrocatalysis is a major challenge for the oxygen evolution reaction. As improved stability of Ru catalysts has been shown for bulk surfaces with low-index facets, there is an opportunity to incorporate these stable facets into Ru nanoparticles. Now, a new solution synthesis is presented in which hexagonal close-packed structured Ru is grown on Au to form nanoparticles with 3D branches. Exposing low-index facets on these 3D branches creates stable reaction kinetics to achieve high activity and the highest stability observed for Ru nanoparticle oxygen evolution reaction catalysts. These design principles provide a synthetic strategy to achieve stable and active electrocatalysts.

Impregnation of High-Magnetization FeCo Nanoparticles in Mesoporous Silicon: An Experimental Approach.

This paper deals with the synthesis of high-magnetization porous silicon-based nanocomposites. Using well-controlled organometallic synthesis of ferromagnetic FeCo nanoparticles, the impregnation of mesoporous silicon has been performed by immersion of porous silicon in a colloidal solution. The technique was optimized by controlling the temperature, the immersion duration, and the solvent nature. The characterization of the nanocomposites showed a homogeneous filling of the pores and a high magnetization of 135 emu/cm3. Such composites present a great interest for many applications including data storage, medical instrumentations, catalysis, or electronics.

Platinum tripods as nanometric frequency multiplexing devices.

Electrical and structural characterization studies of nano-particles are very important steps to determine their potential applications in microelectronics. In this paper, we address the crystallographic and electric transport properties of soft-chemistry-grown nanometric Pt tribranches. We report that Pt nanostars grown from the reduction of H2PtCl6 salt in pure oleylamine present a remarkable crystalline structure and deeply metallic character despite being grown under mild conditions. We demonstrate that such devices are able to operate at current densities surpassing 200 MA cm-2, actuating as highly compact frequency multiplexers in the non-ohmic regime.

Surface-Engineering of Ultrathin Gold Nanowires: Tailored Self-Assembly and Enhanced Stability.

Gold nanowires with a mean diameter of 1.7 nm were synthesized by reduction of HAuCl4 in a solution of oleylamine (OY) in hexane. A bilayer of oleylammonium chloride/oleylamine at the surface of the raw nanowires was evidenced by NMR and diffusion ordered spectroscopy (DOSY) experiments. After washing a monolayer of oleylammonium chloride remained at the surface of the nanowires. The oleylammonium chloride layer could be progressively replaced by a phosphine shell as evidenced with NMR and DOSY experiments, which are in good agreement with the adsorption energies given by density functional theory calculations. The nanowires crystallize into hexagonal superlattices with a lattice parameter that can be tailored depending on the ligand shell. Small-angle X-ray scattering showed the following lattice parameters: Au@OY+Cl-(OY) (a = 7.2 nm) > Au@TOPO/OY (a = 6.6 nm) > Au@ OY+Cl- (a = 4.1 nm) > Au@TOP (a = 3.75 nm). This is one of a few examples of surface modification of ultrathin nanowires that does not alter their morphology. Moreover, the nanowires coated with phosphines exhibited long time stability (at the opposite of other ligands like thiols) opening the way to more complex functionalization.

Magnetically Induced Continuous CO2 Hydrogenation Using Composite Iron Carbide Nanoparticles of Exceptionally High Heating Power.

The use of magnetic nanoparticles to convert electromagnetic energy into heat is known to be a key strategy for numerous biomedical applications but is also an approach of growing interest in the field of catalysis. The heating efficiency of magnetic nanoparticles is limited by the poor magnetic properties of most of them. Here we show that the new generation of iron carbide nanoparticles of controlled size and with over 80 % crystalline Fe2.2 C leads to exceptional heating properties, which are much better than the heating properties of currently available nanoparticles. Associated to catalytic metals (Ni, Ru), iron carbide nanoparticles submitted to magnetic excitation very efficiently catalyze CO2 hydrogenation in a dedicated continuous-flow reactor. Hence, we demonstrate that the concept of magnetically induced heterogeneous catalysis can be successfully applied to methanation of CO2 and represents an approach of strategic interest in the context of intermittent energy storage and CO2 recovery.

Size-Specific Spin Configurations in Single Iron Nanomagnet: From Flower to Exotic Vortices.

The different spin configurations in the vicinity of the single-domain/vortex transition are reported in isolated magnetic nanoparticles. By combining chemical synthesis, electron holography in a dedicated transmission electron microscope and micromagnetic simulations, we establish the "magnetic configurations vs size" phase diagram of Fe single-crystalline nanocubes. Room temperature high resolution magnetic maps reveal the transition between single-domain and vortex states for Fe nanocubes from 25 to 27 nm, respectively. An intermediate spin configuration consisting of an ⟨111⟩ vortex is for the first time evidenced.

Directed assembly of single colloidal gold nanowires by AFM nanoxerography.

Ultrathin gold nanowires (NWs) dispersed in hexane were prepared by chemical reduction of HAuCl4 in oleylamine, along with nanospheres (NSs), side products of the reaction. X-ray photoelectron spectroscopy and small-angle X-ray scattering evidenced a stabilization of these nano-objects by oleylammonium chloride surfactants. The directed assembly of these nano-objects on surfaces was performed by atomic force microscopy (AFM) nanoxerography in a few seconds. Selective assembly of gold NWs only occurred on positively charged patterns, while NSs assembled more specifically on the negatively charged ones. This sorting suggests that the strong electric field generated by the charge patterns induced a negative effective charge on the gold NWs and a weak positive effective charge on the NSs. Such difference could be explained by the ion organization at the colloid surface, monolayered in the case of NWs, and bilayered in the case of NSs. By adjusting the design of the positive patterns and the experimental conditions of development, single gold nanowires were successfully assembled by AFM nanoxerography on predefined sites of surfaces without damaging them, opening the way for future electrical and mechanical characterizations.