Design of Metal@Titanium Oxide Nano-heterodimers by Laser-Driven Photodeposition: Growth Mechanism and Modeling.

In order to circumvent the usual nucleation of randomly distributed tiny metallic dots photodeposited on TiO2 nanoparticles (NPs) induced by conventional UV lamps, we propose to synthesize well-controlled nanoheterodimers (NHDs) using lasers focused inside microfluidic reactors to strongly photoactivate redox reactions of active ions flowing along with nanoparticles in water solution. Since the flux of photons issued from a focused laser may be orders of magnitude higher than that reachable with classical lamps, the production of electron-hole pairs is tremendously increased, ensuring a large availability of carriers for the deposition and favoring the growth of a single metallic dot as compared to secondary nucleation events. We show that the growth of single silver or gold nanodots can be controlled by varying the beam intensity, the concentration of the metallic salt, and the flow velocity inside the microreactor. The confrontation to a build-in model of the metallic nanodot light-induced growth onto the surface of TiO2 NPs shows the emergence of a predictable "master behavior" on which individual growths obtained from various tested conditions do collapse. We also characterized the associated quantum yield. Eventually, we successfully confronted our model to growth data from the literature in the case of silver on TiO2 and gold on II-VI semiconducting NPs triggered by UV lamps. It shows that for the photosynthesis of NHDs the efficiency of the electron-hole pair production rate matters much more than the number of pairs produced and that the use of laser light can provide a photodeposition-based synthesis at the nanoscale.

Versatile template-directed synthesis of gold nanocages with a predefined number of windows.

Highly symmetrical gold nanocages can be produced with a controllable number of circular windows of either 2, 3, 4, 6 or 12 via an original fabrication route. The synthetic pathway includes three main stages: the synthesis of silica/polystyrene multipod templates, the regioselective seeded growth of a gold shell on the unmasked part of the silica surface and the development of gold nanocages by dissolving/etching the templates. Electron microscopy and tomography provide evidence of the symmetrical features of the as-obtained nanostructures. The optical properties of nanocages with 4 and 12 windows were measured at the single particle level by spatial modulation spectroscopy and correlated with numerical simulations based on finite-element modeling. The new multi-step synthesis approach reported here also allows the synthesis of rattle-like nanostructures through filling of the nanocages with a guest nano-object. With the potential to adjust the chemical composition, size and geometry of both the guest particle and the host cage, it opens new routes towards the fabrication of hollow nanostructures of high interest for a variety of applications including sensing devices, catalytic reactors and biomedicine.

Colloidal molecules and patchy particles: complementary concepts, synthesis and self-assembly.

This review describes the latest advances in the synthesis and assembly of specific colloids such as the colloidal molecules as defined by van Blaaderen in 2003 and the patchy particles imagined a few years later. The two concepts are closely related because some may serve as precursors of others and vice versa. To best mimic the molecular structures, it is necessary to introduce the notions of directed binding and valence which result in the concept of patches arranged on the particle surface according to the conventional repulsion figures. The assembly of patchy particles has made it possible to reconstitute molecules and macromolecules of simple geometry. But the existence of extended assemblies of larger dimensions has been demonstrated mostly by simulation and it struggles experimentally with the purity of the batches of building blocks.

Controlling the {111}/{110} Surface Ratio of Cuboidal Ceria Nanoparticles.

The ability to control the size and morphology is crucial in optimizing nanoceria catalytic activity as this is governed by the atomistic arrangement of species and structural features at the surfaces. Here, we show that cuboidal cerium oxide nanoparticles can be obtained via microwave-assisted hydrothermal synthesis in highly alkaline media. High-resolution transmission electron microscopy (HRTEM) revealed that the cube edges were truncated by CeO2{110} surfaces and the cube corners were truncated by CeO2{111} surfaces. When adjusting synthesis conditions by increasing NaOH concentration, the average particle size increased. Although this was accompanied by an increase of the cube faces, CeO2{100}, the cube edges, CeO2{110}, and cube corners, CeO2{111}, remained of constant size. Molecular dynamics (MD) was used to rationalize this behavior and revealed that energetically, the corners and edges cannot be atomically sharp, rather they are truncated by {111} and {110} surfaces, respectively, to stabilize the nanocube; both the experiment and simulation showed agreement regarding the minimum size of ∼1.6 nm associated with this truncation. Moreover, HRTEM and MD revealed {111}/{110} faceting of the {110} edges, which balances the surface energy associated with the exposed surfaces, which follows {111} > {110} > {100}, although only the {110} surface facets because of the ease of extracting oxygen from its surface and follows {111} > {100} > {110}. Finally, MD revealed that the {100} surfaces are "liquid-like" with a surface oxygen mobility 5 orders of magnitude higher than that on the {111} surfaces; this arises from the flexibility of the surface species network that can access many different surface arrangements because of very small energy differences. This finding has implications for understanding the surface chemistry of nanoceria and provides avenues to rationalize the design of catalytically active materials at the nanoscale.

Effect of solvent on silicon nanoparticle formation and size: a mechanistic study.

Silicon has emerged as the most desirable material for optical dielectric metamaterials, however chemists struggle to obtain the required silicon nanoparticle dimensions. Here the average diameter of silicon nanoparticles is varied between 3 and 15 nm by changing the reaction solvent. Electrochemistry and NMR elucidate the role of solvent on the synthetic mechanism. Surprisingly the solvent does not stabilize the nanoparticles and there is no trend associated with chain length or open-chain versus cyclical solvent molecules. The solvent's main role is to stabilize the by-products, which prolongs the reaction lifetime.

Template-Directed Synthesis of Titania Nanocages with Four Tetrahedrally Arranged Open Windows.

Original titania nanocages are fabricated from sacrificial silica/polystyrene tetrapod-like templates. Here the template synthesis, titania deposition and nanocage development through polystyrene dissolution and subsequent silica etching are described. Discussion about the competitive deposition of titania on the biphasic templates is particularly emphasized. The morphology of the nanocages is investigated by TEM, STEM, EDX mapping and electron tomography.

New insights into the side-face structure, growth aspects, and reactivity of Ag(n) nanoprisms.

We report an improved synthesis of colloidal Ag(n) nanoprisms using carboxyl compounds (citrate or succinate) and long chain macromolecules (polyvinylpyrrolidone (PVP)). The side-facet structure of the triangular nanostructure was determined in detail using electron tomography in scanning transmission mode (3D STEM) and HRTEM. It has been found that they are built up by {100} facets with a single parallel twin plane. The best conditions for producing uniform Ag nanoprisms with tunable sizes and high yields in the presence of carboxyl compounds additive system are described, and a growth mechanism is proposed. This approach provides also a route to synthesize Ag nanodisks and Au-Ag alloyed nanoprisms.

Stabilisation of carbon-supported palladium nanoparticles through the formation of an alloy with gold: application to the Sonogashira reaction.

Oh my Gold! Gold atoms stabilise catalytically active palladium nanoparticles when engaged in an alloy heterogenised on carbon. The increased durability makes the Pd-Au/C catalyst more recyclable than the gold-free Pd/C catalyst for the Sonogashira reaction.

Synthesis and site-specific functionalization of tetravalent, hexavalent, and dodecavalent silica particles.

Different shapes: Tetravalent, hexavalent, and dodecavalent silica particles were obtained by the growth of the silica core of binary tetrapods, hexapods, and dodecapods, respectively. The surface of the multivalent particles can be regioselectively functionalized, thereby leading to particles with anisotropic geometry and chemistry.

Surface plasmon resonance properties of single elongated nano-objects: gold nanobipyramids and nanorods.

The spectral characteristics (wavelength and line width) and the optical extinction cross-section of the longitudinal localized surface plasmon resonance (LSPR) of individual gold nanobipyramids have been quantitatively measured using the spatial modulation spectroscopy technique. The morphology of the same individual nanoparticles has been determined by transmission electron microscopy (TEM). The experimental results are thus interpreted with a numerical model using the TEM measured sizes of the particles as an input, and either including the substrate or assuming a mean homogeneous environment. Results are compared to those obtained for individual nanorods and also show the importance of the local environment of the particle on the detailed description of its spectral position and extinction amplitude.

3D morphology of Au and Au@Ag nanobipyramids.

The morphologies of Au and Au@Ag nanobipyramids were investigated using electron tomography. The 3D reconstruction reveals that the Au bipyramids have an irregular six-fold twinning structure with highly stepped dominant {151} facets. These short steps/edges stabilized via surface adsorbed CTAB favor the growth of silver on the lateral facets leading to strong blue shifts in longitudinal plasmon surface resonance.

Europium-doped mesoporous titania thin films: rare-earth locations and emission fluctuations under illumination.

Herein, Eu(III)-doped 3D mesoscopically ordered arrays of mesoporous and nanocrystalline titania are prepared and studied. The rare-earth-doped titania thin films-synthesized via evaporation-induced self-assembly (EISA)-are characterized by using environmental ellipsoporosimetry, electronic microscopy (i.e. high-resolution scanning electron microscopy, HR-SEM, and transmission electron microscopy, HR-TEM), X-ray diffraction, and luminescence spectroscopy. Structural characterizations show that high europium-ion loadings can be incorporated into the titanium-dioxide walls without destroying the mesoporous arrangement. The luminescence properties of Eu(III) are investigated by using steady-state and time-resolved spectroscopy via excitation of the Eu(III) ions through the titania host. Using Eu(III) luminescence as a probe, the europium-ion sites can be addressed with at least two different environments within the mesoporous framework, namely, a nanocrystalline environment and a glasslike one. Emission fluctuations ((5)D(0)-->(7)F(2)) are observed upon continuous UV excitation in the host matrix. These fluctuations are attributed to charge trapping and appear to be strongly dependent on the amount of europium and the level of crystallinity.

Coupling sol-gel synthesis and microwave-assisted techniques: a new route from amorphous to crystalline high-surface-area aluminium fluoride.

A non-aqueous sol-gel Al-based fluoride has been subjected to the microwave solvothermal process. The final material depends on the temperature heat treatment used. Three types of material have been prepared: 1) for low temperature heat treatment (90 degrees C) X-ray amorphous alkoxy fluoride was obtained; 2) for the highest temperature used (200 degrees C) the metastable form beta-AlF3 was obtained with a very large surface area of 125 m2 g(-1). The mechanism of the amorphous=crystalline transformation has been rationalised by the occurrence of a decomposition reaction of the gel fluoride induced by the microwave irradiation. 3) Finally, at intermediate temperature (180 degrees C) a multi-component material mixture exhibiting a huge surface area of 525 m2 g(-1) has been obtained and further investigated after mild post-treatment fluorination using F2 gas. The resulting aluminium-based fluoride still possesses a high-surface-area of 330 m2 g(-1). HRTEM revealed that the solid is built from large particles (50 nm) identified as alpha-AlF3, and small ones (10 nm), relative to an unidentified phase. This new high-surface-area material exhibits strong Lewis acidity as revealed by pyridine adsorption and catalytic tests. By comparison with other materials, it has been shown that whatever the composition/structure of the Al-based fluoride materials, the number of strong Lewis acid sites is related to the surface area, highlighting the role of surface reconstruction occurring on a nanoscopic scale on the formation of the strongest Lewis acid sites.

Synthesis of hybrid gold-gold sulfide colloidal particles.

The nucleation and growth mechanism of nanometer size gold onto gold sulfide colloidal particles by irradiation-induced reduction is reported. The process is characterized by ultraviolet-visible spectroscopy, electronic diffraction, and high-resolution transmission electron microscopy, allowing for observation of several key intermediates and characteristics of the growth mechanism. The formation mechanism of gold on the surface of the gold sulfide particles is shown to depend strongly on the deposition rate. At low dose rate, gold nucleates preferentially onto specific gold-rich Au2S facets {110}, resulting in epitaxial growth. The gold crystal lattice plastically deforms near the interface to accommodate a substantial lattice mismatch. Upon increasing gold precursor concentration, this low dose rate results in growth of elongated gold island on the gold sulfide surface. At a high dose rate, several randomly oriented gold particles are simultaneously produced on gold sulfide, resulting in a layered structure. The absorption spectra of these particles show a dominant surface plasmon band, whose peak wavelength shifts markedly to the red as layered structure is formed.

Dissymmetric carbon nanotubes by bipolar electrochemistry.

Short carbon nanotubes have been modified selectively on one end with metal using a bulk technique based on bipolar electrochemistry. A stabilized suspension of nanotubes is introduced in a capillary containing an aqueous metal salt solution, and a high electric field is applied to orientate and polarize the individual tubes. During their transport through the capillary under sufficient polarization (30 kV), each nanotube is the site of water oxidation on one end and the site of metal ion reduction on the other end with the size of the formed metal cluster being proportional to the potential drop along the nanotube.