Juan C. Hernández-Garrido

Unknown aspects of self-assembly of PbS microscale superstructures.

A lot of interesting and sophisticated examples of nanoparticle (NP) self-assembly (SA) are known. From both fundamental and technological standpoints, this field requires advancements in three principle directions: (a) understanding the mechanism and driving forces of three-dimensional (3D) SA with both nano- and microlevels of organization; (b) understanding disassembly/deconstruction processes; and (c) finding synthetic methods of assembly into continuous superstructures without insulating barriers. From this perspective, we investigated the formation of well-known star-like PbS superstructures and found a number of previously unknown or overlooked aspects that can advance the knowledge of NP self-assembly in these three directions. The primary one is that the formation of large seemingly monocrystalline PbS superstructures with multiple levels of octahedral symmetry can be explained only by SA of small octahedral NPs. We found five distinct periods in the formation PbS hyperbranched stars: (1) nucleation of early PbS NPs with an average diameter of 31 nm; (2) assembly into 100-500 nm octahedral mesocrystals; (3) assembly into 1000-2500 nm hyperbranched stars; (4) assembly and ionic recrystallization into six-arm rods accompanied by disappearance of fine nanoscale structure; (5) deconstruction into rods and cuboctahedral NPs. The switches in assembly patterns between the periods occur due to variable dominance of pattern-determining forces that include van der Waals and electrostatic (charge-charge, dipole-dipole, and polarization) interactions. The superstructure deconstruction is triggered by chemical changes in the deep eutectic solvent (DES) used as the media. PbS superstructures can be excellent models for fundamental studies of nanoscale organization and SA manufacturing of (opto)electronics and energy-harvesting devices which require organization of PbS components at multiple scales.

Nanoporous oxidic solids: the confluence of heterogeneous and homogeneous catalysis

The several factors that render certain kinds of nanoporous oxidic solids valuable for the design of a wide range of new heterogeneous catalysts are outlined and exemplified. These factors include: (i), their relative ease of preparation, when both mesoporous siliceous frameworks (ca. 20 to 250 A diameter pores) and microporous framework-substituted aluminophosphates (ca. 4 to 14 A diameter pores) can be tailored to suit particular catalytic needs according to whether regiospecific or enantio- or shape-selective conversions are the goal; (ii), the enormous internal (three-dimensional) areas that these nanoporous solids possess (typically 10(3) m(2) g(-1)) and the consequential ease of access of reactants through the internal pores of the solids; (iii), the ability, by judicious solid-state preparative methods to assemble spatially isolated, single-site active centres at the internal surfaces of these open-structure solids, thereby making the heterogeneous catalyst simulate the characteristic features of homogenous and enzymatic catalysts; (iv), the wide variety of in situ, time-resolved and ex situ experimental techniques, coupled with computational methods, that can pin-point the precise structure of the active site under operating conditions and facilitate the formulation of reaction intermediates and mechanisms. Varieties of catalysts are described for the synthesis (often under environmentally benign and solvent-free conditions) of a wide range of organic materials including commodity chemicals (such as adipic and terephthalic acid), fine and pharmaceutical chemicals (e.g. vitamin B(3)), alkenes, epoxides, and for the photocatalytic preferential destruction of carbon monoxide in the presence of hydrogen. Nanoporous oxidic solids are ideal materials to investigate the phenomenology of catalysis because, in many of them, little distinction exists between a model and a real catalyst.

Using highly accurate 3D nanometrology to model the optical properties of highly irregular nanoparticles: a powerful tool for rational design of plasmonic devices.

The realization of materials at the nanometer scale creates new challenges for quantitative characterization and modeling as many physical and chemical properties at the nanoscale are highly size and shape-dependent. In particular, the accurate nanometrological characterization of noble metal nanoparticles (NPs) is crucial for understanding their optical response that is determined by the collective excitation of conduction electrons, known as localized surface plasmons. Its manipulation gives place to a variety of applications in ultrasensitive spectroscopies, photonics, improved photovoltaics, imaging, and cancer therapy. Here we show that by combining electron tomography with electrodynamic simulations an accurate optical model of a highly irregular gold NP synthesized by chemical methods could be achieved. This constitutes a novel and rigorous tool for understanding the plasmonic properties of real three-dimensional nano-objects.

An endogenous nanomineral chaperones luminal antigen and peptidoglycan to intestinal immune cells

In humans and other mammals, it is known that calcium and phosphate ions are secreted from the distal small intestine into the lumen. However, why this secretion occurs is unclear. Here, we show that the process leads to the formation of amorphous magnesium-substituted calcium phosphate nanoparticles that trap soluble macromolecules, such as bacterial peptidoglycan and orally-fed protein antigens, in the lumen and transport them to immune cells of the intestinal tissue. The macromolecule-containing nanoparticles utilize epithelial M cells to enter Peyer’s patches - small areas of the intestine concentrated with particle-scavenging immune cells. In wild type mice, intestinal immune cells containing these naturally-formed nanoparticles expressed the immune tolerance-associated molecule ‘programmed death-ligand 1 (PD-L1)’, whereas in NOD1/2 double knock-out mice, which cannot recognize peptidoglycan, PD-L1 was undetected. Our results explain a role for constitutively formed calcium phosphate nanoparticles in the gut lumen and how this helps to shape intestinal immune homeostasis.

The promotional effect of Sn-beta zeolites on platinum for the selective hydrogenation of α,β-unsaturated aldehydes

Pt impregnated on a Sn-beta catalyst results in a very promising catalyst for the selective hydrogenation of α,β-unsaturated aldehydes, compared to the PtSn co-impregnated beta catalysts. Framework tin ions in the Sn-beta sample stabilize the nucleation of platinum nanoparticles inside the zeolite channel. These Pt(0)-Sn(4+) sites, which are only observed in the Pt/Sn-beta catalyst, have been shown to strongly activate the carbonyl group enhancing the hydrogenation rate of the C=O bond.

Rational design of nanostructured, noble metal free, ceria–zirconia catalysts with outstanding low temperature oxygen storage capacity

On the basis of detailed previous knowledge about the correlation existing between the Oxygen Storage Capacity (OSC) of ceria–zirconia mixed oxides, the nature of redox pretreatments and the nanostructure of this family of complex materials, it has been possible to design a synthetic strategy allowing one to prepare ceria–zirconia and ceria–yttria-doped zirconia materials, with total ceria contents below 20%, featuring OSC values higher than those observed for catalysts which incorporate supported noble metal particles in their formulation, especially in the very low, 373–473 K, temperature range. These novel, noble-metal free and highly reducible, ceria–zirconia materials allow a much more efficient usage of ceria as a component of oxygen storage formulations, which is nowadays considered one of the key innovation targets in the field of lanthanide oxide based catalysts.

Exceptionally Active Single-Site Nanocluster Multifunctional Catalysts for Cascade Reactions

Clusters last stand: Metal nanoparticles, which are well known for their catalytic properties, contain 103-106 atoms in each particle, giving rise to a continuous band of electronic energy levels. As a result, they are very different electronically from metal nanoclusters composed of aggregates of approximately 3-20 atoms. Such nanoclusters themselves exhibit remarkable catalytic performances in hydrogenation and ammoxidation cascade reactions.

Fabrication and characterization of TiN–Ag nano-dice

TiN-Ag nanocomposite was synthesized by dc arc-plasma method. Microstructures of TiN-Ag nanocomposite were carefully characterized by powder X-ray diffraction method and transmission electron microscopy, and nano-morphologies by three-dimensional electron tomography. It was found that the surface of nanocrystalline TiN matrix was densely covered by finely dispersed Ag nanoparticles, and it was found that they were physically attached but not chemically bonded from their orientation relationships.

Nanoconfinement of Ni clusters towards a high sintering resistance of steam methane reforming catalysts

This study reports an improvement of the stability of steam reforming catalysts at relatively low temperatures, such as for pre-reforming, and reforming of biomass derived compounds, by enhanced stabilization of Ni nanoparticles through spatial confinement in a mixed oxides matrix. We revealed a simple approach of three dimensional engineering of Ni particles by means of self-assembly of Ni atoms inside the nanoribbon of hydrotalcite-derived mixed oxides. Taking advantage of Transmission Electron Microscopy (TEM), together with electron tomography, the three dimensional (3D) structure of the catalyst was investigated at a nanometer scale, including the Ni particle size, shape, location and spatial distribution, as well as pore size and morphology of the mixed oxides. Porous nano-ribbons were formed by high temperature treatment, adopting the layer structure of the hydrotalcite-like materials. Ni particles formed by selective reduction of mixed oxides embedded in the nano-ribbons with connected pore channels, allowing good access for the reactants. These spatially confined and well distributed Ni particles increased catalyst stability significantly compared to the Ni particles supported on the support surfaces in a commercial catalyst during the steam methane reforming.

Advanced Electron Microscopy Investigation of Ceria–Zirconia-Based Catalysts

The potentials of advanced transmission and scanning transmission electron microscopy in nanostructural studies of ceria–zirconia mixed oxides are overviewed. The crystallographic criteria that allow us to discriminate the different CeO2–ZrO2 polymorphs and the nanocrystal size range within which they can be applied are discussed. The combined use of high resolution electron microscopy (HREM) and high‐angle annular dark field scanning transmission electron microscopy (HAADF‐STEM) to detect disorder–order transitions in the cation sublattice of this family of oxides and the size limit down to which each of them can be used for that purpose are also analyzed. Criteria to discriminate, on the basis of HREM images, the oxygen arrangement of the so called κ‐Ce2Zr2O8 phase from that of an oxidized pyrochlore Ce2Zr2O8 phase are presented and applied to the interpretation of experimental HREM images. HAADF‐STEM tomography studies and detailed analysis of HAADF‐STEM images establish both the crystallographic and compositional features of the surfaces of the mixed oxides that give enhanced redox activity. These findings allow deeper understanding of the influence of different thermal ageing pretreatments on the redox behavior of this family of mixed oxides. Novel characterization data do evidence that this model does not only fruitfully apply to binary ceria–zirconia oxides but also to more complex ternary oxides containing terbium.