Mechanism of formation of Co-Ru nanoalloys: the key role of Ru in the reduction pathway of Co.

The chemical synthesis of alloy nanoparticles requires adequate conditions to enable co-reduction instead of separate reduction of the two metal cations. The mechanism of formation of bimetallic cobalt-ruthenium nanoalloys by reducing metal salts in an alcohol medium was explored to draw general rules to extrapolate to other systems. The relative kinetics of the reduction of both metal cations were studied by UV-visible and in situ Quick-X-ray absorption spectroscopies as well as H2 evolution. The addition of Co(II) ions does not influence the reduction kinetics of Ru(III) but adding Ru(III) to a Co(II) solution promotes the reduction of cobalt cations. Indeed, while CoO is formed when reaching the boiling temperature of the solvent for the monometallic system, a direct reduction of Co is observed at this temperature without formation of the oxide for the bimetallic one. The co-reduction of the metal cations results in the formation of bimetallic nanoplatelets, the size of which can be tuned by changing the Ru content.

Green synthesis of water splitting electrocatalysts: IrO2 nanocages via Pearson's chemistry.

Highly porous iridium oxide structures are particularly well-suited for the preparation of porous catalyst layers needed in proton exchange membrane water electrolyzers. Herein, we report the formation of iridium oxide nanostructured cages, via a water-based process performed at room temperature, using cheap Cu2O cubes as the template. In this synthetic approach, based on Pearson's hard and soft acid-base theory, the replacement of the Cu2O core by an iridium shell is permitted by the difference in hardness/softness of cations and anions of the two reactants Cu2O and IrCl3. Calcination followed by acid leaching allow the removal of residual copper oxide cores and leave IrO2 hierarchical porous structures with outstanding activity toward the oxygen evolution reaction. Fundamental understanding of the reaction steps and identification of the intermediates are permitted by coupling a set of ex situ and in situ techniques including operando time-resolved X-ray absorption spectroscopy during the synthesis.

High-Entropy-Alloy Nanocrystal Based Macro- and Mesoporous Materials.

High-entropy-alloy (HEA) nanoparticles are attractive for several applications in catalysis and energy. Great efforts are currently devoted to establish composition-property relationships to improve catalytic activity or selectivity. Equally importantly, developing practical fabrication methods for shaping HEA-based materials into complex architectures is a key requirement for their utilization in catalysis. However, shaping nano-HEAs into hierarchical structures avoiding demixing or collapse remains a great challenge. Herein, we overcome this issue by introducing a simple soft-chemistry route to fabricate ordered macro- and mesoporous materials based on HEA nanoparticles, with high surface area, thermal stability, and catalytic activity toward CO oxidation. The process is based on spray-drying from an aqueous solution containing five different noble metal precursors and polymer latex beads. Upon annealing, the polymer plays a double role: templating and reducing agent enabling formation of HEA nanoparticle-based porous networks at only 350 °C. The formation mechanism and the stability of the macro- and mesoporous materials were investigated by a set of in situ characterization techniques; notably, in situ transmission electron microscopy unveiled that the porous structure is stable up to 800 °C. Importantly, this process is green, scalable, and versatile and could be potentially extended to other classes of HEA materials.

Deep X-ray lithography on "sol-gel" processed noble metal mesoarchitectured films.

Noble metal coordination xerogel films (mesostructured with block-copolymers) exhibit solubility switching with increasing X-ray irradiation. Different from other sol-gel systems, these are attributed to film deconstruction under irradiation. These materials can be used as recyclable negative tone resists for deep X-ray lithography that can be further converted into metallic nanoarchitectured films.

Block-Copolymers Enable Direct Reduction and Structuration of Noble Metal-Based Films.

Noble metal nanostructured films are of great interest for various applications including electronics, photonics, catalysis, and photocatalysis. Yet, structuring and patterning noble metals, especially those of the platinum group, is challenging by conventional nanofabrication. Herein, an approach based on solution processing to obtain metal-based films (rhodium, ruthenium (Ru) or iridium in the presence of residual organic species) with nanostructuration at the 20 nm-scale is introduced. Compared to existing approaches, the dual functionality of block-copolymers acting both as structuring and as reducing agent under inert atmosphere is exploited. A set of in situ techniques has allowed for the capturing of the carbothermal reduction mechanism occurring at the hybrid organic/inorganic interface. Differently from previous literature, a two-step reduction mechanism is unveiled with the formation of a carbonyl intermediate. From a technological point of view, the materials can be solution-processed on a large scale by dip-coating as polymers and simultaneously structured and reduced into metals without requiring expensive equipment or treatments in reducing atmosphere. Importantly, the metal-based films can be patterned directly by block-copolymer lithography or by soft-nanoimprint lithography on various substrates. As proof-of-concept of application, the authors demonstrate that nanostructured Ru films can be used as efficient catalysts for H2 generation into microfluidic reactors.

The origin of the high electrochemical activity of pseudo-amorphous iridium oxides.

Combining high activity and stability, iridium oxide remains the gold standard material for the oxygen evolution reaction in acidic medium for green hydrogen production. The reasons for the higher electroactivity of amorphous iridium oxides compared to their crystalline counterpart is still the matter of an intense debate in the literature and, a comprehensive understanding is needed to optimize its use and allow for the development of water electrolysis. By producing iridium-based mixed oxides using aerosol, we are able to decouple the electronic processes from the structural transformation, i.e. Ir oxidation from IrO2 crystallization, occurring upon calcination. Full characterization using in situ and ex situ X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and transmission electron microscopy allows to unambiguously attribute their high electrochemical activity to structural features and rules out the iridium oxidation state as a critical parameter. This study indicates that short-range ordering, corresponding to sub-2nm crystal size for our samples, drives the activity independently of the initial oxidation state and composition of the calcined iridium oxides.

Replacing Metals with Oxides in Metal-Assisted Chemical Etching Enables Direct Fabrication of Silicon Nanowires by Solution Processing.

Metal-assisted chemical etching (MACE) has emerged as an effective method to fabricate high aspect ratio nanostructures. This method requires a catalytic mask that is generally composed of a metal. Here, we challenge the general view that the catalyst needs to be a metal by introducing oxide-assisted chemical etching (OACE). We perform etching with metal oxides such as RuO2 and IrO2 by transposing materials used in electrocatalysis to nanofabrication. These oxides can be solution-processed as polymers exhibiting similar capabilities of metals for MACE. Nanopatterned oxides can be obtained by direct nanoimprint lithography or block-copolymer lithography from chemical solution on a large scale. High aspect ratio silicon nanostructures were obtained at the sub-20 nm scale exclusively by cost-effective solution processing by halving the number of fabrication steps compared to MACE. In general, OACE is expected to stimulate new fundamental research on chemical etching assisted by other materials, providing new possibilities for device fabrication.

On the importance of the crystalline surface structure on the catalytic activity and stability of tailored unsupported cobalt nanoparticles for the solvent-free acceptor-less alcohol dehydrogenation.

Unsupported nanoparticles are now recognized as model catalysts to evaluate the intrinsic activity of metal particles, irrespectively of that of the support. Co nanoparticles with different morphologies, rods, diabolos and cubes have been prepared by the polyol process and tested for the acceptorless catalytic dehydrogenation of alcohols under solvent-free conditions. Rods crystallize with the pure hcp structure, diabolos with a mixture of hcp and fcc phases, while the cubes crystallize in a complex mixture of hcp, fcc and ε-Co phases. All the cobalt particles are found to be highly selective towards the oxidation of a model secondary alcohol, octan-2-ol, into the corresponding ketone while no significant activity is found with octan-1-ol. Our results show the strong influence of particle shape on the activity and catalytic stability of the catalysts: Co nanorods display the highest conversion (85%), selectivity (95%) and recyclability compared to Co diabolos and Co cubes. We correlate the nanorods excellent stability with a strong binding of carboxylate ligands on their {1 1 2¯ 0} facets, preserving their crystalline superficial structure, as evidenced by phase modulation infrared reflection absorption spectroscopy.

One-Pot Seed-Mediated Growth of Co Nanoparticles by the Polyol Process: Unraveling the Heterogeneous Nucleation.

The one-step seed-mediated synthesis is widely used for the preparation of ferromagnetic metal nanoparticles (NPs) since it offers a good control of particle morphology. Nevertheless, this approach suffers from a lack of mechanistic studies because of the difficulties of following in real time the heterogeneous nucleation and predicting structure effects with seeds that are generated in situ. Here, we propose a complete scheme of the heteronucleation process involved in one-pot seed-mediated syntheses of cobalt nanoparticles in liquid polyols, relying on geometrical phase analysis (GPA) of high-resolution high-angle annular dark field (HAADF)-STEM images and in situ measurements of the molecular hydrogen evolution. Cobalt particles of different shapes (rods, platelets, or hourglass-like particles) were grown by reducing cobalt carboxylate in liquid polyols in the presence of iridium or ruthenium chloride as the nucleating agent. A reaction scheme was established by monitoring the H2 evolution resulting from the decomposition of metal hydrides, formed in situ by ß-elimination of metal alkoxides, and from the polyol dehydrogenation, catalytically activated by the metal particles. This is a very good probe for both the noble metal nucleation and the heterogeneous nucleation of cobalt, showing a good separation of these two steps. Ir and Ru seeds with a size in the range 1-2 nm were found exactly in the center of the cobalt particles, whatever the cobalt particle shape, and high-resolution images revealed an epitaxial growth of the hcp Co on fcc Ir or hcp Ru seeds. The microstructure analysis around the seeds made evident two different ways of relaxing the lattice mismatch between the seeds and the cobalt, with the presence of dislocations around the Ir seeds and compression zones of the cobalt lattice near the Ru seeds. The relationship between the nature of the nucleating agent, the reaction steps, and the microstructure is discussed.

Dynamic Shaping of Femtoliter Dew Droplets.

Herein, we show that wetting properties such as giant wetting anisotropy and dynamic shaping can be observed when femtoliter (submicron scale) dew droplets are condensed on nanopatterned mildly hydrophilic surfaces. Large-scale, optically transparent, nanopatterned TiO2 surfaces were fabricated by direct nanoimprinting lithography of sol-gel-derived films. Square, infinitely elongated, or circular droplets were obtained with square, line, or concentric patterns, respectively, and were visualized in situ during formation and recession using optical microscopy and environmental scanning electronic microscopy. We first describe how extremely elongated droplets could form on mildly hydrophilic surfaces, naturally contaminated in real environmental conditions. In this configuration, the dew droplet shape can be dynamically and reversibly varied by controlling the out-of-equilibrium conditions associated with condensation/evaporation kinetics. As an example of the application, we propose a "morphological" sensor that exploits the shape of the dew droplets as a transduction mode for detecting organic vapors in the outer atmosphere. Importantly, this study is underlining that environmentally stable, purely hydrophilic surfaces can be smartly engineered to induce wetting phenomena at very small scale never observed so far for hydrophobic or heterogeneous surfaces. Our versatile approach based on nanoimprinted, transparent sol-gel films could open great perspectives for the implementation of environmentally stable, mildly hydrophilic materials for "dew engineering" applications such as open microfluidics, fuming for fingerprints, vapor sensing, or water harvesting on glass windows, for instance.