Induction heating: an efficient methodology for the synthesis of functional core-shell nanoparticles.

Induction heating has been applied for a variety of purposes over the years, including hyperthermia-induced cell death, industrial manufacturing, and heterogeneous catalysis. However, its potential in materials synthesis has not been extensively studied. Herein, we have demonstrated magnetic induction heating-assisted synthesis of core-shell nanoparticles starting from a magnetic core. The induction heating approach allows an easy synthesis of FeNi3@Mo and Fe2.2C@Mo nanoparticles containing a significantly higher amount of molybdenum on the surface than similar materials synthesized using conventional heating. Exhaustive electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy characterization data are presented to establish the core-shell structures. Furthermore, the molybdenum shell was transformed into the Mo2C phase, and the catalytic activity of the resulting nanoparticles tested for the propane dry reforming reaction under induction heating. Lastly, the beneficial role of induction heating-mediated synthesis was extended toward the preparation of the FeNi3@WOx core-shell nanoparticles.

Highly dispersed Rh single atoms over graphitic carbon nitride as a robust catalyst for the hydroformylation reaction.

Rhodium-catalysed hydroformylation, effective tool in bulk and fine-chemical synthesis, predominantly uses soluble metal complexes. For that reason, the metal leaching and the catalyst recycling are still the major drawbacks of this process. Single-atom catalysts have emerged as a powerful tool to combine the advantages of both homogeneous and heterogeneous catalysts. Since using an appropriate support material is key to create stable, finely dispersed, single-atom catalysts, here we show that Rh atoms anchored on graphitic carbon nitride are robust catalysts for the hydroformylation reaction of styrene.

Water-soluble NHC Pd/Ni bimetallic nanoparticles for H/D exchange in aromatic amino-acids.

Labelling of amino-acids is important for the production of deuterated proteins. However, aromatic amino-acid reduction is a common undesired process with noble-metal nanocatalysts. In this work, we describe a new NHC-stabilized water-soluble Pd/Ni system able to perform H/D exchange reactions in an enantiospecific fashion without reducing the aromatic ring of phenylalanine and tyrosine thanks to a synergetic Pd-Ni effect.

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.

Grafting Copper Atoms and Nanoparticles on Double-Walled Carbon Nanotubes: Application to Catalytic Synthesis of Propargylamine.

The decoration of carbon nanotubes (CNTs) by metal nanoparticles (NPs) combines the advantages of a high specific surface material with catalytic properties of metal nanocrystals. Little work has been devoted to the decoration of CNTs with copper NPs, and no evidence of copper atomic decoration of CNTs has shown up until now. Herein, we demonstrate that the strong acidic oxidation of double-walled CNTs (dwCNTs) is very efficient for the decoration of the carbon surface by copper NPs and atoms. This treatment severely degraded the CNT walls and generated a large amount of disordered sp3 carbon. This amorphous carbon film bears many chemically active functions like carboxyl and hydroxyl ones. In such conditions, the CNT walls behave as very efficient ligands for the stabilization of copper obtained by the thermolysis of the mesityl precursor in organic solution under mild dihydrogen pressure. In addition to copper NPs, we evidenced the presence of a regular coverage with copper atoms over the dwCNTs. This nanocomposite catalyzes the quantitative synthesis of propargylamines via one A3-type coupling reaction. Five consecutive catalytic cycles with 100% yield could be performed with no loss of activity, and the combination of Cu supported on dwCNTs allows a facile recycling of the catalytic material.

Synthesis of NiFeOx nanocatalysts from metal-organic precursors for the oxygen evolution reaction.

Production of hydrogen from a renewable source that is water requires the development of sustainable catalytic processes. This implies, among others, developing efficient catalytic materials from abundant and low-cost resources and investigating their performance, especially in the oxidation of water as this half-reaction is the bottleneck of the water splitting process. For this purpose, NiFe-based nanoparticles with sizes ca. 3-4 nm have been synthesized by an organometallic approach and characterized by complementary techniques (WAXS, TEM, STEM-HAADF, EDX, XPS, and ATR-FTIR). They display a Ni core and a mixed Ni-Fe oxide shell. Once deposited onto FTO electrodes, they have been assessed in the electrocatalytic oxygen evolution reaction under alkaline conditions. Three different Ni/Fe ratios (2/1, 1/1 and 1/9) have been studied in comparison with their monometallic counterparts. The Ni2Fe1 nanocatalyst displayed the lowest overpotential (320 mV at j = 10 mA cm-2) as well as excellent stability over 16 h.

Covalent Grafting of Ruthenium Complexes on Iron Oxide Nanoparticles: Hybrid Materials for Photocatalytic Water Oxidation.

The present environmental crisis prompts the search for renewable energy sources such as solar-driven production of hydrogen from water. Herein, we report an efficient hybrid photocatalyst for water oxidation, consisting of a ruthenium polypyridyl complex covalently grafted on core/shell Fe@FeOx nanoparticles via a phosphonic acid group. The photoelectrochemical measurements were performed under 1 sun illumination in 1 M KOH. The photocurrent density of this hybrid photoanode reached 20 µA/cm2 (applied potential of +1.0 V vs reversible hydrogen electrode), corresponding to a turnover frequency of 0.02 s-1. This performance represents a 9-fold enhancement of that achieved with a mixture of Fe@FeOx nanoparticles and a linker-free ruthenium polypyridyl photosensitizer. This increase in performance could be attributed to a more efficient electron transfer between the ruthenium photosensitizer and the Fe@FeOx catalyst as a consequence of the covalent link between these two species through the phosphonate pendant group.

An air-stable, reusable Ni@Ni(OH)2 nanocatalyst for CO2/bicarbonate hydrogenation to formate.

Production of formate via CO2/bicarbonate hydrogenation using cheap metal-based heterogeneous catalysts is attractive. Herein, we report the organometallic synthesis of a foam-like Ni@Ni(OH)2 composite nanomaterial which exhibited remarkable air stability and over 2 times higher catalytic activity than commercial RANEY® Ni catalyst in formate synthesis. Formate generation was achieved with an optimal rate of 6.0 mmol gcat-1 h-1 at 100 °C, a significantly lower operation temperature compared to the 200-260 °C reported in the literature. Deep characterization evidenced that this nanomaterial was made of an amorphous Ni(OH)2 phase covering metallic Ni sites; a core-shell structure which is crucial for the stability of the catalyst. The adsorption of bicarbonates onto the Ni@Ni(OH)2 catalyst was found to be a kinetically relevant step in the reaction, and the Ni-Ni(OH)2 interface was found to be beneficial for both CO2 and H2 activation thanks to a cooperative effect. Our findings emphasize the underestimated potential of Ni-based catalysts in CO2 hydrogenation to formate, indicating a viable strategy to develop stable, cheap metal catalysts for greener catalytic applications.

Industrially scalable surface treatments to enhance the current density output from graphite bioanodes fueled by real domestic wastewater.

Acid and electrochemical surface treatments of graphite electrode, used individually or in combination, significantly improved the microbial anode current production, by +17% to +56%, in well-regulated and duplicated electroanalytical experimental systems. Of all the consequences induced by surface treatments, the modifications of the surface nano-topography preferentially justify an improvement in the fixation of bacteria, and an increase of the specific surface area and the electrochemically accessible surface of graphite electrodes, which are at the origin of the higher performances of the bioanodes supplied with domestic wastewater. The evolution of the chemical composition and the appearance of C-O, C=O, and O=C-O groups on the graphite surface created by combining acid and electrochemical treatments was prejudicial to the formation of efficient domestic-wastewater-oxidizing bioanodes. The comparative discussion, focused on the positioning of the performances, shows the industrial interest of applying the surface treatment method to the world of bioelectrochemical systems.

Chemical Interactions at the Al/Poly-Epoxy Interface Rationalized by DFT Calculations and a Comparative XPS Analysis.

A metal-polymer interface is pertinent to numerous technological applications, especially in spatial sectors. The focus of this work is to elaborate on the metallization process of the poly-epoxy surface with aluminum thin films, using atomistic details. To this end, X-ray photoelectron spectroscopy (XPS) under ultrahigh vacuum and density functional theory calculations are employed. The interfacial bonding between Al atoms and the poly-epoxide surface, represented by a dimer model, is studied by determining adsorption energies and by simulating XPS spectra. The latter simulations are mainly performed using the ΔKS method, taking into account the initial and the final state effects. Simulated atom-by-atom metal deposition on model epoxy systems is attempted to further elucidate energetics of metallization and preferential arrangement of metal atoms at the interface. A fair agreement obtained between XPS experiments and computations rationalizes the interaction mechanism at the atomic scale explaining the formation of the Al/poly-epoxy interface. Electronic structure properties highlight the charge transfer from the Al atom(s) to dehydrogenated model epoxy system.

Bidimensional lamellar assembly by coordination of peptidic homopolymers to platinum nanoparticles.

A key challenge for designing hybrid materials is the development of chemical tools to control the organization of inorganic nanoobjects at low scales, from mesoscopic (~µm) to nanometric (~nm). So far, the most efficient strategy to align assemblies of nanoparticles consists in a bottom-up approach by decorating block copolymer lamellae with nanoobjects. This well accomplished procedure is nonetheless limited by the thermodynamic constraints that govern copolymer assembly, the entropy of mixing as described by the Flory-Huggins solution theory supplemented by the critical influence of the volume fraction of the block components. Here we show that a completely different approach can lead to tunable 2D lamellar organization of nanoparticles with homopolymers only, on condition that few elementary rules are respected: 1) the polymer spontaneously allows a structural preorganization, 2) the polymer owns functional groups that interact with the nanoparticle surface, 3) the nanoparticles show a surface accessible for coordination.

When organophosphorus ruthenium complexes covalently bind to ruthenium nanoparticles to form nanoscale hybrid materials.

A hybrid material made of mononuclear organophosphorus polypyridyl ruthenium complexes covalently bonded to ruthenium nanoparticles has been synthesized via a one-pot organometallic procedure and finely characterized. These results open new avenues to access unique hybrid transition metal nanomaterials.

Organometallic Synthesis of CuO Nanoparticles: Application in Low-Temperature CO Detection.

A metal-organic approach has been employed for the preparation of anisotropic CuO nanoparticles. These nanostructures have been characterized by transmission and high resolution transmission electron microscopy, field-emission scanning electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The CuO nanoparticles have been deposited as gas-sensitive layers on miniaturized silicon devices. At an operating temperature of 210 °C, the sensors present an optimum response toward carbon monoxide correlated with a fast response (Rn) and short recovery time. A high sensitivity to CO (Rn≈150 %, 100 ppm CO, RH 50 %) is achieved. These CuO nanoparticles serve as a very promising sensing layer for the fabrication of selective CO gas sensors working at a low temperature.

Solution Layer Deposition: A Technique for the Growth of Ultra-Pure Manganese Oxides on Silica at Room Temperature.

With the ever increasing miniaturization in microelectronic devices, new deposition techniques are required to form high-purity metal oxide layers. Herein, we report a liquid route to specifically produce thin and conformal amorphous manganese oxide layers on silicon substrate, which can be transformed into a manganese silicate layer. The undesired insertion of carbon into the functional layers is avoided through a solution metal-organic chemistry approach named Solution Layer Deposition (SLD). The growth of a pure manganese oxide film by SLD takes place through the decoordination of ligands from a metal-organic complex in mild conditions, and coordination of the resulting metal atoms on a silica surface. The mechanism of this chemical liquid route has been elucidated by solid-state (29) Si MAS NMR, XPS, SIMS, and HRTEM.