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Magnetically induced heterogeneous catalysis has been attracting attention due to its high energy efficiency and flexibility for dynamic reactor control. Iron wool is a commercial, low-cost, and versatile heating agent, which has been used in several magnetic catalysis studies, but its heating properties have never been investigated. Here, the properties of three types of Fe wool were studied using optical and electronic microscopy, x-ray diffraction, and measurements of both heating power and high-frequency hysteresis loops. The effects of strand width, packing, and magnetic field amplitude and frequency were studied. A maximum specific absorption rate (SAR) around 700 W/g under a rms field of 47.4 mT at 93 kHz was measured for the larger width Fe wool. High-frequency hysteresis loops were used to quantify the contribution of hysteresis losses and eddy currents to total heating. Eddy currents contribute 65%–90% to the global heating depending on the strand width. Coating the wool with SiO2 and Ni has negative effects on the SAR but none on hysteresis losses. It is interpreted as originating from the cut-off of inter-wire eddy currents due to the insulating (SiO2, oxidized Ni) nature of the coating. Last, it was found that adding more Fe wool in a given volume mostly decreases the SAR. This effect could be not only due to the absorption and/or screening of the field by surface strands but also due to magnetic interactions. The results described in this work give insights into the magnetic heating of microscale magnetic materials and optimize their use for heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

The addition of zinc complexes to the syntheses of indium phosphide nanocrystals (InP NCs) has become commonplace, due to their ability to alter and significantly improve observed optical properties. In this paper, the role of zinc complexes on the synthesis and observed properties of InP is carefully examined. Produced InP and InP:Zn2+ NCs are thoroughly characterized from both structural (core and surface) and optical perspectives over a wide range of Zn2+ compositions (0%–43% atomic content). We find no differences in the physical (NC size and polydispersity) and structural properties (crystallographic phase) of InP and InP:Zn2+ NCs. Optically, significant changes are observed when zinc is added to InP syntheses, including blueshifted absorption edges and maxima, increased quantum yields, and the near elimination of surface state emission. These improved optical properties result from surface passivation by zinc carboxylate moieties. Changes to the optical properties begin at zinc concentrations as low as 5%, demonstrating the high sensitivity of InP optical properties to exogenous species. [ABSTRACT FROM AUTHOR]

The synthesis of tertiary amines from alcohols (i.e. heptanol, dodecanol, cyclohexanol, benzylalcohol) and secondary amines (Me 2 NH (DMA), n Pr 2 NH, n Bu 2 NH) has been achieved in one step using trimetallic nanoparticles (NPs) displaying a magnetic core (Co 4 Ni 6 and Fe 3 Ni 7 ) and a Cu shell as both catalysts and heating agent in the presence of an alternating magnetic field. This methodology limits the redistribution reactions occurring on amines at high temperature leading to both much higher conversion and selectivity in the absence of solvent than usually observed using conventional heating. Moreover, Co 4 Ni 6 @Cu NPs were found moisture resistant, thereby allowing for performing the reaction with commercial DMA in water (40 % wt) with again high conversion and selectivity., (© 2024 Wiley-VCH GmbH.)

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 FeNi 3 @Mo and Fe 2.2 C@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 Mo 2 C 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 FeNi 3 @WO x core-shell nanoparticles.

We have studied the photoredox-catalyzed hydrogen isotope exchange (HIE) reaction with deuterium or tritium gas as isotope sources and in situ formed transition metal nanoparticles as hydrogen atom transfer pre-catalysts. By this means we have found synergistic reactivities applying two different HIE mechanisms, namely photoredox-catalyzed and CH-functionalization HIE leading to the synthesis of highly deuterated complex molecules. Finally, we adopted these findings successfully to tritium chemistry., (© 2023 Wiley-VCH GmbH.)

The reduction of biomass-derived compounds gives access to valuable chemicals from renewable sources, circumventing the use of fossil feedstocks. Herein, we describe the use of iron-nickel magnetic nanoparticles for the reduction of biomass model compounds in aqueous media under magnetic induction. Nanoparticles with a hydrophobic ligand (FeNi 3 -PA, PA=palmitic acid) have been employed successfully, and their catalytic performance is intended to improve by ligand exchange with lysine (FeNi 3 -Lys and FeNi 3 @Ni-Lys NPs) to enhance water dispersibility. All three catalysts have been used to hydrogenate 5-hydroxymethylfurfural into 2,5-bis(hydroxymethyl)furan with complete selectivity and almost quantitative yields, using 3 bar of H 2 and a magnetic field of 65 mT in water. These catalysts have been recycled up to 10 times maintaining high conversions. Under the same conditions, levulinic acid has been hydrogenated to γ-valerolactone, and 4'-hydroxyacetophenone hydrodeoxygenated to 4-ethylphenol, with conversions up to 70 % using FeNi 3 -Lys, and selectivities above 85 % in both cases. This promising catalytic system improves biomass reduction sustainability by avoiding noble metals and expensive ligands, increasing energy efficiency via magnetic induction heating, using low H 2 pressure, and proving good reusability while working in an aqueous medium., (© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

In the present paper, we compare the activity, selectivity, and stability of a supported nickel catalyst in classical heating conditions and in magnetically activated catalysis by using iron wool as a heating agent. The catalyst, 5 wt% Ni supported on titania (Degussa P25), was prepared via an organometallic decomposition method and was thoroughly characterized by using elemental, microscopic, and diffraction techniques. In the event of magnetic induction heating, the % CO 2 conversion reached a maximum of ~85% compared to ~78% for thermal conditions at a slightly lower temperature (~335 °C) than the thermal heating (380 °C). More importantly, both processes were found to be stable for 45 h on stream. Moreover, the effects of magnetic induction and classical heating over the catalyst evolution were discussed. This study demonstrated the potential of magnetic heating-mediated methanation, which is currently under investigation for the development of pilot-scale reactors.

Ru and Rh nanoparticles catalyze the selective H/D exchange in phosphines using D 2 as the deuterium source. The position of the deuterium incorporation is determined by the structure of the P-based substrates, while activity depends on the nature of the metal, the properties of the stabilizing agents, and the type of the substituent on phosphorus. The appropriate catalyst can thus be selected either for the exclusive H/D exchange in aromatic rings or also for alkyl substituents. The selectivity observed in each case provides relevant information on the coordination mode of the ligand. Density functional theory calculations provide insights into the H/D exchange mechanism and reveal a strong influence of the phosphine structure on the selectivity. The isotope exchange proceeds via C-H bond activation at nanoparticle edges. Phosphines with strong coordination through the phosphorus atom such as PPh 3 or PPh 2 Me show preferred deuteration at ortho positions of aromatic rings and at the methyl substituents. This selectivity is observed because the corresponding C-H moieties can interact with the nanoparticle surface while the phosphine is P-coordinated, and the C-H activation results in stable metallacyclic intermediates. For weakly coordinating phosphines such as P( o -tolyl) 3 , the interaction with the nanoparticle can occur directly through phosphine substituents, and then, other deuteration patterns are observed.

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.

A new selective and efficient catalytic system for magnetically induced catalytic CO 2 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 (TiO 2 , ZrO 2 , CeO 2 , and CeZrO 2 ) 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., (© 2022 Wiley-VCH GmbH.)

II-V semiconductor nanocrystals such as Cd 3 P 2 and Zn 3 P 2 have enormous potential as materials in next-generation optoelectronic devices requiring active optical properties across the visible and infrared range. To date, this potential has been unfulfilled due to their inherent instability with respect to air and moisture. Core-shell system Cd 3 P 2 /Zn 3 P 2 is synthesized and studied from structural (morphology, crystallinity, shell diameter), chemical (composition of core, shell, and ligand sphere), and optical perspectives (absorbance, emission-steady state and time resolved, quantum yield, and air stability). The improvements achieved by coating with Zn 3 P 2 are likely due to its identical crystal structure to Cd 3 P 2 (tetragonal), highlighting the key role crystallographic concerns play in creating cutting edge core-shell NCs.

Magnetic nanoparticles (NPs) are attractive both for their fundamental properties and for their potential in a variety of applications ranging from nanomedicine and biology to micro/nanoelectronics and catalysis. While these fields are dominated by the use of iron oxides, reduced metal NPs are of interest since they display high magnetization and adjustable anisotropy according to their size, shape and composition. The use of organometallic precursors makes it possible to adjust the size, shape (sphere, cube, rod, wire, urchin, …) and composition (alloys, core-shell, composition gradient, dumbbell, …) of the resulting NPs and hence their magnetic properties. We discuss here the synthesis of magnetic metal NPs from organometallic precursors carried out in Toulouse, as well as their associated properties and their potential in applications., (© 2022 Wiley-VCH GmbH.)

The development of energetically efficient processes for the aqueous reduction of biomass-derived compounds into chemicals is key for the optimal transformation of biomass. Herein we report an early example of the reduction of biomass-derived oxygenated compounds in water by magnetically induced catalysis. Non-coated and carbon-coated core-shell FeCo@Ni magnetic nanoparticles were used as the heating agent and the catalyst simultaneously. In this way it was possible to control the product distribution by adjusting the field amplitude applied during the magnetic catalysis, opening a precedent for this type of catalysis. Finally, the encapsulation of the magnetic nanoparticles in carbon ( FeCo@Ni@C ) strongly improved the stability of the magnetic catalyst in solution, making its reuse possible up to at least eight times in dioxane and four times in water., Competing Interests: The authors declare no competing financial interest., (© 2022 American Chemical Society.)

The synthesis of metallic nanoparticles (MNP) with high surface area and controlled shape is of paramount importance to increase their catalytic performance. The detailed growing process of NP is mostly unknown and understanding the specific steps would pave the way for a rational synthesis of the desired MNP. Here we take advantage of the stabilization properties exerted by the tetragonal prismatic supramolecular nanocapsule 8·(BArF) 8 to develop a synthetic methodology for sub-nanometric RuNP (0.6-0.7 nm). The catalytic properties of these sub-nanometric nanoparticles were tested on the hydrogenation of styrene, obtaining excellent selectivity for the hydrogenation of the alkene moiety. In addition, the encapsulation of [Ru 5 ] clusters inside the nanocapsule is strikingly observed in most of the experimental conditions, as ascertained by HR-MS. Moreover, a thorough DFT study enlightens the nature of the [Ru 5 ] clusters as tb-Ru 5 H 2 (η 6 -PhH) 2 (η 6 -pyz) 3 (2) trapped by two arene moieties of the clip, or as tb-Ru 5 H 2 (η 1 -pyz) 6 (η 6 -pyz) 3 (3) trapped between the two Zn-porphyrin units of the nanocapsule. Both options fulfill the Wade-Mingos counting rules, i.e. 72 CVEs for the closo tb. The trapped [Ru 5 ] metallic clusters are proposed to be the first-grown seeds of subsequent formation of the subnanometric RuNP. Moreover, the double role of the nanocapsule in stabilising ∼0.7 nm NPs and also in hosting ultra-small Ru clusters, is unprecedented and may pave the way towards the synthesis of ultra-small metallic clusters for catalytic purposes.

Copper chromite is decorated with iron carbide nanoparticles, producing a magnetically activatable multifunctional catalytic system. This system (ICNPs@Cu 2 Cr 2 O 5 ) can reduce aromatic ketones to aromatic alcohols when exposed to magnetic induction. Under magnetic excitation, the ICNPs generate locally confined hot spots, selectively activating the Cu 2 Cr 2 O 5 surface while the global temperature remains low (≈80 °C). The catalyst selectively hydrogenates a scope of benzylic and non-benzylic ketones under mild conditions (3 bar H 2 , heptane), while ICNPs@Cu 2 Cr 2 O 5 or Cu 2 Cr 2 O 5 are inactive when the same global temperature is adjusted by conventional heating. A flow reactor is presented that allows the use of magnetic induction for continuous-flow hydrogenation at elevated pressure. The excellent catalytic properties of ICNPs@Cu 2 Cr 2 O 5 for the hydrogenation of biomass-derived furfuralacetone are conserved for at least 17 h on stream, demonstrating for the first time the application of a magnetically heated catalyst to a continuously operated hydrogenation reaction in the liquid phase., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Herein we describe a new method for the determination of the surface temperature of magnetically heated nanoparticles in solution using the temperature dependency of the catalytic performances of iron carbide nanoparticles coated with ruthenium (Fe 2.2 C@Ru) for acetophenone hydrodeoxygenation. A correlation between nanoparticle surface temperature and magnetic field could be established. Very high surface temperatures could be estimated in different solvents, which were also found similar at a given magnetic field and well above some solvent boiling points.

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 ( M s = 235 A·m 2 ·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.

Formation of stable carbides during CO bond dissociation on small ruthenium nanoparticles (RuNPs) is demonstrated, both by means of DFT calculations and by solid state 13 C NMR techniques. Theoretical calculations of chemical shifts in several model clusters are employed in order to secure experimental spectroscopic assignations for surface ruthenium carbides. Mechanistic DFT investigations, carried out on a realistic Ru 55 nanoparticle model (∼1 nm) in terms of size, structure and surface composition, reveal that ruthenium carbides are obtained during CO hydrogenation. Calculations also indicate that carbide formation via hydrogen-assisted hydroxymethylidyne (COH) pathways is exothermic and occurs at reasonable kinetic cost on standard sites of the RuNPs, such as 4-fold ones on flat terraces, and not only in steps as previously suggested. Another novel outcome of the DFT mechanistic study consists of the possible formation of μ 6 ruthenium carbides in the tip-B 5 site, similar examples being known only for molecular ruthenium clusters. Moreover, based on DFT energies, the possible rearrangement of the surface metal atoms around the same tip-site results in a μ-Ru atom coordinated to the remaining RuNP moiety, reminiscent of a pseudo-octahedral metal center on the NP surface.