How to Modulate Catalytic Properties in Nanosystems: The Case of Iron–Ruthenium Nanoparticles

Abstract

Ultrasmall FeRu bimetallic nanoparticles were prepared by co‐decomposition of two organometallic precursors, {Fe[N(Si(CH3)3)2]2}2 and (η4‐1,5‐cyclooctadiene)(η6‐1,3,5‐cyclooctatriene)ruthenium(0) (Ru(COD)(COT)), under dihydrogen at 150 °C in mesitylene. A series of FeRu nanoparticles of sizes of approximately 1.8 nm and incorporating different ratios of iron to ruthenium were synthesized by varying the quantity of the ruthenium complex introduced (Fe/Ru=1:1, 1:0.5, 1:0.2, and 1:0.1). FeRu nanoparticles were characterized by TEM, high‐resolution TEM, and wide‐angle X‐ray scattering analyses. Their surface was studied by hydride titration and IR spectroscopy after CO adsorption and their magnetic properties were analyzed by using a superconducting quantum interference device (SQUID). The FeRu nanoparticles were used as catalysts in the hydrogenation of styrene and 2‐butanone. The results indicate that the selectivity of the nanoparticle catalysts can be modulated according to their composition and therefore represent a case study on fine‐tuning the reactivity of nanocatalysts and adjusting their selectivity in a given reaction.

Controlled metal nanostructures: Fertile ground for coordination chemists

“…Low values of ca. 0.4 H/Ms were observed for FeRu NPs as the consequence of the dilution of Ru atoms by Fe ones at the surface of the NPs [254]. Fe NPs were reported to have between 0.4 and 0.6 H/Fes thus evidencing the metallic character of these particles [255].…”

Geometries and electronic properties of bimetallic CuVn (n=1–5) clusters and their cations: Insight from density functional calculations

“…The performance of bimetallic clusters can be tuned by controlling their structures, components and sizes. Transition metal clusters doping with a different transition metal have been studied to devise the desired catalytic, optical, electronic, and magnetic applications in materials science, microelectronics, and medical science [8][9][10][11]. Sauvage and coworkers investigated mechanical properties of Cu/V nanocomposite wire by both scanning transmission electron microscopy and atom probe tomography [12].…”

Influence of Chemical Composition on the Catalytic Activity of Small Bimetallic FeRu Nanoparticles for Fischer–Tropsch Syntheses

“…The main preparation routes for FeRu alloys involve co-impregnation of a solid support with solutions of metallic salts, ionic liquids and their reduction [27][28][29][30], microwave irradiation [26,31] or metal organic chemical vapor deposition (MOCVD) [32]. Very recently, Kelsen et al reported a new organometallic approach for the synthesis of FeRu bimetallic nanoparticles under mild conditions [33,34]. This approach which is based on the reduction of various organometallic precursors in the presence of a reducing agent under mild conditions was originally developed in the Toulouse group for the synthesis of monodisperse magnetic nanoparticles which can be mono or bimetallic [35][36][37], or even associated with a main group element to form e.g.…”

“…carbides [38]. Thus, for the synthesis of iron-based nanoparticles, the iron bis(amide) complex {Fe[N(SiMe 3 ) 2 ] 2 } 2 (Me = CH 3 ) was chosen due to its reactivity and versatility for producing welldefined nanostructures with unprecedented magnetic [35][36][37][38][39][40][41][42][43][44], catalytic [33,34] or hyperthermia properties [38][39][40][41][42].…”

“…In a previous paper [33], the Toulouse group reported on the preparation of bimetallic FeRu nanoparticles through co-decomposition of two organometallic precursors, {Fe[N (Si(CH 3 ) 3 ) 2 ] 2 } 2 and (g 4 -1,5-cyclooctadiene)(g 6 -1,3,5-cyclooctatriene) ruthenium(0) Ru(COD)(COT), under H 2 at 150°C in mesitylene. The NPs were fully characterized by combining transmission electron microscopy (TEM), high resolution electron microscopy (HREM), wide angle X-ray scattering (WAXS) and Quantum design model MPMS 5.5 SQUID magnetometry.…”