Colloidal Ru nanoparticles (NP) display interesting catalytic properties for the hydrogenation of (hetero)arenes as they proceed efficiently in mild reaction conditions. In this work, a series of Ru based materials was used in order to selectively hydrogenate quinaldine and assess the impact of the stabilizing agent on their catalytic performances. Ru nanoparticles stabilized with polyvinylpyrrolidone (PVP) and 1-adamantanecarboxylic acid (AdCOOH) allowed to obtain 5,6,7,8-tetrahydroquinaldine with a remarkable selectivity in mild reaction conditions by choosing the suitable solvent. The presence of a carboxylate ligand on the surface of the Ru NP led to an increase in the activity when compared to Ru/PVP catalyst. The stabilizing agent had also an impact on the selectivity, as carboxylate ligand modified catalysts promoted the selectivity towards 1,2,3,4-tetrahydroquinaldine, with bulky carboxylate displaying the highest ones.
A series of ruthenium nanoparticles (RuNPs) were synthesized by the organometallic approach in different functionalized imidazolium ionic liquids (FILs). Transmission electron microscopy (TEM) showed well-dispersed and narrow-sized RuNPs ranging from 1.3 to 2.2 nm, depending on the IL functionalization. Thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) allowed the interaction between the RuNPs and the ILs to be studied. The RuNPs stabilized by methoxy-based FILs (MEM and MME) displayed a good balance between catalytic activity and stability when evaluated in the hydrogenation of styrene (S) under mild reaction conditions. Moreover, the catalysts showed total selectivity towards ethylbenzene (EB) under milder reaction conditions (5 bar, 30 °C) than reported in the literature for other RuNP catalysts.
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.
Exploiting biomass to synthesise compounds that may replace fossil-based ones is of high interest in order to reduce dependence on non-renewable resources. 1,2-pentanediol and 1,5-pentanediol can be produced from furfural, furfuryl alcohol or tetrahydrofurfuryl alcohol following a metal catalysed hydrogenation/C-O cleavage procedure. Colloidal ruthenium nanoparticles stabilized with polyvinylpyrrolidone in situ modified with different organic compounds are able to produce 1,2-pentanediol directly from furfural in a 36% of selectivity at 125 °C under 20 bar of H2 pressure.
Ultrasmall gold nanoparticles (NPs) stabilized in networks by polymantane ligands (diamondoids) were successfully used as precatalysts for highly selective heterogeneous gold-catalyzed dimethyl allyl(propargyl)malonate cyclization to 5-membered conjugated diene. Such reaction usually suffers from selectivity issues with homogeneous catalysts. This control over selectivity further opened the way to one-pot cascade reaction, as illustrated by the 1,6-enyne cycloisomerization-Diels-Alder reaction of dimethyl allyl propargyl malonate with maleic anhydride. The ability to assemble nanoparticles with controllable sizes and shapes within networks concerns research in sensors, medical diagnostics, information storage, and catalysis applications. Herein, the control of the synthesis of sub-2-nm gold NPs is achieved by the formation of dense networks, which are assembled in a single step reaction by employing ditopic polymantanethiols. By using 1,1'-bisadamantane-3,3'-dithiol (BAd-SH) and diamantane-4,9-dithiol (DAd-SH), serving both as bulky surface stabilizers and short-sized linkers, we provide a simple method to form uniformly small gold NPs (1.3 ± 0.2 nm to 1.6 ± 0.3 nm) embedded in rigid frameworks. These NP arrays are organized alongside short interparticular distances ranging from 1.9 to 2.7 nm. The analysis of gold NP surfaces and their modification were achieved in joint experimental and theoretical studies, using notably XPS, NMR, and DFT modeling. Our experimental studies and DFT analyses highlighted the necessary oxidative surface reorganization of individual nanoparticles for an effective enyne cycloisomerization. The modifications at bulky stabilizing ligands allow surface steric decongestion for the alkyne moiety activation but also result in network alteration by overoxidation of sulfurs. Thus, sub-2-nm nanoparticles originating from networks building create convenient conditions for generating reactive Au(I) surface single-sites-in the absence of silver additives-useful for heterogeneous gold-catalyzed enyne cyclization. These nanocatalysts, which as such ease organic products separation, also provide a convenient access for building further polycyclic complexity, owing to their high reactivity and selectivity.
This review provides a synthetic overview of the recent research advancements addressing the topic of catalysis with colloidal ruthenium metal nanoparticles through the last five years. The aim is to enlighten the interest of ruthenium metal at the nanoscale for a selection of catalytic reactions performed in solution condition. The recent progress in nanochemistry allowed providing well-controlled ruthenium nanoparticles which served as models and allowed study of how their characteristics influence their catalytic properties. Although this parameter is not enough often taken into consideration the surface chemistry of ruthenium nanoparticles starts to be better understood. This offers thus a strong basis to better apprehend catalytic processes on the metal surface and also explore how these can be affected by the stabilizing molecules as well as the ruthenium crystallographic structure. Ruthenium nanoparticles have been reported for their application as catalysts in solution for diverse reactions. The main ones are reduction, oxidation, Fischer-Tropsch, C-H activation, CO2 transformation, and hydrogen production through amine borane dehydrogenation or water-splitting reactions, which will be reviewed here. Results obtained showed that ruthenium nanoparticles can be highly performant in these reactions, but efforts are still required in order to be able to rationalize the results. Beside their catalytic performance, ruthenium nanocatalysts are very good models in order to investigate key parameters for a better controlled nanocatalysis. This is a challenging but fundamental task in order to develop more efficient catalytic systems, namely more active and more selective catalysts able to work in mild conditions.
Sulfur- (S-CNT) and nitrogen-doped (N-CNT) carbon nanotubes have been produced by catalytic chemical vapor deposition (c-CVD) and were subject to an annealing treatment. These CNTs were used as supports for small (≈2 nm) Pt3M (M = Co or Ni) alloyed nanoparticles that have a very homogeneous size distribution (in spite of the high metal loading of ≈40 wt % Pt), using an ionic liquid as a stabilizer. The electrochemical surface area, the activity for the oxygen reduction reaction and the amount of H2O2 generated during the oxygen reduction reaction (ORR) have been evaluated in a rotating ring disk electrode experiment. The Pt3M/N-CNT catalysts revealed excellent electrochemical properties compared to a commercial Pt3Co/Vulcan XC-72 catalyst. The nature of the carbon support plays a key role in determining the properties of the metal nanoparticles, on the preparation of the catalytic layer, and on the electrocatalytic performance in the ORR. On N-CNT supports, the specific activity followed the expected order Pt3Co > Pt3Ni, whereas on the annealed N-CNT support, the order was reversed.
The C66 (COOH)12 hexa-adduct has been successfully used as a building block to construct carboxylate bridged 3D networks with very homogeneous sub-1.8â nm ruthenium nanoparticles. The obtained nanostructures are active in nitrobenzene selective hydrogenation.
Core-shell RuPt (Ru core-Pt shell) and PtRu (Pt core-Ru shell) nanoparticles were prepared by decomposing in a two-step procedure a ruthenium ([Ru(COD)(COT)] (COD = 1,5-cyclooctadiene, COT = 1,3,5-cyclooctatriene)) and a platinum complex ([Pt2(dba)3] (dba = dibenzylideneacetone) or [Pt(CH3)2(COD)]) in the presence of 4-(3-phenylpropyl)pyridine (PPP) as a stabilizer and using different Ru/Pt ratios. The data obtained from a combination of several analyses (TEM, HRTEM, WAXS and IR) indicate that the so-obtained nanoparticles present a core-shell structure. The catalytic performances of these bimetallic nanoparticles for the selective hydrogenation of trans-cinnamaldehyde were investigated, which provided interesting results as well as useful information to elucidate their structure and composition. Indeed, the catalytic results evidence that: (1) the combination of both metals led in some cases to a synergistic effect on the selectivity of the reaction, and (2) the structure and the composition affected the selectivity of the reaction.
The morphology of platinum nanoparticles synthesized using an organometallic approach from PtMe(2) (C(8) H(12) ) is influenced by the nature of the ligands used as stabilizing agents. The use of long alkyl chain amines leads to the formation of multipodal nanoparticles that transform into compact nano-objects, adopting cubic, truncated cubic, or cuboctahedral shapes. In contrast, the use of diamine ligands allows the growth of compact (111) arrowlike faces, forming polycrystalline nanoparticles of an overall desert-rose aspect. Different reaction parameters are studied ([ligand]/[metal] ratio, temperature, solvent identity) in order to optimize the various shapes.
Metal Nanoparticles/chemistry , Platinum/chemistry , Metal Nanoparticles/ultrastructure , Microscopy, Electron, Transmission , Nanotechnology
The synthesis, X-ray structure determination, and photophysical investigation of a novel series of heteroleptic ruthenium(II) polypyridine complexes with organometallic linkers are reported. The displayed panchromatic absorption features are assigned by means of time-dependent density functional theory studies.
Ruthenium nanoparticles (RuNPs) were prepared through the hydrogenation of [Ru(COD)(COT)] (COD = 1,5-cyclooctadiene, COT = 1,3,5-cyclooctatriene) in the presence of diphosphites derived from carbohydrates as stabilizing agents, and interestingly, structural modifications of the diphosphite backbone were found to influence nanoparticle size and dispersity, as well as their catalytic activity in arene hydrogenation.
Alkenes/chemistry , Hydrogen/chemistry , Nanoparticles/chemistry , Organometallic Compounds/chemistry , Ruthenium/chemistry , Carbon/chemistry , Magnetic Resonance Spectroscopy/methods , Organometallic Compounds/chemical synthesis , Particle Size , Phosphines/chemistry , Surface Properties , Temperature , Titrimetry
