SBA-15/POSS-Imidazolium Hybrid as Catalytic Nanoreactor
Supported imidazolium modified polyhedral oligomeric silsesquioxanes (POSS) on SBA-15 have been used as platform for Pd(II) species. The so-obtained material was firstly characterized by means of TGA, solid state NMR, TEM, XPS, SAXS, porosimetry and ICP-OES and it was successfully tested as pre-catalyst in C−C cross couplings, namely Suzuki-Miyaura and Heck reactions. In both cases, the solid proved to be highly efficient and easily recoverable from the reaction mixture. The recyclability was verified for up to seven cycles without showing any activity decrease. Interestingly, only Pd(II) was detected in the reused catalyst in the Heck reaction. Therefore, the versatility of the material w…
Materiali ibridi a base di POSS-Imidazolio per la conversione della CO2 in carbonati ciclici
Lo sviluppo di catalizzatori per i processi di conversione della CO2 è una tematica che sta rivestendo un ruolo di rilevante importanza in ambito non soltanto accademico ma anche industriale grazie alla possibilità di trasformare un rifiuto, quale il diossido di carbonio, in una vasta gamma di prodotti. Nel presente lavoro, nuovi materiali ibridi costituiti da silsesquiossani poliedrici oligomerici (POSS) supportati su silice e funzionalizzati con sali di imidazolio sono stati progettati per la fissazione della CO2. 1 Tutti i solidi sono stati ampiamente caratterizzati e testati per la sintesi di carbonati ciclici tramite reazione tra CO2 ed epossidi in condizioni di reazione solvent-free (…
Design of POSS-Imidazolium Supported Hybrids for the Conversion of Carbon Dioxide into Cyclic Carbonates
Nowadays, the design of heterogeneous catalysts for the conversion of CO2 into useful chemical products is attracting the attention of the scientific community. The catalytic processes involving carbon dioxide as C1 feedstock are of growing interest for the sustainable development.1 The synthesis of cyclic carbonates by coupling CO2 with epoxides is one of the most interesting pathways for the conversion of carbon dioxide in terms of both atom economy and final products applications. Moreover, ionic liquids emerged as one of the most active catalysts for the production of cyclic carbonates starting from CO2 and epoxides.2 Herein, a series of heterogeneous catalytic systems bearing imidazoli…
Heterogenizing palladium tetraiodide catalyst for carbonylation reactions
We report the first example of successful heterogenization of the classical PdI42- carbonylation catalyst, achieved in two simple steps from ionic liquid-functionalized multi-walled carbon nanotubes (MWCNTs). The newly developed materials (PdI4@MWCNT-imi-X, X = Br, I) present the PdI42- anion supported on an imidazolium network (imi) grown on MWCNTs and have been fully characterized. The activity of PdI4@MWCNT-imi-X has been successfully tested in a paradigmatic carbonylation reaction, the oxidative monoaminocarbonylation of 1-alkynes with amines to give high value added 2-ynamides (obtained in good yields, 50–84%, starting from various substrates). The heterogeneous catalyst could be easil…
Correction: Supported C60-IL-PdNPs as extremely active nanocatalysts for C–C cross-coupling reactions
Correction for ‘Supported C60-IL-PdNPs as extremely active nanocatalysts for C–C cross-coupling reactions’ by Francesco Giacalone et al., J. Mater. Chem. A, 2016, 4, 17193–17206.
Supported Imidazolium Functionalized POSS Hybrids as Palladium Platform for C-C Cross-Couplings
Lo sviluppo di catalizzatori per i processi di conversione della CO2 è una tematica che sta rivestendo un ruolo di rilevante importanza in ambito non soltanto accademico ma anche industriale grazie alla possibilità di trasformare un rifiuto, quale il diossido di carbonio, in una vasta gamma di prodotti. Nel presente lavoro, nuovi materiali ibridi costituiti da silsesquiossani poliedrici oligomerici (POSS) supportati su silice e funzionalizzati con sali di imidazolio sono stati progettati per la fissazione della CO2. 1 Tutti i solidi sono stati ampiamente caratterizzati e testati per la sintesi di carbonati ciclici tramite reazione tra CO2 ed epossidi in condizioni di reazione solvent-free (…
Imidazolium-Functionalized Carbon Nanohorns for the Conversion of CO2 Unprecedented Increase of Catalytic Activity after Recycling
Carbon nanohorns (CNHs) were selected as a novel catalytic platform for the design of imidazolium based hybrid materials able to promote the conversion of carbon dioxide into cyclic carbonates. Several heterogeneous catalysts were prepared using a one-step procedure based on the radical polymerization of various bis-vinylimidazolium salts in the presence of pristine CNHs. The as-synthesized materials were tested for the fixation of CO2 into epoxides. The excellent catalytic performances were evaluated in terms of turnover number and productivity. The versatility of the above hybrids was proved using several epoxides as substrate. Catalysts recyclability was successfully verified for several…
Materiali catalitici a base di nanoparticelle di palladio immobilizzate su nanoforme di carbonio
Front Cover Picture: SBA‐15/POSS‐Imidazolium Hybrid as Catalytic Nanoreactor: the role of the Support in the Stabilization of Palladium Species for C−C Cross Coupling Reactions. (Adv. Synth. Catal. 16/2019)
Hybrid catalysts for CO 2 conversion into cyclic carbonates
The conversion of carbon dioxide into valuable chemicals such as cyclic carbonates is an appealing topic for the scientific community due to the possibility of valorizing waste into an inexpensive, available, nontoxic, and renewable carbon feedstock. In this regard, last-generation heterogeneous catalysts are of great interest owing to their high catalytic activity, robustness, and easy recovery and recycling. In the present review, recent advances on CO 2 cycloaddition to epoxide mediated by hybrid catalysts through organometallic or organo-catalytic species supported onto silica-, nanocarbon-, and metal-organic framework (MOF)-based heterogeneous materials, are highlighted and discussed.
Imidazolium-Functionalized Carbon Nanohorns for the Conversion of Carbon Dioxide
Six new hybrid materials composed of carbon nanohorns (CNHs) and highly cross-linked imidazolium salts were easily synthesized using a one-step procedure based on the radical oligomerization of bis-vinylimidazolium salts (bVImiX) in the presence of pristine CNHs. The hybrid materials were characterized and employed as the sole catalysts for the conversion of carbon dioxide into cyclic carbonate by reaction with epoxides. The solids displayed excellent turnover number and productivity. Moreover, four catalysts were investigated in recycling experiments. Two catalysts containing an octyl linker between the imidazolium units and a bromide or an iodide anion showed no loss in activity after thr…
Single-Walled Carbon Nanotube–Polyamidoamine Dendrimer Hybrids for Heterogeneous Catalysis
We report the synthesis and catalytic properties of single-walled carbon nanotube-polyamidoamine dendrimers hybrids (SWCNT-PAMAM), prepared via a convergent strategy. The direct reaction of cystamine-based PAMAM dendrimers (generations 2.5 and 3.0) with pristine SWCNTs in refluxing toluene, followed by immobilization and reduction of [PdCl4](2-), led to the formation of highly dispersed small palladium nanoparticles homogeneously confined throughout the nanotube length. One of these functional materials proved to be an efficient catalyst in Suzuki and Heck reactions, able to promote the above processes down to 0.002 mol % showing a turnover number (TON) of 48 000 and a turnover frequency (T…
DESIGN OF NOVEL IMIDAZOLIUM BASED NANOSTRUCTURES FOR SUSTAINABLE CATALYTIC APPLICATIONS
Templating effect of carbon nanoforms on highly cross-linked imidazolium network: Catalytic activity of the resulting hybrids with Pd nanoparticles
Two different carbon nanoforms (CNFs), namely multi-walled carbon nanotubes (MWCNTs) and carbon nanohorns (CNHs), have been chosen as support for the direct polymerization of a bis-vinylimidazolium salt. Transmission electron microscopy analyses revealed a templating effect of the CNFs on the growth of the polymeric network, which perfectly covers their whole surfaces creating a cylindrical or spherical coating for MWCNTs and CNHs, respectively. Subsequently, the CNFs-polyimidazolium have been used as stabilizers for Pd nanoparticles (Pd NPs), and the obtained materials have been characterized by means of analytical and spectroscopic techniques and then employed as easily recoverable and re…
Supported C60-IL-PdNPs as extremely active nanocatalysts for C-C cross-coupling reactions
A C60-ionic liquid hybrid has been covalently linked to three different solid supports, namely amorphous silica, SBA-15 and Fe2O3@SiO2, and the resulting materials have been employed as covalently supported ionic liquid phases (cSILP) in order to immobilize and stabilize palladium nanoparticles (PdNPs). These novel hybrid materials are based on a sort of "matryoshka" system (PdNPs@imidazolium-salt@C60@support) in which the imidazolium-based moieties have not been directly linked to the surface of the support, but they are present in an octopus-like spatial arrangement on the uniformly surface-distributed fullerenes. These materials have been fully characterized and successfully employed as …
Efficient Conversion of Carbon Dioxide by Imidazolium-Based Cross-Linked Nanostructures Containing Polyhedral Oligomeric Silsesquioxane (POSS) Building Blocks
Polyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular building blocks for the synthesis of imidazolium cross-linked networks, to be used as heterogeneous catalysts for the conversion of carbon dioxide into cyclic carbonates. Two hybrid materials with different nucleophilic species (bromide and iodide) have been prepared and characterized by means of elemental analysis, 13C and 29Si solid-state NMR spectroscopy, thermogravimetric analysis and IR spectroscopy. The solids were tested as the sole catalyst under metal- and solvent-free reaction conditions showing full selectivity toward the formation of cyclic carbonates. High turnover number (TON) and productivity values,…
POSS nanostructures in catalysis
Polyhedral oligomeric silsesquioxanes (POSS) are organic-inorganic hybrid molecules piquing the interest of researchers thanks to their synergistic features. The great versatility of POSS nanostructures arises from the easy tunability of peripheral organic moieties combined with the high thermal and chemical stability of the inner inorganic core. In this review, we highlight the use of POSS nanostructures as molecular precursors for the synthesis of homogeneous and heterogeneous catalysts able to promote many processes including alkene epoxidation, C-C bond formation, CO2 conversion, "click reactions", hydrogenation, and ethylene polymerisation, among others. In this scenario, POSS units fo…
Catalizzatori a base di nanocorni di carbonio-liquidi ionici per la conversione della CO2
Nel presente lavoro sono stati impiegati nanocorni di carbonio (CNHs) come piattaforma catalitica per il design di nuovi materiali ibridi a base di sali di imidazolio per la conversione della CO2 in carbonati ciclici. A tale scopo sono stati preparati una serie di catalizzatori eterogenei mediante una procedura sintetica one-pot basata sulla polimerizzazione radicalica di vari sali di bis vinilimidazolio in presenza di nanocorni di carbonio. I suddetti materiali sono stati caratterizzati e testati con successo per la reazione di fissazione della CO2 in epossidi (Figura 1). Figura 1 Conversione della CO2 catalizzata da liquidi ionici supportati su CNHs Le performances catalitiche, valutate i…
Supported Fullerene C60-Ionic Liquid Hybryds as New Catalytic Materials
Imidazolium Based Cross-Linked Nanostructures from POSS molecular bricks for the Efficient Conversion of Carbon Dioxide
Polyhedral oligomeric silsesquioxanes (POSS) have been employed as molecular bricks for the synthesis of imidazolium cross-linked networks as heterogeneous catalyst for the conversion of carbon dioxide into cyclic carbonates via reaction with epoxides. Two hybrid materials with different nucleophilic species (bromide and iodide) have been prepared and characterized by means of elemental analysis, 13C and 29Si solid state NMR, thermogravimetric analysis and IR spectroscopy. The solids were tested as the sole catalyst under metal- and solvent-free reaction conditions showing full selectivity toward the formation of cyclic carbonates and outstanding productivity values. Several epoxides were r…
Supported Polyhedral Oligomeric Silsesquioxane-Based (POSS) Materials as Highly Active Organocatalysts for the Conversion of CO2
Very high turnover numbers (TON) and productivity values up to 7875 and 740 respectively have been obtained for the conversion of CO2 into cyclic carbonates by using hybrid materials based on imidazolium modified polyhedral oligomeric silsesquioxanes (POSS-Imi) grafted on amorphous silica (SiO2) and mesostructured SBA-15. The heterogeneous organocatalysts were easily prepared via a straightforward synthetic procedure allowing to generate high local concentration spots of imidazolium active sites surrounding the POSS core. This synthetic procedure is also a promising approach for the design of a wide library of hybrid functional materials. The materials do not possess other co-catalytic spec…
New Hybrid Organic-inorganic Multifunctional Materials Based on Polydopamine-like Chemistry
Taking inspiration from the chemistry of dopamine, a simple and economic synthetic approach toward the synthesis of a series of silica-based polydopamine-like materials has been developed. Mild conditions and easy manipulation are the strongest aspects of this methodology. Such hybrid materials were successfully used as recyclable catalysts for Knoevenagel reactions.
Straightforward preparation of highly loaded MWCNT-polyamine hybrids and their application in catalysis
Multiwalled carbon nanotubes (MWCNTs) were easily and efficiently functionalised with highly cross-linked polyamines. The radical polymerisation of two bis-vinylimidazolium salts in the presence of pristine MWCNTs and azobisisobutyronitrile (AIBN) as a radical initiator led to the formation of materials with a high functionalisation degree. The subsequent treatment with sodium borohydride gave rise to the reduction of imidazolium moieties with the concomitant formation of secondary and tertiary amino groups. The obtained materials were characterised by thermogravimetric analysis (TGA), elemental analysis, solid state 13C-NMR, Fourier-transform infrared spectroscopy (FT-IR), transmission ele…
Design of novel imidazolium based nanostructures for sustainable catalytic applications
Reconsidering TOF calculation in the transformation of epoxides and CO2 into cyclic carbonates
Abstract The combination of Lewis acids and Lewis bases, currently defined as catalysts and co-catalysts (or promoter) respectively, in the reaction between epoxides and CO2 to give cyclic carbonates, is discussed, starting from examples in which the Lewis base was used in larger amount with respect to the Lewis acid. In these cases, turnover frequency (TOF) values have been usually calculated taking into account solely the amount of the Lewis acid employed. The occurrence of two distinct reaction pathways, one catalysed by the sole Lewis base and the other one catalysed by the Lewis acid/Lewis base couple, in which the Lewis acid alone does not play a catalytic role, should bring researche…