Synthesis of nanocomposites from Pd(0) and a hyper-cross-linked functional resin obtained from a conventional gel-type precursor.

Hyper-cross-linked resins stemming from a gel-type poly-chloromethylated poly(styrene-co-divinylbenzene) resin (GT) have been investigated by a multi-methodological approach based on elemental analysis, scanning electron microscopy, X-ray microanalysis, and solvent absorption. The hyper-cross-linking of the parent resin was accomplished by Friedel-Crafts alkylation of the phenyl rings of the resins with the chloromethyl groups. This produced a permanent pore system comprising both micropores (<2.

Highly hydrophilic copolymers of N,N-dimethylacrylamide, acrylamido-2-methylpropanesulfonic acid, and ethylenedimethacrylate: nanoscale morphology in the swollen state and use as exotemplates for synthesis of nanostructured ferric oxide.

The polymer framework of water-swollen copolymers of N,N-dimethylacrylamide, acrylamido-2-methylpropanesulfonic acid, and ethylenedimethacrylate (nominal cross-linking degrees of 4, 8, and 20 mol %) is composed of highly expanded domains, with "pores" not less than 6 nm in diameter. When the 4% cross-linked copolymer (DAE 26-4) is swollen with a 10(-4) M solution of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL) in water, MeOH, EtOH, or nBuOH, the molecules of the paramagnetic probe rotate rapidly (τ<1000 ps) and as fast as in the bulk liquid in the case of water. The swelling degree of DAE 26-4 is related to the Hansen solubility parameters of a number of liquids, including linear alcohols up to n-octanol.

Characterisation of solute mobility in hypercross-linked resins in solvents of different polarity: two promising supports for catalysis.

Two hypercross-linked resins stemming from a gel-type poly-chloromethylated styrene-divinylbenzene resin (GT) in beaded form are investigated with a combination of spectroscopic techniques (EPR and time-domain (TD)-NMR spectroscopy) to evaluate their use as supports for the development of operationally flexible heterogeneous metal catalysts, suitable to be employed in liquid and gas phase. The first resin (HGT) is the direct product of the hypercross-linking reaction, whereas the second one (HGS) is the sulphonated analogue of HGT obtained by exchanging approximately 3 wt % of the chloromethyl groups with sulphonic groups. HGT and HGS absorb both polar and apolar solvents in the permanent nanoporosity created by the hypercross-linking, and NMR data highlight that the pore size is not affected by the different properties of the investigated liquid media.

Synthesis of hydrogen peroxide from H2 and O2 in water and ethanol catalyzed by nanoclustered Pd(0) on silica: strong selectivity enhancement exerted by the addition of ionic liquids.

Hydrogen peroxide (H(2)O(2)) synthesis directly from dioxygen and dihydrogen was carried out using a continuous flow reactor with a Pd catalyst. The effects of ionic liquids on the selectivity to H(2)O(2) were studied on a Pd/SiO(2) catalyst. It was found that the ionic liquid [BMIM][BF(4)] in water or ethanol is quite beneficial to the selectivity to H(2)O(2).

Synthesis and catalytic activity of metal nanoclusters inside functional resins: an endeavour lasting 15 years.

Cross-linked functional polymers (functional resins) are versatile, designable and useful supports for metal nanoclusters that are able to provide reasonably thermally and mechanically stable multi-functional metal catalysts characterized by good activity and selectivity. The paper reviews authors' contributions to the field from the early 1990s to the present.

Electrochemical, pulsed-field-gradient spin-echo NMR spectroscopic, and ESR spectroscopic study of the diffusivity of molecular probes inside gel-type cross-linked polymers.

The permeability of five gel-type synthetic resins, obtained by polymerization of 1-vinylpyrrolidin-2-one cross-linked with N,N'-methylenebisacrylamide (1, 2, 3, 4, and 5 wt %) and swollen by N,N-dimethylformamide (DMF), has been analyzed. The diffusion of 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxyl (TEMPONE) was studied by ultramicroelectrode voltammetry. Similar measurements were performed for solutions of non-cross-linked poly(vinylpyrrolidone) in DMF.

Gel-type polyacrylic resins cross-linked with trimethylolpropanetrimethacrylate: the issue of their nanostructure and molecular accessibility unveiled with a combination of inverse steric exclusion chromatography (ISEC), and ESR and CP-MAS 13C NMR spectroscopy.

Six gel-type functional resins, that is, three poly-DMAA-co-TMPTP (DMAA = N,N-dimethylacrylamide, TMPTP = trimethylolpropyltrimethacrylate) samples with different degrees of cross-linking (0.6, 1.2, 1.

Nanomorphology of polymer frameworks and their role as templates for generating size-controlled metal nanoclusters.

The microporous (gel-type) functional resin co-poly-N,N-dimethylacrylamide (DMAA) (88 % mol)/methacrylic acid (MAA) (8 % mol)/N,N'-methylenebisacrylamide (MBAA) (4 % mol) (MPIF(H)) is employed as the hosting framework for the production of resin-supported Pd(0) nanoclusters. The obtained composite MPIF(-)Na(+)/Pd(0) is prepared upon reducing, in ethanol, MPIF(-)Pd(2+) (0.5), obtained upon previous homogeneous dispersion of "Pd(2+)" inside the resin particles (XRMA control) through ion-exchange.

Metal catalysis inside polymer frameworks: evaluation of catalyst stability and reusability.

The polymer framework of a resin-based catalyst built up with Pd nanoclusters (ca. 3 nm) dispersed inside the nanoporous domains of a thermally stable gel-type polyacrylic resin exhibits a good chemical stability under 5 bar H(2) at 40 degrees C for reasonable contact times. Chemical and physico-chemical integrity of the polymer framework are checked with a variety of instrumental analytical methods.

Highly chemoselective hydrogenation of 2-ethylanthraquinone to 2-ethylanthrahydroquinone catalyzed by palladium metal dispersed inside highly lipophilic functional resins.

Most hydrogen peroxide is currently produced by the selective hydrogenation of 2-ethylanthraquinone (EAQ) to 2-ethylanthrahydroquinone (EAHQ), followed by treatment with dioxygen; this produces hydrogen peroxide and regenerates 2-ethylanthraquinone. We have developed novel catalysts for this process that are based on palladium supported on very lipophilic functional resins and that are able to promote a chemoselectivity for EAHQ slightly but definitely superior to that provided by an industrial catalyst under identical conditions. This finding demonstrates the potential of variations of the lipophilic/hydrophilic character of the support as a tool for the improvement of the chemoselectivity of resin-based metal catalysts.

Polybenzimidazole-supported [Rh(cod)Cl]2 complex: effective catalyst for the polymerization of substituted acetylenes.

The first heterogeneous catalyst which affords polymerization of substituted acetylenes into readily available high molecular weight polymers is reported. The catalyst (Rh/PBI) has been prepared by supporting di-mu-chloro-bis(eta4-cycloocta-1,5-diene)dirhodium(I), [Rh(cod)Cl]2, on commercial polybenzimidazole (PBI) porous beads by means of a simple quantitative adsorption from THF solution, and tested in polymerization of phenylacetylene, 4-fluorophenylacetylene, and 4-pentylphenylacetylene. The polymer molecules formed were found to be released from the Rh/PBI to surrounding solution during the polymerization performed in THF.