No abstract

A method for homogenizing heterogeneous catalyst is described. The method is based on growing polyaminoamido (PAMAM) dendrons on silica-coated magnetic nanoparticles. After the dendronizing process, the silica-coated magnetic nanoparticles are more stable and more soluble in organic solvents. The dendronized particles are phosphonated, complexed with [Rh(COD)Cl]2, and applied in catalytic hydroformylation reactions. These new catalysts are proven to be highly selective and reactive.

Cu-ion-modified graphene oxide nanoparticles, Cu-GO NPs, act as a heterogeneous catalyst mimicking functions of horseradish peroxidase, HRP, and of NADH peroxidase. The Cu-GO NPs catalyze the oxidation of dopamine to aminochrome by HO and catalyze the generation of chemiluminescence in the presence of luminol and HO. The Cu-GO NPs provide an active material for the chemiluminescence detection of HO and allow the probing of the activity of HO-generating oxidases and the detection of their substrates. This is exemplified with detecting glucose by the aerobic oxidation of glucose by glucose oxidase and the Cu-GO NP-stimulated chemiluminescence intensity generated by the HO product. Similarly, the Cu-GO NPs catalyze the HO oxidation of NADH to the biologically active NAD cofactor. This catalytic system allows its conjugation to biocatalytic transformations involving NAD-dependent enzyme, as exemplified for the alcohol dehydrogenase-catalyzed oxidation of benzyl alcohol to benzoic acid through the Cu-GO NPs-catalyzed regeneration of NAD.

A method for supporting platinum nanoparticles on magnetite nanoparticles is described. The method requires modification of the surface of the magnetic nanoparticles with ionic liquid groups. Before modification, the magnetic nanoparticles are not stable and easily aggregate and, after modification, the magnetite nanoparticles become highly stable and soluble in polar or non‐polar organic solvents depending on the alkyl group of the linked ionic liquids. The supporting of platinum nanoparticles on the modified magnetic nanoparticles was achieved by adsorbing platinum salts (K2PtCl4) on the surface of the magnetite nanoparticles via ion exchange with the linked ionic liquid groups and then reducing them by hydrazine. The supported platinum nanoparticles were applied in the catalytic hydrogenation of alkynes in which cis‐alkenes were selectively produced, and in the hydrogenation of α,β‐unsaturated aldehydes where the allyl alcohols were obtained as the exclusive products. The new catalyst can be easily separated from the reaction mixtures by applying an external magnetic field and recycled.

A novel family of composite materials, organically doped metals, has been recently introduced. Here, we demonstrate their use as a new platform for heterogeneous catalysis, namely the doping of a metal with a catalytic organometallic complex. Specifically, a rhodium(I) catalyst, (RhCl(COD)(Ph2P(C6H4SO3Na))), ([Rh]), was physically entrapped within silver, thus creating a new type of catalytic material: [Rh]@Ag. Several aspects were demonstrated with the development of this heterogeneous catalyst: a metal can be used as a support for heterogenizing a homogeneous catalyst; the homogeneous catalyst is stabilized by the entrapment within the metal; the products of the composite catalyst are different compared to those obtained from the homogeneous one; and the adsorption of [Rh] on the surface of Ag and its entrapment are very different processes only the latter provided appreciable catalytic activity. Thus, while homogeneous [Rh] was entirely destroyed after converting styrene to ethylbenzne at 50%, [Rh]@Ag remained active after effecting the same reaction to a yield of 85% (compared to only 7% for [Rh] adsorbed on Ag), and while homogeneous [Rh] hydrogenated diphenylacetylene to bibenzyl (and was completely deactivated after one cycle) with no trace of cis-stilbene, [Rh]@Ag afforded that compound as the main product and could be reused.