Palladium catalysts supported on zinc oxide modified with polyethylene glycol or pectin were synthesized and investigated in the hydrogenation of acetylene compounds. It was established that the polymercontaining catalysts reduce acetylene hyrbons to olefins with high activity, selectivity, and stability. The composition and structure of the obtained composites were studied by elemental analysis, transmission electron microscopy, and XPS spectroscopy. It was found that the nanosized particles of palladium uniformly immobilized on the surface of zinc oxide were formed in the course of the synthesis of a supported polymer/oxide complex.
1 September 2020 in Reaction Kinetics, Mechanisms and Catalysis
Recently, the use of plant-origin materials has become especially important due to the aggravation of environmental problems and the shortage and high cost of synthetic materials. One of the potential candidates among natural organic compounds is polysaccharides, characterized by a number of advantages over synthetic polymers. In recent years, natural polysaccharides have been used to design composite catalysts for various organic syntheses. This review is devoted to the current state of application of polysaccharides (chitosan, starch, pectin, cellulose, and hydroxyethylcellulose) and composites based on their catalysis. The article is divided into four main sections based on the type of polysaccharide: (1) chitosan-based nanocomposites; (2) pectin-based nanocomposites; (3) cellulose (hydroxyethylcellulose)-based nanocomposites; and (4) starch-based nanocomposites. Each section describes and summarizes recent studies on the preparation and application of polysaccharide-containing composites in various chemical transformations. It is shown that by modifying polysaccharides, polymers with special properties can be obtained, thus expanding the range of biocomposites for catalytic applications.
The proposed paper describes a simple and environmentally friendly method for the synthesis of three-component polymer–inorganic composites, which includes the modification of zinc oxide or montmorillonite (MMT) with chitosan (CS), followed by the immobilization of palladium on the resulting two-component composites. The structures and properties of the obtained composites were characterized by physicochemical methods (IRS, TEM, XPS, SEM, EDX, XRD, BET). Pd–CS species covered the surface of inorganic materials through two different mechanisms. The interaction of chitosan polyelectrolyte with zinc oxide led to the deprotonation of its amino groups and deposition on the surface of ZnO. The immobilization of Pd on CS/ZnO occurred by the hydrolysis of [PdCl4]2−, followed by forming PdO particles by interacting with amino groups of chitosan. In the case of CS/MMT, protonated amino groups of CS interacted with negative sites of MMT, forming a positively charged CS/MMT composite. Furthermore, [PdCl4]2− interacted with the –NH3+ sites of CS/MMT through electrostatic force. According to TEM studies of 1%Pd–CS/ZnO, the presence of Pd nanoclusters composed of smaller Pd nanoparticles of 3–4 nm in size were observed on different sites of CS/ZnO. For 1%Pd–CS/MMT, Pd nanoparticles with sizes of 2 nm were evenly distributed on the support surface. The prepared three-component CS–inorganic composites were tested through the hydrogenation of 2-propen-1-ol and acetylene compounds (phenylacetylene, 2-hexyn-1-ol) under mild conditions (T—40 °C, PH2—1 atm). It was shown that the efficiency of 1%Pd–CS/MMT is higher than that of 1%Pd–CS/ZnO, which can be explained by the formation of smaller Pd particles that are evenly distributed on the support surface. The mechanism of 2-hexyn-1-ol hydrogenation over an optimal 1%Pd–CS/MMT catalyst was proposed.