Microwave Synthesis of Copper Phyllosilicates as Effective Catalysts for Hydrogenation of C≡C Bonds

For the first time, the new microwave-assisted method for the synthesis of copper phyllosilicates on a commercial SiO2 carrier was developed. The application of microwave synthesis allowed to decrease the synthesis time from 9 to 6 h compared to the traditional DPU method of preparing chrysocolla. The synthesized catalysts were studied by N2 adsorption, TEM and XRD methods. Catalysts prepared by microwave method are highly effective in the selective hydrogenation of the С≡С bond in 1,4-butynediol to 1,4-butenediol and 2-phenylethinylaniline with a selectivity of 96.5% and 100% at full conversion for 2 and 0.5 h of the reaction, respectively

Unsupported Copper Nanoparticles in the Arylation of Amines

Commercially available copper and copper (II) oxide nanoparticles (CuNPs and CuO NPs) were characterized using TEM and electronography methods to elucidate their true average size and composition. The catalytic amine arylation using unsupported copper nanoparticles differing in their size and copper oxidation state was investigated. The reaction of the model iodobenzene with n-octylamine was shown to be successfully catalyzed by CuNPs of average size 25 and 10/80 nm in the presence of the ligands such as 2-isobutyrylcyclohexanone (L1) and rac-1,1′-bi-2-naphthol (BINOL, L2), giving high yields (up to 95%) of the target N-octylaniline. CuO in bulk and nano forms was shown to be almost equally efficient in this process. Studies on the Cu-catalyzed amination of substituted iodobenzenes and 2-iodopyridine, as well as the arylation of different aliphatic amines and NH-heterocycles, verified that CuNPs (25 or 10/80 nm) with L1 and L2 are the most versatile and efficient nanocatalysts for a variety of substrates. Investigation of copper leaching under different conditions was carried out

Unsupported Copper Nanoparticles in the Arylation of Amines

Commercially available copper and copper (II) oxide nanoparticles (CuNPs and CuO NPs) were characterized using TEM and electronography methods to elucidate their true average size and composition. The catalytic amine arylation using unsupported copper nanoparticles differing in their size and copper oxidation state was investigated. The reaction of the model iodobenzene with n-octylamine was shown to be successfully catalyzed by CuNPs of average size 25 and 10/80 nm in the presence of the ligands such as 2-isobutyrylcyclohexanone (L1) and rac-1,1′-bi-2-naphthol (BINOL, L2), giving high yields (up to 95%) of the target N-octylaniline. CuO in bulk and nano forms was shown to be almost equally efficient in this process. Studies on the Cu-catalyzed amination of substituted iodobenzenes and 2-iodopyridine, as well as the arylation of different aliphatic amines and NH-heterocycles, verified that CuNPs (25 or 10/80 nm) with L1 and L2 are the most versatile and efficient nanocatalysts for a variety of substrates. Investigation of copper leaching under different conditions was carried out

Facile Redox Synthesis of Novel Bimetallic Crn+/Pd0 Nanoparticles Supported on SiO2 and TiO2 for Catalytic Selective Hydrogenation with Molecular Hydrogen

The bimetallic Crn+/Pd0 nanoparticles have been synthesized for the first time by a two-step redox method. The method includes the deposition of Pd0 nanoparticles on the surface of SiO2 and TiO2 carriers followed by the deposition of Crn+ on the surface of Pd0 nanoparticles using the redox procedures, which are based on the catalytic reduction of Crn+ with H2 in aqueous suspensions at ambient conditions. Transmission (TEM) and scanning (SEM) electron microscopy, X-ray photoelectron spectroscopy (XPS), Fourie-transformed infrared spectroscopy of adsorbed CO (FTIR-CO), and CO chemisorption studies were performed to characterize the morphology, nanoparticle size, element, and particle distribution, as well as the electronic state of deposited metals in the obtained catalysts. A decrease in nanoparticle size from 22 nm (Pd/SiO2) to 2–6 nm (Pd/TiO2) makes possible deposition of up to 1.1 wt.% Cr most likely as Cr3+. The deposition of CrOx species on the surface of Pd nanoparticles was confirmed using FTIR of adsorbed CO and the method of temperature-programmed reduction with hydrogen (TPR-H2). The intensive hydrogen consumption in the temperature ranges from −50 °C to 40 °C (Cr/Pd/SiO2) and from −90 °C to −40 °C (Cr/Pd/TiO2) was first observed for the supported Pd catalysts. The decrease in the temperature of β-PdHx decomposition indicates the strong interaction between the deposited Crn+ species and Pd0 nanoparticle after reduction with H2 at 500 °C. The novel Crn+/Pd/TiO2 catalysts demonstrated a considerably higher activity in selective hydrogenation of phenylacetylene than the Pd/TiO2 catalyst at ambient conditions

CuO-Fe2O3 Nanoparticles Supported on SiO2 and Al2O3 for Selective Hydrogenation of 2-Methyl-3-Butyn-2-ol

In this study, novel SiO2- and Al2O3-supported Cu-Fe catalysts are developed for selective hydrogenation of 2-methyl-3-butyne-2-ol to 2-methyl-3-butene-2-ol under mild reaction conditions. TEM, XRD, and FTIR studies of adsorbed CO and TPR-H2 are performed to characterize the morphology, nanoparticle size, and particle distribution, as well as electronic state of deposited metals in the prepared catalysts. The deposition of Fe and Cu metal particles on the aluminum oxide carrier results in the formation of a mixed oxide phase with a strong interaction between the Fe and Cu precursors during the calcination. The highly dispersed nanoparticles of Fe2O3 and partially reduced CuOx, with an average size of 3.5 nm and with strong contact interactions between the metals in 5Cu-5Fe/Al2O3 catalysts, provide a high selectivity of 93% toward 2-methyl-3-butene-2-ol at complete conversion of the unsaturated alcohol

Layered Ferrihydrite and BN Nanoparticle Heterostructures Doped with Ag for CO₂ Hydrogenation

Iron-based catalysts are gaining increased attention as promising and cost-effective materials for CO2 recycling. Their properties can be tuned by careful selection of the appropriate synthesis route, substrate, and catalytic system components. For the first time, a nanostructured material consisting of heterostructures of layered ferrihydrite (Fh) and hexagonal boron nitride (h-BN) nanoparticles has been obtained. Subsequent annealing ensures a uniform distribution of Fe nanoparticles (FeNPs) on the h-BN surfaces. Small Ag additions to the system lead to a significant decrease in the average size of FeNPs, presumably due to a seeding mechanism. Catalytic tests have shown that a low Ag content has a positive effect on the catalytic activity. Stability testing has demonstrated that the catalytic properties of the Fh/BN system improve over time, as does selectivity toward high-value-added hydrocarbons. Computational methods suggest a surface atomic configuration in which one Ag atom substitutes for one Fe atom in the (110) plane, resulting in better CO2 adsorption