Liquid-Phase Partial Hydrogenation of Phenylacetylene at Ambient Conditions Catalyzed by Pd-Fe-O Nanoparticles Supported on Silica.

Catalysts with no hazardous or toxic components are required for the selective hydrogenation of acetylenic bonds in the synthesis of pharmaceuticals, vitamins, nutraceuticals, and fragrances. The present work demonstrates that a high selectivity to alkene can be reached over a Pd-Fe-O/SiO2 system prepared by the co-impregnation of a silica support with a solution of the metal precursors (NH4)3[Fe(C2O4)3] and [Pd(NH3)4]Cl2 followed by thermal treatment in hydrogen or in air at 400 °C. A DRIFT spectroscopic study of CO adsorption revealed large shifts in the position of the Pdn+-CO bands for this system, indicating the strong effect of Fen+ on the Pd electronic state, resulting in a decreased rate of double C=C bond hydrogenation and an increased selectivity of alkyne hydrogenation to alkene. The prepared catalysts consisted of mono- and bimetallic nanoparticles on an SiO2 carrier and exhibited a selectivity as high as that of the commonly used Lindlar catalyst (which contains such hazardous components as lead and barium), while the activity of the Fe-Pd-O/SiO2 catalyst was an order of magnitude higher. The hydrogenation of a triple bond over the proposed Pd-Fe catalyst opens the way to selective hydrogenation over nontoxic catalysts with a high yield and productivity. Taking into account a simple procedure of catalyst preparation, this direction provides a rationale for the large-scale implementation of these catalysts.

Rhodium-Based Catalysts: An Impact of the Support Nature on the Catalytic Cyclohexane Ring Opening.

Because of the growing demand for high-quality fuels, the light cycle oil fraction improvement including cetane number improvement is important. The main way to reach this improvement is the ring opening of cyclic hydrocarbons, and a highly effective catalyst should be found. Cyclohexane ring openings are a possible option to investigate the catalyst activity. In this work, we investigated rhodium-loaded catalysts prepared using the commercially available industrial supports: single-component ones, SiO2 and Al2O3; and mixed oxides CaO + MgO + Al2O3 and Na2O + SiO2 + Al2O3. The catalysts were prepared by incipient wetness impregnation and investigated by N2 low-temperature adsorption-desorption, XRD, XPS, DRS UV-Vis and DRIFT spectroscopy, SEM, and TEM with EDX. The catalytic tests were performed in cyclohexane ring opening in the range of 275-325 °C. The best result was demonstrated by the sample 1Rh/CaMgAlO: the selectivity to n-hexane was about 75% while the cyclohexane conversion was about 25% at 275 °C. The space-time yield was up to 12 mmoln-hexane gcat-1h-1.

Understanding the Working Mechanism of the Novel HKUST-1@BPS Composite Materials as Stationary Phases for Liquid Chromatography.

Composite materials have been used based on coordination polymers or microporous metal-organic frameworks (MOFs) combined with mesoporous matrices for adsorption-related techniques, which enable outflanking some adverse phenomena manifested during pristine components operation and enhance the performance and selectivity of the resulting materials. In this work, for the first time, the novel HKUST-1@BPS composites synthesized by the microwave-assisted (MW) technique starting from microporous HKUST-1 (Cu3(btc)2) MOF and biporous silica matrix (BPS) with bimodal mesopore size distribution were comparatively studied as materials for liquid-phase adsorption techniques utilizing the high-performance liquid chromatography (HPLC) method and benzene as a model adsorbate. It was established that the studied HKUST-1@BPS composites can function as stationary phases for HPLC, unlike the pristine HKUST-1 and bare BPS materials, due to the synergetic effect of both components based on the preliminary enhanced adsorbate mass transfer throughout the silica mesopores and, subsequently, its penetrating into HKUST-1 micropores. The suggested mechanism involves the initial deactivation of open metal Cu2+ sites in the HKUST-1 framework structure by isopropanol molecules upon adding this polar component into the mobile phase in the region of the isopropanol concentration of 0.0 to 0.2 vol.%. Thereafter, at the medium range of varying the isopropanol concentration in the eluent of 0.2 to 0.3 vol.%, there is an expansion of the previously inaccessible adsorption centers in the HKUST-1@BPS composites. Subsequently, while further increasing the isopropanol volume fraction in the eluent in the region of 0.3 to 5.0 vol.%, the observed behavior of the studied chromatographic systems is similar to the quasi-normal-phase HPLC pattern. According to the obtained thermodynamic data, benzene adsorption into HKUST-1 micropores from solutions with a vol.% of isopropanol in the range of 0.4 to 5.0 follows the unique entropy-driven mechanism previously described for the MIL-53(Al) framework. It was found that HKUST-1 loading in the composites and their preparation conditions have pronounced effects on their physicochemical properties and adsorption performance, including the adsorption mechanism.

Hydroamination of Phenylacetylene with Aniline over Gold Nanoparticles Embedded in the Boron Imidazolate Framework BIF-66 and Zeolitic Imidazolate Framework ZIF-67.

The hydroamination of alkynes is an atom-economy process in the organic synthesis for the C-N bond formation, thereby allowing the production of fine chemicals and intermediates. However, direct interaction between alkynes and amines is complicated due to the electron enrichment of both compounds. Therefore, efficient hydroamination catalysts, especially heterogeneous ones, are in great demand. This work aimed at the development of novel heterogeneous catalysts based on zeolite-like metal-organic frameworks for phenylacetylene hydroamination. The sodalite (SOD) type zeolitic imidazolate framework ZIF-67 (Co(meim)2, meim = 2-methylimidazolate) and boron imidazolate framework BIF-66 ({Co[B(im)4]2}n, im = imidazolate) were studied as the carriers for the gold nanoparticles (Au-NPs). Au-NPs were embedded in the ZIF-67 and BIF-66 matrices by incipient wetness impregnation. Au@ZIF-67 and Au@BIF-66 hybrids were studied for the first time in the liquid phase hydroamination of phenylacetylene with aniline in an air atmosphere and have shown high activity and selectivity in respect to imine in this process. The pronounced impact of the nature of the metal-organic carrier, Au source, and reducing agent on the catalytic performance of the synthesized nanomaterials was found. To the best of our knowledge, it is the first example of using the zeolitic imidazolate framework and boron-imidazolate framework as the components of the gold-containing catalytic systems for the alkyne hydroamination.

Preparation of Propanols by Glycerol Hydrogenolysis over Bifunctional Nickel-Containing Catalysts.

The paper presents the results obtained in studying glycerol hydrogenolysis into 1-propanol and 2-propanol over bifunctional Ni/WO3-TiO2 and Ni/WO3-ZrO2 catalysts in the flow system. Due to the optimal combination of acidic and hydrogenation properties of the heterogeneous catalysts, they exhibit higher performance in glycerol conversion into C3 alcohols, although the process is carried out in rather mild conditions. At the reaction temperature of 250 °C and hydrogen pressure of 3 MPa, the total yield of 1-propanol and 2-propanol reaches 95%, and the glycerol conversion is close to 100%.

Ethanol to Acetaldehyde Conversion under Thermal and Microwave Heating of ZnO-CuO-SiO2 Modified with WC Nanoparticles.

The nonoxidative conversion of ethanol to acetaldehyde under thermal and microwave heating was studied on mixed oxide ZnO-CuO-SiO2 catalysts modified with additives of tungsten carbide nanoparticles. The results revealed that the WC-modified catalyst exhibited superior activity and selectivity under microwave heating conditions. It is assumed that when microwave heating is used, hot zones can appear at the contact points of WC nanoparticles and active centers of the mixed oxide ZnO-CuO-SiO2 catalyst, which intensively absorb microwave energy, allowing the more efficient formation of acetaldehyde at moderate temperatures. Thermodynamic calculations of equilibrium concentrations of reagents and products allowed us to identify the optimal conditions for effective acetaldehyde production. The initial catalyst and the catalyst prepared by the coprecipitation of the oxides with the addition of WC were characterized by physicochemical methods (TPR-H2, XRD, DRIFTS of adsorbed CO). The active centers of the oxide catalyst can be Cu+ cations.

Glucose Oxidase Immobilized on Magnetic Zirconia: Controlling Catalytic Performance and Stability.

Here, we report the structures and properties of biocatalysts based on glucose oxidase (GOx) macromolecules immobilized on the mesoporous zirconia surface with or without magnetic iron oxide nanoparticles (IONPs) in zirconia pores. Properties of these biocatalysts were studied in oxidation of d-glucose to d-gluconic acid at a wide range of pH and temperatures. We demonstrate that the calcination temperature (300, 400, or 600 °C) of zirconia determines its structure, with crystalline materials obtained at 400 and 600 °C. This, in turn, influences the catalytic behavior of immobilized GOx, which was tentatively assigned to the preservation of GOx conformation on the crystalline support surface. IONPs significantly enhance the biocatalyst activity due to synergy with the enzyme. At the same time, neither support porosity nor acidity/basicity shows correlations with the properties of this biocatalyst. The highest relative activity of 98% (of native GOx) at a pH 6-7 and temperature of 40-45 °C was achieved for the biocatalyst based on ZrO2 calcined at 600 °C and containing IONPs. This process is green as it is characterized by a high atom economy due to the formation of a single product with high selectivity and conversion and minimization of waste due to magnetic separation of the catalyst from an aqueous solution. These and an exceptional stability of this catalyst in 10 consecutive reactions (7% relative activity loss) make it favorable for practical applications.

Adsorption of 2,4-dichlorophenoxyacetic acid in an aqueous medium on nanoscale MIL-53(Al) type materials.

A series of flexible metal-organic frameworks (MOFs) belonging to the MIL-53 family, such as MIL-53(Al), its amino-functionalized analog NH2-MIL-53(Al), and MIL-53(Al) type materials with Al3+ ions and mixed benzene-1,4-dicarboxylate and 2-aminobenzene-1,4-dicarboxylate linkers (MixLR) in various proportions were prepared in a nanocrystalline form using MW-activation under atmospheric pressure according to the original solvothermal procedure. The MIL-53(Al) and NH2-MIL-53(Al) samples feature nanocrystals with sizes of 200-300 nm, while MixLR matrices synthesized in this manner are composed of small nanoparticles with sizes of about 20-30 nm. MIL-53(Al) type materials (MIL-53(Al), NH2-MIL-53(Al) and MixLR) were probed in the adsorption of a typical herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) in an aqueous medium. This study revealed a strong impact of the flexibility and porosity of the synthesized MIL-53(Al) type matrices on their physicochemical characteristics. MIL-53(Al) type materials show much higher 2,4-D adsorption rates than an activated carbon matrix (CSAC). The structural characteristics of the studied MIL-53(Al) type materials were established with a high resolution X-ray powder diffractometer equipped with a synchrotron radiation source. The obtained results can be used for the development of advanced adsorbents based on MIL-53(Al) type materials for water remediation.

Immobilized glucose oxidase on magnetic silica and alumina: Beyond magnetic separation.

Here we report immobilization of glucose oxidase (GOx) on magnetic silica (Fe3O4-SiO2) and alumina (Fe3O4-Al2O3) functionalized with amino groups using glutaraldehyde as a linker. Magnetic support based biocatalysts demonstrate high catalytic activity in d-glucose oxidation to D-gluconic acid at pH 5-7.5 and temperature of 30-50 °C with the best activities of 95% and 91% for magnetic silica and alumina, respectively. A comparison of magnetic and non-magnetic alumina and silica shows a significant enhancement of the relative catalytic activity for magnetic supports, while the silica based biocatalysts show a higher activity than the biocatalysts based on alumina. A noticeably higher activity of GOx immobilized on magnetic supports is explained by synergy of the GOx inherent activity and enzyme-like activity of iron oxide nanoparticles, while the enhancement with silica based catalysts is most likely due to a larger pore size and stronger Brønsted acid sites. Excellent relative activity of Fe3O4-SiO2-GOx (95% of native GOx) in a tolerant pH and temperature range as well as high stability in a repeated use (6% relative activity loss after five catalytic cycles) makes this catalyst promising for practical applications.

Metal-Ion Distribution and Oxygen Vacancies That Determine the Activity of Magnetically Recoverable Catalysts in Methanol Synthesis.

Here, we report on the development of novel Zn-, Zn-Cr-, and Zn-Cu-containing catalysts using magnetic silica (Fe3O4-SiO2) as the support. Transmission electron microscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) showed that the iron oxide nanoparticles are located in mesoporous silica pores and the magnetite (spinel) structure remains virtually unchanged despite the incorporation of Zn and Cr. According to XPS data, the Zn and Cr species are intermixed within the magnetite structure. In the case of the Zn-Cu-containing catalysts, a separate Cu2O phase was also observed along with the spinel structure. The catalytic activity of these catalysts was tested in methanol synthesis from syngas (CO + H2). The catalytic experiments showed an improved catalytic performance of Zn- and Zn-Cr-containing magnetic silicas compared to that of the ZnO-SiO2 catalyst. The best catalytic activity was obtained for the Zn-Cr-containing magnetic catalyst prepared with 1 wt % Zn and Cr each. X-ray absorption spectroscopy demonstrated the presence of oxygen vacancies near Fe and Zn in Zn-containing, and even more in Zn-Cr-containing, magnetic silica (including oxygen vacancies near Cr ions), revealing a correlation between the catalytic properties and oxygen vacancies. The easy magnetic recovery, robust synthetic procedure, and high catalytic activity make these catalysts promising for practical applications.

A Study of Ziegler-Natta Propylene Polymerization Catalysts by Spectroscopic Methods.

Ziegler-Natta polymerization catalysts were characterized by a complex of surface- and bulk-sensitive methods (DRIFTS, XPS, ESR, and XAS = XANES + EXAFS). A diffuse-reflectance Fourier-transform IR spectroscopy (DRIFTS) study showed the presence of strong Lewis acid sites in different concentrations and absence of strong basic sites in the polymerization catalysts. X-ray photoelectron spectroscopy (XPS), electron-spin resonance (ESR), and (X-ray absorption near-edge structure (XANES) analysis revealed the presence of Ti4+, Ti3+, Ti2+, and Ti1+ species in the surface layers and in the bulk of catalysts. The samples under study differ drastically in terms of the number of ESR-visible paramagnetic sites. The EXAFS study shows the presence of a Cl atom as a nearest neighbor of the absorbing Ti atom.

Pd-Fe nanoparticles stabilized by chitosan derivatives for perchloroethene dechlorination.

A series of chitosan-stabilized Pd-NZVI (nano-zero-valent-iron) catalysts for dechlorination with variation in their composition and in the nature of the polymer has been prepared. The synthesis procedures and palladium and chitosan contents were optimized. It was demonstrated by the XPS method that Fe and Pd in Fe-Pd/chitosan samples exist in the metallic state. The positive shift of the binding energy as compared with the bulk metal shows that the iron metal in the surface layers exists as very small nanoparticles. The prepared materials were characterized also by the XAS method. The presence of O and N atoms in the first coordination shell of the central Fe atom in the Fe-Pd/chitosan samples certifies the binding of the Fe metal particles with the chitosan surface via OH and NH(2) groups. The samples are characterized by the high stability of the nanoparticles as compared to unstabilized Pd-NZVI. The materials were tested to evaluate their catalytic activity in the perchloroethene (PCE) dechlorination reaction. Some samples of chitosan-stabilized Pd-NZVI revealed a good performance in PCE degradation as compared to unstabilized Pd-NZVI.

Lanthanum cobaltite perovskite supported onto mesoporous zirconium dioxide: nature of active sites of VOC oxidation.

Novel catalytic nano-sized materials based on LaCoO(x) perovskite nanoparticles incapsulated in the mesoporous matrix of zirconia were prepared, characterized by physicochemical methods and tested in complete methanol oxidation. LaCoO(x) nanoparticles were prepared inside the mesopores of ZrO(2) by decomposition of bimetallic La-Co glycine precursor complexes. The catalysts have been studied by diffuse-reflectance FTIR-spectroscopy using such probe molecules as CO, CD(3)CN and CDCl(3) to test low-coordinated metal ions. At low temperatures of decomposition of complexes (up to 400°C), low-coordinated Co(3+) ions predominate in the LaCoO(x) nanoparticles, whereas basically Co(2+) ions are found upon increasing the decomposition temperature to 600°C. The novel nano-sized perovskite catalysts exhibit a very high catalytic activity in the abatement of volatile organic compounds present in air, like methanol and light hydrocarbons.