•Hydrogenation of furfural to furfuryl alcohol in the presence of Pd/C and Ru/C.•The effect of carbon support nature on the formation of Pd and Ru sites.•The effect of supported metal on the ...catalytic performances of Pd/C and Ru/C.
The study considered the formation and catalytic properties of the active sites in Pd/C and Ru/C catalysts supported on carbon nanotubes (CNT) and carbon black (CB). The nature of carbon support was shown to affect the dispersion of supported metal and its catalytic properties in the aqueous-phase hydrogenation of furfural. The 1.5% Pd/CB catalyst demonstrated a high selectivity (99%) for furfuryl alcohol during hydrogenation of furfural at a temperature of 50°C and hydrogen pressure of 0.5MPa. The 1.5% Pd/CNT catalyst was not active under mild conditions of the reaction (50°C, 0.5MPa), but had a greater tendency to reduce the furan ring under severe conditions (90°C, 0.5 or 2.0MPa) as demonstrated by an increased yield of tetrahydrofurfuryl alcohol. The ruthenium samples showed a low activity in aqueous-phase hydrogenation of furfural irrespective of the support nature and reaction conditions, possibly due to irreversible adsorption of water on the active sites.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
The results of studies related to the development of synthesis, determination of formation conditions and elucidation of the mechanism of palladium–carbon catalyst action are integrated and ...critically analyzed. The attention is focused on Pd/NGC compositions (NGC is nanoglobular carbon). Methods for NGC preparation with an emphasis on its most common form, carbon black, are considered. The following issues are addressed: mechanisms of formation of carbon nanoglobules and their aggregates, methods of varying the size of nanoglobules, functionalization of the NGC surface to make it suitable as a support for palladium nanoparticles, views on the formation mechanism of palladium clusters and nanoparticles on the carbon support surface and effect of the structure and surface chemistry of carbon nanoglobules on the state of palladium sites in Pd/NGC compositions. The published data on selective hydrogenation of organic compounds in the presence of Pd/NGC catalytic compositions are integrated and systematized. The catalytic properties of Pd/NGC are analyzed in comparison with the properties of palladium catalysts supported on other carbon materials (activated carbon, carbon nanotubes). The influence of preparation conditions of NGC-based palladium compositions on their catalytic properties in practically important hydrogenation reactions is discussed. Promising trends for further research on the development of molecular design methods, study of the genesis of Pd/NGC compositions and extension of their applications in hydrogenation processes are considered. The bibliography includes 623 references.
Porous carbon–carbon composite materials (PCCCM) were synthesized by the alkaline dehydrochlorination of polyvinyl chloride solutions in dimethyl sulfoxide containing the modifying additives of a ...nanostructured component (NC): graphite oxide (GO), reduced graphite oxide (RGO) or nanoglobular carbon (NGC), with subsequent two-step thermal treatment of the obtained polyvinylene–NC composites (carbonization at 400 °C and carbon dioxide activation at 900 °C). The focus of the study was on the analysis and digital processing of transmission electron microscopy images to study local areas of carbon composite materials, as well as to determine the distances between graphene layers. TEM and low-temperature nitrogen adsorption studies revealed that the structure of the synthesized PCCCM can be considered as a porous carbon matrix in which either carbon nanoglobules (in the case of NGC) or carbon particles with the “crumpled sheet” morphology (in the case of GO or RGO used as the modifying additives) are distributed. Depending on the features of the introduced 5–7 wt.% nanostructured component, the fraction of mesopores was shown to vary from 11% to 46%, and SBET—from 791 to 1115 m2 g−1. The synthesis of PCCNC using graphite oxide and reduced graphite oxide as the modifying additives can be considered as a method for synthesizing a porous carbon material with the hierarchical structure containing both the micro- and meso/macropores. Such materials are widely applied and can serve as adsorbents, catalyst supports, elements of power storage systems, etc.
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•Synergistic effect between Pd and Ru in benzaldehyde hydrogenation was observed.•Pd-Ru/NGC catalysts are highly selective for benzyl alcohol.•Pd-Ru/CNTs are highly active in ...hydrogenolysis of CO bonds.•The formation of Pd-Ru alloy is one of the reasons of synergistic effect.
Bimetallic Pd-Ru/C catalysts prepared with different carbon supports were shown to be much more active in the liquid-phase hydrogenation of benzaldehyde in comparison with their monometallic analogs. In the case of systems based on nanoglobular carbon, the synergistic effect manifested itself as an increased selectivity for benzyl alcohol (86–90%) at a complete conversion of benzaldehyde, whereas the catalysts containing carbon nanotubes were highly active in hydrogenolysis of the CO bonds, which caused an increased yield of toluene (up to 56%). The synergistic effect between palladium and ruthenium in the reaction under study can be related to the changes in the electronic and dispersion state of the supported metals upon interaction with each other and formation of Pd-Ru alloy. In terms of the electronic factor, the enhanced catalytic performance of bimetallic systems can be a result of facilitation of electrophilic activation of the CO bond in benzaldehyde owing to an increased fraction of the electron-deficient palladium species. The nature of carbon support was shown to affect the electronic state of supported metals and thus catalytic properties of bimetallic Pd-Ru/C systems.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
The effect of hydrothermal treatment (HTT) of gamma -alumina on the state of its surface functional cover, anchoring of hexachloroplatinate, and properties of platinum sites was investigated. ...Hydrothermal treatment of gamma -Al2O3 was found to increase the fraction of surface bridging OH groups and concentration of Lewis acid sites (LAS) and alter the metal complex-support interaction. Adsorption of hexachloroplatinate on the support surface is accompanied mainly by the formation of outer-sphere complexes, which are characterized by a lower reduction temperature. As a result, dispersion and electronic state of supported platinum are changed. Influence of gamma -Al2O3 hydrothermal treatment on the catalytic properties of Pt/Al2O3 in n-hexane transformations and propane dehydrogenation was demonstrated. The revealed effect of gamma -Al2O3 hydrothermal treatment on the formation of platinum sites in Pt/Al2O3 catalysts can be of fundamental importance for the steps of supported system synthesis where solid phase is contacting with water and aqueous solutions (impregnation and drying).
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Ni(Mg)Al-layered double hydroxides (LDH) were synthesized by coprecipitation. Structural properties of LDH and mixed oxides Ni(Mg)AlOx, obtained by LDH calcination, were studied by XRD and SEM. ...Textural properties of Ni(Mg)AlOx were studied by the nitrogen adsorption-desorption method. It was found that the formation of the single-phase LDH was occurred for any nickel content in the samples. The mixed oxides have a high specific surface area, the value of which decreases with increasing nickel content in the samples. Ni(Mg)AlOx are characterized by high activity in furfural hydrogenation. Selectivity of the formation of different reaction products depends on the nickel content in the catalysts. The full furfural conversion with the furfuryl alcohol selectivity no more than 65% was observed for the catalyst with a low nickel content. At the same time an increase in selectivity for furfuryl alcohol up to 84% occurs for the NiAl-catalyst with a furfural conversion not exceeding 43%.
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•Synthesis of single-phase Ni(Mg)Al-layered hydroxides by coprecipitation.•Structural and textural properties of the Ni(Mg)Al-layered hydroxides and their calcined forms.•High activity of the Ni(Mg)AlOx catalysts in the reaction of aqua-phase furfural hydrogenation.•Selectivity of products formation can vary by changing the nickel amount in the Ni(Mg)AlOx catalysts.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Due to a detailed analysis of NMR spectra of the reaction solutions with different composition obtained by the aqueous‐phase catalytic (Pd/C) hydrogenation of 2,4,6‐trinitrobenzoic acid, the ...intermediate compounds were identified and a more substantiated mechanism was proposed for the formation of the main reaction products—1,3,5‐triaminobenzene and cyclohexane‐1,3,5‐trione trioxime. The condensation of the 1,3,5‐triaminobenzene molecules produced by a complete hydrogenation of 2,4,6‐trinitrobenzoic acid was shown to result in the formation of a paramagnetic heterocyclic compound.
The reaction mixture NMR study of the aqueous‐phase catalytic (Pd/C) 2,4,6‐trinitrobenzoic acid hydrogenation was performed, and the mechanism of the reaction going via azoxybenzene semi‐product formation was updated. New heterocyclic paramagnetic product of three 1,3,5‐triaminobenzene molecules condensation produced during the hydrogenation process was detected.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Nickel catalysts with carbon-mineral supports derived from sapropel were synthesized; the effect exerted by the nature of the support (type of the initial sapropel) and active component precursor on ...the activity of the catalysts in the model reaction of liquid-phase nitrobenzene hydrogenation was studied. The catalysts, synthesized using the support with a smaller fraction of carbon, were more active irrespective of the precursor nature. The highest activity was observed for the catalysts synthesized from nickel nitrate and formate; nitrobenzene conversion was 65% and 51%, respectively, after 1 h of reaction. The catalysts retained high activity after six reaction cycles at 100% aniline selectivity. The presence of sulfur in the nickel precursor deteriorated the catalytic activity (convection less than 3%) due to formation of the sulfide phase.
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•Controllable activity and selectivity of Pd/C hydrogenation catalysts.•Effect of the carbon support on the structure and catalytic properties of Pd NPs.•Effect of the Pd precursor on ...the structure and catalytic properties of Pd NPs.•Addition of a second metal and the synergistic effect in Pd-based bimetallic catalysts.
Carbon-supported palladium catalysts are widely used for hydrogenation of various organic compounds in the fine chemical industry. The nanoscale geometry and electronic structure of supported Pd nanoparticles play a crucial role in providing the necessary catalytic properties. To improve catalytic activity and selectivity of Pd nanoparticles, it is possible to fine tune their intrinsic properties (e.g., size and oxidation state) by controlling the chemical transformations at different stages of catalyst preparation. Recent years have seen considerable advancement in developing new catalyst preparation techniques as well as in understanding the mechanism of active site formation. This review summarizes some of the existing approaches to regulating the catalytic properties of carbon-supported palladium by variation of the carbon support, the composition of palladium precursor and its reduction conditions, as well as the addition of a second active metal. The data presented may be useful for researchers developing efficient Pd/C catalysts for hydrogenation of polyfunctional organic compounds.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Changes in the structural and textural properties of NiAl-layered double hydroxides (LDHs) (with 2–4 molar ratios of metals) and state of nickel that occur in different steps of the synthesis of ...nickel catalysts were studied using XRD, thermal analysis, TPR, low-temperature nitrogen adsorption, XANES, EXAFS, and electron microscopy methods. Relations between nickel content, catalyst reduction conditions, state of nickel, and its catalytic properties were revealed. It was shown that the use of NiAl LDH as the catalyst precursor even at a high content of active metal allows for the obtaining of the dispersed particles of supported nickel that are active in the aqueous-phase hydrogenation of furfural. The catalyst activity and conversion of furfural were found to increase with elevation of the catalyst reduction temperature and the corresponding growth of the fraction of reduced nickel. However, a lower reduction temperature (500 °C) makes it possible to form smaller nickel particles with the size of 4–6 nm, and a high Ni content (Ni:Al = 4) can be used to obtain the active Ni@NiAlOx catalyst. Under mild reaction conditions (90 °C, 2.0 MPa), the furfural conversion reached 93%, and furfuryl alcohol was formed with the selectivity of 70%. Under more severe reaction conditions (150 °C, 3.0 MPa), complete conversion of furfural was achieved, and cyclopentanol and tetrahydrofurfuryl alcohol were the main hydrogenation products.
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