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1.
Chemoselective hydrogenation of nitroarenes with carbon nanofiber-supported platinum and palladium nanoparticles 总被引:1,自引:0,他引:1
Platinum and palladium nanoparticles supported on three types of carbon nanofibers (CNFs) are synthesized and used as catalysts in the hydrogenation of nitroarenes. Nanosized platinum particles dispersed on platelet-type CNF efficiently catalyze the reduction of functionalized nitroarenes to the corresponding substituted anilines in high turnover numbers with other functional groups remaining intact. 相似文献
2.
Regina Xavier V. Mahadevan 《Journal of polymer science. Part A, Polymer chemistry》1992,30(13):2665-2676
The synthesis of new hydrogel copolymers and their use for anchoring Pd and Pt species is described. The supported catalysts are effective for the reduction of alkenes, dienes, alkynes, and nitroaromatics under mild conditions. The catalysts have been characterized by chemical analysis, particle size measurement, IR, TGA, and x-ray photoelectron spectra. Relative reactivities and the effects of substrate structure, solvents, catalyst loading, particle size of the catalysts, and partial pressure of hydrogen have been determined. The kinetics of hydrogenation have been analyzed using concepts useful under slurry reaction conditions. The recycling efficiencies of the catalysts and product analysis to establish selectivities have been assessed. © 1992 John Wiley & Sons, Inc. 相似文献
3.
Palladium nanoparticles were synthesized in aqueous medium via reduction by hydrazine using various polymers (polyvinylpyrrolidone and polystyrene sulfonate) and the clay mineral hectorite as stabilizers. The kinetics of homogeneous and heterogeneous nucleation processes was studied by UV-visible spectrophotometry. The effect of the polymer and concentration of the silicate and palladium ions on particle formation rate was investigated. The size of the nanoparticles were determined by transmission electron microscopy. Both polymers and the silicate lamellae were found to be capable of stabilizing the particles. The rate of reduction is decreased by increasing amounts of stabilizing agents and increased by increasing concentrations of precursor ions. The kinetics of heterogeneous nucleation was determined by the adsorption of the palladium species at the clay mineral particles and the viscosity of the hectorite dispersion. 相似文献
4.
Ornelas C Salmon L Aranzaes JR Astruc D 《Chemical communications (Cambridge, England)》2007,(46):4946-4948
1,2,3-Ferrocenyl triazole ligands generated by click reactions in dendrimers bind Pd(OAc)2 with a systematic one-to-one stoichiometry as monitored by titration using the ferrocenyl redox sensor attached to the triazole ring, and the dendritic PdII complexes formed are best reduced by methanol to form palladium nanoparticles of designed types and sizes that show excellent efficiency and selectivity in olefin hydrogenation. 相似文献
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Juttukonda V Paddock RL Raymond JE Denomme D Richardson AE Slusher LE Fahlman BD 《Journal of the American Chemical Society》2006,128(2):420-421
Tin(IV) oxide nanoparticles were synthesized via the reaction of carbon dioxide with stannate ions immobilized by dendritic polymers. For PAMAM and PPI dendrimer hosts, resultant nanoparticle diameters were 2.5-3 nm; 3-3.5 nm nanoparticles resulted from use of a poly(ethyleneimine) hyperbranched polymer. Our conditions represent the only precedent for SnO2 nanoparticulate growth using dendritic architectures, as well as a novel application for CO2 as a reactive gas for the controlled growth of metal oxide nanoparticles. 相似文献
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Floriana Vitale Rosa Vitaliano Ilaria Fratoddi Emanuela Piscopiello Maria Vittoria Russo 《Journal of organometallic chemistry》2008,693(6):1043-1048
This work is focused on the synthesis of innovative hybrids made by linking gold nanoparticles to protected organometallic Pd(II) thiolate. The organometallic protected Pd(II) thiolate, i.e. trans-thioacetate-ethynylphenyl-bis(tributylphosphine)palladium(II) has been synthesized, in situ deprotected and linked to Au nanoparticles. In this way new hybrid, with a direct link between Pd(II) and Au nanoparticles through a single S bridge, has been isolated. The combination of the organometallic Pd(II) thiol with gold nanoparticles allows the enhancement and tailoring of electronic and optical properties of the new organic-inorganic nano-compound. Single-crystal gold nanoparticles, uniform in shape and size were obtained by applying a modified two-phase method (improved Brust-Schiffrin reaction). In addition, the chemical environment of the Au nanoparticles was investigated and a covalent bonding between Au nanoparticles and the organometallic thiols was observed. 相似文献
9.
《Journal of molecular catalysis. A, Chemical》1998,130(3):279-284
Competitive hydrogenation of alkene, alkyne and diene substrates (C6–C8) over palladium and platinum catalysts were studied at 20°C and atmospheric pressure. Selectivities of these reactions were determined and the substrates relative adsorption coefficients calculated. It was found that hydrogenations of alkynic and dienic substrates were preferred in alkyne–alkene and diene–alkene systems, respectively. In these systems palladium catalyst selectivity was higher than selectivity of the platinum catalyst, due to higher relative adsorption coefficients of corresponding substrate couples on the palladium catalyst. 相似文献
10.
Structure sensitivity of selective acetylene hydrogenation over the catalysts with shape-controlled palladium nanoparticles 总被引:1,自引:0,他引:1
A. E. Yarulin R. M. Crespo-Quesada E. V. Egorova L. L. Kiwi-Minsker 《Kinetics and Catalysis》2012,53(2):253-261
The structure sensitivity of acetylene hydrogenation on catalysts with controlled shape of palladium nanoparticles was studied. Palladium particles of cubic (Pdcub), cuboctahedral (Pdco) and octahedral (Pdoct) shapes were obtained by a colloidal method. Poly(N-vinyl)pyrrolidone (PVP) was used as the stabilizer of colloidal solutions. In order to eliminate the effect of the polymer on the properties of the catalyst, PVP was removed from the surface of the particles after their transfer to the support by simultaneous treatment with ozone and UV radiation. This allowed complete cleaning of the catalyst surface from the organic stabilizer without any change in the morphology of particles. The effectiveness of this treatment method was confirmed by X-ray photoelectron spectroscopy and scanning electron microscopy. It was found experimentally that the shape of nanoparticles does not influence the catalyst selectivity, but the activity decreases in the order Pdoct > Pdco > Pdcub. Since octahedrons consist of (111) faces, the cubes contain only (100) faces, and the cuboctahedrons are composed of faces of both types, Pd111 is more active than Pd100. Calculations with the use of a statistical method showed that the ~3-nm Pd octahedrons are nanoparticles with optimum shape and size, giving maximum catalyst activity. 相似文献
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Azzam T Bronstein L Eisenberg A 《Langmuir : the ACS journal of surfaces and colloids》2008,24(13):6521-6529
A study is presented of the stabilization of gold and palladium nanoparticles (NPs) via a place-exchange reaction. Au and Pd NPs of approximately 3.5 nm were prepared by a conventional method using tetraoctylammonium bromide (TOAB) as the stabilizing agent. The resulting nanoparticles, referred to as Au-TOAB or Pd-TOAB, were later used as templates for the replacement of TOAB ligand with poly(ethylene oxide)- b-polystyrene- b-poly(4-vinylpyridine) (PEO- b-PS- b-P4VP) triblock copolymer. This biamphiphilic triblock copolymer was synthesized by atom transfer radical polymerization (ATRP) with control over the molecular weight and polydispersity. The place-exchange reaction was mediated through strong coordination forces between the 4-vinylpyridine copolymer and the metal species located on the surface of the nanoparticles. In addition, the displacement of the outgoing low molecular weight TOAB ligands by high molecular weight polymers is an entropy-assisted process and is believed to contribute to stabilization. The prepared complex, polymer-NP, exhibits greatly improved stability over the metal-NP complex in common organic solvents for the triblock copolymer. Self-assembly in water after ligand exchange resulted in micellar structures of about approximately 20 nm (electron microscopy) with the metal NP found located on the surface of the micelles. The stability of the nanoparticles in water was shown to depend greatly on the grafting density of the copolymer, with high stability (more than 6 months) at high grafting density and low stability, accompanied with irreversible agglomeration, at relatively low grafting densities. The surprising location of the metal NP (for both Au and Pd) on the surface of the micelles in water is explained by the fact that, upon self-assembly in THF/water system, the most hydrophobic chains (i.e., PS) undergo self-assembly first at low water content forming the core, followed by the P4VP (whether or not associated with the metal) forming a shell, and finally the PEO forming the corona. In lower metal content assemblies, the P4VP chains located in the shell undergo swelling in an acidic medium causing a substantial increase in micellar corona size, as confirmed by dynamic light scattering measurements. The present study offers a simple approach for the stabilization of various metal nanoparticles of catalytic interest, using a unique polymeric support that can be dispersed in organic solvents as well as aqueous solutions. 相似文献
13.
Palladium nanoparticles stabilized by a polyion complex composed of poly{4-chloromethylstyrene-co-(4-vinylbenzyl) tributylammonium chloride} and poly(acrylic acid) were easily recovered by filtration after pH treatment. The polyion complex stabilized palladium nanoparticles have high catalytic activity for the Suzuki and Heck reactions in water. 相似文献
14.
Micelle-hosted palladium nanoparticles catalyze citral molecule hydrogenation in supercritical carbon dioxide 总被引:2,自引:0,他引:2
A new approach of employing metal particles in micelles for the hydrogenation of organic molecules in the presence of fluorinated surfactant and water in supercritical carbon dioxide has very recently been introduced. This is allegedly to deliver many advantages for carrying out catalysis including the use of supercritical carbon dioxide (scCO2) as a greener solvent. Following this preliminary account, the present work aims to provide direct visual evidence on the formation of metal microemulsions and to investigate whether metal located in the soft micellar assemblies could affect reaction selectivity. Synthesis of Pd nanoparticles in perfluorohydrocarboxylate anionic micelles in scCO2 is therefore carried out in a stainless steel batch reactor at 40 degrees C and in a 150 bar CO2/H2 mixture. Homogeneous dispersion of the microemulsion containing Pd nanoparticles in scCO2 is observed through a sapphire window reactor at W0 ratios (molar water-to-surfactant ratios) ranging from 2 to 30. It is also evidenced that the use of micelle assemblies as new metal catalyst nanocarriers could indeed exert a great influence on product selectivity. The hydrogenation of a citral molecule that contains three reducible groups (aldehyde, double bonds at the 2,3-position and the 6,7-position) is studied. An unusually high selectivity toward citronellal (a high regioselectivity toward the reduction of the 2,3-unsaturation) is observed in supercritical carbon dioxide. On the other hand, when the catalysis is carried out in the conventional liquid or vapor phase over the same reaction time, total hydrogenation of the two double bonds is achieved. It is thought that the high kinetic reluctance for double bond hydrogenation of the citral molecule at the hydrophobic end (the 6,7-position) is due to the unique micelle environment that is in close proximity to the metal surface in supercritical carbon dioxide that guides a head-on attack of the molecule toward the core metal particle. 相似文献
15.
Palladium nanoparticles stabilized by Pluronic F68 triblock copolymer effectively catalyzed Suzuki-Miyaura reaction in water.
The reactions with water-soluble aryl iodides and aryl bromides containing electron-withdrawing or electron-donating substituent
occurred at room temperature. The catalytic efficiency was found to depend on the size of palladium nanoparticles and their
morphology. 相似文献
16.
Zhu W Yang H Yu Y Hua L Li H Feng B Hou Z 《Physical chemistry chemical physics : PCCP》2011,13(30):13492-13500
The highly water-soluble palladium nanoparticles (NPs) were synthesized by using the amphiphilic poly(ethylene glycol)-functionalized dicationic imidazolium-based ionic liquid (C(12)Im-PEG IL) as a stabilizing agent. The aqueous dispersed palladium NPs in the range of 1.9 ± 0.3 nm were observed by transmission electron microscopy (TEM). The physicochemical properties of C(12)Im-PEG IL in aqueous phase have been characterized by electrical conductivity, surface tension and dynamic light scattering (DLS) measurements. It was demonstrated that the amphiphilic ionic liquid can form micelles above its critical micelle concentration (CMC) in aqueous solution and the micelles played a crucial role in stabilizing the palladium NPs and thus promoted catalytic hydrogenation. Furthermore, the dicationic ionic liquid can also act as a gemini surfactant and generated emulsion between hydrophobic substrates and the catalytic aqueous phase during the reaction. The aqueous dispersed palladium NPs showed efficient activity for the catalytic hydrogenation of various substrates under very mild conditions and the stabilizing Pd(0) nanoparticles (NPs) can be reused at least eight times with complete conservation of activity. 相似文献
17.
Makowski P Demir Cakan R Antonietti M Goettmann F Titirici MM 《Chemical communications (Cambridge, England)》2008,(8):999-1001
Selective hydrogenation of phenol to cyclohexanol in the aqueous phase was achieved using a new catalytic system based on palladium particles supported on hydrophilic carbon prepared by one-pot hydrothermal carbonisation. 相似文献
18.
《Journal of Energy Chemistry》2015,(5)
This work reports a facile and efficient seed-mediated method for the synthesis of dendritic platinum(Pt)nanoparticles(NPs) at low temperatures of 55–60 °C in water, using L-ascorbic acid as a reducing agent and sodium citrate as a capping agent. It is found that the dendritic Pt NPs(10–150 nm) are composed of tiny Pt nanocrystals, which nucleate and grow through the introduced smaller Pt seeds with diameters of 3–5 nm.Further investigation shows that the dendritic Pt nanostructures display excellent catalytic performance in an aqueous-phase aromatic ketone hydrogenation reaction, including:(i) acetophenone conversion rate of 90%, with smaller dendritic Pt NPs(10–46 nm) offering a higher conversion efficiency;(ii) high chemoselectivity toward carbonyl group(90.6%–91.5%), e.g., the selectivity to 1-phenylethanol is ~90.1% with nearly100% acetophenone conversion for 10 nm dendritic Pt NPs within 60 min, under mild reaction conditions(20 °C, 1.5 bar H2 pressure, and 1.5 mol% catalyst). The high catalytic activity, selectivity and stability of the dendritic Pt nanostructures under the organic solvent-free conditions make them promising for many potential applications in green catalytic conversion of hydrophilic biomass derived compounds. 相似文献
19.
Kinetics and Catalysis - The properties of phosphorus-modified palladium catalysts in the liquid-phase hydrogenation of nitrobenzene and o-nitrochlorobenzene have been investigated. A general... 相似文献
20.
A new bisphosphine ligand, C8-BINAP, and C8-BINAP-stabilized palladium nanoparticles have been prepared; C8-BINAP was found to be an effective protecting ligand for preparing and stabilizing palladium nanoparticles with very small core size and narrow size distribution and the C8-BINAP-Pd nanoparticles behave as an efficient catalyst for carbon-carbon coupling reactions at room temperature. 相似文献