Preparation of well-dispersed and anti-oxidized Ni nanoparticles using polyamioloamine dendrimers as templates and their catalytic activity in the hydrogenation of <Emphasis Type="Italic">p</Emphasis>-nitrophenol to <Emphasis Type="Italic">p</Emphasis>-aminophenol

p-Aminophenol was synthesized by catalytic hydrogenation of p-nitrophenol on Ni nanoparticles prepared by a chemical reduction method using polyamidoamine (PAMAM) dendrimers as templates. The as-prepared Ni nanoparticles were characterized by XRD, LRS, EDS, FTIR, FESEM, HRTEM and N₂ sorption analysis. Smaller-sized, better-dispersed and more active Ni nanoparticles can be successfully achieved using PAMAM dendrimers as templates. Analysis results show the as-prepared Ni nanoparticles are pure f.c.c. nickel. In hydrogenation reactions of p-nitrophenol, Ni nanoparticles show higher catalytic activity than that of Ni nanoparticles prepared in the absence of PAMAM dendrimers. The weight ratio of PAMAM/Ni²⁺ is proved to be an important parameter on the catalytic activity of Ni nanoparticles and the optimal ratio is 15%. The reason proposed for higher catalytic activity of Ni nanoparticles is a combination effect of smaller particle size, better dispersion and more active Ni nanoparticles.     

Selective Production of 2-Phenylhexane from Benzene and <Emphasis Type="Italic">n</Emphasis>-Hexane Over Pt- and Ga-Modified Zeolites

Abstract  

Alkylation of benzene with n-hexane was performed over H-ZSM-5 and monometallic Ga- and Pt- and bimetallic Ga- and Pt-modified ZSM-5. The influence of the particle size and the method of incorporation of Ga (during hydrothermal synthesis, by solid-state ion exchange, or by liquid-state ion exchange) was determined. The presence of Pt and well-dispersed extraframework Ga in H-ZSM-5 increased the selectivity in alkylation and suppressed cracking reactions. Well-dispersed Pt particles led to better catalytic performance. The method of Ga incorporation played an important role in obtaining higher selectivity to alkylation products and in the suppression of side reactions. Up to 93% selectivity in alkylation (of which >95% was to 2-phenylhexane) was reached over 2 wt% Pt/H-Ga^fZSM5, in which Ga occupied framework positions. We propose that the close proximity of very small Pt nanoparticles and Ga–(OH)–Si acid sites results in the optimal bifunctional catalyst for selective production of 2-phenylhexane from benzene and n-hexane. During the reaction, the catalyst deactivated, most probably due to the sintering of the Pt particles.     

Palladium Nanoparticles Immobilized on Nano‐Silica Triazine Dendritic Polymer (Pdnp‐nSTDP): An Efficient and Reusable Catalyst for Suzuki–Miyaura Cross‐Coupling and Heck Reactions

A new catalyst based on palladium nanoparticles immobilized on nano‐silica triazine dendritic polymer (Pd_np‐nSTDP) was synthesized and characterized by FT‐IR spectroscopy, thermogravimetric analysis, field emission scanning electron microscopy, energy dispersive X‐ray, transmission electron microscopy and elemental analysis. The size of the palladium nanoparticles was determined to be 3.1±0.5 nm. This catalytic system showed high activity in the Suzuki–Miyaura cross‐coupling of aryl iodides, bromides and chlorides with arylboronic acids and also in the Heck reaction of these aryl halides with styrenes. These reactions were best performed in a dimethylformamide (DMF)/water mixture (1:3) in the presence of only 0.006 mol% and 0.01 mol% of the catalyst, respectively, under conventional conditions and microwave irradiation to afford the desired coupling products in high yields. The Pd_np‐nSTDP was also used as an efficient catalyst for the preparation of a series of star‐ and banana‐shaped compounds with a benzene, pyridine, pyrimidine or 1,3,5‐triazine unit as the central core. Moreover, the catalyst could be recovered easily and reused several times without any considerable loss of its catalytic activity.     

Ionic Liquid‐Promoted Oxidant‐Free Dehydrogenation of Alcohols with Water‐Soluble Ruthenium Nanoparticles in Aqueous Phase

An oxidant‐free dehydrogenation of alcohols in the aqueous phase was developed for the first time using water‐soluble poly(N‐vinyl‐2‐pyrrolidone) (PVP)‐stabilized ruthenium nanoparticles with an ionic liquid as a promoter. The present catalytic system was highly efficient and stable for the catalytic dehydrogenation of various alcohols. It was found that the basic ionic liquid 1‐n‐butyl‐2,3‐dimethylimidazolium acetate ([BMMIM] OAc) additive played a crucial role in enhancing the catalytic activity and stability of ruthenium(0) nanoparticles. A reaction kinetics study and ¹H NMR analysis demonstrated that the basic ionic liquid and ruthenium nanoparticles exerted a synergetic effect for the dehydrogenation reaction.     

Cr(III)‐containing Fe3O4/mercaptopropanoic acid‐poly(2‐hydroxyethyl acrylate) nanocomposite: Highly active magnetic catalyst for direct hydroxylation of benzene

In this study, polymer‐grafted magnetic nanoparticles containing chromium(III) ions incorporated onto Fe₃O₄/mercaptopropanoic acid‐poly(2‐hydroxyethyl acrylate) was prepared via a simple and in situ method. The obtained magnetic nanocomposite exhibited high catalytic activity and excellent selectivity in direct hydroxylation of benzene in the presence of hydrogen peroxide under solvent‐free condition. The magnetic catalyst could be also separated by an external magnet and reused seven times without any significant loss of activity/selectivity. Due to the Lewis acidity of the Fe³⁺ groups in the structure of magnetic nanoparticles, the high efficiency of this catalyst is possibly due to the synergetic effect of Cr³⁺ and Fe³⁺ groups in the structure of magnetic nanocomposite. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40383.     

Hexagonal boron nitride nanosheets as metal-free electrochemical catalysts for oxygen reduction reactions

A high-performance ball milling technique was developed for synthesizing hexagonal boron nitride (h-BN) carbon paper (CP) electrodes as metal-free catalyst for the oxygen reduction reaction (ORR) and hydrogen storage (electrochemically) in acidic media. The h-BN nanosheets were functionalized with glycine to enhance the number of active sites and to boost the catalytic activity. The ball-milled h-BN catalytic electrodes demonstrated ultra-high catalytic activity toward electrochemical hydrogen adsorption/desorption (～3.5 times higher than pristine electrodes) as well as ORR in acidic electrolytes. Furthermore, in-situ durability analysis of the h-BN electrodes was performed via conducting a long-duration cycling experiment (>200 cycles). A mechanistic reaction pathway (sequential) including chemisorption and charge transfer reactions (four-electron and two-electron pathways) was also proposed for the ORR. Considering superior catalytic activity of as-prepared h-BN/CP electrodes, this class of metal-free nanostructured materials can be employed as inexpensive catalysts for the electrochemical H-storage and ORR within various energy storage/conversion devices (e.g., batteries, electrolyzers, and fuel cells).     

Synthesis and Reactions of Enantiopure Substituted Benzene cis‐Hexahydro‐1,2‐diols

Enantiopure cis‐dihydro‐1,2‐diol metabolites, obtained from toluene dioxygenase‐catalysed cis‐dihydroxylation of six monosubstituted benzene substrates, have been converted to their corresponding cis‐hexahydro‐1,2‐diol derivatives by catalytic hydrogenation via their cis‐tetrahydro‐1,2‐diol intermediates. Optimal reaction conditions for total catalytic hydrogenation of the cis‐dihydro‐1,2‐diols have been established using six heterogeneous catalysts. The relative and absolute configurations of the resulting benzene cis‐hexahydro‐1,2‐diol products have been unequivocally established by X‐ray crystallography and NMR spectroscopy. Methods have been developed to obtain enantiopure cis‐hexahydro‐1,2‐diol diastereoisomers, to desymmetrise a meso‐cis‐hexahydro‐1,2‐diol and to synthesise 2‐substituted cyclohexanols. The potential of these enantiopure cyclohexanols as chiral reagents was briefly evaluated through their application in the synthesis of two enantiomerically enriched phosphine oxides from the corresponding racemic phosphine precursors.     

Improvements of the structural,thermal, and mechanical properties of structural adhesive with functionalized boron nitride nanoparticles

Investigations on the production and development of nanoparticle-reinforced polymer materials have been attracted attention by researchers. Various nanoparticles have been used to improve the mechanical, chemical, thermal, and physical properties of polymer matrix composites. Boron compounds come to the fore to improve the mechanical and thermal properties of polymers. In this study, mechanical, thermal, and structural properties of structural adhesive have been examined by adding nano hexagonal boron nitride (h-BN) to epoxy matrix at different percentages (0.5, 1, 2, 3, 4, and 5%). For this purpose, nano h-BN particles were functionalized with 3-aminopropyltriethoxysilane (APTES) to disperse the h-BN nanoparticles homogeneously in epoxy matrix and to form a strong bond at the matrix interface. Two-component structural epoxy adhesive was modified by using functionalized h-BN nanoparticles. The structural and thermal properties of the modified adhesives were investigated by scanning electron microscopy and energy dispersion X-ray spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis techniques. Tensile test and dynamic mechanical analysis were performed to determine the mechanical properties of the adhesives. When the results obtained from analysis were examined, it was seen that the nano h-BN particles functionalized with APTES were homogeneously dispersed in the epoxy matrix and formed a strong bond. In addition that, it was concluded from the experimental results that the thermal and mechanical properties of adhesives were improved by adding functionalized nano h-BN particles into epoxy at different ratios.     

Temperature‐responsive catalytic performance of Ag nanoparticles endowed by poly (N‐isopropylacrylamide‐co‐acrylic acid) microgels

In this study, we facilely introduce silver nanoparticles into Poly(N‐isopropylacrylamide‐co‐acrylic acid)(Poly(NIPAM‐co‐AA)) microgels and specially focus on the effect of hydrophilic acrylic acid segments on the responsive catalytic performance of silver nanoparticles. The obtained Poly(NIPAM‐co‐AA)/AgNPs composites are characterized by Fourier transform infrared spectra, X‐ray diffraction, X‐ray photoelectron spectroscopy, and transmission electron microscopy. The composites as catalysts are applied to the hydrogenation reaction of p‐nitrophenol and the related conditions such as reaction temperature, concentration of p‐nitrophenol, and the loadings of Ag nanoparticles are studied in detail. NIPAM segments of composites conveniently give silver nanoparticles a controllable characteristic for catalytic reaction by their conformation variation. AA segments of composites not only provide good stability and dispersibility for silver nanoparticles but also favor an easier diffusion of p‐nitrophenol to Ag NPs. POLYM. COMPOS., 38:708–718, 2017. © 2015 Society of Plastics Engineers     

Magnetic polymeric nanoparticles functionalized by mannose‐rhodamine conjugate for detection of E. coli

Mannose‐rhodamine (Rh) conjugate (80% yield) was synthesized in a one‐pot reaction and immobilized onto magnetic polymeric nanoparticles (MPNP; 43% magnetic content) of poly(styrene/divinyl benzene/acrylic acid). The resulting nanoparticles contained MPNP as a substrate, mannose as an E. coli receptor and Rh as a fluorescent signaling unit. TEM imaging clearly demonstrated that multiple mannose‐Rh MPNPs could be captured by E. coli strain ORN178. The fluorescent signal from captured nanoparticles was emitted at 580 nm. These results indicate that mannose‐Rh MPNP offers a simple and rapid strategy for bacterial detection. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40012.     

Investigation of inter‐relationship between tensile behavior and photocatalytic activity of an acrylic‐based composite upon UVA exposure

The aim of this work is to produce a photocatalytic pseudo‐paint for benzene removal from air and find the role of TiO₂ nanoparticles, TiO₂ pigment, and CaCO₃ extender on photocatalytic performance of this paint along with their role on stress–strain behavior after ultraviolet (UV) exposure. For this purpose, TiO₂ nanoparticles were dispersed into an indoor paint resin (i.e., copolymer acrylic–styrene). The impact of main components of the paint on photocatalytic oxidation (PCO) rate of benzene was studied. It was found that dispersion of nanoparticles had the most dramatic effect on photo activity of nanocomposite. TiO₂ pigment generally increased PCO rate and also made the paint more stable under tensile stress. CaCO₃ may increase and/or decrease PCO of benzene, whether there is pigment in the formulation or not. However, it does not generally contribute to making the formulation resistant to UV exposure. Nanoparticles bring PCO and mechanical strength into the paint, but fail to strengthen the composite against UV deterioration. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44447.     

Adsorption and Catalytic Activation of the Molecular Oxygen on the Metal Supported h-BN

Adsorption and catalytic activation of the molecular oxygen on the hexagonal boron nitride (h-BN) monolayer supported on Ni(111) and Cu(111) surfaces have been studied theoretically using density functional theory. It is demonstrated that an inert h-BN monolayer can be functionalized and become catalytically active on the transition metal support as a result of mixing of the metal d and h-BN π bands.     

Decorated‐magnetic‐nanoparticle‐supported bromine as a recyclable catalyst for the oxidation of sulfides

Herein, we present a strategy for supporting bromine as a catalyst for the oxidation of sulfides. In this strategy, branched poly(ethylene imine) was first decorated by magnetic oxide and then used to support liquid bromine to obtain solid polymeric bromine (M@PEI@Br) nanoparticles. Compared with free bromine, the stability of the M@PEI@Br nanoparticles improved obviously. The oxidation of thioanisole to methyl phenyl sulfoxide was chosen as a reaction model to evaluate the catalytic activity of the M@PEI@Br nanoparticles. All of the obtained results verify that the M@PEI@Br nanoparticles exhibited excellent catalytic efficiency and could accelerate the oxidation process under solvent‐free conditions at room temperature; this highlighted the potential of decorated polymers to support active and unstable small‐molecule organic catalysts. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46036.     

Synergistic effects on the enhancement of thermal conductive properties of thermal greases

Efficient heat dissipation from electronic devices with high-degree integration and high-power density has become an urgent and complex problem. We report here novel thermal greases with an enhanced thermal conductivity using graphene flakes (GFs), hexagonal boron nitride (h-BN), and hydroxypropyl cellulose (HPC) as fillers. The obtained GF/h-BN/HPC thermal grease at 23 vol % h-BN loading exhibits a thermal conductivity enhancement 555%, compared with the pure PDMS matrix, and also about 50, 169, and 115% higher than that with GF/h-BN, h-BN/HPC and h-BN as the filler for the thermal grease, respectively. We attribute it to the synergistic effects among GF, h-BN, and HPC, due to the formation of thermally conductive networks. This study provides a strategy for preparing thermal greases for thermal management applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47726.     

Direct Amide Synthesis from Alcohols and Amines by Phosphine‐Free Ruthenium Catalyst Systems

Amides are synthesized directly from alcohols and amines in high yields using an in situ generated catalyst from easily available ruthenium complexes such as the (p‐cymene)ruthenium dichloride dimer, [Ru(p‐cymeme)Cl₂]₂, or the (benzene)ruthenium dichloride dimer, [Ru(benzene)Cl₂]₂, an N‐heterocyclic carbene (NHC) ligand, and a nitrogen containing L‐type ligand such as acetonitrile. The phosphine‐free catalyst systems showed improved or comparable activity compared to previous phosphine‐based catalytic systems. The in situ generated catalyst from [Ru(benzene)Cl₂]₂, an NHC ligand, and acetonitrile showed excellent activity toward reactions with cyclic secondary amines such as piperidine and morpholine.     

Synthesis of CdS‐ and ZnS‐modified bentonite nanoparticles and their applications to the degradation of eosin B

BACKGROUND: In the present study, nanocomposites of cadmium sulphide (CdS) and zinc sulphide (ZnS) on a bentonite have been prepared via an in‐situ precipitation route and their catalytic behaviour was evaluated in the degradation of eosin B. RESULTS: It was found that the basal space of bentonite increased from 1.23 to 1.49 nm after CdS or ZnS nanoparticles were deposited on layers of the bentonite. The resulting CdS–bentonite and ZnS–bentonite nanocomposites can degrade eosin B from aqueous solution after 2 h under UV irradiation. CONCLUSION: A soft method for in situ synthesis of monodispersed, CdS and ZnS nanoparticles, using a reverse micelle type procedure, is reported. The synthesized CdS‐ and ZnS–bentonite composites combined the adsorptive ability of bentonite and the catalytic degradation ability of CdS and ZnS to remove eosin B from its aqueous solution efficiently. Copyright © 2009 Society of Chemical Industry     

A Novel Method to Immobilize Ru Nanoparticles on SBA-15 Firmly by Ionic Liquid and Hydrogenation of Arene

A novel support of the Ru nanoparticles was achieved by combination of electrostatic force and coordination. The Ru catalyst was used as heterogeneous catalyst for hydrogenation of arene. This catalyst is very active for the hydrogenation of benzene to cyclohexane even under mild conditions. The TOF of this Ru catalyst is 85.3 mol mol⁻¹ h⁻¹ at 20 °C and 1.0 MPa for complete hydrogenation of benzene. The catalytic activity did not decrease after other five runs. The excellent performance of this catalyst demonstrated that there existed synergistic effects among 1,1,3,3-tetramethylguanidinium, mesoporous SBA-15, and Ru nanoparticles.     

Immobilized Co/Rh Heterobimetallic Nanoparticle‐Catalyzed Pauson–Khand‐Type Reaction

Co/Rh heterobimetallic nanoparticles were prepared from cobalt‐rhodium carbonyl clusters [Co₂Rh₂(CO)₁₂ and Co₃Rh(CO)₁₂] and immobilized on charcoal. HR‐TEM revealed that the size of the heterobimetallic nanoparticles was ca. 2 nm and ICP‐AES analysis showed a 2 : 2 and a 3 : 1 cobalt‐rhodium stoichiometry (Co₂Rh₂ and Co₃Rh₁) in the heterobimetallic nanoparticles. The Co/Rh heterobimetallic nanoparticles immobilized on charcoal were used as a catalyst in the Pauson–Khand‐type reaction under 1 atm of CO. The catalytic reactivity was highly dependent upon the ratio of Co : Rh with the highest reactivity being observed when the ratio was 2 : 2 (Co₂Rh₂). The Co₂Rh₂ immobilized catalyst is quite an effective catalyst for intra‐ and intermolecular Pauson–Khand‐type reactions. When the immobilized Co₂Rh₂ catalyst was used as a catalyst in the Pauson–Khand‐type reaction in the presence of an aldehyde instead of carbon monoxide, the catalytic system was highly efficient. When the reaction was carried out in the presence of chiral diphosphines, ee values up to 87% were observed. The catalytic system can be reused at least five times in the presence of chiral diphosphines without loss of catalytic activity and enantioselectivity. The addition of Hg(0), a known heterogeneous catalyst poison, completely inhibits further catalysis. Thus, an environmentally friendly and sustainable process was developed.     

Platinum Nanoparticles Supported on Ionic Liquid‐Modified Magnetic Nanoparticles: Selective Hydrogenation Catalysts

A method for supporting platinum nanoparticles on magnetite nanoparticles is described. The method requires modification of the surface of the magnetic nanoparticles with ionic liquid groups. Before modification, the magnetic nanoparticles are not stable and easily aggregate and, after modification, the magnetite nanoparticles become highly stable and soluble in polar or non‐polar organic solvents depending on the alkyl group of the linked ionic liquids. The supporting of platinum nanoparticles on the modified magnetic nanoparticles was achieved by adsorbing platinum salts (K₂PtCl₄) on the surface of the magnetite nanoparticles via ion exchange with the linked ionic liquid groups and then reducing them by hydrazine. The supported platinum nanoparticles were applied in the catalytic hydrogenation of alkynes in which cis‐alkenes were selectively produced, and in the hydrogenation of α,β‐unsaturated aldehydes where the allyl alcohols were obtained as the exclusive products. The new catalyst can be easily separated from the reaction mixtures by applying an external magnetic field and recycled.     

Catalytic membrane reactor for Suzuki‐Miyaura C−C cross‐coupling: Explanation for its high efficiency via modeling

A polymeric catalytic membrane was previously prepared that showed remarkable efficiency for Suzuki‐Miyaura C‐C cross‐coupling in a flow‐through configuration. A mathematic model was developed and fitted to the experimental data to understand the significant apparent reaction rate increase exhibited by the catalytic membrane reactor compared to the catalytic system under batch reaction conditions. It appears that the high palladium nanoparticles concentration inside the membrane is mainly responsible for the high apparent reaction rate achieved. In addition, the best performance of the catalytic membrane could be achieved only in the forced flow‐through configuration, that, conditions permitting to the reactants be brought to the catalytic membrane by convection. © 2016 American Institute of Chemical Engineers AIChE J, 63: 698–704, 2017