An Evaluation of the Potential Phototoxicity of CeO2 Nanoparticles in Retinal Pigment Epithelial Cells in-vitro

EPA Science Inventory

Cerium dioxide (CeO2) engineered nanoparticles (NP) are used as fuel-borne catalysts in off-road diesel engines, which can lead to exhaust emissions of respirable CeO2 NP. Other metal oxides may act as photo-catalysts which induce the generation of free radicals upon exposure to ...

Biofabricated zinc oxide nanoparticles coated with phycomolecules as novel micronutrient catalysts for stimulating plant growth of cotton

NASA Astrophysics Data System (ADS)

Priyanka, N.; Venkatachalam, P.

2016-12-01

This study describes the bioengineering of phycomolecule-coated zinc oxide nanoparticles (ZnO NPs) as a novel type of plant-growth-enhancing micronutrient catalyst aimed at increasing crop productivity. The impact of natural engineered phycomolecule-loaded ZnO NPs on plant growth characteristics and biochemical changes in Gossypium hirsutum L. plants was investigated after 21 days of exposure to a wide range of concentrations (0, 25, 50, 75, 100, and 200 mg l-l). ZnO NP exposure significantly enhanced growth and biomass by 125.4% and 132.8%, respectively, in the treated plants compared to the untreated control. Interestingly, photosynthetic pigments, namely, chlorophyll a (134.7%), chlorophyll b (132.6%), carotenoids (160.1%), and total soluble protein contents (165.4%) increased significantly, but the level of malondialdehyde (MDA) content (73.8%) decreased in the ZnO-NP-exposed plants compared to the control. The results showed that there were significant increases in superoxide dismutase (SOD, 267.8%) and peroxidase (POX, 174.5%) enzyme activity, whereas decreased catalase (CAT, 83.2%) activity was recorded in the NP-treated plants compared to the control. ZnO NP treatment did not show distinct alterations (the presence or absence of DNA) in a random amplified polymorphic DNA (RAPD) banding pattern. These results suggest that bioengineered ZnO NPs coated with natural phycochemicals display different biochemical effects associated with enhanced growth and biomass in G. hirsutum. Our results imply that ZnO NPs have tremendous potential in their use as an effective plant-growth-promoting micronutrient catalyst in agriculture.

Preparation of an agar-silver nanoparticles (A-AgNp) film for increasing the shelf-life of fruits.

PubMed

Gudadhe, Janhavi A; Yadav, Alka; Gade, Aniket; Marcato, Priscyla D; Durán, Nelson; Rai, Mahendra

2014-12-01

Preparation of protective coating possessing antimicrobial properties is present day need as they increase the shelf life of fruits and vegetables. In the present study, preparation of agar-silver nanoparticle film for increasing the shelf life of fruits is reported. Silver nanoparticles (Ag-NPs) biosynthesised using an extract of Ocimum sanctum leaves, were mixed with agar-agar to prepare an agar-silver nanoparticles (A-AgNp) film. This film was surface-coated over the fruits, Citrus aurantifolium (Thornless lime) and Pyrus malus (Apple), and evaluated for the determination of antimicrobial activity of A-AgNp films using disc diffusion method, weight loss and shelf life of fruits. This study demonstrates that these A-AgNp films possess antimicrobial activity and also increase the shelf life of fruits.

Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Lu-Cun; Friend, C. M.; Fushimi, Rebecca

The activation of molecular O 2as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O 2activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O 2dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O 2dissociationmore » is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O 2dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction.« less

Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Lu-Cun; Friend, C. M.; Fushimi, Rebecca

2016-01-01

The activation of molecular O 2as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O 2activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O 2dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O 2dissociationmore » is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O 2dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction.« less

Morphological Effect of Pd Catalyst on Ethanol Electro-Oxidation Reaction

PubMed Central

Cerritos, Raúl Carrera; Guerra-Balcázar, Minerva; Ramírez, Rosalba Fuentes; Ledesma-García, Janet; Arriaga, Luis Gerardo

2012-01-01

In the present study, three different structures with preferentially exposed crystal faces were supported on commercial carbon black by the polyol method (nanoparticles (NP/C), nanobars (NB/C) and nanorods (NR/C)). The electrocatalysts were characterized by XRD, TEM, TGA and cyclic voltammetry at three different ethanol concentrations. Considerable differences were found in terms of catalytic electroactivity. At all ethanol concentrations, the trend observed for the ethanol oxidation peak potential was preserved as follows: NB/C < NP/C< NR/C < commercial Pd/C. This result indicates that, from a thermodynamics point of view, the NB/C catalyst enclosed by Pd(100) facets presented the highest activity with respect to ethanol electro-oxidation among all of the catalysts studied.

Oxygen Reduction at Very Low Overpotential on Nanoporous Ag Catalysts

DOE PAGES

Zhou, Yang; Lu, Qi; Zhuang, Zhongbin; ...

2015-05-07

Here we report a monolithic nanoporous Ag (np-Ag) material, synthesized using the dealloying method, as high-performance catalysts for ORR in alkaline media. As shown in Scheme 1, when there is insufficient potential input, the O 2 molecules are more likely to rebound off from a planar electrode surface (i.e. bulk polycrystalline metal, films made from nanoparticles or nanowires) before they could be reduced. In contrast, they are more likely to be trapped inside the monolithic nanoporous structure, contacting with catalytic surface for multiple time, which greatly enhances the chance for them to be fully reduced. As a result, the np-Agmore » catalyst is able to achieve an equivalent or better ORR performance than the state-of the-art Pt/C catalyst at low overpotentials, which is most desired in electrochemical energy applications for maximizing efficiency.« less

Palladium nanoparticles dispersed on the hollow aluminosilicate microsphere@hierarchical γ-AlOOH as an excellent catalyst for the hydrogenation of nitroarenes under ambient conditions

NASA Astrophysics Data System (ADS)

Tian, Meng; Cui, Xueliang; Dong, Chunxu; Dong, Zhengping

2016-12-01

In this study, a novel catalyst has been prepared through supporting Pd nanoparticles (NPs) on the surface of boehmite (γ-AlOOH) based hollow aluminosilicate microspheres (HAM@γ-AlOOH). The prepared Pd/HAM@γ-AlOOH catalyst has high catalytic activity for the hydrogenation of nitroarenes to their corresponding amino derivatives with high yields at ambient conditions. The high catalytic efficiency is attributed to the large pore size of the flower-like hierarchical flakes structure of HAM@γ-AlOOH, that gives Pd NPs on the support surface easy accessibility. Moreover, the Pd/HAM@γ-AlOOH catalyst can also be easily recycled at least five times without obvious decrease of catalytic activity. This work may provide a useful method for the fabrication of supported noble metal NP-based catalysts on the surface of mesoporous hierarchical structure materials with easy accessibility and superior activity.

Synthesis and characterization of supported polysugar-stabilized palladium nanoparticle catalysts for enhanced hydrodechlorination of trichloroethylene

NASA Astrophysics Data System (ADS)

Bacik, Deborah B.; Zhang, Man; Zhao, Dongye; Roberts, Christopher B.; Seehra, Mohinar S.; Singh, Vivek; Shah, Naresh

2012-07-01

Palladium (Pd) nanoparticle catalysts were successfully synthesized within an aqueous phase using sodium carboxymethyl cellulose (CMC) as a capping ligand which offers a green alternative to conventional nanoparticle synthesis techniques. The CMC-stabilized Pd nanoparticles were subsequently dispersed within support materials using the incipient wetness impregnation technique for utilization in heterogeneous catalyst systems. The unsupported and supported (both calcined and uncalcined) Pd nanoparticle catalysts were characterized using transmission electron microscopy, energy dispersive x-ray spectrometry, x-ray diffraction, and Brunauer-Emmett-Teller surface area measurement and their catalytic activity toward the hydrodechlorination of trichloroethylene (TCE) in aqueous media was examined using homogeneous and heterogeneous catalyst systems, respectively. The unsupported Pd nanoparticles showed considerable activity toward the degradation of TCE, as demonstrated by the reaction kinetics. Although the supported Pd nanoparticle catalysts had a lower catalytic activity than the unsupported particles that were homogeneously dispersed in the aqueous solutions, the supported catalysts retained sufficient activity toward the degradation of TCE. In addition, the use of the hydrophilic Al2O3 support material induced a mass transfer resistance to TCE that affected the initial hydrodechlorination rate. This paper demonstrates that supported Pd catalysts can be applied to the heterogeneous catalytic hydrodechlorination of TCE.

Principles and Methods for the Rational Design of Core-Shell Nanoparticle Catalysts with Ultralow Noble Metal Loadings.

PubMed

Hunt, Sean T; Román-Leshkov, Yuriy

2018-05-15

Conspecuts Commercial and emerging renewable energy technologies are underpinned by precious metal catalysts, which enable the transformation of reactants into useful products. However, the noble metals (NMs) comprise the least abundant elements in the lithosphere, making them prohibitively scarce and expensive for future global-scale technologies. As such, intense research efforts have been devoted to eliminating or substantially reducing the loadings of NMs in various catalytic applications. These efforts have resulted in a plethora of heterogeneous NM catalyst morphologies beyond the traditional supported spherical nanoparticle. In many of these new architectures, such as shaped, high index, and bimetallic particles, less than 20% of the loaded NMs are available to perform catalytic turnovers. The majority of NM atoms are subsurface, providing only a secondary catalytic role through geometric and ligand effects with the active surface NM atoms. A handful of architectures can approach 100% NM utilization, but severe drawbacks limit general applicability. For example, in addition to problems with stability and leaching, single atom and ultrasmall cluster catalysts have extreme metal-support interactions, discretized d-bands, and a lack of adjacent NM surface sites. While monolayer thin films do not possess these features, they exhibit such low surface areas that they are not commercially relevant, serving predominantly as model catalysts. This Account champions core-shell nanoparticles (CS NPs) as a vehicle to design highly active, stable, and low-cost materials with high NM utilization for both thermo- and electrocatalysis. The unique benefits of the many emerging NM architectures could be preserved while their fundamental limitations could be overcome through reformulation via a core-shell morphology. However, the commercial realization of CS NPs remains challenging, requiring concerted advances in theory and manufacturing. We begin by formulating seven

Recent Advances in the Application of Magnetic Nanoparticles as a Support for Homogeneous Catalysts

PubMed Central

Govan, Joseph; Gun’ko, Yurii K.

2014-01-01

Magnetic nanoparticles are a highly valuable substrate for the attachment of homogeneous inorganic and organic containing catalysts. This review deals with the very recent main advances in the development of various nanocatalytic systems by the immobilisation of homogeneous catalysts onto magnetic nanoparticles. We discuss magnetic core shell nanostructures (e.g., silica or polymer coated magnetic nanoparticles) as substrates for catalyst immobilisation. Then we consider magnetic nanoparticles bound to inorganic catalytic mesoporous structures as well as metal organic frameworks. Binding of catalytically active small organic molecules and polymers are also reviewed. After that we briefly deliberate on the binding of enzymes to magnetic nanocomposites and the corresponding enzymatic catalysis. Finally, we draw conclusions and present a future outlook for the further development of new catalytic systems which are immobilised onto magnetic nanoparticles. PMID:28344220

Development of preservative-free nanoparticles-based emulsions: Effects of NP surface properties and sterilization process.

PubMed

Rowenczyk, Laura; Picard, Céline; Duclairoir-Poc, Cécile; Hucher, Nicolas; Orange, Nicole; Feuilloley, Marc; Grisel, Michel

2016-08-20

Model emulsions were developed with or without commercial titanium dioxide nanoparticles (NP) carrying various surface treatments in order to get close physicochemical properties whatever the NP surface polarity (hydrophilic and hydrophobic). Rheology and texturometry highlighted that the macroscopic properties of the three formulated emulsions were similar. However, characterizations by optical microscopy, static light scattering and zetametry showed that their microstructures reflected the diversity of the incorporated NP surface properties. In order to use these model emulsions as tools for biological evaluations of the NP in use, they had to show the lowest initial microbiological charge and, specifically for the NP-free emulsion, the lowest bactericidal effect. Hence, formulae were developed preservative-free and a thermal sterilization step was conducted. Efficiency of the sterilization and its impact on the emulsion integrity were monitored. Results highlighted the effect of the NP surface properties: only the control emulsion and the emulsion containing hydrophilic NP fulfilled both requirements. To ensure the usability of these model emulsions as tools to evaluate the 'NP effect' on representative bacteria of the skin microflora (S. aureus and P. fluorescens), impact on the bacterial growth was measured on voluntary inoculated formulae. Copyright © 2016 Elsevier B.V. All rights reserved.

Highly coke-resistant ni nanoparticle catalysts with minimal sintering in dry reforming of methane.

PubMed

Han, Joung Woo; Kim, Chanyeon; Park, Jun Seong; Lee, Hyunjoo

2014-02-01

Nickel catalysts are typically used for hydrogen production by reforming reactions. Reforming methane with carbon dioxide, called dry reforming of methane (DRM), is a good way to produce hydrogen or syngas (a mixture of hydrogen and carbon monoxide) from two notable greenhouse gases. However, Ni catalysts used for DRM suffer from severe coke deposition. It has been known that small Ni nanoparticles are advantageous to reduce coke formation, but the high reaction temperature of DRM (800 °C) inevitably induces aggregation of the nanoparticles, leading to severe coke formation and degraded activity. Here, we develop highly coke-resistant Ni catalysts by immobilizing premade Ni nanoparticles of 5.2 nm in size onto functionalized silica supports, and then coating the Ni/SiO2 catalyst with silica overlayers. The silica overlayers enable the transfer of reactants and products while preventing aggregation of the Ni nanoparticles. The silica-coated Ni catalysts operate stably for 170 h without any degradation in activity. No carbon deposition was observed by temperature programmed oxidation (TPO), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy. The Ni catalysts without silica coating show severe sintering after DRM reaction, and the formation of filamentous carbon was observed. The coke-resistant Ni catalyst is potentially useful in various hydrocarbon transformations. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetic nanoparticles entrapped in siliceous mesocellular foam: a new catalyst support.

PubMed

Lee, Su Seong; Riduan, Siti Nurhanna; Erathodiyil, Nandanan; Lim, Jaehong; Cheong, Jian Liang; Cha, Junhoe; Han, Yu; Ying, Jackie Y

2012-06-11

γ-Fe(2)O(3) nanoparticles were formed inside the cage-like pores of mesocellular foam (MCF). These magnetic nanoparticles showed a uniform size distribution that could be easily controlled by the MCF pore size, as well as by the hydrocarbon chain length used for MCF surface modification. Throughout the entrapment process, the pore structure and surface area of the MCF remained intact. The resulting magnetic MCF facilitated the immobilization of biocatalysts, homogeneous catalysts, and nanoclusters. Moreover, the MCF allowed for facile catalyst recovery by using a simple magnet. The supported catalysts exhibited excellent catalytic efficiencies that were comparable to their homogeneous counterparts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct evidence of atomic-scale structural fluctuations in catalyst nanoparticles.

PubMed

Lin, Pin Ann; Gomez-Ballesteros, Jose L; Burgos, Juan C; Balbuena, Perla B; Natarajan, Bharath; Sharma, Renu

2017-05-01

Rational catalyst design requires an atomic scale mechanistic understanding of the chemical pathways involved in the catalytic process. A heterogeneous catalyst typically works by adsorbing reactants onto its surface, where the energies for specific bonds to dissociate and/or combine with other species (to form desired intermediate or final products) are lower. Here, using the catalytic growth of single-walled carbon nanotubes (SWCNTs) as a prototype reaction, we show that the chemical pathway may in-fact involve the entire catalyst particle, and can proceed via the fluctuations in the formation and decomposition of metastable phases in the particle interior. We record in situ and at atomic resolution, the dynamic phase transformations occurring in a Cobalt catalyst nanoparticle during SWCNT growth, using a state-of-the-art environmental transmission electron microscope (ETEM). The fluctuations in catalyst carbon content are quantified by the automated, atomic-scale structural analysis of the time-resolved ETEM images and correlated with the SWCNT growth rate. We find the fluctuations in the carbon concentration in the catalyst nanoparticle and the fluctuations in nanotube growth rates to be of complementary character. These findings are successfully explained by reactive molecular dynamics (RMD) simulations that track the spatial and temporal evolution of the distribution of carbon atoms within and on the surface of the catalyst particle. We anticipate that our approach combining real-time, atomic-resolution image analysis and molecular dynamics simulations will facilitate catalyst design, improving reaction efficiencies and selectivity towards the growth of desired structure.

Dislocation-induced nanoparticle decoration on a GaN nanowire.

PubMed

Yang, Bing; Yuan, Fang; Liu, Qingyun; Huang, Nan; Qiu, Jianhang; Staedler, Thorsten; Liu, Baodan; Jiang, Xin

2015-02-04

GaN nanowires with homoepitaxial decorated GaN nanoparticles on their surface along the radial direction have been synthesized by means of a chemical vapor deposition method. The growth of GaN nanowires is catalyzed by Au particles via the vapor-liquid-solid (VLS) mechanism. Screw dislocations are generated along the radial direction of the nanowires under slight Zn doping. In contrast to the metal-catalyst-assisted VLS growth, GaN nanoparticles are found to prefer to nucleate and grow at these dislocation sites. High-resolution transmission electron microscopy (HRTEM) analysis demonstrates that the GaN nanoparticles possess two types of epitaxial orientation with respect to the corresponding GaN nanowire: (I) [1̅21̅0]np//[1̅21̅0]nw, (0001)np//(0001)nw; (II) [1̅21̅3]np//[12̅10]nw, (101̅0)np//(101̅0)nw. An increased Ga signal in the energy-dispersive spectroscopy (EDS) profile lines of the nanowires suggests GaN nanoparticle growth at the edge surface of the wires. All the crystallographic results confirm the importance of the dislocations with respect to the homoepitaxial growth of the GaN nanoparticles. Here, screw dislocations situated on the (0001) plane provide the self-step source to enable nucleation of the GaN nanoparticles.

A smart strategy to fabricate Ru nanoparticle inserted porous carbon nanofibers as highly efficient levulinic acid hydrogenation catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ying; Sun, Cheng-Jun; Brown, Dennis E.

2016-01-01

Herein, we first put forward a smart strategy to in situ fabricate Ru nanoparticle (NP) inserted porous carbon nanofibers by one-pot conversion of Ru-functionalized metal organic framework fibers. Such fiber precursors are skillfully constructed by cooperative assembly of different proportional RuCl3 and Zn(Ac)2·2H2O along with trimesic acid (H3BTC) in the presence of N,N-dimethylformamide. The following high-temperature pyrolysis affords uniform and evenly dispersed Ru NPs (ca. 12-16 nm), which are firmly inserted into the hierarchically porous carbon nanofibers formed simultaneously. The resulting Ru-carbon nanofiber (Ru-CNF) catalysts prove to be active towards the liquid-phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL),more » a biomass-derived platform molecule with wide applications in the preparation of renewable chemicals and liquid transportation fuels. The optimal GVL yield of 96.0% is obtained, corresponding to a high activity of 9.23 molLAh–1gRu–1, 17 times of that using the commercial Ru/C catalyst. Moreover, the Ru-CNF catalyst is extremely stable, and can be cycled up to 7 times without significant loss of reactivity. Our strategy demonstrated here reveals new possibilities to make proficient metal catalysts, and provides a general way to fabricate metal-carbon nanofiber composites available for other applications.« less

Advanced STEM microanalysis of bimetallic nanoparticle catalysts

NASA Astrophysics Data System (ADS)

Lyman, Charles E.; Dimick, Paul S.

2012-05-01

Individual particles within bimetallic nanoparticle populations are not always identical, limiting the usefulness of bulk analysis techniques such as EXAFS. The scanning transmission electron microscope (STEM) is the only instrument able to characterize supported nanoparticle populations on a particle-by-particle basis. Quantitative elemental analyses of sub-5-nm particles reveal phase separations among particles and surface segregation within particles. This knowledge can lead to improvements in bimetallic catalysts. Advanced STEMs with field-emission guns, aberration-corrected optics, and efficient signal detection systems allow analysis of sub-nanometer particles.

Pd nanoparticles Supported on Cellulose as a catalyst for vanillin conversion in aqueous media.

PubMed

Li, Dan-Dan; Zhang, Jia-Wei; Cai, Chun

2018-05-17

Palladium nanoparticles were firstly anchored on modified biopolymer as an efficient catalyst for biofuel upgradation. Fluorinated compounds was grafted onto cellulose to obtain amphiphilic supports for on water reactions. Pd catalyst was prepared by straightforward deposition of metal nanoparticles on modified cellulose. The catalyst exhibited excellent catalytic activity and selectivity in hydrodeoxygenation of vanillin (a typical model compound of lignin) to 2-methoxy-4-methylphenol under atmospheric hydrogen pressure in neat water without any other additives under mild conditions.

Hollow spheres of iron carbide nanoparticles encased in graphitic layers as oxygen reduction catalysts.

PubMed

Hu, Yang; Jensen, Jens Oluf; Zhang, Wei; Cleemann, Lars N; Xing, Wei; Bjerrum, Niels J; Li, Qingfeng

2014-04-01

Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low-temperature fuel cells. A novel type of catalysts prepared by high-pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting of uniform iron carbide (Fe3 C) nanoparticles encased by graphitic layers, with little surface nitrogen or metallic functionalities. In acidic media the outer graphitic layers stabilize the carbide nanoparticles without depriving them of their catalytic activity towards the oxygen reduction reaction (ORR). As a result the catalyst is highly active and stable in both acid and alkaline electrolytes. The synthetic approach, the carbide-based catalyst, the structure of the catalysts, and the proposed mechanism open new avenues for the development of ORR catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First-principles configurational thermodynamics of alloyed nanoparticles with adsorbates

NASA Astrophysics Data System (ADS)

Wang, Lin-Lin; Tan, Teck L.; Johnson, Duane D.

2014-03-01

Transition-metal, alloyed nanoparticles (NPs) are key components in current and emerging energy technologies because they are found to improve catalytic activity and selectivity for many energy-conversion processes. However, thermodynamic investigations of the compositional profile of alloyed nanoparticles, which determines their catalytic properties, have been limited mostly to NP core-shell preference without the presence of adsorbates. Here, by extending cluster expansion methods to treat both alloyed nanoparticles and adsorbates, we study the configurational thermodynamics of bimetallic NPs under chemically reactive conditions, using databases from density functional theory calculations. With a few examples, we show that such simulations can provide information needed for rational design of NP catalysts. DOE/BES under DE-FG02-03ER15476 (Catalysis) and DE-AC02-07CH11358 at the Ames Laboratory.

pH-Responsive Mercaptoundecanoic Acid Functionalized Gold Nanoparticles and Applications in Catalysis

PubMed Central

Ansar, Siyam M.; Chakraborty, Saptarshi

2018-01-01

Mercaptoundecanoic acid (MUA) functionalized gold nanoparticles (AuNP-MUA) were synthesized and demonstrated to possess pH-triggered aggregation and re-dispersion, as well as the capability of phase transfer between aqueous and organic phases in response to changes in pH. The pH of aggregation for AuNP-MUA is consistent with the pKa of MUA (pH ~4) in solution, while AuNP-MUA phase transition between aqueous and organic phases occurs at pH ~9. The ion pair formation between the amine group in octadecylamine (ODA), the carboxylate group in MUA, and the hydrophobic alkyl chain of ODA facilitates the phase transfer of AuNP-MUA into an organic medium. The AuNP-MUA were investigated as a reusable catalyst in the catalytic reduction of 4-nitrophenol by borohydride—a model reaction for AuNPs. It was determined that 100% MUA surface coverage completely inhibits the catalytic activity of AuNPs. Decreasing the surface coverage was shown to increase catalytic activity, but this decrease also leads to decreased colloidal stability, recoverability, and reusability in subsequent reactions. At 60% MUA surface coverage, colloidal stability and catalytic activity were achieved, but the surface coverage was insufficient to enable redispersion following pH-induced recovery. A balance between AuNP colloidal stability, recoverability, and catalytic activity with reusability was achieved at 90% MUA surface coverage. The AuNP-MUA catalyst can also be recovered at different pH ranges depending on the recovery method employed. At pH ~4, protonation of the MUA results in reduced surface charge and aggregation. At pH ~9, ODA will form an ion-pair with the MUA and induce phase transfer into an immiscible organic phase. Both the pH-triggered aggregation/re-dispersion and aqueous/organic phase transfer methods were employed for catalyst recovery and reuse in subsequent reactions. The ability to recover and reuse the AuNP-MUA catalyst by two different methods and different pH regimes is

High-temperature-stable and regenerable catalysts: platinum nanoparticles in aligned mesoporous silica wells.

PubMed

Xiao, Chaoxian; Maligal-Ganesh, Raghu V; Li, Tao; Qi, Zhiyuan; Guo, Zhiyong; Brashler, Kyle T; Goes, Shannon; Li, Xinle; Goh, Tian Wei; Winans, Randall E; Huang, Wenyu

2013-10-01

We report the synthesis, structural characterization, thermal stability study, and regeneration of nanostructured catalysts made of 2.9 nm Pt nanoparticles sandwiched between a 180 nm SiO2 core and a mesoporous SiO2 shell. The SiO2 shell consists of 2.5 nm channels that are aligned perpendicular to the surface of the SiO2 core. The nanostructure mimics Pt nanoparticles that sit in mesoporous SiO2 wells (Pt@MSWs). By using synchrotron-based small-angle X-ray scattering, we were able to prove the ordered structure of the aligned mesoporous shell. By using high-temperature cyclohexane dehydrogenation as a model reaction, we found that the Pt@MSWs of different well depths showed stable activity at 500 °C after the induction period. Conversely, a control catalyst, SiO2 -sphere-supported Pt nanoparticles without a mesoporous SiO2 shell (Pt/SiO2 ), was deactivated. We deliberately deactivated the Pt@MSWs catalyst with a 50 nm deep well by using carbon deposition induced by a low H2 /cyclohexane ratio. The deactivated Pt@MSWs catalyst was regenerated by calcination at 500 °C with 20 % O2 balanced with He. After the regeneration treatments, the activity of the Pt@MSWs catalyst was fully restored. Our results suggest that the nanostructured catalysts-Pt nanoparticles confined inside mesoporous SiO2 wells-are stable and regenerable for treatments and reactions that require high temperatures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A thermoresponsive nanorattle containing two different catalysts for controllable one-pot tandem catalysis

NASA Astrophysics Data System (ADS)

Niu, Chengrong; Hu, Jie; Li, Yinfeng; Leng, Jinghang; Li, Songjun

2018-03-01

In the present work, a thermoresponsive nanorattle with a Ag nanoparticle (NP) core (one catalyst in the nanorattle), and a poly(N-isopropylacrylamide) shell was developed. An imidazole group was grafted on the polymer shell by copolymerization as the other catalyst. Owing to the catalytic activities of the imidazole group and Ag NP with regards to hydrolysis and reduction, respectively, this nanorattle exhibited tandem-reaction catalytic abilities. In addition, because of the shrinkage of the poly(N-isopropylacrylamide) shell at high temperatures, the tandem reaction could be controlled to stop at the first reaction step. That is to say, only the hydrolysis reaction was catalyzed by the imidazole group being grafted on the surface of the shell. The reduction step in the tandem reaction catalyzed by the Ag particle, however, was switched off by the shrinkage of the poly(N-isopropylacrylamide) shell. This protocol opens up an opportunity to develop controllable catalysts for complicated chemical processes.

Magnetic nanoparticles conjugated to chiral imidazolidinone as recoverable catalyst

NASA Astrophysics Data System (ADS)

Mondini, Sara; Puglisi, Alessandra; Benaglia, Maurizio; Ramella, Daniela; Drago, Carmelo; Ferretti, Anna M.; Ponti, Alessandro

2013-11-01

The immobilization of an ad hoc designed chiral imidazolidin-4-one onto iron oxide magnetic nanoparticles (MNPs) is described, to afford MNP-supported MacMillan's catalyst. Morphological and structural analysis of the materials, during preparation, use, and recycle, has been carried out by transmission electron microscopy. The supported catalyst was tested in the Diels-Alder reaction of cyclopentadiene with cinnamic aldehyde, affording the products in good yields and enantiomeric excesses up to 93 %, comparable to those observed with the non-supported catalyst. Recovery of the chiral catalyst has been successfully performed by simply applying an external magnet to achieve a perfect separation of the MNPs from the reaction product. The recycle of the catalytic system has been also investigated. Noteworthy, this immobilized MacMillan's catalyst proved to be able to efficiently promote the reaction in pure water.

Synthesis and characterization of Acacia gum-Fe0Np-silica nanocomposite: an efficient Fenton-like catalyst for the degradation of Remazol Brilliant Violet dye

NASA Astrophysics Data System (ADS)

Singh, Vandana; Singh, Jadveer; Srivastava, Preeti

2018-04-01

Acacia gum-Fe0Np-silica nanocomposite (GFS1) has been crafted through sol-gel technique using a two-step process that involved the reduction of iron salt to zerovalent iron nanoparticles (Fe0Nps) followed by their impregnation within Acacia gum-silica matrix. GFS1 was characterized using Fourier transform infrared spectroscopy (FTIR), high-resolution transmission electron microscopy (HR-TEM), energy dispersive X-ray analysis (EDX), field emission scanning electron microscopy (FE-SEM), vibrating sample magnetometry (VSM), and X-ray photoelectron spectroscopy (XPS) techniques. GFS1 is decorated with Fe0Nps of 5 nm average size. The VSM study revealed that GFS1 has ferromagnetic nature. GFS1 was used as a heterogeneous Fenton-like catalyst for the degradation of azo dyes using Remazol Brilliant Violet (RBV) dye as a model dye. In first 5 min of operation, > 86% dye degradation was achieved and 94% dye (from 100 mg L-1 dye solution) was successfully degraded in 50 min. The dye degradation followed pseudo-first-order kinetics. The GFS1 performed efficiently well over the wide range of dye concentrations (25-200 mg L-1). The catalyst was reused for eight repeated cycles where 12.5% dye degradation was possible even in the eighth cycle. The catalyst behaved fairly well for the degradation of Metanil Yellow (MY) and Orange G (OG) dyes also. Under the optimum conditions of RBV dye degradation, Metanil Yellow (MY) and Orange G (OG) dyes were degraded to the extent of 97 and 26.3%, respectively.

Electrochemical Catalyst-Support Effects and Their Stabilizing Role for IrOx Nanoparticle Catalysts during the Oxygen Evolution Reaction.

PubMed

Oh, Hyung-Suk; Nong, Hong Nhan; Reier, Tobias; Bergmann, Arno; Gliech, Manuel; Ferreira de Araújo, Jorge; Willinger, Elena; Schlögl, Robert; Teschner, Detre; Strasser, Peter

2016-09-28

Redox-active support materials can help reduce the noble-metal loading of a solid chemical catalyst while offering electronic catalyst-support interactions beneficial for catalyst durability. This is well known in heterogeneous gas-phase catalysis but much less discussed for electrocatalysis at electrified liquid-solid interfaces. Here, we demonstrate experimental evidence for electronic catalyst-support interactions in electrochemical environments and study their role and contribution to the corrosion stability of catalyst/support couples. Electrochemically oxidized Ir oxide nanoparticles, supported on high surface area carbons and oxides, were selected as model catalyst/support systems for the electrocatalytic oxygen evolution reaction (OER). First, the electronic, chemical, and structural state of the catalyst/support couple was compared using XANES, EXAFS, TEM, and depth-resolved XPS. While carbon-supported oxidized Ir particle showed exclusively the redox state (+4), the Ir/IrOx/ATO system exhibited evidence of metal/metal-oxide support interactions (MMOSI) that stabilized the metal particles on antimony-doped tin oxide (ATO) in sustained lower Ir oxidation states (Ir(3.2+)). At the same time, the growth of higher valent Ir oxide layers that compromise catalyst stability was suppressed. Then the electrochemical stability and the charge-transfer kinetics of the electrocatalysts were evaluated under constant current and constant potential conditions, where the analysis of the metal dissolution confirmed that the ATO support mitigates Ir(z+) dissolution thanks to a stronger MMOSI effect. Our findings raise the possibility that MMOSI effects in electrochemistry-largely neglected in the past-may be more important for a detailed understanding of the durability of oxide-supported nanoparticle OER catalysts than previously thought.

Solvothermal synthesis of platinum alloy nanoparticles for oxygen reduction electrocatalysis.

PubMed

Carpenter, Michael K; Moylan, Thomas E; Kukreja, Ratandeep Singh; Atwan, Mohammed H; Tessema, Misle M

2012-05-23

Platinum alloy nanoparticles show great promise as electrocatalysts for the oxygen reduction reaction (ORR) in fuel cell cathodes. We report here on the use of N,N-dimethylformamide (DMF) as both solvent and reductant in the solvothermal synthesis of Pt alloy nanoparticles (NPs), with a particular focus on Pt-Ni alloys. Well-faceted alloy nanocrystals were generated with this method, including predominantly cubic and cuboctahedral nanocrystals of Pt(3)Ni, and octahedral and truncated octahedral nanocrystals of PtNi. X-ray diffraction (XRD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), coupled with energy dispersive spectroscopy (EDS), were used to characterize crystallite morphology and composition. ORR activities of the alloy nanoparticles were measured with a rotating disk electrode (RDE) technique. While some Pt(3)Ni alloy nanoparticle catalysts showed specific activities greater than 1000 μA/cm(2)(Pt), alloy catalysts prepared with a nominal composition of PtNi displayed activities close to 3000 μA/cm(2)(Pt), or almost 15 times that of a state-of-the-art Pt/carbon catalyst. XRD and EDS confirmed the presence of two NP compositions in this catalyst. HAADF-STEM examination of the PtNi nanoparticle catalyst after RDE testing revealed the development of hollows in a number of the nanoparticles due to nickel dissolution. Continued voltage cycling caused further nickel dissolution and void formation, but significant activity remained even after 20,000 cycles.

Solid Catalyst Nanoparticles derived from Oil-Palm Empty Fruit Bunches (OP-EFB) as a Renewable Catalyst for Biodiesel Production

NASA Astrophysics Data System (ADS)

Husin, H.; Asnawi, T. M.; Firdaus, A.; Husaini, H.; Ibrahim, I.; Hasfita, F.

2018-05-01

Solid nanocatalyst derived from oil-palm empty fruit bunches (OP-EFB) fiber was successfully synthesized and its application for biodiesel production was investigated. The OPEFB was treated by burning, milling and heating methods to generate ashes in a nanoparticle size. The nanoparticle palm-bunch ash was characterized by scanning electron microscopy (SEM) and x-ray diffraction (XRD). The effects of the calcination temperature and catalyst amounts for transesterification reactions were investigated. XRD analysis of palm bunch ash exhibited that the highest composition of peaks characteristic were potassium oxide (K2O). SEM analysis showed that the nano palm bunch ash have a particle size ranging of 150-400 nm. The highest conversion of palm-oil to biodiesel reach to 97.90% was observed by using of palm bunch ash nanocatalyst which heated at 600°C, 3 h reaction time and 1% catalyst amount. Reusability of palm bunch ash catalysts was also examined. It was found that of its high active sites, reusable solid catalyst was obtained by just heating of palm bunch ash. It has a capability to reduce not only the amount of catalyst consumption but also reduce the reaction time of transesterification process.

Gold nanoparticles: novel catalyst for the preparation of direct methanol fuel cell.

PubMed

Kuralkar, Mayuri; Ingle, Avinash; Gaikwad, Swapnil; Gade, Aniket; Rai, Mahendra

2015-04-01

The authors report the biosynthesis of gold nanoparticles (Au-NPs) using plant pathogenic Phoma glomerata (MTCC 2210). The synthesis of nanoparticles was characterised by visual observation followed UV-visible spectrophotometric analysis, Fourier transform infrared spectroscopy and nanoparticle tracking analysis. Later, direct methanol fuel cell (DMFC) was constructed using two chambers (anodic chamber and cathodic chamber). These Au-NPs as catalysts have various advantages over the other catalysts that are used in the DMFC. Most importantly, it is cheaper as compared with other catalysts like platinum, and showed higher catalytic activity because of its effective surface structure. Being nano in size, it provides more surface area for the attachment of reactant molecules (methanol molecules). The DMFC catalysed by Au-NPs are found to be suitable to replace lithium ion battery technology in consumer electronics like cell phones, laptops and so on due to the fact that they can produce a high amount of energy in a small space. As long as fuel and air are supplied to the DMFC, it will continue to produce power, so it does not need to be recharged. The use of Au-NPs as catalyst in DMFC has not been reported in the past; it is reported here the first time.

Janus structured Pt–FeNC nanoparticles as a catalyst for the oxygen reduction reaction

DOE PAGES

Kuttiyiel, Kurian A.; Sasaki, Kotaro; Park, Gu -Gon; ...

2017-01-03

Here, we present a new Janus structured catalyst consisting of Pt nanoparticles on Fe–N–C nanoparticles encapsulated by graphene layers for the ORR. The ORR activity of the catalyst increases under potential cycling as the unique Janus nanostructure is further bonded due to a synergetic effect. The present study describes an important advanced approach for the future design of efficient, stable, and low-cost Pt-based electrocatalytic systems.

Chitosan nanocomposite films based on Ag-NP and Au-NP biosynthesis by Bacillus Subtilis as packaging materials.

PubMed

Youssef, Ahmed M; Abdel-Aziz, Mohamed S; El-Sayed, Samah M

2014-08-01

Chitosan-silver (CS-Ag) and Chitosan-gold (CS-Au) nanocomposites films were synthesized by a simple chemical method. A local bacterial isolate identified as Bacillus subtilis ss subtilis was found to be capable to synthesize both silver nanoparticles (Ag-NP) and gold nanoparticles (Au-NP) from silver nitrate (AgNO3) and chloroauric acid (AuCl(4-)) solutions, respectively. The biosynthesis of both Ag-NP and Au-NP characterize using UV/vis spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD), and then added to chitosan by different ratios (0.5, 1 and 2%). The prepared chitosan nanocomposites films were characterize using UV, XRD, SEM and TEM. Moreover, the antibacterial activity of the prepared films was evaluated against gram positive (Staphylococcus aureus) and gram negative bacteria (Pseudomonas aerugenosa), fungi (Aspergillus niger) and yeast (Candida albicans). Therefore, these materials can be potential used as antimicrobial agents in packaging applications. Copyright © 2014 Elsevier B.V. All rights reserved.

An Exploration of Geometric and Electronic Effects in Metal Nanoparticle Catalysts

NASA Astrophysics Data System (ADS)

Childers, David

The goal of this thesis is to investigate the influence geometric and electronic effects on metal nanoparticle catalysis. There are three main methods which alter a catalyst's properties: changing support material, changing nanoparticle size and alloying a second metal. This work will focus on the latter two methods using Pt-group metals and alloys. Platinum and palladium were chosen as the active metals due to a large amount of industry significance and prior literature to draw upon. Neopentane conversion and propane dehydrogenation were the two probe reactions used to evaluate these catalysts mainly due to their relative simplicity and ease of operation on a laboratory scale. The effect of particle size was studied with Pt and Pd monometallic catalysts using neopentane hydrogenolysis/isomerization as the probe reaction. Particle size studies have been done previously using this reaction so there is literature data to compare this study's results. This data will also be used as comparison for the bimetallic studies conducted later so that particle size effects can be accounted for when attempting to determine the effect of alloying a second metal. Bimetallic catalysts have several different possible structures depending on a number of factors from the identity of the two metals to the synthesis procedure. Homogeneous, core-shell and intermetallic alloys are the three structures evaluated in this work. Determining the surface composition of a homogeneous alloy can be difficult especially if both metals adsorb CO. PtPd homogeneous alloys were used to evaluate the ability of EXAFS to give information about surface composition using CO adsorption. These catalysts were also tested using neopentane conversion to evaluate changes in catalytic performance. Core-shell catalysts can also exhibit unique properties although it is not clear whether the identity of the core metal is relevant or if surface changes are most important to changing catalytic behavior. PdAu catalysts

Palladium-metalated porous organic polymers as recyclable catalysts for chemoselective decarbonylation of aldehydes.

PubMed

Li, Wen-Hao; Li, Cun-Yao; Li, Yan; Tang, Hai-Tao; Wang, Heng-Shan; Pan, Ying-Ming; Ding, Yun-Jie

2018-06-07

A novel palladium nanoparticle (NP)-metalated porous organic ligand (Pd NPs/POL-xantphos) has been prepared for the chemoselective decarbonylation of aldehydes. This heterogenous catalyst not only has excellent catalytic activity and chemoselectivity, but also holds high activity after 10 runs of reuse. The effective usage of this method is demonstrated through the synthesis of biofuels such as furfuryl alcohol (FFA) via the highly chemoselective decarbonylation of biomass-derived 5-hydroxy-methylfurfural (HMF) with a TON up to 1540. More importantly, 9-fluorenone could be obtained in one step through the decarbonylation of 2-bromobenzaldehyde by using this heterogeneous catalyst.

Perovskite-nitrogen-doped carbon nanotube composite as bifunctional catalysts for rechargeable lithium-air batteries.

PubMed

Park, Hey Woong; Lee, Dong Un; Park, Moon Gyu; Ahmed, Raihan; Seo, Min Ho; Nazar, Linda F; Chen, Zhongwei

2015-03-01

Developing an effective bifunctional catalyst is a significant issue, as rechargeable metal-air batteries are very attractive for future energy systems. In this study, a facile one-pot process is introduced to prepare an advanced bifunctional catalyst (op-LN) incorporating nitrogen-doped carbon nanotubes (NCNTs) into perovskite La0.5 Sr0.5 Co0.8 Fe0.2 O3 nanoparticles (LSCF-NPs). Confirmed by half-cell testing, op-LN exhibits synergistic effects of LSCF-NP and NCNT with excellent bifunctionality for both the oxygen reduction reaction and the oxygen evolution reaction. Furthermore, op-LN exhibits comparable performances in these reactions to Pt/C and Ir/C, respectively, which highlights its potential for use as a commercially viable bifunctional catalyst. Moreover, the results obtained by testing op-LN in a practical Li-air battery demonstrate improved and complementary charge/discharge performance compared to those of LSCF-NP and NCNT, and this confirms that simply prepared op-LN is a promising candidate as a highly effective bifunctional catalyst for rechargeable metal-air batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size and morphology controlled NiSe nanoparticles as efficient catalyst for the reduction reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Subbarao, Udumula; Marakatti, Vijaykumar S.; Amshumali, Mungalimane K.

Facile and efficient ball milling and polyol methods were employed for the synthesis of nickel selenide (NiSe) nanoparticle. The particle size of the NiSe nanoparticle has been controlled mechanically by varying the ball size in the milling process. The role of the surfactants in the formation of various morphologies was studied. The compounds were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray energy dispersive spectroscopy (EDS). The efficiency of the NiSe nanoparticle as a catalyst was tested for the reduction of para-nitroaniline (PNA) to para-phenyldiamine (PPD) and para-nitrophenol (PNP) to para-aminophenol (PAP)more » using NaBH{sub 4} as the reducing agent. Particle size, morphology and the presence of surfactant played a crucial role in the reduction process. - Graphical abstract: NiSe nanoparticles in different size and morphology were synthesized using facile ball milling and polyol methods. Particle size, morphology and the presence of surfactant in these materials played a crucial role in the hydrogenation of PNA and PNP. - Highlights: • NiSe nanoparticles synthesized using ball milling and solution phase methods. • NiSe nanoparticle is an efficient catalyst for the reduction of PNA and PNP. • NiSe is found to be better than the best reported noble metal catalysts.« less

Plasmonic photocatalysts based on silver nanoparticles - layered double hydroxides for efficient removal of toxic compounds using solar light

NASA Astrophysics Data System (ADS)

Gilea, Diana; Radu, Teodora; Muresanu, Mihaela; Carja, Gabriela

2018-06-01

Plasmon-enhanced photocatalysis holds important promise for chemical processes and outcomes. We present here the self-assemblies of silver nanoparticles (AgNP)/layered double hydroxides (LDHs: MeAlLDHs with Me2+ = Zn2+;Mg2+) and their derived AgNP/MMOs (type AgNP/MgAl2O4; AgNP/ZnO/ZnAl2O4) as novel plasmonic photocatalysts exhibiting activity for phenol photodegradation from aqueous solution by solar-light. The fabrication procedure of AgNP/LDHs assemblies is simple and cost effective and is based on the in-situ synthesis of AgNP on the LDHs matrices during the reconstruction of MgAlLDH and ZnAlLDH in the aqueous solution of Ag2SO4. The tested catalysts were thoroughly investigated - techniques to obtain information on their crystalline structure (XRD), surface properties (XPS), morphological features (TEM) and optical properties (UV-vis). The results show that the solar photocatalytic response of the catalysts is ascribed to the plasmonic response of AgNP though the catalytic efficiency is strongly influenced by the composition of the MeAlLDHs. The best photocatalytic performance was obtained on AgNP/ZnAlLDH750 catalyst that degraded 100% of phenol after 80 min of irradiation with solar light. The results reveal the high potential to tailor AgNP/LDHs and AgNP/MMOs as efficient photo-functional plasmonic hybrids for waste-water cleaning.

Bimetallic Nanoparticles as Efficient Catalysts: Facile and Green Microwave Synthesis

PubMed Central

Blosi, Magda; Ortelli, Simona; Costa, Anna Luisa; Dondi, Michele; Lolli, Alice; Andreoli, Sara; Benito, Patricia; Albonetti, Stefania

2016-01-01

This work deals with the development of a green and versatile synthesis of stable mono- and bi-metallic colloids by means of microwave heating and exploiting ecofriendly reagents: water as the solvent, glucose as a mild and non-toxic reducer and polyvinylpirrolidone (PVP) as the chelating agent. Particle size-control, total reaction yield and long-term stability of colloids were achieved with this method of preparation. All of the materials were tested as effective catalysts in the reduction of p-nitrophenol in the presence of NaBH4 as the probe reaction. A synergistic positive effect of the bimetallic phase was assessed for Au/Cu and Pd/Au alloy nanoparticles, the latter showing the highest catalytic performance. Moreover, monoand bi-metallic colloids were used to prepare TiO2- and CeO2-supported catalysts for the liquid phase oxidation of 5-hydroxymethylfufural (HMF) to 2,5-furandicarboxylic acid (FDCA). The use of Au/Cu and Au/Pd bimetallic catalysts led to an increase in FDCA selectivity. Finally, preformed Pd/Cu nanoparticles were incorporated into the structure of MCM-41-silica. The resulting Pd/Cu MCM-41 catalysts were tested in the hydrodechlorination of CF3OCFClCF2Cl to CF3OCF=CF2. The effect of Cu on the hydrogenating properties of Pd was demonstrated. PMID:28773672

Microwave irradiation for the facile synthesis of transition-metal nanoparticles (NPs) in ionic liquids (ILs) from metal-carbonyl precursors and Ru-, Rh-, and Ir-NP/IL dispersions as biphasic liquid-liquid hydrogenation nanocatalysts for cyclohexene.

PubMed

Vollmer, Christian; Redel, Engelbert; Abu-Shandi, Khalid; Thomann, Ralf; Manyar, Haresh; Hardacre, Christopher; Janiak, Christoph

2010-03-22

Stable chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, and iridium metal nanoparticles (M-NPs) have been reproducibly obtained by facile, rapid (3 min), and energy-saving 10 W microwave irradiation (MWI) under an argon atmosphere from their metal-carbonyl precursors [M(x)(CO)(y)] in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF(4)]). This MWI synthesis is compared to UV-photolytic (1000 W, 15 min) or conventional thermal decomposition (180-250 degrees C, 6-12 h) of [M(x)(CO)(y)] in ILs. The MWI-obtained nanoparticles have a very small (<5 nm) and uniform size and are prepared without any additional stabilizers or capping molecules as long-term stable M-NP/IL dispersions (characterization by transmission electron microscopy (TEM), transmission electron diffraction (TED), and dynamic light scattering (DLS)). The ruthenium, rhodium, or iridium nanoparticle/IL dispersions are highly active and easily recyclable catalysts for the biphasic liquid-liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 522 (mol product) (mol Ru)(-1) h(-1) and 884 (mol product) (mol Rh)(-1) h(-1) and give almost quantitative conversion within 2 h at 10 bar H(2) and 90 degrees C. Catalyst poisoning experiments with CS(2) (0.05 equiv per Ru) suggest a heterogeneous surface catalysis of Ru-NPs.

Retraction: Gold nanoparticles immobilized on electrospun titanium dioxide nanofibers for catalytic reduction of 4-nitrophenol.

PubMed

Cavusoglu, Halit; Buyukbekar, Burak Zafer; Sakalak, Huseyin; Kohsakowski, Sebastian

2017-02-13

This study involves the preparation and catalytic properties of anatase titanium dioxide nanofibers (TiO2 NFs) supported gold nanoparticles (Au NPs) using a model reaction based on the reduction of 4-nitrophenol (NP) into 4-aminophenol (AP) by sodium borohydride (NaBH4). The fabrication of surfactant-free Au NPs was performed using pulsed laser ablation in liquid (PLAL) technique. The TiO2 NFs were fabricated by a combination of electrospinning and calcination process using a solution containing poly(vinyl pyrolidone)(PVP) and titanium isopropoxide. The adsorption efficiency of laser-generated surfactant-free Au NPs to TiO2 NF supports as a function of pH was analyzed. Our results show that the electrostatic interaction mainly controls the adsorption of the nanoparticles. Au NPs/TiO2 NFs composite exhibited good catalytic activity for the reduction of 4-NP to 4-AP. The unique combination of these materials leads to the development of highly efficient catalysts. Our heterostructured nanocatalysts possibly form an efficient path to fabricate various metal NP/metal-oxide supported catalysts. Thus the applications of PLAL-noble metal NPs can widely broaden. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-throughput continuous flow synthesis of nickel nanoparticles for the catalytic hydrodeoxygenation of guaiacol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roberts, Emily J.; Habas, Susan E.; Wang, Lu

2016-11-07

The translation of batch chemistries to high-throughput continuous flow methods dresses scaling, automation, and reproducibility concerns associated with the implementation of colloidally prepared nanoparticle (NP) catalysts for industrial catalytic processes. Nickel NPs were synthesized by the high-temperature amine reduction of a Ni2+ precursor using a continuous millifluidic (mF) flow method, achieving yields greater than 60%. The resulting Ni NP catalysts were compared against catalysts prepared in a batch reaction under conditions analogous to the continuous flow conditions with respect to total reaction volume, time, and temperature and by traditional incipient wetness (IW) impregnation for the hydrodeoxygenation (HDO) of guaiacol undermore » ex situ catalytic fast pyrolysis conditions. Compared to the IW method, the colloidally prepared NPs displayed increased morphological control and narrowed size distributions, and the NPs prepared by both methods showed similar size, shape, and crystallinity. The Ni NP catalyst synthesized by the continuous flow method exhibited similar H-adsorption site densities, site-time yields, and selectivities towards deoxygenated products as compared to the analogous batch reaction, and outperformed the IW catalyst with respect to higher selectivity to lower oxygen content products and a 6.9-fold slower deactivation rate. These results demonstrate the utility of synthesizing colloidal Ni NP catalysts using continuous flow methods while maintaining the catalytic properties displayed by the batch equivalent. Finally, this methodology can be extended to other catalytically relevant base metals for the high-throughput synthesis of metal NPs for the catalytic production of biofuels.« less

Reactor for tracking catalyst nanoparticles in liquid at high temperature under a high-pressure gas phase with X-ray absorption spectroscopy.

PubMed

Nguyen, Luan; Tao, Franklin Feng

2018-02-01

Structure of catalyst nanoparticles dispersed in liquid phase at high temperature under gas phase of reactant(s) at higher pressure (≥5 bars) is important for fundamental understanding of catalytic reactions performed on these catalyst nanoparticles. Most structural characterizations of a catalyst performing catalysis in liquid at high temperature under gas phase at high pressure were performed in an ex situ condition in terms of characterizations before or after catalysis since, from technical point of view, access to the catalyst nanoparticles during catalysis in liquid phase at high temperature under high pressure reactant gas is challenging. Here we designed a reactor which allows us to perform structural characterization using X-ray absorption spectroscopy including X-ray absorption near edge structure spectroscopy and extended X-ray absorption fine structure spectroscopy to study catalyst nanoparticles under harsh catalysis conditions in terms of liquid up to 350 °C under gas phase with a pressure up to 50 bars. This reactor remains nanoparticles of a catalyst homogeneously dispersed in liquid during catalysis and X-ray absorption spectroscopy characterization.

In situ characterization of catalytic activity of graphene stabilized small-sized Pd nanoparticles for CO oxidation

NASA Astrophysics Data System (ADS)

Mao, Bao-Hua; Liu, Chang-Hai; Gao, Xu; Chang, Rui; Liu, Zhi; Wang, Sui-Dong

2013-10-01

The room-temperature ionic liquid assisted sputtering method is utilized to achieve the Pd-nanoparticle (NP)-graphene hybrid. The supported Pd NPs possess uniformly small sizes of 1-2 nm, which create huge surface area with ultralow Pd consumption and high NP stability. The Pd-NP-graphene hybrid is in situ characterized by the ambient pressure X-ray photoelectron spectroscopy using synchrotron radiation, and the results demonstrate high catalytic activity of the hybrid for CO oxidation. The catalytic behavior is reproducible for several catalytic cycles. The present simple and clean approach is promising to produce metal-NP-based high-efficiency catalysts for CO oxidation.

Degradation of 4-Chlorophenol Under Sunlight Using ZnO Nanoparticles as Catalysts

NASA Astrophysics Data System (ADS)

Rajar, Kausar; Sirajuddin; Balouch, Aamna; Bhanger, M. I.; Sherazi, Tufail H.; Kumar, Raj

2018-03-01

Herein we demonstrate a simplistic microwave assisted chemical precipitation approach regarding the synthesis of zinc oxide nanoparticles. As-prepared ZnO nanoparticles (NPs) were characterized by UV-visible spectroscopy, Fourier transform infra-red spectroscopy, atomic force microscopy and x-ray diffractometry and scrutinized as photo-catalysts for degradation of 4-chlorophenol (4-CP) under sunlight. The study substantiated that 98.5% of 4-CP was degraded within 20 min in the absence of initiator like H2O2 which reflects an outstanding prospective use for ZnO NPs as photo-catalysts. The nanocatalysts were recycled four times and still showed catalytic efficiency up to 95.5% for degradation of 4-CP in the specified 20 min.

Photo-reduced Cu/CuO nanoclusters on TiO2 nanotube arrays as highly efficient and reusable catalyst

NASA Astrophysics Data System (ADS)

Jin, Zhao; Liu, Chang; Qi, Kun; Cui, Xiaoqiang

2017-01-01

Non-noble metal nanoparticles are becoming more and more important in catalysis recently. Cu/CuO nanoclusters on highly ordered TiO2 nanotube arrays are successfully developed by a surfactant-free photoreduction method. This non-noble metal Cu/CuO-TiO2 catalyst exhibits excellent catalytic activity and stability for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with the presence of sodium borohydride (NaBH4). The rate constant of this low-cost Cu/CuO based catalyst is even higher than that of the noble metal nanoparticles decorated on the same TiO2 substrate. The conversion efficiency remains almost unchanged after 7 cycles of recycling. The recycle process of this Cu/CuO-TiO2 catalyst supported by Ti foil is very simple and convenient compared with that of the common powder catalysts. This catalyst also exhibited great catalytic activity to other organic dyes, such as methylene blue (MB), rhodamine B (RhB) and methyl orange (MO). This highly efficient, low-cost and easily reusable Cu/CuO-TiO2 catalyst is expected to be of great potential in catalysis in the future.

Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts

DOE PAGES

Hunt, Sean T.; Milina, Maria; Alba-Rubio, Ana C.; ...

2016-05-20

Here, we demonstrated the self-assembly of transition metal carbide nanoparticles coated with atomically thin noble metal monolayers by carburizing mixtures of noble metal salts and transition metal oxides encapsulated in removable silica templates. This approach allows for control of the final core-shell architecture, including particle size, monolayer coverage, and heterometallic composition. Carbon-supported Ti 0.1W 0.9C nanoparticles coated with Pt or bimetallic PtRu monolayers exhibited enhanced resistance to sintering and CO poisoning, achieving an order of magnitude increase in specific activity over commercial catalysts for methanol electrooxidation after 10,000 cycles. These core-shell materials provide a new direction to reduce the loading,more » enhance the activity, and increase the stability of noble metal catalysts.« less

Functionalized Natural Carbon-Supported Nanoparticles as Excellent Catalysts for Hydrocarbon Production.

PubMed

Sun, Jian; Guo, Lisheng; Ma, Qingxiang; Gao, Xinhua; Yamane, Noriyuki; Xu, Hengyong; Tsubaki, Noritatsu

2017-02-01

We report a one-pot and eco-friendly synthesis of carbon-supported cobalt nanoparticles, achieved by carbonization of waste biomass (rice bran) with a cobalt source. The functionalized biomass provides carbon microspheres as excellent catalyst support, forming a unique interface between hydrophobic and hydrophilic groups. The latter, involving hydroxyl and amino groups, can catch much more active cobalt nanoparticles on surface for Fischer-Tropsch synthesis than chemical carbon. The loading amount of cobalt on the final catalyst is much higher than that prepared with a chemical carbon source, such as glucose. The proposed concept of using a functionalized natural carbon source shows great potential compared with conventional carbon sources, and will be meaningful for other fields concerning carbon support, such as heterogeneous catalysis or electrochemical fields. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Calcium oxide supported gold nanoparticles as catalysts for the selective epoxidation of styrene by t-butyl hydroperoxide.

PubMed

Dumbre, Deepa K; Choudhary, Vasant R; Patil, Nilesh S; Uphade, Balu S; Bhargava, Suresh K

2014-02-01

Gold nanoparticles are deposited on basic CaO supports as catalysts for the selective conversion of styrene into styrene oxide. Synthetic methods, gold loading and calcination temperatures are varied to permit an understanding of their influence on gold nanoparticle size, the presence of cationic gold species and the nature of interaction between the gold nanoparticles and the CaO support. Based on these studies, optimal conditions are designed to make the Au/CaO catalyst efficient for the selective epoxidation of styrene. Copyright © 2013 Elsevier Inc. All rights reserved.

Core-shell Au-Pd nanoparticles as cathode catalysts for microbial fuel cell applications

PubMed Central

Yang, Gaixiu; Chen, Dong; Lv, Pengmei; Kong, Xiaoying; Sun, Yongming; Wang, Zhongming; Yuan, Zhenhong; Liu, Hui; Yang, Jun

2016-01-01

Bimetallic nanoparticles with core-shell structures usually display enhanced catalytic properties due to the lattice strain created between the core and shell regions. In this study, we demonstrate the application of bimetallic Au-Pd nanoparticles with an Au core and a thin Pd shell as cathode catalysts in microbial fuel cells, which represent a promising technology for wastewater treatment, while directly generating electrical energy. In specific, in comparison with the hollow structured Pt nanoparticles, a benchmark for the electrocatalysis, the bimetallic core-shell Au-Pd nanoparticles are found to have superior activity and stability for oxygen reduction reaction in a neutral condition due to the strong electronic interaction and lattice strain effect between the Au core and the Pd shell domains. The maximum power density generated in a membraneless single-chamber microbial fuel cell running on wastewater with core-shell Au-Pd as cathode catalysts is ca. 16.0 W m−3 and remains stable over 150 days, clearly illustrating the potential of core-shell nanostructures in the applications of microbial fuel cells. PMID:27734945

Pt-Pd bimetallic nanoparticles on MWCNTs: catalyst for hydrogen peroxide electrosynthesis

NASA Astrophysics Data System (ADS)

Félix-Navarro, R. M.; Beltrán-Gastélum, M.; Salazar-Gastélum, M. I.; Silva-Carrillo, C.; Reynoso-Soto, E. A.; Pérez-Sicairos, S.; Lin, S. W.; Paraguay-Delgado, F.; Alonso-Núñez, G.

2013-08-01

Bimetallic nanoparticles of Pt-Pd were deposited by the microemulsion method on a multiwall carbon nanotube (MWCNTs) to obtain a Pt-Pd/MWCNTs for electrocatalytic reduction of O2 to H2O2. The activity and selectivity of the catalyst was determined qualitatively by the rotating disk electrode method in acidic medium. The catalyst was spray-coated onto a reticulated vitreous carbon substrate and quantitatively was tested in bulk electrolysis for 20 min under potentiostatic conditions (0.5 V vs Ag/AgCl) in a 0.5 M H2SO4 electrolyte using dissolved O2. The bulk electrolysis experiments show that the Pt-Pd/MWCNTs catalyst is more efficient for H2O2 electrogeneration than a MWCNTs catalyst. Nitrobenzene degradation by electrogenerated H2O2 alone and Electro-Fenton process were also tested. Our results show that both processes decompose nitrobenzene, but the Electro-Fenton process does it more efficiently. The prepared nanoparticulated catalyst shows a great potential in environmental applications.

The shape conversion of silver nanoparticles through heating and its application as homogeneous catalyst in reduction of 4- nitrophenol

NASA Astrophysics Data System (ADS)

Ariyanta, H. A.; Yulizar, Y.

2016-02-01

The shape conversion of silver nanoparticles (AgNPs) through heating and its application as a homogeneous catalyst in the reduction of 4-nitrophenol is reported here. Synthesis of AgNPs by reduction of AgNO3 using NaBH4 and sodium citrate as reducing agent were successfully conducted. The addition of PVP was used as stabilizing agent. The synthesized AgNPs were heated at 95 °C and observed using UV-Vis spectrophotometer, transmission electron microscopy (TEM), Fourier-transformed infrared (FTIR) spectroscopy and particle size analyzer (PSA). Characteristics of AgNPs before heated were blue with UV- Vis absorbance spectrum at λmax = 786 nm and the shape was pseudo nano prism sized ± 28 nm. During the heating process, the color changed gradually from blue (λmax = 786 nm) to orange (λmax = 486 nm) and also its shape from nano prism to nanodisk. Silver nano prism has a lattice constant, 4.160 Å, larger than the silver nanodisk, 4.081 Å, which was possibly achieved through rearrangement of silver atoms on the surface of AgNPs. Both silver nanodisk and nano prism were tested as a homogeneous catalyst for the reduction of 4-nitrophenol (4- NP) with NaBH4.

Design and Preparation of Supported Au Catalyst with Enhanced Catalytic Activities by Rationally Positioning Au Nanoparticles on Anatase.

PubMed

Wang, Liang; Wang, Hong; Rice, Andrew E; Zhang, Wei; Li, Xiaokun; Chen, Mingshu; Meng, Xiangju; Lewis, James P; Xiao, Feng-Shou

2015-06-18

A synergistic effect between individual components is crucial for increasing the activity of metal/metal oxide catalysts. The greatest challenge is how to control the synergistic effect to obtain enhanced catalytic performance. Through density functional theory calculations of model Au/TiO2 catalysts, it is suggested that there is strong interaction between Au nanoparticles and Ti species at the edge/corner sites of anatase, which is favorable for the formation of stable oxygen vacancies. Motivated by this theoretical analysis, we have rationally prepared Au nanoparticles attached to edge/corner sites of anatase support (Au/TiO2-EC), confirmed by their HR-TEM images. As expected, this strong interaction is well characterized by Raman, UV-visible, and XPS techniques. Very interestingly, compared with conventional Au catalysts, Au/TiO2-EC exhibits superior catalytic activity in the oxidations using O2. Our approach to controlling Au nanoparticle positioning on anatase to obtain enhanced catalytic activity offers an efficient strategy for developing more novel supported metal catalysts.

Biogenic gold nanoparticles for reduction of 4-nitrophenol to 4-aminophenol: an eco-friendly bioremediation.

PubMed

Nabikhan, Asmathunisha; Rathinam, Suji; Kandasamy, Kathiresan

2018-06-01

The present study investigated the synthesis of gold nanoparticles (AuNPs) using mangrove plant extract from Avicennia marina as bioreductant for eco-friendly bioremediation of 4-nitrophenol (4-NP) . The AuNPs synthesised were confirmed by UV spectrum, transmission electron microscopy (TEM), X-ray diffraction, Fourier transmission infrared spectroscopy (FTIR), dynamic light scattering (DLS), and zeta potential. The AuNPs were found to be spherical in shape with size ranging from 4 to 13 nm, as evident by TEM and DLS. Further, the AuNPs were encapsulated with sodium alginate in the form of gold nano beads and used as heterogeneous catalyst and degrading agent to reduce 4-NP. This reduction in 4-NP into 4-aminophenol was confirmed by UV and FTIR. The aqueous solution of 4-NP peaked its absorbance at 320 nm, and shifted to 400 nm, with an intense yellow colour, appeared due to formation of 4-nitrophenolate ion. After the addition of AuNps, the 4-NP solution became colourless and peaked at 400 nm and reduced to 290 nm corresponding to the formation of 4-aminophenol. Hence, the present work suggested the AuNPs as the potent, eco-friendly bionanocomposite catalyst for bioremediation of 4-NP.

Nano-palladium is a cellular catalyst for in vivo chemistry

NASA Astrophysics Data System (ADS)

Miller, Miles A.; Askevold, Bjorn; Mikula, Hannes; Kohler, Rainer H.; Pirovich, David; Weissleder, Ralph

2017-07-01

Palladium catalysts have been widely adopted for organic synthesis and diverse industrial applications given their efficacy and safety, yet their biological in vivo use has been limited to date. Here we show that nanoencapsulated palladium is an effective means to target and treat disease through in vivo catalysis. Palladium nanoparticles (Pd-NPs) were created by screening different Pd compounds and then encapsulating bis[tri(2-furyl)phosphine]palladium(II) dichloride in a biocompatible poly(lactic-co-glycolic acid)-b-polyethyleneglycol platform. Using mouse models of cancer, the NPs efficiently accumulated in tumours, where the Pd-NP activated different model prodrugs. Longitudinal studies confirmed that prodrug activation by Pd-NP inhibits tumour growth, extends survival in tumour-bearing mice and mitigates toxicity compared to standard doxorubicin formulations. Thus, here we demonstrate safe and efficacious in vivo catalytic activity of a Pd compound in mammals.

AuNP-PE interface/phase and its effects on the tensile behaviour of AuNP-PE composites

NASA Astrophysics Data System (ADS)

Wang, Yue; Wang, Ruijie; Wang, Chengyuan; Yu, Xiaozhu

2018-06-01

A comprehensive study was conducted for a gold nanoparticle (AuNP)-polyethylene (PE) composite. Molecular dynamic (MD) simulations were employed to construct the AuNP-PE systems, achieve their constitutive relations, and measure their tensile properties. Specifically, the AuNP-PE interface/phase was studied via the mass density profile, and its effect was evaluated by comparing the composite with a pure PE matrix. These research studies were followed by the study of the fracture mechanisms and the size and volume fraction effects of AuNPs. Efforts were also made to reveal the underlying physics of the MD simulations. In the present work, an AuNP-PE interface and a densified PE interphase were achieved due to the AuNP-PE van der Waals interaction. Such an interface/phase is found to enhance the Young's modulus and yield stress but decrease the fracture strength and strain.

Acid monolayer functionalized iron oxide nanoparticle catalysts

NASA Astrophysics Data System (ADS)

Ikenberry, Myles

Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide

Palladium Nanoparticle-Loaded Cellulose Paper: A Highly Efficient, Robust, and Recyclable Self-Assembled Composite Catalytic System.

PubMed

Zheng, Guangchao; Kaefer, Katharina; Mourdikoudis, Stefanos; Polavarapu, Lakshminarayana; Vaz, Belén; Cartmell, Samantha E; Bouleghlimat, Azzedine; Buurma, Niklaas J; Yate, Luis; de Lera, Ángel R; Liz-Marzán, Luis M; Pastoriza-Santos, Isabel; Pérez-Juste, Jorge

2015-01-15

We present a novel strategy based on the immobilization of palladium nanoparticles (Pd NPs) on filter paper for development of a catalytic system with high efficiency and recyclability. Oleylamine-capped Pd nanoparticles, dispersed in an organic solvent, strongly adsorb on cellulose filter paper, which shows a great ability to wick fluids due to its microfiber structure. Strong van der Waals forces and hydrophobic interactions between the particles and the substrate lead to nanoparticle immobilization, with no desorption upon further immersion in any solvent. The prepared Pd NP-loaded paper substrates were tested for several model reactions such as the oxidative homocoupling of arylboronic acids, the Suzuki cross-coupling reaction, and nitro-to-amine reduction, and they display efficient catalytic activity and excellent recyclability and reusability. This approach of using NP-loaded paper substrates as reusable catalysts is expected to open doors for new types of catalytic support for practical applications.

CO2 to methanol conversion using hydride terminated porous silicon nanoparticles.

PubMed

Dasog, M; Kraus, S; Sinelnikov, R; Veinot, J G C; Rieger, B

2017-03-09

Porous silicon nanoparticles (Si-NPs) prepared via magnesiothermic reduction were used to convert carbon dioxide (CO 2 ) into methanol. The hydride surface of the silicon nanoparticles acted as a CO 2 reducing reagent without any catalyst at temperatures above 100 °C. The Si nanoparticles were reused up to four times without significant loss in methanol yields. The reduction process was monitored using in situ FT-IR and the materials were characterized using SEM, TEM, NMR, XPS, and powder XRD techniques. The influence of reaction temperature, pressure, and Si-NP concentration on CO 2 reduction were also investigated. Finally, Si particles produced directly from sand were used to convert CO 2 to methanol.

Facile synthesis of palladium nanoparticle doped polyaniline nanowires in soft templates for catalytic applications

NASA Astrophysics Data System (ADS)

Kshirasagar, Krushna J.; Markad, Uddhav S.; Saha, Abhijit; Sharma, Kiran Kumar K.; Sharma, Geeta K.

2017-02-01

Palladium nanoparticles doped polyaniline (Pd-PANI) nanocomposite (NCs) is synthesized in surfactant based liquid crystalline mesophase by chemical oxidation followed by radiolysis. The confinement of the liquid crystalline mesophase facilitates polymerization of aniline monomers and their 1D growth into polyaniline (PANI) nanowires by using ammonium persulfate. The PANI nanowires have an average diameter of 30-40 nm. The in situ radiolytic reduction of palladium ions ensures uniform size distribution of the palladium (Pd) nanoparticles on the surface of the PANI nanowires. The synthesized Pd-PANI nanocomposites show wire like structures of PANI (diameter ~30-40 nm) on which Pd nanoparticles of the size 10 nm are decorated. The identical average diameter of the PANI nanowires before and post gamma irradiation suggest high stability of the PANI nanowires in liquid crystalline mesophase. Surface characterization of the NCs were carried out using BET and XPS. The catalytic activity of Pd-PANI NCs are investigated in the reduction of methylene blue (MB) and 4-nitro phenol (4-NP) by sodium borohydride (NaBH4). The kinetics of the Pd-PANI NCs catalysed reactions are analysed using the Langmuir-Hinshelwood model. The apparent rate constant (k app) for the MB and 4-NP reduction reactions is 29  ×  10-3 s-1 and 20  ×  10-3 s-1 respectively with an actual Pd catalyst loading of 2.665  ×  10-4 ppm. Further, the recyclability of the Pd-PANI NCs catalyst in both the reduction reactions shows the stability of the catalyst up to four reaction cycles tested in this investigation and the multifunctional nature of the catalyst. The study provides a new approach for the directional synthesis of conducting polymer-metal nanocomposites and their possible application as a nanocatalyst in environmental remediation.

PdNP Decoration of Halloysite Lumen via Selective Grafting of Ionic Liquid onto the Aluminol Surfaces and Catalytic Application.

PubMed

Dedzo, Gustave K; Ngnie, Gaëlle; Detellier, Christian

2016-02-01

The synthesis of selectively deposited palladium nanoparticles (PdNPs) inside tubular halloysite lumens is reported. This specific localization was directed by the selective modification of the aluminol surfaces of the clay mineral through stable Al-O-C bonds. An ionic liquid (1-(2-hydroxyethyl)-3-methylimidazolium) was grafted onto halloysite following the guest displacement method (generally used for kaolinite) using halloysite-DMSO preintercalate. The characterization of this clay nanohybrid material (XRD, NMR, TGA) showed characteristics reminiscent of similar materials synthesized from kaolinite. The grafting on halloysite lumens was also effective without using the DMSO preintercalate. The presence of these new functionalities in halloysite directs the synthesis of uniform PdNPs with size ranging between 3 and 6 nm located exclusively in the lumens. This results from the selective adsorption of PdNPs precursors in functionalized lumens through an anion exchange mechanism followed by in situ reduction. In contrast, the unmodified clay mineral displayed nanoparticles both inside and outside the tubes. These catalysts showed significant catalytic activity for the reduction of 4-nitrophenol (4-NP). The most efficient catalysts were recycled up to three times without reducing significantly the catalytic activities.

Nanoparticle-supported and magnetically recoverable ruthenium hydroxide catalyst: efficient hydration of nitriles to amides in aqueous medium.

PubMed

Polshettiwar, Vivek; Varma, Rajender S

2009-01-01

Magnetic attraction not filtration: A magnetic nanoparticle-supported ruthenium hydroxide catalyst (see figure) was readily prepared from inexpensive starting materials and shown to catalyze the hydration of nitriles with excellent yield in a benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity, and the inherent stability of the catalyst system are additional sustainable attributes of this protocol.

Semiconductor-metal transition of Se in Ru-Se Catalyst Nanoparticles

NASA Astrophysics Data System (ADS)

Babu, P. K.; Lewera, Adam; Oldfield, Eric; Wieckowski, Andrzej

2009-03-01

Ru-Se composite nanoparticles are promising catalysts for the oxygen reduction reaction (ORR) in fuel cells. Though the role of Se in enhancing the chemical stability of Ru nanoparticles is well established, the microscopic nature of Ru-Se interaction was not clearly understood. We carried out a combined investigation of ^77Se NMR and XPS on Ru-Se nanoparticles and our results indicate that Se, a semiconductor in elemental form, becomes metallic when interacting with Ru. ^77Se spin-lattice relaxation rates are found to be proportional to T, the well-known Korringa behavior characteristic of metals. The NMR results are supported by the XPS binding energy shifts which suggest that a possible Ru->Se charge transfer could be responsible for the semiconductor->metal transition of Se which also makes Ru less susceptible to oxidation during ORR.

Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Lei; Luo, Langli; Feng, Zhenxing

Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhanced reaction kinetics but are limited by their scarce resource. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides etc. are their low electronic conductivity and poor durability. Here, we report OER catalysts of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells derived from bimetallic metal–organic frameworks (MOFs) precursors. The optimal OER catalyst shows excellent activity (360 mV overpotential atmore » 10 mA cm–2GEO) and durability (no obvious degradation after 20 000 cycles). The electron-donation from Fe and tuned electronic structure of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity. We further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by chemical state of precursors. Severe metal particle growth probably caused by oxidation of carbon shells and encapsulated nanoparticles is believed to the main mechanism for activity degradation in these catalysts.« less

Magnetic nanoparticle supported phosphotungstic acid: An efficient catalyst for the synthesis of xanthene derivatives

NASA Astrophysics Data System (ADS)

Patel, Nipun; Katheriya, Deepak; Dadhania, Harsh; Dadhania, Abhishek

2018-05-01

Magnetic nanoparticle supported phosphotungstic acid (Fe3O4@SiO2-HPW) was applied as a highly efficient catalyst for the synthesis of 14H-dibenzoxanthene derivatives via condensation reaction of 2-naphthol and aryl aldehydes. The catalyst was found highly efficient for the synthesis of xanthene derivatives under solvent free condition. The catalyst showed high activity and stability during the reaction and provided excellent yield of the corresponding products in short reaction time. All the synthesized compounds were characterized through FT-IR, 1H-NMR and 13C-NMR spectroscopic techniques. Furthermore, the catalyst is magnetically recoverable and can be reused several times without significant loss of its catalytic activity.

Nanoparticle-supported and magnetically recoverable palladium (Pd) catalyst: a selective and sustainable oxidation protocol with high turnover number

EPA Science Inventory

A magnetic nanoparticle-supported ruthenium hydroxide catalyst was readily prepared from inexpensive starting materials and shown to catalyze hydration of nitriles with excellent yield in benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity...

Binary metal oxide nanoparticle incorporated composite multilayer thin films for sono-photocatalytic degradation of organic pollutants

NASA Astrophysics Data System (ADS)

Gokul, Paramasivam; Vinoth, Ramalingam; Neppolian, Bernaurdshaw; Anandhakumar, Sundaramurthy

2017-10-01

We report reduced graphene oxide (rGO) supported binary metal oxide (CuO-TiO2/rGO) nanoparticle (NP) incorporated multilayer thin films based on Layer-by-Layer (LbL) assembly for enhanced sono-photocatalytic degradation of methyl orange under exposure to UV radiation. Multilayer thin films were fabricated on glass and quartz slides, and investigated using scanning electron microscopy and UV-vis spectroscopy. The loading of catalyst NPs on the film resulted in the change of morphology of the film from smooth to rough with uniformly distributed NPs on the surface. The growth of the control and NP incorporated films followed a linear regime as a function of number of layers. The%degradation of methyl orange as a function of time was investigated by UV-vis spectroscopy and total organic carbon (TOC) measurements. Complete degradation of methyl orange was achieved within 13 h. The amount of NP loading in the film significantly influenced the%degradation of methyl orange. Catalyst reusability studies revealed that the catalyst thin films could be repeatedly used for up to five times without any change in photocatalytic activity of the films. The findings of the present study support that the binary metal oxide catalyst films reported here are very useful for continuous systems, and thus, making it an option for scale up.

Non-Invasive Magnetic Resonance Imaging of Nanoparticle Migration and Water Velocity Inside Sandstone

NASA Astrophysics Data System (ADS)

Phoenix, V. R.; Shukla, M.; Vallatos, A.; Riley, M. S.; Tellam, J. H.; Holmes, W. M.

2015-12-01

Manufactured nanoparticles (NPs) are already utilized in a diverse array of applications, including cosmetics, optics, medical technology, textiles and catalysts. Problematically, once in the natural environment, NPs can have a wide range of toxic effects. To protect groundwater from detrimental NPs we must be able to predict nanoparticle movement within the aquifer. The often complex transport behavior of nanoparticles ensures the development of NP transport models is not a simple task. To enhance our understanding of NP transport processes, we utilize novel magnetic resonance imaging (MRI) which enables us to look inside the rock and image the movement of nanoparticles within. For this, we use nanoparticles that are paramagnetic, making them visible to the MRI and enabling us to collect spatially resolved data from which we can develop more robust transport models. In this work, a core of Bentheimer sandstone (3 x 7 cm) was saturated with water and imaged inside a 7Tesla Bruker Biospec MRI. Firstly the porosity of the core was mapped using a MSME MRI sequence. Prior to imaging NP transport, the velocity of water (in absence on nanoparticles) was mapped using an APGSTE-RARE sequence. Nano-magnetite nanoparticles were then pumped into the core and their transport through the core was imaged using a RARE sequence. These images were calibrated using T2 parameter maps to provide fully quantitative maps of nanoparticle concentration at regular time intervals throughout the column (T2 being the spin-spin relaxation time of 1H nuclei). This work demonstrated we are able to spatially resolve porosity, water velocity and nanoparticle movement, inside rock, using a single technique (MRI). Significantly, this provides us with a unique and powerful dataset from which we are now developing new models of nanoparticle transport.

Film fabrication of Fe or Fe3O4 nanoparticles mixed with palmitic acid for vertically aligned carbon nanotube growth using Langmuir-Blodgett technique

NASA Astrophysics Data System (ADS)

Nakamura, Kentaro; Kuriyama, Naoki; Takagiwa, Shota; Sato, Taiga; Kushida, Masahito

2016-03-01

Vertically aligned carbon nanotubes (VA-CNTs) were studied as a new catalyst support for polymer electrolyte fuel cells (PEFCs). Controlling the number density and the diameter of VA-CNTs may be necessary to optimize PEFC performance. As the catalyst for CNT growth, we fabricated Fe or Fe3O4 nanoparticle (NP) films by the Langmuir-Blodgett (LB) technique. The catalyst Fe or Fe3O4 NPs were widely separated by mixing with filler molecules [palmitic acid (C16)]. The number density of VA-CNTs was controlled by varying the ratio of catalyst NPs to C16 filler molecules. The VA-CNTs were synthesized from the catalyst NP-C16 LB films by thermal chemical vapor deposition (CVD) using acetylene gas as the carbon source. The developing solvents used in the LB technique and the hydrogen reduction conditions of CVD were optimized to improve the VA-CNT growth rate. We demonstrate that the proposed method can independently control both the density and the diameter of VA-CNTs.

Synergistic Enhancement of Electrocatalytic CO 2 Reduction with Gold Nanoparticles Embedded in Functional Graphene Nanoribbon Composite Electrodes

DOE PAGES

Rogers, Cameron; Perkins, Wade S.; Veber, Gregory; ...

2017-02-24

Regulating the complex environment accounting for the stability, selectivity, and activity of catalytic metal nanoparticle interfaces represents a challenge to heterogeneous catalyst design. Here in this paper, we demonstrate the intrinsic performance enhancement of a composite material composed of gold nanoparticles (AuNPs) embedded in a bottom-up synthesized graphene nanoribbon (GNR) matrix for the electrocatalytic reduction of CO 2. Electrochemical studies reveal that the structural and electronic properties of the GNR composite matrix increase the AuNP electrochemically active surface area (ECSA), lower the requisite CO 2 reduction overpotential by hundreds of millivolts (catalytic onset > -0.2 V versus reversible hydrogen electrodemore » (RHE)), increase the Faraday efficiency (>90%), markedly improve stability (catalytic performance sustained over >24 h), and increase the total catalytic output (>100-fold improvement over traditional amorphous carbon AuNP supports). The inherent structural and electronic tunability of bottom-up synthesized GNR-AuNP composites affords an unrivaled degree of control over the catalytic environment, providing a means for such profound effects as shifting the rate-determining step in the electrocatalytic reduction of CO 2 to CO, and thereby altering the electrocatalytic mechanism at the nanoparticle surface.« less

Structurally ordered Pt–Zn/C series nanoparticles as efficient anode catalysts for formic acid electrooxidation

DOE PAGES

Zhu, Jing; Zheng, Xin; Wang, Jie; ...

2015-09-15

Controlling the size, composition, and structure of bimetallic nanoparticles is of particular interest in the field of electrocatalysts for fuel cells. In the present work, structurally ordered nanoparticles with intermetallic phases of Pt 3Zn and PtZn have been successfully synthesized via an impregnation reduction method, followed by post heat-treatment. The Pt 3Zn and PtZn ordered intermetallic nanoparticles are well dispersed on a carbon support with ultrasmall mean particle sizes of ~5 nm and ~3 nm in diameter, respectively, which are credited to the evaporation of the zinc element at high temperature. These catalysts are less susceptible to CO poisoning relativemore » to Pt/C and exhibited enhanced catalytic activity and stability toward formic acid electrooxidation. The mass activities of the as-prepared catalysts were approximately 2 to 3 times that of commercial Pt at 0.5 V (vs. RHE). As a result, this facile synthetic strategy is scalable for mass production of catalytic materials.« less

Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst

DOE PAGES

Du, Lei; Luo, Langli; Feng, Zhenxing; ...

2017-07-05

Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhancing reaction kinetics but are limited by their scarcity. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides are their low electronic conductivity and durability. The carbon encapsulating transition metal nanoparticles are expected to address these challenges. However, the relationship between precursor compositions and catalyst properties, and the intrinsic functions of each component has been rarely studied. In this paper,more » we report a highly durable (no degradation after 20,000 cycles) and highly active (360 mV overpotential at 10 mA cm –2 GEO) OER catalyst derived from bimetallic metal–organic frameworks (MOFs) precursors. This catalyst consists of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells. The electron–donation/deviation from Fe and tuned lattice and electronic structures of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity, whereas N concentration contributes negligibly. Finally, we further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by the chemical state of precursors.« less

Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Lei; Luo, Langli; Feng, Zhenxing

Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhancing reaction kinetics but are limited by their scarcity. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides are their low electronic conductivity and durability. The carbon encapsulating transition metal nanoparticles are expected to address these challenges. However, the relationship between precursor compositions and catalyst properties, and the intrinsic functions of each component has been rarely studied. In this paper,more » we report a highly durable (no degradation after 20,000 cycles) and highly active (360 mV overpotential at 10 mA cm –2 GEO) OER catalyst derived from bimetallic metal–organic frameworks (MOFs) precursors. This catalyst consists of NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells. The electron–donation/deviation from Fe and tuned lattice and electronic structures of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity, whereas N concentration contributes negligibly. Finally, we further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by the chemical state of precursors.« less

Diamond nanoparticles as a support for Pt and PtRu catalysts for direct methanol fuel cells.

PubMed

La-Torre-Riveros, Lyda; Guzman-Blas, Rolando; Méndez-Torres, Adrián E; Prelas, Mark; Tryk, Donald A; Cabrera, Carlos R

2012-02-01

Diamond in nanoparticle form is a promising material that can be used as a robust and chemically stable catalyst support in fuel cells. It has been studied and characterized physically and electrochemically, in its thin film and powder forms, as reported in the literature. In the present work, the electrochemical properties of undoped and boron-doped diamond nanoparticle electrodes, fabricated using the ink-paste method, were investigated. Methanol oxidation experiments were carried out in both half-cell and full fuel cell modes. Platinum and ruthenium nanoparticles were chemically deposited on undoped and boron doped diamond nanoparticles through the use of NaBH(4) as reducing agent and sodium dodecyl benzene sulfonate (SDBS) as a surfactant. Before and after the reduction process, samples were characterized by electron microscopy and spectroscopic techniques. The ink-paste method was also used to prepare the membrane electrode assembly with Pt and Pt-Ru modified undoped and boron-doped diamond nanoparticle catalytic systems, to perform the electrochemical experiments in a direct methanol fuel cell system. The results obtained demonstrate that diamond supported catalyst nanomaterials are promising for methanol fuel cells.

Synergistic Interaction within Bifunctional Ruthenium Nanoparticle/SILP Catalysts for the Selective Hydrodeoxygenation of Phenols.

PubMed

Luska, Kylie L; Migowski, Pedro; El Sayed, Sami; Leitner, Walter

2015-12-21

Ruthenium nanoparticles immobilized on acid-functionalized supported ionic liquid phases (Ru NPs@SILPs) act as efficient bifunctional catalysts in the hydrodeoxygenation of phenolic substrates under batch and continuous flow conditions. A synergistic interaction between the metal sites and acid groups within the bifunctional catalyst leads to enhanced catalytic activities for the overall transformation as compared to the individual steps catalyzed by the separate catalytic functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transport and abatement of fluorescent silica nanoparticle (SiO2 NP) in granular filtration: effect of porous media and ionic strength

NASA Astrophysics Data System (ADS)

Zeng, Chao; Shadman, Farhang; Sierra-Alvarez, Reyes

2017-03-01

The extensive production and application of engineered silica nanoparticles (SiO2 NPs) will inevitably lead to their release into the environment. Granular media filtration, a widely used process in water and wastewater treatment plants, has the potential for NP abatement. In this work, laboratory-scale column experiments were performed to study the transport and retention of SiO2 NPs on three widely used porous materials, i.e., sand, anthracite, and granular activated carbon (GAC). Synthetic fluorescent core-shell SiO2 NPs (83 nm) were used to facilitate NP detection. Sand showed very low capacity for SiO2 filtration as this material had a surface with limited surface area and a high concentration of negative charge. Also, we found that the stability and transport of SiO2 NP were strongly dependent on the ionic strength of the solution. Increasing ionic strength led to NP agglomeration and facilitated SiO2 NP retention, while low ionic strength resulted in release of captured NPs from the sand bed. Compared to sand, anthracite and GAC showed higher affinity for SiO2 NP capture. The superior capacity of GAC was primarily due to its porous structure and high surface area. A process model was developed to simulate NP capture in the packed bed columns and determine fundamental filtration parameters. This model provided an excellent fit to the experimental data. Taken together, the results obtained indicate that GAC is an interesting material for SiO2 NP filtration.

Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

PubMed Central

Varnell, Jason A.; Tse, Edmund C. M.; Schulz, Charles E.; Fister, Tim T.; Haasch, Richard T.; Timoshenko, Janis; Frenkel, Anatoly I.; Gewirth, Andrew A.

2016-01-01

The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites. PMID:27538720

Supramolecular regulation of bioorthogonal catalysis in cells using nanoparticle-embedded transition metal catalysts

NASA Astrophysics Data System (ADS)

Tonga, Gulen Yesilbag; Jeong, Youngdo; Duncan, Bradley; Mizuhara, Tsukasa; Mout, Rubul; Das, Riddha; Kim, Sung Tae; Yeh, Yi-Cheun; Yan, Bo; Hou, Singyuk; Rotello, Vincent M.

2015-07-01

Bioorthogonal catalysis broadens the functional possibilities of intracellular chemistry. Effective delivery and regulation of synthetic catalytic systems in cells are challenging due to the complex intracellular environment and catalyst instability. Here, we report the fabrication of protein-sized bioorthogonal nanozymes through the encapsulation of hydrophobic transition metal catalysts into the monolayer of water-soluble gold nanoparticles. The activity of these catalysts can be reversibly controlled by binding a supramolecular cucurbit[7]uril ‘gate-keeper’ onto the monolayer surface, providing a biomimetic control mechanism that mimics the allosteric regulation of enzymes. The potential of this gated nanozyme for use in imaging and therapeutic applications was demonstrated through triggered cleavage of allylcarbamates for pro-fluorophore activation and propargyl groups for prodrug activation inside living cells.

Microemulsion flame pyrolysis for hopcalite nanoparticle synthesis: a new concept for catalyst preparation.

PubMed

Biemelt, T; Wegner, K; Teichert, J; Kaskel, S

2015-04-07

A new route to highly active hopcalite catalysts via flame spray pyrolysis of an inverse microemulsion precursor is reported. The nitrate derived nanoparticles are around 15 nm in diameter and show excellent conversion of CO under ambient conditions, outperforming commercial reference hopcalite materials produced by co-precipitation.

Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets

DOE PAGES

Perry, Albert; Kabir, Sadia; Matanovic, Ivana; ...

2017-06-16

This paper reports the fabrication and electrochemical performance of a hybrid catalyst composed of Pd nanoparticles and atomically dispersed Mn active centers integrated into the nitrogen-doped three-dimensional graphene nanosheets (Pd/Mn-N-3D-GNS). Our results show that the synergistic integration of both Pd nanoparticles and atomically dispersed Mn can be used to enhance the activity toward the electrochemical oxidation of organic acids at biologically relevant pH values. The hybrid catalyst (Pd/Mn-N-3D-GNS) showed increased maximum currents toward the oxidation of oxalic acid when compared to its individual catalysts, namely, Pd/3D-GNS and Mn N-3D-GNS catalysts. The hybrid also showed a decreased onset potential for oxidationmore » of mesoxalic acid as compared to Mn-N-3D-GNS and decreased onset potentials for the oxidation of glyoxalic acid when compared to both of its constituent catalysts. Oxidation of formic acid was also tested and the hybrid was shown to catalyze both dehydration and dehydrogenation mechanisms of formic acid electro-oxidation. Using density functional theory calculations, it was elucidated that a two-site catalysis most likely promotes dehydrogenation reaction for formic acid oxidation, which can explain the selectivity of Pd nanoparticles and atomically dispersed Mn towards the dehydrogenation/ dehydration pathway.« less

Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perry, Albert; Kabir, Sadia; Matanovic, Ivana

This paper reports the fabrication and electrochemical performance of a hybrid catalyst composed of Pd nanoparticles and atomically dispersed Mn active centers integrated into the nitrogen-doped three-dimensional graphene nanosheets (Pd/Mn-N-3D-GNS). Our results show that the synergistic integration of both Pd nanoparticles and atomically dispersed Mn can be used to enhance the activity toward the electrochemical oxidation of organic acids at biologically relevant pH values. The hybrid catalyst (Pd/Mn-N-3D-GNS) showed increased maximum currents toward the oxidation of oxalic acid when compared to its individual catalysts, namely, Pd/3D-GNS and Mn N-3D-GNS catalysts. The hybrid also showed a decreased onset potential for oxidationmore » of mesoxalic acid as compared to Mn-N-3D-GNS and decreased onset potentials for the oxidation of glyoxalic acid when compared to both of its constituent catalysts. Oxidation of formic acid was also tested and the hybrid was shown to catalyze both dehydration and dehydrogenation mechanisms of formic acid electro-oxidation. Using density functional theory calculations, it was elucidated that a two-site catalysis most likely promotes dehydrogenation reaction for formic acid oxidation, which can explain the selectivity of Pd nanoparticles and atomically dispersed Mn towards the dehydrogenation/ dehydration pathway.« less

A general method for multimetallic platinum alloy nanowires as highly active and stable oxygen reduction catalysts

DOE PAGES

Bu, Lingzheng; Ding, Jiabao; Yao, Jianlin; ...

2015-10-13

The production of inorganic nanoparticles (NPs) with precise control over structures has always been a central target in various fields of chemistry and physics because the properties of NPs can be desirably manipulated by their structure. [1-4] There has been an intense search for high-performance noble metal NP catalysts particular for Pt. [5-9] Precious platinum (Pt) NPs are active catalysts for various heterogeneous reactions and show particularly superior performance in both the anodic oxidation reaction and the cathodic ORR in the fuel cells, but their rare content and high cost largely impede the practical application. [10-12] A potential strategy tomore » address this tremendous challenge is alloying Pt NPs with the transition metals (TM). [13-16]« less

Revealing the Dynamics of Platinum Nanoparticle Catalysts on Carbon in Oxygen and Water Using Environmental TEM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Langli; Engelhard, Mark H.; Shao, Yuyan

Deactivation of supported metal nanoparticle catalysts, especially in relevant gas condition, is a critical challenge for many technological applications, including heterogeneous catalysis, electrocatalysis, fuel cells, biomedical imaging and drug delivery. It has been far more commonly realized that deactivation of catalysts stems from surface area loss due to particle coarsening, however, for which the mechanism remains largely unclear. Herein, we use aberration corrected environmental transmission electron microscopy, at atomic level, to in-situ observe the dynamics of Pt catalyst in fuel cell relevant gas conditions. Particles migration and coalescence is observed to be the dominant coarsening process. As compared with themore » case of H2O, O2 promotes Pt nanoparticle migration on carbon surface. Surprisingly, coating Pt/carbon with a nanofilm of electrolyte (Nafion ionomer) leads to a faster migration of Pt in H2O than in O2, a consequence of Nafion-carbon interface water “lubrication” effect. Atomically, the particles coalescence is featured by re-orientation of particles towards lattice matching, a process driven by orientation dependent van der Waals force. These results provide direct observations of dynamics of metal nanoparticles at critical surface/interface under relevant conditions and yield significant insights into the multi-phase interaction in related technological processes.« less

High-resolution TEM Studies of Carbon Nanotubes and Catalyst Nanoparticles Produced During CVD from Metal Multilayer Films

NASA Astrophysics Data System (ADS)

Howe, Jane Y.; Puretzky, Alex A.; Geohegan, David B.; Cui, Hongtao; Eres, Varela; Maria, Alex A.; Lowndes, Douglas H.

2003-03-01

The structure of single-wall and multiwall carbon nanotubes and associated metal catalyst nanoparticles produced during chemical vapor deposition from multilayered metal films deposited on Si and Mo substrates were studied by high-resolution TEM and EDS. Electron beam-evaporated metal multilayer films (e.g. Al-Fe-Mo, typically 11-50 nm total thickness) roughen upon heat treatment to form a variety of catalyst particle sizes suitable for carbon nanotube growth by chemical vapor deposition using acetylene, hydrogen, and argon flow gases. This study investigates these nanoparticles, the type of nanotubes grown, their wall, tip, and basal structures, as well as the associated amounts of amorphous carbon deposited on their walls in different temperature and pressure ranges. Mixtures of SWNT and MWNT are found even for low growth temperatures (650-700 C), while rapid growth of vertically-aligned multiwall nanotubes (VA-MWNTs) predominate in a narrow temperature range at a given pressure. Arrested growth experiments were performed to determine the time periods for SWNT vs. MWNT growth. The nature of the catalyst nanoparticles, their support structure, and insights on the mechanisms of growth will be discussed.

Aqueous-Phase Hydrogenolysis of Glycerol over Re Promoted Ru Catalysts Encapuslated in Porous Silica Nanoparticles

PubMed Central

Li, Kuo-Tseng; Yen, Ruey-Hsiang

2018-01-01

Activity improvement of Ru-based catalysts is needed for efficient production of valuable chemicals from glycerol hydrogenolysis. In this work, a series of Re promoted Ru catalysts encapuslated in porous silica nanoparticles (denoted as Re-Ru@SiO2) were prepared by coating silica onto the surface of chemically reduced Ru-polyvinylpyrrolidone colloids, and were used to catalyze the conversion of glycerol to diols and alcohols in water. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption, X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) were used to characterize these nanoparticles. Effects of Ru/Si atomic ratio, Re addition, glycerol and catalyst concentrations, reaction time, temperature, and hydrogen pressure were investigated. Re addition retarded the reduction of ruthenium oxide, but increased the catalyst reactivity for glycerol hydrogenolysis. Due to its greater Ru content, Re-Ru@ SiO2 showed much better activity (reacted at much lower temperature) and more yields of 1,2-propanediol and overall liquid-phase products than Re-Ru/SiO2 (prepared by conventional impregnation method) reported before. The rate of glycerol disappearance exhibited first-order dependence on glycerol concentration and hydrogen pressure, with an activation energy of 107.8 kJ/mol. The rate constant increased linearly with increasing Ru/Si atomic ratio and catalyst amount. The yield of overall liquid-phase products correlated well with glycerol conversion. PMID:29522432

Dehydration of glucose to 5-hydroxymethylfurfural by a core-shell Fe3O4@SiO2-SO3H magnetic nanoparticle catalyst

USDA-ARS?s Scientific Manuscript database

This paper discusses the potential use of (Fe3O4@SiO2-SO3H) nanoparticle catalyst for the dehydration of glucose into 5-hydroxymethylfurfural (HMF). A magnetically recoverable (Fe3O4@SiO2-SO3H) nanoparticle catalyst was successfully prepared by supporting sulfonic acid groups (SO3H) on the surface o...

Poly-lactic acid nanoparticles (PLA-NP) promote physiological modifications in lung epithelial cells and are internalized by clathrin-coated pits and lipid rafts.

PubMed

da Luz, Camila Macedo; Boyles, Matthew Samuel Powys; Falagan-Lotsch, Priscila; Pereira, Mariana Rodrigues; Tutumi, Henrique Rudolf; de Oliveira Santos, Eidy; Martins, Nathalia Balthazar; Himly, Martin; Sommer, Aniela; Foissner, Ilse; Duschl, Albert; Granjeiro, José Mauro; Leite, Paulo Emílio Corrêa

2017-01-31

Poly-lactic acid nanoparticles (PLA-NP) are a type of polymeric NP, frequently used as nanomedicines, which have advantages over metallic NP such as the ability to maintain therapeutic drug levels for sustained periods of time. Despite PLA-NP being considered biocompatible, data concerning alterations in cellular physiology are scarce. We conducted an extensive evaluation of PLA-NP biocompatibility in human lung epithelial A549 cells using high throughput screening and more complex methodologies. These included measurements of cytotoxicity, cell viability, immunomodulatory potential, and effects upon the cells' proteome. We used non- and green-fluorescent PLA-NP with 63 and 66 nm diameters, respectively. Cells were exposed with concentrations of 2, 20, 100 and 200 µg/mL, for 24, 48 and 72 h, in most experiments. Moreover, possible endocytic mechanisms of internalization of PLA-NP were investigated, such as those involving caveolae, lipid rafts, macropinocytosis and clathrin-coated pits. Cell viability and proliferation were not altered in response to PLA-NP. Multiplex analysis of secreted mediators revealed a low-level reduction of IL-12p70 and vascular epidermal growth factor (VEGF) in response to PLA-NP, while all other mediators assessed were unaffected. However, changes to the cells' proteome were observed in response to PLA-NP, and, additionally, the cellular stress marker miR155 was found to reduce. In dual exposures of staurosporine (STS) with PLA-NP, PLA-NP enhanced susceptibility to STS-induced cell death. Finally, PLA-NP were rapidly internalized in association with clathrin-coated pits, and, to a lesser extent, with lipid rafts. These data demonstrate that PLA-NP are internalized and, in general, tolerated by A549 cells, with no cytotoxicity and no secretion of pro-inflammatory mediators. However, PLA-NP exposure may induce modification of biological functions of A549 cells, which should be considered when designing drug delivery systems. Moreover

A Ni(iii) complex stabilized by silica nanoparticles as an efficient nanoheterogeneous catalyst for oxidative C-H fluoroalkylation.

PubMed

Khrizanforov, Mikhail N; Fedorenko, Svetlana V; Strekalova, Sofia O; Kholin, Kirill V; Mustafina, Asiya R; Zhilkin, Mikhail Ye; Khrizanforova, Vera V; Osin, Yuri N; Salnikov, Vadim V; Gryaznova, Tatyana V; Budnikova, Yulia H

2016-07-26

We have developed Ni(III)-doped silica nanoparticles ([(bpy)xNi(III)]@SiO2) as a recyclable, low-leaching, and efficient oxidative functionalization nanocatalyst for aromatic C-H bonds. The catalyst is obtained by doping the complex [(bpy)3Ni(II)] on silica nanoparticles along with its subsequent electrooxidation to [(bpy)xNi(III)] without an additional oxidant. The coupling reaction of arenes with perfluoroheptanoic acid occurs with 100% conversion of reactants in a single step at room temperature under nanoheterogeneous conditions. The catalyst content is only 1% with respect to the substrates under electrochemical regeneration conditions. The catalyst can be easily separated from the reaction mixture and reused a minimum of five times. The results emphasize immobilization on the silica support and the electrochemical regeneration of Ni(III) complexes as a facile route for developing an efficient nanocatalyst for oxidative functionalization.

In situ assembly of well-dispersed Ni nanoparticles on silica nanotubes and excellent catalytic activity in 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Zhang, Shenghuan; Gai, Shili; He, Fei; Ding, Shujiang; Li, Lei; Yang, Piaoping

2014-09-01

The easy aggregation nature of ferromagnetic nanoparticles (NPs) prepared by conventional routes usually leads to a large particle size and low loading, which greatly limits their applications to the reduction of 4-nitrophenol (4-NP). Herein, we developed a novel in situ thermal decomposition and reduction strategy to prepare Ni nanoparticles/silica nanotubes (Ni/SNTs), which can markedly prevent the aggregation and growth of Ni NPs, resulting in an ultra-small particle size (about 6 nm), good dispersion and especially high loading of Ni NPs. It was found that Ni/SNTs, which have a high specific surface area (416 m2 g-1), exhibit ultra-high catalytic activity in the 4-NP reduction (complete reduction of 4-NP within only 60 s at room temperature), which is superior to most noble metal (Au, Pt, and Pd) supported catalysts. Ni/SNTs still showed high activity even after re-use for several cycles, suggesting good stability. In particular, the magnetic property of Ni/SNTs makes it easy to recycle for reuse.The easy aggregation nature of ferromagnetic nanoparticles (NPs) prepared by conventional routes usually leads to a large particle size and low loading, which greatly limits their applications to the reduction of 4-nitrophenol (4-NP). Herein, we developed a novel in situ thermal decomposition and reduction strategy to prepare Ni nanoparticles/silica nanotubes (Ni/SNTs), which can markedly prevent the aggregation and growth of Ni NPs, resulting in an ultra-small particle size (about 6 nm), good dispersion and especially high loading of Ni NPs. It was found that Ni/SNTs, which have a high specific surface area (416 m2 g-1), exhibit ultra-high catalytic activity in the 4-NP reduction (complete reduction of 4-NP within only 60 s at room temperature), which is superior to most noble metal (Au, Pt, and Pd) supported catalysts. Ni/SNTs still showed high activity even after re-use for several cycles, suggesting good stability. In particular, the magnetic property of Ni

Catalytic hydrolysis of ammonia borane via cobalt palladium nanoparticles.

PubMed

Sun, Daohua; Mazumder, Vismadeb; Metin, Önder; Sun, Shouheng

2011-08-23

Monodisperse 8 nm CoPd nanoparticles (NPs) with controlled compositions were synthesized by the reduction of cobalt acetylacetonate and palladium bromide in the presence of oleylamine and trioctylphosphine. These NPs were active catalysts for hydrogen generation from the hydrolysis of ammonia borane (AB), and their activities were composition dependent. Among the 8 nm CoPd catalysts tested for the hydrolysis of AB, the Co(35)Pd(65) NPs exhibited the highest catalytic activity and durability. Their hydrolysis completion time and activation energy were 5.5 min and 27.5 kJ mol(-1), respectively, which were comparable to the best Pt-based catalyst reported. The catalytic performance of the CoPd/C could be further enhanced by a preannealing treatment at 300 °C under air for 15 h with the hydrolysis completion time reduced to 3.5 min. This high catalytic performance of Co(35)Pd(65) NP catalyst makes it an exciting alternative in pursuit of practical implementation of AB as a hydrogen storage material for fuel cell applications. © 2011 American Chemical Society

Controllable pt nanoparticle deposition on carbon nanotubes as an anode catalyst for direct methanol fuel cells.

PubMed

Mu, Yongyan; Liang, Hanpu; Hu, Jinsong; Jiang, Li; Wan, Lijun

2005-12-01

We report a novel process to prepare well-dispersed Pt nanoparticles on CNTs. Pt nanoparticles, which were modified by the organic molecule triphenylphosphine, were deposited on multiwalled carbon nanotubes by the organic molecule, which acts as a cross linker. By manipulating the relative ratio of Pt nanoparticles and multiwalled carbon nanotubes in solution, Pt/CNT composites with different Pt content were achieved. The so-prepared Pt/CNT composite materials show higher electrocatalytic activity and better tolerance to poisoning species in methanol oxidation than the commercial E-TEK catalyst, which can be ascribed to the high dispersion of Pt nanoparticles on the multiwalled carbon nanotube surface.

Water-medium and solvent-free organic reactions over a bifunctional catalyst with Au nanoparticles covalently bonded to HS/SO3H functionalized periodic mesoporous organosilica.

PubMed

Zhu, Feng-Xia; Wang, Wei; Li, He-Xing

2011-08-03

An operationally simple approach for the preparation of a new class of bifunctional Au nanoparticle-acid catalysts has been developed. In situ reduction of Au(3+) with HS-functionalized periodic mesoporous organosilicas (PMOs) creates robust, fine Au nanoparticles and concomitantly produces a sulfonic acid moiety strongly bonded to PMOs. Characterizations of the nanostructures reveal that Au nanoparticles are formed with uniformed, narrow size distribution around 1-2 nm, which is very critical for essential catalytic activities. Moreover, the Au nanoparticles are mainly attached onto the pore surface rather than onto the outer surface with ordered mesoporous channels, allowing for maximal exposure to reaction substrates while minimizing Au nanoparticle leaching. Their higher S(BET), V(P), and D(P) than either the Au-HS-PMO(Et) or the Au/SO(3)H-PMO(Et) render the catalyst with comparably even higher catalytic efficiency than its homogeneous counterparts. Furthermore, the unique amphiphilic compartment of the Au-HS/SO(3)H-PMO(Et) nanostructures enables organic reactions to proceed efficiently in a pure aqueous solution without using any organic solvents or even without water. As demonstrated experimentally, remarkably, the unique bifunctional Au-HS/SO(3)H-PMO(Et) catalyst displays higher efficiencies in promoting water-medium alkyne hydration, intramolecular hydroamination, styrene oxidation, and three-component coupling reactions and even the solvent-free alkyne hydration process than its homogeneous catalysts. The robust catalyst can be easily recycled and used repetitively at least 10 times without loss of catalytic efficiency. These features render the catalyst particularly attractive in the practice of organic synthesis in an environmentally friendly manner.

Cobalt nanoparticles encapsulated in nitrogen-rich carbon nanotubes as efficient catalysts for organic pollutants degradation via sulfite activation.

PubMed

Wu, Deming; Ye, Peng; Wang, Manye; Wei, Yi; Li, Xiaoxia; Xu, Aihua

2018-06-15

The activation of sulfite by heterogeneous catalysts displays a great potential in the development of new sulfate radials based technologies for wastewater treatment. Herein, cobalt nanoparticles embedded in N-doped carbon nanotubes (Co@NC) were prepared by a simple pyrolysis method. Due to the synergistic effects of the cobalt nanoparticles and N-doped carbon nanotubes, the Co@NC catalyst intrinsically shows an outstanding efficiency, excellent reusability and high stability in the catalytic oxidation of methyl orange (MO) in the presence of sulfite and dioxygen. The structure and efficiency of the catalyst was significantly affected by the content of cobalt and pyrolysis temperature. Several quenching experiments and electron paramagnetic resonance were carried out to investigate the catalytic mechanism. It is found that hydroxyl and sulfate radicals worked together to degrade MO in the system. The formation and decomposition of peroxymonosulfate may be an important route of these reactive radicals production. The effect of different anions, bicarbonate concentration, initial solution pH and dye types on the performance of the catalyst was also studied. This study can open a new approach for design and preparation of encapsulated cobalt in carbon materials as effective catalysts for pollutants degradation via sulfite activation. Copyright © 2018 Elsevier B.V. All rights reserved.

Synthesis and Characterization of Cobalt Containing Nanoparticles on Alumina A Potential Catalyst for Gas to Liquid Fuels Production

NASA Technical Reports Server (NTRS)

Cowen, Jonathan; Hepp, Aloysius F.

2016-01-01

Fisher-Tröpsch synthesis (FTS) is a century-old gas-to-liquid (GTL) technology that commonly employs cobalt (Co, on an oxide support) or iron (supported or not) species catalysts. It has been well established that the activity of the Co catalyst depends directly upon the number of surface Co atoms. The addition of promoter (mainly noble) metals has been widely utilized to increase the fraction of Co that is available for surface catalysis. Direct synthesis of Co nanoparticles is a possible alternative approach; our preliminary synthesis and characterization efforts are described. Materials were characterized by various transmission microscopies and energy dispersive spectroscopy. Tri-n-octylphosphine oxide (TOPO) and dicobalt octacarbonyl were heated under argon to a temperature of 180 deg with constant stirring for 1 hr. Quenching the reaction in toluene produced Co-containing nanoparticles with a diameter of 5 to 10 nm. Alternatively, an alumina support (SBA-200 Al2O3) was added; the reaction was further stirred and the temperature was decreased to 140 deg to reduce the rate of further growth/ripening of the nucleated Co nanoparticles. A typical size of Co-containing NPs was also found to be in the range of 5 to 10 nm. This can be contrasted with a range of 50 to 200 nm for conventionally-produced Co-Al2O3 Fischer-Tröpsch catalysts. This method shows great potential for production of highly dispersed catalysts that are either supported or unsupported.

Metal Nanoparticle Catalysts for Carbon Nanotube Growth

NASA Technical Reports Server (NTRS)

Pierce, Benjamin F.

2003-01-01

Work this summer involved and new and unique process for producing the metal nanoparticle catalysts needed for carbon nanotube (CNT) growth. There are many applications attributed to CNT's, and their properties have deemed them to be a hot spot in research today. Many groups have demonstrated the versatility in CNT's by exploring a wide spectrum of roles that these nanotubes are able to fill. A short list of such promising applications are: nanoscaled electronic circuitry, storage media, chemical sensors, microscope enhancement, and coating reinforcement. Different methods have been used to grow these CNT's. Some examples are laser ablation, flame synthesis, or furnace synthesis. Every single approach requires the presence of a metal catalyst (Fe, Co, and Ni are among the best) that is small enough to produce a CNT. Herein lies the uniqueness of this work. Microemulsions (containing inverse micelles) were used to generate these metal particles for subsequent CNT growth. The goal of this summer work was basically to accomplish as much preliminary work as possible. I strived to pinpoint which variable (experimental process, metal product, substrate, method of application, CVD conditions, etc.) was the determining factor in the results. The resulting SEM images were sufficient for the appropriate comparisons to be made. The future work of this project consists of the optimization of the more promising experimental procedures and further exploration onto what exactly dictated the results.

Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

PubMed

Liu, Lichen; Corma, Avelino

2018-05-23

Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal-support interaction, and metal-reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results obtained from different systems and try to give a picture on how different types of metal species work in different reactions and give perspectives on the future directions toward better understanding of the catalytic behavior of different metal entities (single atoms, nanoclusters, and nanoparticles) in a unifying manner.

Magnetic induced heating of nanoparticle solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murph, S. Hunyadi; Brown, M.; Coopersmith, K.

2016-12-02

Magnetic induced heating of nanoparticles (NP) provides a useful advantage for many energy transfer applications. This study aims to gain an understanding of the key parameters responsible for maximizing the energy transfer leading to nanoparticle heating through the use of simulations and experimental results. It was found that magnetic field strength, NP concentration, NP composition, and coil size can be controlled to generate accurate temperature profiles in NP aqueous solutions.

Effect of nanoparticle metal composition: mono- and bimetallic gold/copper dendrimer stabilized nanoparticles as solvent-free styrene oxidation catalysts

NASA Astrophysics Data System (ADS)

Blanckenberg, A.; Kotze, G.; Swarts, A. J.; Malgas-Enus, R.

2018-02-01

A range of mono- and bimetallic AumCun nanoparticles (NPs), with varying metal compositions, was prepared by using a third-generation diaminobutane poly(propylene imine) (G3 DAB-PPI) dendrimer, modified with alkyl chains, as a stabilizer. It was found that the length of the peripheral alkyl chain, ( M1 (C15), M2 (C11), and M3 (C5)), had a direct influence on the average nanoparticle size obtained, confirming the importance of the nanoparticle stabilizer during synthesis. The Au NPs showed the highest degree of agglomeration and polydispersity, whereas the Cu NPs were the smallest and most monodisperse of the NPs. The bimetallic NPs sizes were found to vary between those of the monometallic NPs, depending on the metal composition. Interestingly, the bimetallic NPs were found to be the most stable, showing very little variation in size over time, even up to 9 months. The DSNs were evaluated in the catalytic oxidation of styrene, using either H2O2 or TBHP as oxidant. Here, we show that the bimetallic DSNs are indeed the superior catalysts when compared to their monometallic analogues, under the same reaction conditions, since a good compromise between stability and activity can be achieved where the Au provides catalytic activity and the Cu serves as a stabilizer. These AumCun bimetallic DSNs present a less expensive and more stable catalyst with negligible loss of activity, opening the door to green catalysis.

Near-infrared mediated tumor destruction by photothermal effect of PANI-Np in vivo

NASA Astrophysics Data System (ADS)

Ibarra, L. E.; Yslas, E. I.; Molina, M. A.; Rivarola, C. R.; Romanini, S.; Barbero, C. A.; Rivarola, V. A.; Bertuzzi, M. L.

2013-06-01

Photothermal therapy is a therapy in which photon energy is converted into heat to kill cancer. The purpose of this study is to evaluate the in vivo efficacy of photothermal therapy, toxicity and hepatic and renal function of polyaniline nanoparticles (PANI-Np) in a tumor-bearing mice model. The in vivo efficacy of nanoparticles, following NIR light exposure, was assessed by examining tumor growth over time compared to the untreated control. Signs of drug toxicity and the histopathology and morphology of tumor and tissues, after intratumoral injection treatment, were examined or monitored. Excellent photothermal therapy efficacy is achieved upon intratumoral injection of PANI-Np followed by near-infrared light exposure. These results suggest that PANI-Np could be considered as an effective photothermal agent and pave the way to future cancer therapeutics.

Photosensitized H2 Production Using a Zinc Porphyrin-Substituted Protein, Platinum Nanoparticles, and Ascorbate with No Electron Relay: Participation of Good's Buffers.

PubMed

Clark, Emily R; Kurtz, Donald M

2017-04-17

Development of efficient light-driven splitting of water, 2H 2 O → 2H 2 + O 2 , often attempts to optimize photosensitization of the reductive and oxidative half-reactions individually. Numerous homogeneous and heterogeneous systems have been developed for photochemical stimulation of the reductive half reaction, 2H + + 2e - → H 2 . These systems generally consist of various combinations of a H + reduction catalyst, a photosensitizer (PS), and a "sacrificial" electron donor. Zinc(II)-porphyrins (ZnPs) have frequently been used as PSs for H 2 generation, but they are subject to various self-quenching processes in aqueous solutions. Colloidal platinum in nanoparticle form (Pt NP) is a classical H + reduction catalyst using ZnP photosensitizers, but efficient photosensitized H 2 generation requires an electron relay molecule between ZnP and Pt NP. The present report describes an aqueous system for visible (white) light-sensitized generation of H 2 using a protein-embedded Zn(II)-protoporphyrin IX as PS and Pt NP as H + reduction catalyst without an added electron relay. This system operated efficiently in piperazino- and morpholino-alkylsulfonic acid (Good's buffers), which served as sacrificial electron donors. The system also required ascorbate at relatively modest concentrations, which stabilized the Zn(II)-protoporphyrin IX against photodegradation. In the absence of an electron relay molecule, the photosensitized H 2 generation must involve formation of at least a transient complex between a protein-embedded Zn(II)-protoporphyrin IX species and Pt NP.

Hollow mesoporous silica nanotubes modified with palladium nanoparticles for environmental catalytic applications.

PubMed

Tian, Meng; Long, Yu; Xu, Dan; Wei, Shuoyun; Dong, Zhengping

2018-07-01

Nowadays, chemical catalytic methods for the treatment of organic wastes are attracting more and more research attention. In the current research, novel catalysts with palladium nanoparticles (Pd NPs) supported on the hollow mesoporous silica nanotubes (h-mSiO 2 ) were synthesized for the catalytic reduction of 4-nitrophenol (4-NP) and hydrodechlorination (HDC) of 4-chlorophenol (4-CP). The key point for the fabrication of the catalysts is that a certain thickness of the silica shell was wrapped on the multiwalled carbon nanotubes (MWNTs) or Pd/MWNTs through biphase stratification approach, and then the samples were calcined to remove the MWNTs. Thereby, h-mSiO 2 and Pd@h-mSiO 2 samples were obtained. The prepared materials have excellent pore structure and exhibit high specific surface areas. The reduction of 4-NP by the Pd/h-mSiO 2 and Pd@h-mSiO 2 catalysts showed higher TOF values than many other catalysts, and the yield of HDC of 4-CP to phenol reached 100% with a low loading of Pd in water solvent. The excellent catalytic activities of the Pd/h-mSiO 2 and Pd@h-mSiO 2 catalysts should attribute to the excellent connectivity of the h-mSiO 2 which not only can increase the accessibility of the Pd active sites but also enhance the mass transfer of the reactants. It is worth mention that, there is almost no Pd NPs aggregation or losing during the reaction process, and the prepared catalysts still showed good catalytic activity and physical stability after recycling. Moreover, the catalyst shows potential for catalytic reduction of nitroarenes in a fixed bed reactor, thus could be used for continuously treat nitroarenes polluted water. Copyright © 2018 Elsevier Inc. All rights reserved.

Highly efficient hydrogen release from formic acid using a graphitic carbon nitride-supported AgPd nanoparticle catalyst

NASA Astrophysics Data System (ADS)

Yao, Fang; Li, Xiao; Wan, Chao; Xu, Lixin; An, Yue; Ye, Mingfu; Lei, Zhao

2017-12-01

Bimetallic AgPd nanoparticles with various molar ratios immobilized on graphitic carbon nitride (g-C3N4) were successfully synthesized via a facile co-reduction approach. The powder XRD, XPS, TEM, EDX, ICP-AES and BET were employed to characterize the structure, size, composition and loading metal electronic states of the AgPd/g-C3N4 catalysts. The catalytic property of as-prepared catalysts for the dehydrogenation of formic acid (FA) with sodium formate (SF) as the additive was investigated. The performance of these catalysts, as indicated by the turnover frequency (TOF), depended on the composition of the prepared catalysts. Among all the AgPd/g-C3N4 catalysts tested, Ag9Pd91/g-C3N4 was found to be an exceedingly high activity for decomposing FA into H2 with TOF up to 480 h-1 at 323 K. The prepared catalyst is thus a potential candidate for triggering the widespread use of FA for H2 storage.

Crystal Structural Effect of AuCu Alloy Nanoparticles on Catalytic CO Oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhan, Wangcheng; Wang, Jinglin; Wang, Haifeng

2017-06-07

Controlling the physical and chemical properties of alloy nanoparticles (NPs) is an important approach to optimize NP catalysis. Unlike other tuning knobs, such as size, shape, and composition, crystal structure has received limited attention and not been well understood for its role in catalysis. This deficiency is mainly due to the difficulty in synthesis and fine-tuning of the NPs’ crystal structure. Here, Exemplifying by AuCu alloy NPs with face centered cubic (fcc) and face centered tetragonal (fct) structure, we demonstrate a remarkable difference in phase segregation and catalytic performance depending on the crystal structure. During the thermal treatment in air,more » the Cu component in fcc-AuCu alloy NPs segregates more easily onto the alloy surface as compared to that in fct-AuCu alloy NPs. As a result, after annealing at 250 °C in air for 1 h, the fcc- and fct-AuCu alloy NPs are phase transferred into Au/CuO and AuCu/CuO core/shell structures, respectively. More importantly, this variation in heterostructures introduces a significant difference in CO adsorption on two catalysts, leading to a largely enhanced catalytic activity of AuCu/CuO NP catalyst for CO oxidation. Furthermore, the same concept can be extended to other alloy NPs, making it possible to fine-tune NP catalysis for many different chemical reactions.« less

Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

NASA Astrophysics Data System (ADS)

Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

2016-07-01

For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

Synthesis of carbon nanofibers by CVD as a catalyst support material using atomically ordered Ni3C nanoparticles

NASA Astrophysics Data System (ADS)

Li, Meifeng; Li, Na; Shao, Wei; Zhou, Chungen

2016-12-01

Atomically ordered nickel carbide (Ni3C) nanoparticles in polygonal shapes were prepared through the reduction of nickelocene. A novel type of carbon nanofiber (CNF) with twisted conformation was synthesized successfully by catalytic chemical vapor deposition (CCVD) using the obtained Ni3C nanoparticles at a relatively low temperature of 350 °C, which is below the lower limit temperature of 400 °C for the growth of CNFs using metal catalysts. The growth mechanism of the twisted CNFs from Ni3C was freshly derived based on the detailed characterizations. Compared with the growth of CNFs from Ni, graphene layers nucleate at monoatomic step edges and grow in a layer-by-layer manner, while the rotation of the polygonal Ni3C nanoparticles fabricates the twisted conformation during the CNF growth. The electrochemical activity and performance of the twisted CNFs loaded with Pt as electrode catalysts for a polymer electrolyte membrane fuel cell (PEMFC) were measured to be better than those of straight CNFs grown from Ni nanoparticles at 500 °C, since the specific surface conformation helps to make the loaded Pt more homogeneous.

Synthesis of carbon nanofibers by CVD as a catalyst support material using atomically ordered Ni3C nanoparticles.

PubMed

Li, Meifeng; Li, Na; Shao, Wei; Zhou, Chungen

2016-11-22

Atomically ordered nickel carbide (Ni 3 C) nanoparticles in polygonal shapes were prepared through the reduction of nickelocene. A novel type of carbon nanofiber (CNF) with twisted conformation was synthesized successfully by catalytic chemical vapor deposition (CCVD) using the obtained Ni 3 C nanoparticles at a relatively low temperature of 350 °C, which is below the lower limit temperature of 400 °C for the growth of CNFs using metal catalysts. The growth mechanism of the twisted CNFs from Ni 3 C was freshly derived based on the detailed characterizations. Compared with the growth of CNFs from Ni, graphene layers nucleate at monoatomic step edges and grow in a layer-by-layer manner, while the rotation of the polygonal Ni 3 C nanoparticles fabricates the twisted conformation during the CNF growth. The electrochemical activity and performance of the twisted CNFs loaded with Pt as electrode catalysts for a polymer electrolyte membrane fuel cell (PEMFC) were measured to be better than those of straight CNFs grown from Ni nanoparticles at 500 °C, since the specific surface conformation helps to make the loaded Pt more homogeneous.

Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation

NASA Astrophysics Data System (ADS)

Chan, Chun Wong Aaron; Mahadi, Abdul Hanif; Li, Molly Meng-Jung; Corbos, Elena Cristina; Tang, Chiu; Jones, Glenn; Kuo, Winson Chun Hsin; Cookson, James; Brown, Christopher Michael; Bishop, Peter Trenton; Tsang, Shik Chi Edman

2014-12-01

Lindlar catalysts comprising of palladium/calcium carbonate modified with lead acetate and quinoline are widely employed industrially for the partial hydrogenation of alkynes. However, their use is restricted, particularly for food, cosmetic and drug manufacture, due to the extremely toxic nature of lead, and the risk of its leaching from catalyst surface. In addition, the catalysts also exhibit poor selectivities in a number of cases. Here we report that a non-surface modification of palladium gives rise to the formation of an ultra-selective nanocatalyst. Boron atoms are found to take residence in palladium interstitial lattice sites with good chemical and thermal stability. This is favoured due to a strong host-guest electronic interaction when supported palladium nanoparticles are treated with a borane tetrahydrofuran solution. The adsorptive properties of palladium are modified by the subsurface boron atoms and display ultra-selectivity in a number of challenging alkyne hydrogenation reactions, which outclass the performance of Lindlar catalysts.

Electrochemical Nanoparticle Sizing Via Nano-Impacts: How Large a Nanoparticle Can be Measured?

PubMed Central

Bartlett, Thomas R; Sokolov, Stanislav V; Compton, Richard G

2015-01-01

The field of nanoparticle (NP) sizing encompasses a wide array of techniques, with electron microscopy and dynamic light scattering (DLS) having become the established methods for NP quantification; however, these techniques are not always applicable. A new and rapidly developing method that addresses the limitations of these techniques is the electrochemical detection of NPs in solution. The ‘nano-impacts’ technique is an excellent and qualitative in situ method for nanoparticle characterization. Two complementary studies on silver and silver bromide nanoparticles (NPs) were used to assess the large radius limit of the nano-impact method for NP sizing. Noting that by definition a NP cannot be larger than 100 nm in diameter, we have shown that the method quantitatively sizes at the largest limit, the lower limit having been previously reported as ∼6 nm.1 PMID:26491639

Size and morphology controlled NiSe nanoparticles as efficient catalyst for the reduction reactions

NASA Astrophysics Data System (ADS)

Subbarao, Udumula; Marakatti, Vijaykumar S.; Amshumali, Mungalimane K.; Loukya, B.; Singh, Dheeraj Kumar; Datta, Ranjan; Peter, Sebastian C.

2016-12-01

Facile and efficient ball milling and polyol methods were employed for the synthesis of nickel selenide (NiSe) nanoparticle. The particle size of the NiSe nanoparticle has been controlled mechanically by varying the ball size in the milling process. The role of the surfactants in the formation of various morphologies was studied. The compounds were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray energy dispersive spectroscopy (EDS). The efficiency of the NiSe nanoparticle as a catalyst was tested for the reduction of para-nitroaniline (PNA) to para-phenyldiamine (PPD) and para-nitrophenol (PNP) to para-aminophenol (PAP) using NaBH4 as the reducing agent. Particle size, morphology and the presence of surfactant played a crucial role in the reduction process.

High-Performance Core–Shell Catalyst with Nitride Nanoparticles as a Core: Well-Defined Titanium Copper Nitride Coated with an Atomic Pt Layer for the Oxygen Reduction Reaction

DOE PAGES

Tian, Xinlong; Tang, Haibo; Luo, Junming; ...

2017-04-25

A class of core–shell structured low-platinum catalysts with well-dispersed inexpensive titanium copper nitride nanoparticles as cores and atomic platinum layers as shells exhibiting high activity and stability for the oxygen reduction reaction is successfully developed. In using nitrided carbon nanotubes (NCNTs) as the support greatly improved the morphology and dispersion of the nitride nanoparticles, resulting in significant enhancement of the performance of the catalyst. The optimized catalyst, Ti 0.9Cu 0.1N@Pt/NCNTs, has a Pt mass activity 5 times higher than that of commercial Pt/C, comparable to that of core–shell catalysts with precious metal nanoparticles as the core, and much higher thanmore » that the latter if we take into account the mass activity of all platinum group metals. Furthermore, only a minimal loss of activity can be observed after 10000 potential cycles, demonstrating the catalyst’s high stability. After durability testing, atomic-scale elemental mapping confirmed that the core–shell structure of the catalyst remained intact. This approach may open a pathway for the design and preparation of high-performance inexpensive core–shell catalysts for a wide range of applications in energy conversion processes.« less

High-Performance Core–Shell Catalyst with Nitride Nanoparticles as a Core: Well-Defined Titanium Copper Nitride Coated with an Atomic Pt Layer for the Oxygen Reduction Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Xinlong; Tang, Haibo; Luo, Junming

A class of core–shell structured low-platinum catalysts with well-dispersed inexpensive titanium copper nitride nanoparticles as cores and atomic platinum layers as shells exhibiting high activity and stability for the oxygen reduction reaction is successfully developed. In using nitrided carbon nanotubes (NCNTs) as the support greatly improved the morphology and dispersion of the nitride nanoparticles, resulting in significant enhancement of the performance of the catalyst. The optimized catalyst, Ti 0.9Cu 0.1N@Pt/NCNTs, has a Pt mass activity 5 times higher than that of commercial Pt/C, comparable to that of core–shell catalysts with precious metal nanoparticles as the core, and much higher thanmore » that the latter if we take into account the mass activity of all platinum group metals. Furthermore, only a minimal loss of activity can be observed after 10000 potential cycles, demonstrating the catalyst’s high stability. After durability testing, atomic-scale elemental mapping confirmed that the core–shell structure of the catalyst remained intact. This approach may open a pathway for the design and preparation of high-performance inexpensive core–shell catalysts for a wide range of applications in energy conversion processes.« less

Spatially and size selective synthesis of Fe-based nanoparticles on ordered mesoporous supports as highly active and stable catalysts for ammonia decomposition.

PubMed

Lu, An-Hui; Nitz, Joerg-Joachim; Comotti, Massimiliano; Weidenthaler, Claudia; Schlichte, Klaus; Lehmann, Christian W; Terasaki, Osamu; Schüth, Ferdi

2010-10-13

Uniform and highly dispersed γ-Fe(2)O(3) nanoparticles with a diameter of ∼6 nm supported on CMK-5 carbons and C/SBA-15 composites were prepared via simple impregnation and thermal treatment. The nanostructures of these materials were characterized by XRD, Mössbauer spectroscopy, XPS, SEM, TEM, and nitrogen sorption. Due to the confinement effect of the mesoporous ordered matrices, γ-Fe(2)O(3) nanoparticles were fully immobilized within the channels of the supports. Even at high Fe-loadings (up to about 12 wt %) on CMK-5 carbon no iron species were detected on the external surface of the carbon support by XPS analysis and electron microscopy. Fe(2)O(3)/CMK-5 showed the highest ammonia decomposition activity of all previously described Fe-based catalysts in this reaction. Complete ammonia decomposition was achieved at 700 °C and space velocities as high as 60,000 cm(3) g(cat)(-1) h(-1). At a space velocity of 7500 cm(3) g(cat)(-1) h(-1), complete ammonia conversion was maintained at 600 °C for 20 h. After the reaction, the immobilized γ-Fe(2)O(3) nanoparticles were found to be converted to much smaller nanoparticles (γ-Fe(2)O(3) and a small fraction of nitride), which were still embedded within the carbon matrix. The Fe(2)O(3)/CMK-5 catalyst is much more active than the benchmark NiO/Al(2)O(3) catalyst at high space velocity, due to its highly developed mesoporosity. γ-Fe(2)O(3) nanoparticles supported on carbon-silica composites are structurally much more stable over extended periods of time but less active than those supported on carbon. TEM observation reveals that iron-based nanoparticles penetrate through the carbon layer and then are anchored on the silica walls, thus preventing them from moving and sintering. In this way, the stability of the carbon-silica catalyst is improved. Comparison with the silica supported iron oxide catalyst reveals that the presence of a thin layer of carbon is essential for increased catalytic activity.

Gold Nanoparticles on Polymer-Wrapped Carbon Nanotubes: An Efficient and Selective Catalyst for the Electroreduction of CO2.

PubMed

Jhong, Huei-Ru Molly; Tornow, Claire E; Kim, Chaerin; Verma, Sumit; Oberst, Justin L; Anderson, Paul S; Gewirth, Andrew A; Fujigaya, Tsuyohiko; Nakashima, Naotoshi; Kenis, Paul J A

2017-11-17

Multiple approaches will be needed to reduce the atmospheric CO 2 levels, which have been linked to the undesirable effects of global climate change. The electroreduction of CO 2 driven by renewable energy is one approach to reduce CO 2 emissions while producing chemical building blocks, but current electrocatalysts exhibit low activity and selectivity. Here, we report the structural and electrochemical characterization of a promising catalyst for the electroreduction of CO 2 to CO: Au nanoparticles supported on polymer-wrapped multiwall carbon nanotubes. This catalyst exhibits high selectivity for CO over H 2 : 80-92 % CO, as well as high activity: partial current density for CO as high as 160 mA cm -2 . The observed high activity, originating from a high electrochemically active surface area (23 m 2  g -1 Au), in combination with the low loading (0.17 mg cm -2 ) of the highly dispersed Au nanoparticles underscores the promise of this catalyst for efficient electroreduction of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unique properties of ceria nanoparticles supported on metals: novel inverse ceria/copper catalysts for CO oxidation and the water-gas shift reaction.

PubMed

Senanayake, Sanjaya D; Stacchiola, Dario; Rodriguez, Jose A

2013-08-20

Oxides play a central role in important industrial processes, including applications such as the production of renewable energy, remediation of environmental pollutants, and the synthesis of fine chemicals. They were originally used as catalyst supports and were thought to be chemically inert, but now they are used to build catalysts tailored toward improved selectivity and activity in chemical reactions. Many studies have compared the morphological, electronic, and chemical properties of oxide materials with those of unoxidized metals. Researchers know much less about the properties of oxides at the nanoscale, which display distinct behavior from their bulk counterparts. More is known about metal nanoparticles. Inverse-model catalysts, composed of oxide nanoparticles supported on metal or oxide substrates instead of the reverse (oxides supporting metal nanoparticles), are excellent tools for systematically testing the properties of novel catalytic oxide materials. Inverse models are prepared in situ and can be studied with a variety of surface science tools (e.g. scanning tunneling microscopy, X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, low-energy electron microscopy) and theoretical tools (e.g. density functional theory). Meanwhile, their catalytic activity can be tested simultaneously in a reactor. This approach makes it possible to identify specific functions or structures that affect catalyst performance or reaction selectivity. Insights gained from these tests help to tailor powder systems, with the primary objective of rational design (experimental and theoretical) of catalysts for specific chemical reactions. This Account describes the properties of inverse catalysts composed of CeOx nanoparticles supported on Cu(111) or CuOx/Cu(111) as determined through the methods described above. Ceria is an important material for redox chemistry because of its interchangeable oxidation states (Ce⁴⁺ and Ce³⁺). Cu(111), meanwhile, is

WO3 Nanofiber-Based Biomarker Detectors Enabled by Protein-Encapsulated Catalyst Self-Assembled on Polystyrene Colloid Templates.

PubMed

Choi, Seon-Jin; Kim, Sang-Joon; Cho, Hee-Jin; Jang, Ji-Soo; Lin, Yi-Min; Tuller, Harry L; Rutledge, Gregory C; Kim, Il-Doo

2016-02-17

A novel catalyst functionalization method, based on protein-encapsulated metallic nanoparticles (NPs) and their self-assembly on polystyrene (PS) colloid templates, is used to form catalyst-loaded porous WO3 nanofibers (NFs). The metallic NPs, composed of Au, Pd, or Pt, are encapsulated within a protein cage, i.e., apoferritin, to form unagglomerated monodispersed particles with diameters of less than 5 nm. The catalytic NPs maintain their nanoscale size, even following high-temperature heat-treatment during synthesis, which is attributed to the discrete self-assembly of NPs on PS colloid templates. In addition, the PS templates generate open pores on the electrospun WO3 NFs, facilitating gas molecule transport into the sensing layers and promoting active surface reactions. As a result, the Au and Pd NP-loaded porous WO3 NFs show superior sensitivity toward hydrogen sulfide, as evidenced by responses (R(air)/R(gas)) of 11.1 and 43.5 at 350 °C, respectively. These responses represent 1.8- and 7.1-fold improvements compared to that of dense WO3 NFs (R(air)/R(gas) = 6.1). Moreover, Pt NP-loaded porous WO3 NFs exhibit high acetone sensitivity with response of 28.9. These results demonstrate a novel catalyst loading method, in which small NPs are well-dispersed within the pores of WO3 NFs, that is applicable to high sensitivity breath sensors. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalyst design for enhanced sustainability through fundamental surface chemistry.

PubMed

Personick, Michelle L; Montemore, Matthew M; Kaxiras, Efthimios; Madix, Robert J; Biener, Juergen; Friend, Cynthia M

2016-02-28

Decreasing energy consumption in the production of platform chemicals is necessary to improve the sustainability of the chemical industry, which is the largest consumer of delivered energy. The majority of industrial chemical transformations rely on catalysts, and therefore designing new materials that catalyse the production of important chemicals via more selective and energy-efficient processes is a promising pathway to reducing energy use by the chemical industry. Efficiently designing new catalysts benefits from an integrated approach involving fundamental experimental studies and theoretical modelling in addition to evaluation of materials under working catalytic conditions. In this review, we outline this approach in the context of a particular catalyst-nanoporous gold (npAu)-which is an unsupported, dilute AgAu alloy catalyst that is highly active for the selective oxidative transformation of alcohols. Fundamental surface science studies on Au single crystals and AgAu thin-film alloys in combination with theoretical modelling were used to identify the principles which define the reactivity of npAu and subsequently enabled prediction of new reactive pathways on this material. Specifically, weak van der Waals interactions are key to the selectivity of Au materials, including npAu. We also briefly describe other systems in which this integrated approach was applied. © 2016 The Author(s).

Poly(ethylene glycol) stabilized Co nanoparticles as highly active and selective catalysts for the Pauson-Khand reaction.

PubMed

Muller, Jean-Luc; Klankermayer, Jürgen; Leitner, Walter

2007-05-21

PEG-stabilized cobalt nanoparticles were prepared by thermal decomoposition of [Co2(CO)8] in PEG and were shown to be highly active and selective catalysts, for intra- and intermolecular Pauson-Khand reactions (PKR), in organic solvents or aqueous media.

Design of Highly Selective Platinum Nanoparticle Catalysts for the Aerobic Oxidation of KA-Oil using Continuous-Flow Chemistry.

PubMed

Gill, Arran M; Hinde, Christopher S; Leary, Rowan K; Potter, Matthew E; Jouve, Andrea; Wells, Peter P; Midgley, Paul A; Thomas, John M; Raja, Robert

2016-03-08

Highly active and selective aerobic oxidation of KA-oil to cyclohexanone (precursor for adipic acid and ɛ-caprolactam) has been achieved in high yields using continuous-flow chemistry by utilizing uncapped noble-metal (Au, Pt & Pd) nanoparticle catalysts. These are prepared using a one-step in situ methodology, within three-dimensional porous molecular architectures, to afford robust heterogeneous catalysts. Detailed spectroscopic characterization of the nature of the active sites at the molecular level, coupled with aberration-corrected scanning transmission electron microscopy, reveals that the synthetic methodology and associated activation procedures play a vital role in regulating the morphology, shape and size of the metal nanoparticles. These active centers have a profound influence on the activation of molecular oxygen for selective catalytic oxidations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A hybrid biocatalyst consisting of silver nanoparticle and naphthalenethiol self-assembled monolayer prepared for anchoring glucose oxidase and its use for an enzymatic biofuel cell

NASA Astrophysics Data System (ADS)

Christwardana, Marcelinus; Kim, Do-Heyoung; Chung, Yongjin; Kwon, Yongchai

2018-01-01

A novel hybrid biocatalyst is synthesized by the enzyme composite consisting of silver nanoparticle (AgNP), naphthalene-thiol based couplers (Naph-SH) and glucose oxidase (GOx), which is then bonded with the supporter consisting of polyethyleneimine (PEI) and carbon nanotube (CNT) (CNT/PEI/AgNPs/Naph-SH/GOx) to facilitate glucose oxidation reaction (GOR). Here, the AgNPs play a role in obstructing denaturation of the GOx molecules from the supporter because of Ag-thiol bond, while the PEIs have the AgNPs keep their states without getting ionized by hydrogen peroxide produced during anodic reaction. The Naph-SHs also prevent ionization of the AgNP by forming self-assembled monolayer on their surface. Such roles of each component enable the catalyst to form (i) hydrophobic interaction between the GOx molecules and supporter and (ii) π-conjugated electron pathway between the GOx molecules and AgNP, promoting electron transfer. Catalytic nature of the catalyst is characterized by measuring catalytic activity and performance of enzymatic biofuel cell (EBC) using the catalyst. Regarding the catalytic activity, the catalyst leads to high electron transfer rate constant (9.6 ± 0.4 s-1), low Michaelis-Menten constant (0.51 ± 0.04 mM), and low charge transfer resistance (7.3 Ω cm2) and high amount of immobilized GOx (54.6%), while regarding the EBC performance, high maximum power density (1.46 ± 0.07 mW cm-2) with superior long-term stability result are observed.

Synthesis-atomic structure-properties relationships in metallic nanoparticles by total scattering experiments and 3D computer simulations: case of Pt-Ru nanoalloy catalysts

NASA Astrophysics Data System (ADS)

Prasai, Binay; Ren, Yang; Shan, Shiyao; Zhao, Yinguang; Cronk, Hannah; Luo, Jin; Zhong, Chuan-Jian; Petkov, Valeri

2015-04-01

An approach to determining the 3D atomic structure of metallic nanoparticles (NPs) in fine detail and using the unique knowledge obtained for rationalizing their synthesis and properties targeted for optimization is described and exemplified on Pt-Ru alloy NPs of importance to the development of devices for clean energy conversion such as fuel cells. In particular, PtxRu100-x alloy NPs, where x = 31, 49 and 75, are synthesized by wet chemistry and activated catalytically by a post-synthesis treatment involving heating under controlled N2-H2 atmosphere. So-activated NPs are evaluated as catalysts for gas-phase CO oxidation and ethanol electro-oxidation reactions taking place in fuel cells. Both as-synthesized and activated NPs are characterized structurally by total scattering experiments involving high-energy synchrotron X-ray diffraction coupled to atomic pair distribution functions (PDFs) analysis. 3D structure models both for as-synthesized and activated NPs are built by molecular dynamics simulations based on the archetypal for current theoretical modelling Sutton-Chen method. Models are refined against the experimental PDF data by reverse Monte Carlo simulations and analysed in terms of prime structural characteristics such as metal-to-metal bond lengths, bond angles and first coordination numbers for Pt and Ru atoms. Analysis indicates that, though of a similar type, the atomic structure of as-synthesized and respective activated NPs differ in several details of importance to NP catalytic properties. Structural characteristics of activated NPs and data for their catalytic activity are compared side by side and strong evidence found that electronic effects, indicated by significant changes in Pt-Pt and Ru-Ru metal bond lengths at NP surface, and practically unrecognized so far atomic ensemble effects, indicated by distinct stacking of atomic layers near NP surface and prevalence of particular configurations of Pt and Ru atoms in these layers, contribute to the

A rational design approach to nanostructured catalysts for the oxidation of carbon monoxide

NASA Astrophysics Data System (ADS)

Karwacki, Christopher

The extraordinary energetic properties of subnanometer (<10 nm) structures consisting of reduced metals, metal oxides, and graphitic carbons are emerging as the principal technologies involving catalytic reactions at ambient temperatures, for such applications as respiratory protection, pollution abatement, chemical synthesis, sensors, and energy conversion. Gold nanoparticles (Au NP) possess unique reactive properties not present in the bulk state and have served in the past decade as a model for the nanosciences, where molecular species are synthesized, scaled, and engineered into functional materials. Gold nanoparticles as isolated structures are not useful as real catalysts and must co-exist with supports that provide enhanced stability and activity. Support oxides such as TiO2, Fe2O 3, CeO2, SiO2, Al2O3, ZrO 2, and graphitic (active) carbons have been shown to increase the active nature of AuNP and have been the subject of several thousand publications in the past decade. Zirconia compared to titania as a support for Au NP catalysis has been studied with limited success. In fact, the majority of observations show that zirconia is one of the lowest performing metal oxide supports involving Au NP oxidation catalysis. The likely reason for these observations is a lack of understanding of the relationship between structure and surface functionality as it pertains to ambient temperature oxidation catalysis (ATOC). Furthermore, virtually all substrate and catalyst preparations in earlier work were performed at high temperatures, typically 400--900°C, thus forming progressively monomorphic structures containing larger crystals with reduced surface functionality and porosity. In this research, I established the hypothesis based on a structural model that surface functional hydroxides are important to sustained hydrolytic reactions, such as those involving Au NP for the oxidation of CO to CO 2. Theoretical calculations by Ignatchenko, Vittadini, et al. show that

High Catalytic Efficiency of Nanostructured β-CoMoO₄ in the Reduction of the Ortho-, Meta- and Para-Nitrophenol Isomers.

PubMed

Al-Wadaani, Fahd; Omer, Ahmed; Abboudi, Mostafa; Oudghiri Hassani, Hicham; Rakass, Souad; Messali, Mouslim; Benaissa, Mohammed

2018-02-09

Nanostructured β-CoMoO₄ catalysts have been prepared via the thermal decomposition of an oxalate precursor. The catalyst was characterized by infrared spectroscopy (FTIR), X-ray diffraction (XRD), Brunauer-Emmett-Teller method (BET), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM). The efficiency of these nanoparticles in the reduction of ortho - and meta -nitrophenol isomers (2-NP, 3-NP, and 4-NP) to their corresponding aminophenols was tested using UV-visible spectroscopy measurements. It was found that, with a β-CoMoO₄ catalyst, NaBH₄ reduces 3-NP instantaneously, whilst the reduction of 2-NP and 4-NP is slower at 8 min. This difference is thought to arise from the lower acidity of 3-NP, where the negative charge of the phenolate could not be delocalized onto the oxygen atoms of the meta-nitro group.

Resin-Immobilized Palladium Nanoparticle Catalysts for Organic Reactions in Aqueous Media: Morphological Aspects.

PubMed

Mastrorilli, Piero; Dell'Anna, Maria M; Rizzuti, Antonino; Mali, Matilda; Zapparoli, Mauro; Leonelli, Cristina

2015-10-14

An insight into the nano- and micro-structural morphology of a polymer supported Pd catalyst employed in different catalytic reactions under green conditions is reported. The pre-catalyst was obtained by copolymerization of the metal-containing monomer Pd(AAEMA)₂ [AAEMA-=deprotonated form of 2-(acetoacetoxy) ethyl methacrylate] with ethyl methacrylate as co-monomer, and ethylene glycol dimethacrylate as cross-linker. This material was used in water for the Suzuki-Miyaura cross-coupling of aryl bromides, and for the reduction of nitroarenes and quinolines using NaBH₄ or H₂, as reductants. TEM analyses showed that in all cases the pristine Pd(II) species were reduced in situ to Pd(0), which formed metal nanoparticles (NPs, the real active species). The dependence of their average size (2-10 nm) and morphology on different parameters (temperature, reducing agent, presence of a phase transfer agent) is discussed. TEM and micro-IR analyses showed that the polymeric support retained its porosity and stability for several catalytic cycles in all reactions and Pd NPs did not aggregate after reuse. The metal nanoparticle distribution throughout the polymer matrix after several recycles provided precious information about the catalytic mechanism, which was truly heterogeneous in the hydrogenation reactions and of the so-called "release and catch" type in the Suzuki coupling.

Eco-friendly approach for nanoparticles synthesis and mechanism behind antibacterial activity of silver and anticancer activity of gold nanoparticles.

PubMed

Patil, Maheshkumar Prakash; Kim, Gun-Do

2017-01-01

This review covers general information about the eco-friendly process for the synthesis of silver nanoparticles (AgNP) and gold nanoparticles (AuNP) and focuses on mechanism of the antibacterial activity of AgNPs and the anticancer activity of AuNPs. Biomolecules in the plant extract are involved in reduction of metal ions to nanoparticle in a one-step and eco-friendly synthesis process. Natural plant extracts contain wide range of metabolites including carbohydrates, alkaloids, terpenoids, phenolic compounds, and enzymes. A variety of plant species and plant parts have been successfully extracted and utilized for AgNP and AuNP syntheses. Green-synthesized nanoparticles eliminate the need for a stabilizing and capping agent and show shape and size-dependent biological activities. Here, we describe some of the plant extracts involved in nanoparticle synthesis, characterization methods, and biological applications. Nanoparticles are important in the field of pharmaceuticals for their strong antibacterial and anticancer activity. Considering the importance and uniqueness of this concept, the synthesis, characterization, and application of AgNPs and AuNPs are discussed in this review.

Effect of catalyst concentration on size, morphology and optical properties of silica nanoparticles

NASA Astrophysics Data System (ADS)

Arora, Ekta; Ritu, Kumar, Sacheen; Kumar, Dinesh

2016-05-01

Today, nanomaterials play a key role in various fields such as electronics, aerospace, pharmaceuticals and biomedical because of their unique physical, chemical and biological properties which are different from bulk materials. Nano sized silica particles have gained the prominent position in scientific research and have wide applications. The sol-gel method is the best method to synthesize silica nanoparticles because of its potential to produce monodispersed with narrow size distribution at mild conditions. The silica nanoparticles were obtained by hydrolysis of tetraethyl orthosilicate (TEOS) in ethanol act as solvent. The synthesized nanoparticles were characterized by Field Emission Scanning electron Microscope (FE-SEM), UV Spectrometer. The smallest size of silica particles is around 150nm examined by using FE-SEM. The optical properties and band structure was analyzed using UV-visible spectroscopy which is found to be increase by reducing the size of particles. Concentration effect of catalyst on the size, morphology and optical properties were analyzed.

Effect of catalyst concentration on size, morphology and optical properties of silica nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arora, Ekta; Ritu,; Kumar, Sacheen, E-mail: sacheen3@gmail.com

2016-05-06

Today, nanomaterials play a key role in various fields such as electronics, aerospace, pharmaceuticals and biomedical because of their unique physical, chemical and biological properties which are different from bulk materials. Nano sized silica particles have gained the prominent position in scientific research and have wide applications. The sol-gel method is the best method to synthesize silica nanoparticles because of its potential to produce monodispersed with narrow size distribution at mild conditions. The silica nanoparticles were obtained by hydrolysis of tetraethyl orthosilicate (TEOS) in ethanol act as solvent. The synthesized nanoparticles were characterized by Field Emission Scanning electron Microscope (FE-SEM),more » UV Spectrometer. The smallest size of silica particles is around 150nm examined by using FE-SEM. The optical properties and band structure was analyzed using UV-visible spectroscopy which is found to be increase by reducing the size of particles. Concentration effect of catalyst on the size, morphology and optical properties were analyzed.« less

Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts.

PubMed

Liang, Miao; Wang, Libing; Liu, Xia; Qi, Wei; Su, Rongxin; Huang, Renliang; Yu, Yanjun; He, Zhimin

2013-06-21

Bio-nanomaterials fabricated using a bioinspired templating technique represent a novel class of composite materials with diverse applications in biomedical, electronic devices, drug delivery, and catalysis. In this study, Au nanoparticles (NPs) are synthesized within the solvent channels of cross-linked lysozyme crystals (CLLCs) in situ without the introduction of extra chemical reagents or physical treatments. The as-prepared AuNPs-in-protein crystal hybrid materials are characterized by light microscopy, transmission electron microscopy, x-ray diffraction, and Fourier-transform infrared spectroscopy analyses. Small AuNPs with narrow size distribution reveal the restriction effects of the porous structure in the lysozyme crystals. These composite materials are proven to be active heterogeneous catalysts for the reduction of 4-nitrophenol to 4-aminophenol. These catalysts can be easily recovered and reused at least 20 times because of the physical stability and macro-dimension of CLLCs. This work is the first to use CLLCs as a solid biotemplate for the preparation of recyclable high-performance catalysts.

Cross-linked lysozyme crystal templated synthesis of Au nanoparticles as high-performance recyclable catalysts

NASA Astrophysics Data System (ADS)

Liang, Miao; Wang, Libing; Liu, Xia; Qi, Wei; Su, Rongxin; Huang, Renliang; Yu, Yanjun; He, Zhimin

2013-06-01

Bio-nanomaterials fabricated using a bioinspired templating technique represent a novel class of composite materials with diverse applications in biomedical, electronic devices, drug delivery, and catalysis. In this study, Au nanoparticles (NPs) are synthesized within the solvent channels of cross-linked lysozyme crystals (CLLCs) in situ without the introduction of extra chemical reagents or physical treatments. The as-prepared AuNPs-in-protein crystal hybrid materials are characterized by light microscopy, transmission electron microscopy, x-ray diffraction, and Fourier-transform infrared spectroscopy analyses. Small AuNPs with narrow size distribution reveal the restriction effects of the porous structure in the lysozyme crystals. These composite materials are proven to be active heterogeneous catalysts for the reduction of 4-nitrophenol to 4-aminophenol. These catalysts can be easily recovered and reused at least 20 times because of the physical stability and macro-dimension of CLLCs. This work is the first to use CLLCs as a solid biotemplate for the preparation of recyclable high-performance catalysts.

Screening of cyanobacterial extracts for synthesis of silver nanoparticles.

PubMed

Husain, Shaheen; Sardar, Meryam; Fatma, Tasneem

2015-08-01

Improvement of reliable and eco-friendly process for synthesis of metallic nanoparticles is a significant step in the field of application nanotechnology. One approach that shows vast potential is based on the biosynthesis of nanoparticles using micro-organisms. In this study, biosynthesis of silver nanoparticles (AgNP) using 30 cyanobacteria were investigated. Cyanobacterial aqueous extracts were subjected to AgNP synthesis at 30 °C. Scanning of these aqueous extracts containing AgNP in UV-Visible range showed single peak. The λ max for different extracts varied and ranged between 440 and 490 nm that correspond to the "plasmon absorbance" of AgNP. Micrographs from scanning electron microscope of AgNP from cyanobacterial extracts showed that though synthesis of nanoparticles occurred in all strains but their reaction time, shape and size varied. Majority of the nanoparticles were spherical. Time taken for induction of nanoparticles synthesis by cyanobacterial extracts ranged from 30 to 360 h and their size from 38 to 88 nm. In terms of size Cylindrospermum stagnale NCCU-104 was the best organism with 38 and 40 nm. But in terms of time Microcheate sp. NCCU-342 was the best organism as it took 30 h for AgNP synthesis.

A facile construction of Au nanoparticles stabilized by thermo-responsive polymer-tethered carbon dots for enhanced catalytic performance

NASA Astrophysics Data System (ADS)

Li, Li; Zhang, Tianyi; Lü, Jianhua; Lü, Changli

2018-10-01

Carbon dots (CDs), the youngest member in the carbon nanomaterial family, have drawn considerable attention due to their interesting optical, physicochemical and electronic properties as well as broad promising applications. Here, we developed a facile and effective strategy for the preparation of Au nanoparticles stabilized by thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) functionalized carbon dots (Au@CD@P) under the gentle water media. The as-designed dopamine(DA)-terminated PNIPAM can be easily anchored to CDs via mussel-inspired chemistry route. Both CD@P and CDs could well stabilize the Au nanoparticles with interesting assembled structure. The as-prepared Au@CD and Au@CD@P nanohybrids with good dispersibility and stability exhibited the intriguing catalytic activity for reduction of p-nitrophenol (p-NP). Especially, Au@CD@P as catalyst also played a switching role in regulating the catalytic rate by temperature. In addition, Au@CD@P exhibited excellent recyclability which may have potential in green chemical industry for developing high-activity catalysts and easy production methods.

Evaluating differences in the active-site electronics of supported Au nanoparticle catalysts using Hammett and DFT studies

NASA Astrophysics Data System (ADS)

Kumar, Gaurav; Tibbitts, Luke; Newell, Jaclyn; Panthi, Basu; Mukhopadhyay, Ahana; Rioux, Robert M.; Pursell, Christopher J.; Janik, Michael; Chandler, Bert D.

2018-03-01

Supported metal catalysts, which are composed of metal nanoparticles dispersed on metal oxides or other high-surface-area materials, are ubiquitous in industrially catalysed reactions. Identifying and characterizing the catalytic active sites on these materials still remains a substantial challenge, even though it is required to guide rational design of practical heterogeneous catalysts. Metal-support interactions have an enormous impact on the chemistry of the catalytic active site and can determine the optimum support for a reaction; however, few direct probes of these interactions are available. Here we show how benzyl alcohol oxidation Hammett studies can be used to characterize differences in the catalytic activity of Au nanoparticles hosted on various metal-oxide supports. We combine reactivity analysis with density functional theory calculations to demonstrate that the slope of experimental Hammett plots is affected by electron donation from the underlying oxide support to the Au particles.

Chitosan based polymer matrix with silver nanoparticles decorated multiwalled carbon nanotubes for catalytic reduction of 4-nitrophenol.

PubMed

Alshehri, Saad M; Almuqati, Turki; Almuqati, Naif; Al-Farraj, Eida; Alhokbany, Norah; Ahamad, Tansir

2016-10-20

A novel catalyst for the reduction of 4-nitrophenol (4-NP) was prepared using carboxyl group-functionalized multiwalled carbon nanotubes (MWCNTs), polymer matrix, and silver nanoparticles (AgNPs). The AgNPs were prepared by the reduction of silver nitrate by trisodium citrate in the MWCNTs-polymer nanocomposite; the size of the synthesized AgNPs was found to be 3nm (average diameter). The synthesized nanocomposites were characterized using several analytical techniques. Ag@MWCNTs-polymer composite in the presence of sodium borohydride (NaBH4) in aqueous solution is an effective catalyst for the reduction of 4-NP. The apparent kinetics of reduction has a pseudo-first-order kinetics, and the rate constant and catalytic activity parameter were found to be respectively 7.88×10(-3)s(-1)and 11.64s(-1)g(-1). The MWCNTs-polymer nanocomposite renders stability to AgNPs against the environment and the reaction medium, which means that the Ag@MWCNTs-polymer composite can be re-used for many catalytic cycles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Comparison of the toxicity of silver, gold and platinum nanoparticles in developing zebrafish embryos.

PubMed

Asharani, P V; Lianwu, Yi; Gong, Zhiyuan; Valiyaveettil, Suresh

2011-03-01

Nanoparticles have diverse applications in electronics, medical devices, therapeutic agents and cosmetics. While the commercialization of nanoparticles is rapidly expanding, their health and environmental impact is not well understood. Toxicity assays of silver, gold, and platinum nanoparticles, using zebrafish embryos to study their developmental effects were carried out. Gold (Au-NP, 15-35 nm), silver (Ag-NP, 5-35 nm) and platinum nanoparticles (Pt-NP, 3-10 nm) were synthesized using polyvinyl alcohol (PVA) as a capping agent. Toxicity was recorded in terms of mortality, hatching delay, phenotypic defects and metal accumulation. The addition of Ag-NP resulted in a concentration-dependant increase in mortality rate. Both Ag-NP and Pt-NP induced hatching delays, as well as a concentration dependant drop in heart rate, touch response and axis curvatures. Ag-NP also induced other significant phenotypic changes including pericardial effusion, abnormal cardiac morphology, circulatory defects and absence or malformation of the eyes. In contrast, Au-NP did not show any indication of toxicity. Uptake and accumulation of nanoparticles in embryos was confirmed by inductively coupled plasma optical emission spectroscopy (ICP-OES), which revealed detectable levels in embryos within 72 hpf. Ag-NP and Au-NP were taken up by the embryos in relatively equal amounts whereas lower Pt concentrations were observed in embryos exposed to Pt-NP. This was probably due to the small size of the Pt nanoparticles compared to Ag-NP and Au-NP, thus resulting in fewer metal atoms being retained in the embryos. Among the nanoparticles studied, Ag-NPs were found to be the most toxic and Au-NPs the non-toxic. The toxic effects exhibited by the zebrafish embryos as a consequence of nanoparticle exposure, accompanied by the accumulation of metals inside the body calls for urgent further investigations in this field.

Synthesis, characterization and optimization of platinum-alloy nanoparticle catalysts in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Srivastava, Ratndeep

Renewable hydrogen-fuelled proton exchange membrane (PEMFC) fuel cells have consistently demonstrated great promise as a future source of energy due to their high conversion efficiency, lower temperature of operation and lack of greenhouse emissions. One of the major impediments in the commercialization of polymer electrolyte membrane fuel cells is the insufficient catalytic reactivity and higher cost of Pt electrocatalysts which are utilized for the electroreduction of oxygen from air. This dissertation focuses primarily on a family of Pt alloy fuel cell electrocatalysts referred to as de-alloyed core-shell electrocatalysts. These materials are bimetallic or multimetallic nanoparticles, mostly supported on conductive supports which were first described in a dissertation by Dr. S. Koh earlier in 2009.1 De-alloyed Pt nanoparticle electrocatalysts are formed from base metal rich binary Pt-M and ternary Pt-M1-M 2 (M, M1, M2 = Cu, Co, Ni, Fe and Cr) alloy nanoparticle precursors. The precursors are transformed and activated by electrochemical selective dissolution of the less noble metal component of the precursors (de-alloying). They have shown exceptional activity for oxygen reduction reaction (ORR) in idealized electrochemical half cell measurements, in particular rotating disk electrode experiments. However, these materials were never tested or implemented in realistic Membrane Electrode Assemblies (MEA) and single PEM fuel cells. The objective of this work was to implement de-alloyed Pt particle catalysts in realistic fuel cell electrode layers as well as a detailed characterization of their behavior and stability. The major challenges of MEA implementation consists of the behavior of the new nanostructured electrocatalysts inside the complex three-phase interface of polymer membrane ionomer, liquid water, metal catalyst, support, and reactant gas. Activity measurements were followed by medium and long-term durability analysis by potential cycling of the membrane

Nitrogen–doped graphitized carbon shell encapsulated NiFe nanoparticles: A highly durable oxygen evolution catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Lei; Luo, Langli; Feng, Zhenxing

Oxygen evolution reaction (OER) plays a crucial role in various energy conversion devices such as water electrolyzers and metal–air batteries. Precious metal catalysts such as Ir, Ru and their oxides are usually used for enhancing reaction kinetics but are limited by their scarce resource. The challenges associated with alternative non–precious metal catalysts such as transition metal oxides and (oxy)hydroxides etc. are their low electronic conductivity and durability. Herein, we report a highly active (360 mV overpotential at 10 mA cm–2GEO) and durable (no degradation after 20000 cycles) OER catalyst derived from bimetallic metal–organic frameworks (MOFs) precursors. This catalyst consists ofmore » NiFe nanoparticles encapsulated by nitrogen–doped graphitized carbon shells. The electron-donation/deviation from Fe and tuned electronic structure of metal cores by Ni are revealed to be primary contributors to the enhanced OER activity, whereas N concentration contributes negligibly. We further demonstrated that the structure and morphology of encapsulating carbon shells, which are the key factors influencing the durability, are facilely controlled by the chemical state of precursors.« less

Distinguishing molecular environments in supported Pt catalysts and their influences on activity and selectivity

NASA Astrophysics Data System (ADS)

Jones, Louis Chin

This thesis entails the synthesis, automated catalytic testing, and in situ molecular characterization of supported Pt and Pt-alloy nanoparticle (NP) catalysts, with emphasis on how to assess the molecular distributions of Pt environments that are affecting overall catalytic activity and selectivity. We have taken the approach of (a) manipulating nucleation and growth of NPs using oxide supports, surfactants, and inorganic complexes to create Pt NPs with uniform size, shape, and composition, (b) automating batch and continuous flow catalytic reaction tests, and (c) characterizing the molecular environments of Pt surfaces using in situ infrared (IR) spectroscopy and solid-state 195Pt NMR. The following will highlight the synthesis and characterization of Ag-doped Pt NPs and their influence on C 2H2 hydrogenation selectivity, and the implementation of advanced solid-state 195Pt NMR techniques to distinguish how distributions of molecular Pt environments vary with nanoparticle size, support, and surface composition.

The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds.

PubMed

Kelsen, Vinciane; Wendt, Bianca; Werkmeister, Svenja; Junge, Kathrin; Beller, Matthias; Chaudret, Bruno

2013-04-28

The performance of well-defined ultrasmall iron(0) nanoparticles (NPs) as catalysts for the selective hydrogenation of unsaturated C-C and C=X bonds is reported. Monodisperse iron nanoparticles of about 2 nm size are synthesized by the decomposition of {Fe(N[Si(CH3)3]2)2}2 under dihydrogen. They are found to be active for the hydrogenation of various alkenes and alkynes under mild conditions and weakly active for C=O bond hydrogenation.

In situ generation of highly dispersed metal nanoparticles on two-dimensional layered SiO2 by topotactic structure conversion and their superior catalytic activity

NASA Astrophysics Data System (ADS)

Chen, Zhe; Jia, Da-Shuang; Zhou, Yue; Hao, Jiang; Liang, Yu; Cui, Zhi-Min; Song, Wei-Guo

2018-03-01

Metal nanoparticles such as Ag, Cu and Fe are effective catalysts for many reactions, whereas a facile method to prepare metal nanoparticles with high uniformed dispersion is still desirable. Herein, the topotactic structure conversion of layered silicate, RUB-15, was utilized to support metal nanoparticles. Through simple ion-exchange and following calcination step, metal nanoparticles were generated in situ inside the interlayer space of layered silica, and the topotactic structure conversion process assured nano-sized and highly uniformed dispersion of metal nanoparticles. The obtained Ag/SiO2 composite showed superior catalytic activity for the reduction of 4-nitrophenol (4-NP) and methylene blue (MB), with a rate constant as high as 0.0607 s-1 and 0.0778 s-1. The simple and universal synthesis method as well as high activity of the product composite endow the strategy good application prospect.

Unconventional route to encapsulated ultrasmall gold nanoparticles for high-temperature catalysis.

PubMed

Zhang, Tingting; Zhao, Hongyu; He, Shengnan; Liu, Kai; Liu, Hongyang; Yin, Yadong; Gao, Chuanbo

2014-07-22

Ultrasmall gold nanoparticles (us-AuNPs, <3 nm) have been recently recognized as surprisingly active and extraordinarily effective green catalysts. Their stability against sintering during reactions, however, remains a serious issue for practical applications. Encapsulating such small nanoparticles in a layer of porous silica can dramatically enhance the stability, but it has been extremely difficult to achieve using conventional sol-gel coating methods due to the weak metal/oxide affinity. In this work, we address this challenge by developing an effective protocol for the synthesis of us-AuNP@SiO2 single-core/shell nanospheres. More specifically, we take an alternative route by starting with ultrasmall gold hydroxide nanoparticles, which have excellent affinity to silica, then carrying out controllable silica coating in reverse micelles, and finally converting gold hydroxide particles into well-protected us-AuNPs. With a single-core/shell configuration that prevents sintering of nearby us-AuNPs and amino group modification of the Au/SiO2 interface that provides additional coordinating interactions, the resulting us-AuNP@SiO2 nanospheres are highly stable at high temperatures and show high activity in catalytic CO oxidation reactions. A dramatic and continuous increase in the catalytic activity has been observed when the size of the us-AuNPs decreases from 2.3 to 1.5 nm, which reflects the intrinsic size effect of the Au nanoparticles on an inert support. The synthesis scheme described in this work is believed to be extendable to many other ultrasmall metal@oxide nanostructures for much broader catalytic applications.

Supramolecular Hydrogel from Nanoparticles and Cyclodextrins for Local and Sustained Nanoparticle Delivery.

PubMed

Xu, Shuxin; Yin, Li; Xiang, Yuzhang; Deng, Hongzhang; Deng, Liandong; Fan, Hongxia; Tang, Hua; Zhang, Jianhua; Dong, Anjie

2016-08-01

Injectable and biodegradable supramolecular hydrogel mPECT NP/α-CD(gel) composed of high-concentration nanoparticle dispersion (≤20% W/V) and α-cyclodextrins (α-CD) are prepared by a two-level physical cross-linking using amphiphilic block polymer methoxy poly(ethylene glycol)-b-poly(ε-caprolactone-co-1,4,8-trioxa[4.6]spiro-9-undecanone) (mPECT) and α-CD. The gelation behavior depends on the concentration of nanoparticles and α-CD. The viscoelasticity and shear thinning of mPECT NP/α-CD(gel) are confirmed. In vitro hydrogel erosion is demonstrated to be mainly a concentration-dependent dissociation process with general release of discrete mPECT nanoparticles about 50 nm that can be easily taken up by cells. The in vitro release behavior can be modulated by changing the concentration of nanoparticles or α-CD. In vitro and in vivo cytotoxicity study demonstrates its biocompatibility and biosafety. Gel formation after subcutaneous injection is also confirmed and mPECT NP/α-CD(gel) shows about 2 weeks retention time. This work validates the potential application for this supramolecular hydrogel in local and sustained delivery of nanoparticles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Halloysite nanotube supported Ag nanoparticles heteroarchitectures as catalysts for polymerization of alkylsilanes to superhydrophobic silanol/siloxane composite microspheres.

PubMed

Li, Cuiping; Li, Xueyuan; Duan, Xuelan; Li, Guangjie; Wang, Jiaqiang

2014-12-15

Halloysite nanotube supported Ag nanoparticles heteroarchitectures have been prepared through a very simple electroless plating method. Robust Ag nanocrystals can be reproducibly fabricated by soaking halloysite nanotubes in ethanolic solutions of AgNO3 and butylamine. By simply adjusting the molar ratio of AgNO3 and butylamine, Ag nanoparticles with tunable size and quantity on halloysite nanotube are achieved. It reveals that the Ag nanoparticles are well-dispersed on the surface of halloysite nanotubes. The halloysite nanotube supported Ag nanoparticles heteroarchitectures can serve as active catalysts for the polymerization of an alkylsilane C18H37SiH3 with water to form silanol/siloxane composite microspheres and exhibit interesting superhydrophobicity ascribed to the micro/nanobinary structure. Copyright © 2014 Elsevier Inc. All rights reserved.

Green synthesis of Silver and Gold Nanoparticles for Enhanced catalytic and bactericidal activity

NASA Astrophysics Data System (ADS)

Naraginti, S.; Tiwari, N.; Sivakumar, A.

2017-11-01

A rapid one step green synthetic method using kiwi fruit extract was employed for preparation of silver and gold nanoparticles. The synthesized nanoparticles were successfully used as green catalysts for the reduction of 4-nitrophenol (4-NP) and methylene blue (MB). They also exhibited excellent antimicrobial activity against clinically isolated Pseudomonas aeruginosa (P.aeruginosa) and Staphylococcus aureus (S.aureus). It was noticed that with increase in concentration of the aqueous silver and gold solutions, particle size of the Ag and Au NPS showed increase as evidenced from UV-Visible spectroscopy and TEM micrograph. The method employed for the synthesis required only a few minutes for more than 90% formation of nanoparticles when the temperature was raised to 80°C. It was also noticed that the catalytic activity of nanoparticles depends upon the size of the particles. These nanoparticles were observed to be crystalline from the clear lattice fringes in the transmission electron microscopic (TEM) images, bright circular spots in the selected area electron diffraction (SAED) pattern and peaks in the X-ray diffraction (XRD) pattern. The Fourier-transform infrared (FTIR) spectrum indicated the presence of different functional groups in the biomolecule capping the nanoparticles.

Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 1

NASA Astrophysics Data System (ADS)

Pech-Pech, I. E.; Gervasio, Dominic F.; Godínez-Garcia, A.; Solorza-Feria, O.; Pérez-Robles, J. F.

2015-02-01

Silver (Ag) nanoparticles enriched with platinum (Pt) and palladium (Pd) on their surfaces (Ag@Pt0.1Pd0.1) are supported on Vulcan XC-72 carbon (C) to form a new catalyst (Ag@Pt0.1Pd0.1/C) for the oxygen reduction reaction (ORR) in acid electrolytes. This catalyst is prepared in one pot by reducing Ag and then Pt and Pd metal salts with sodium borohydride in the presence of trisodium citrate then adding XC-72 while applying intense ultrasound. The metallic Ag@Pt0.1Pd0.1 nanoparticles contain 2 weight percent of Pt, are spherical and have an average size less than 10 nm as determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). At the ORR potentials, Ag nanoparticles on carbon (Ag/C) rapidly lose Ag by dissolution and show no more catalytic activity for the ORR than the carbon support, whereas Ag@Pt0.1Pd0.1/C is a stable catalyst and exhibits 1.4 and 1.6 fold greater specific activity, also 3.6 and 2.8 fold greater mass activity for ORR in 0.5 M H2SO4 solution than comparable Pt/C and Pt0.5Pd0.5/C catalysts with the same Pt loading as determined for thin-films of these catalysts on a rotating-disk electrode (TF-RDE). Using silver nanoparticles increases Pt utilization and therefore decreases Pt-loading and cost of a catalyst for a proton exchange membrane fuel cell (PEMFC) electrode.

Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements.

PubMed

Gao, Wenpei; Hood, Zachary D; Chi, Miaofang

2017-04-18

Developing novel catalysts with high efficiency and selectivity is critical for enabling future clean energy conversion technologies. Interfaces in catalyst systems have long been considered the most critical factor in controlling catalytic reaction mechanisms. Interfaces include not only the catalyst surface but also interfaces within catalyst particles and those formed by constructing heterogeneous catalysts. The atomic and electronic structures of catalytic surfaces govern the kinetics of binding and release of reactant molecules from surface atoms. Interfaces within catalysts are introduced to enhance the intrinsic activity and stability of the catalyst by tuning the surface atomic and chemical structures. Examples include interfaces between the core and shell, twin or domain boundaries, or phase boundaries within single catalyst particles. In supported catalyst nanoparticles (NPs), the interface between the metallic NP and support serves as a critical tuning factor for enhancing catalytic activity. Surface electronic structure can be indirectly tuned and catalytically active sites can be increased through the use of supporting oxides. Tuning interfaces in catalyst systems has been identified as an important strategy in the design of novel catalysts. However, the governing principle of how interfaces contribute to catalyst behavior, especially in terms of interactions with intermediates and their stability during electrochemical operation, are largely unknown. This is mainly due to the evolving nature of such interfaces. Small changes in the structural and chemical configuration of these interfaces may result in altering the catalytic performance. These interfacial arrangements evolve continuously during synthesis, processing, use, and even static operation. A technique that can probe the local atomic and electronic interfacial structures with high precision while monitoring the dynamic interfacial behavior in situ is essential for elucidating the role of

Synthesis and Property of Ag(NP)/catechin/Gelatin Nanofiber

NASA Astrophysics Data System (ADS)

Nasir, Muhamad; Apriani, Dita

2017-12-01

Nanomaterial play important role future industry such as for the medical, food, pharmaceutical and cosmetic industry. Ag (NP) and catechin exhibit antibacterial property. Ag(NP) with diameter around 15 nm was synthesis by microwaved method. We have successfully produce Ag(NP)/catechin/gelatin nanofiber composite by electrospinning process. Ag(NP)/catechin/gelatin nanofiber was synthesized by using gelatin from tuna fish, polyethylene oxide (PEO), acetic acid as solvent and silver nanoparticle(NP)/catechin as bioactive component, respectively. Morphology and structure of bioactive catechin-gelatin nanofiber were characterized by scanning electron microscopy (SEM) and fourier transform infrared spectroscopy (FTIR), respectively. SEM analysis showed that morphology of nanofiber composite was smooth and had average diameter 398.97 nm. FTIR analysis results were used to confirm structure of catechin-gelatin nanofiber. It was confirmed by FTIR that specific vibration band peak amide A (N-H) at 3286,209 cm-1, amide B (N-H) 3069,396 cm-1, amide I (C=O) at 1643,813 cm-1, amide II (N-H and CN) at 1538,949 cm-1, amide III (C-N) at 1276,789 cm-1, C-O-C from polyethylene oxide at 1146,418 cm-1, respectively. When examined to S. Aureus bacteria, Ag/catechin/gelatin nanofiber show inhabitation performance around 40.44%. Ag(NP)/catechin/gelatin nanofiber has potential application antibacterial medical application.

Cationic albumin-conjugated pegylated nanoparticles as novel drug carrier for brain delivery.

PubMed

Lu, Wei; Zhang, Yan; Tan, Yu-Zhen; Hu, Kai-Li; Jiang, Xin-Guo; Fu, Shou-Kuan

2005-10-20

In this paper, a novel drug carrier for brain delivery, cationic bovine serum albumin (CBSA) conjugated with poly(ethyleneglycol)-poly(lactide) (PEG-PLA) nanoparticle (CBSA-NP), was developed and its effects were evaluated. The copolymers of methoxy-PEG-PLA and maleimide-PEG-PLA were synthesized by ring opening polymerization of D,L-lactide initiated by methoxy-PEG and maleimide-PEG, respectively, which were applied to prepare pegylated nanoparticles by means of double emulsion and solvent evaporation procedure. Native bovine serum albumin (BSA) was cationized and thiolated, followed by conjugation through the maleimide function located at the distal end of PEG surrounding the nanoparticle's surface. Transmission electron micrograph (TEM) and dynamic light scattering results showed that CBSA-NP had a round and regular shape with a mean diameter around 100 nm. Surface nitrogen was detected by X-ray photoelectron spectroscopy (XPS), and colloidal gold stained around the nanoparticle's surface was visualized in TEM, which proved that CBSA was covalently conjugated onto its surface. To evaluate the effects of brain delivery, BSA conjugated with pegylated nanoparticles (BSA-NP) was used as the control group and 6-coumarin was incorporated into the nanoparticles as the fluorescent probe. The qualitative and quantitative results of CBSA-NP uptake experiment compared with those of BSA-NP showed that rat brain capillary endothelial cells (BCECs) took in much more CBSA-NP than BSA-NP at 37 degrees C, at different concentrations and time incubations. After a dose of 60 mg/kg CBSA-NP or BSA-NP injection in mice caudal vein, fluorescent microscopy of brain coronal sections showed a higher accumulation of CBSA-NP in the lateral ventricle, third ventricle and periventricular region than that of BSA-NP. There was no difference on BCECs' viability between CBSA-conjugated and -unconjugated pegylated nanoparticles. The significant results in vitro and in vivo showed that CBSA-NP was

Bimetallic magnetic PtPd-nanoparticles as efficient catalyst for PAH removal from liquid media

NASA Astrophysics Data System (ADS)

Zanato, A. F. S.; Silva, V. C.; Lima, D. A.; Jacinto, M. J.

2017-11-01

Monometallic Pd- and bimetallic PtPd-nanoparticles supported on a mesoporous magnetic magnetite@silica matrix resembling a core-shell structure (Fe3O4@mSiO2) have been fabricated. The material was characterized by transmission electron microscope (TEM), high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectra (XPS), energy dispersive spectroscopy (EDS) and inductively coupled plasma mass spectrometry (ICP-MS). The catalysts were applied in the removal of anthracene from liquid phase via catalytic hydrogenation. It was found that anthracene as a model compound could be completely converted into the partially hydrogenated species by the monometallic and bimetallic solids. However, during the recycling study the bimetallic material (Fe3O4@mSiO2PtPd-) showed an enhanced activity towards anthracene removal compared with the monometallic materials. A single portion of the PtPd-based catalyst can be used up to 11 times in the hydrogenation of anthracene under mild conditions (6 atm of H2, 75 °C, 20 min). Thanks to the presence of a dense magnetic core, the catalysts were capable of responding to an applied external magnetic field and once the reaction was completed, catalyst/product separation was straightforward.

A Direct Grain-Boundary-Activity Correlation for CO Electroreduction on Cu Nanoparticles

PubMed Central

2016-01-01

Copper catalyzes the electrochemical reduction of CO to valuable C2+ products including ethanol, acetate, propanol, and ethylene. These reactions could be very useful for converting renewable energy into fuels and chemicals, but conventional Cu electrodes are energetically inefficient and have poor selectivity for CO vs H2O reduction. Efforts to design improved catalysts have been impeded by the lack of experimentally validated, quantitative structure–activity relationships. Here we show that CO reduction activity is directly correlated to the density of grain boundaries (GBs) in Cu nanoparticles (NPs). We prepared electrodes of Cu NPs on carbon nanotubes (Cu/CNT) with different average GB densities quantified by transmission electron microscopy. At potentials ranging from −0.3 V to −0.5 V vs the reversible hydrogen electrode, the specific activity for CO reduction to ethanol and acetate was linearly proportional to the fraction of NP surfaces comprised of GB surface terminations. Our results provide a design principle for CO reduction to ethanol and acetate on Cu. GB-rich Cu/CNT electrodes are the first NP catalysts with significant CO reduction activity at moderate overpotential, reaching a mass activity of up to ∼1.5 A per gram of Cu and a Faradaic efficiency >70% at −0.3 V. PMID:27163043

A Direct Grain-Boundary-Activity Correlation for CO Electroreduction on Cu Nanoparticles.

PubMed

Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan; Kanan, Matthew W

2016-03-23

Copper catalyzes the electrochemical reduction of CO to valuable C2+ products including ethanol, acetate, propanol, and ethylene. These reactions could be very useful for converting renewable energy into fuels and chemicals, but conventional Cu electrodes are energetically inefficient and have poor selectivity for CO vs H2O reduction. Efforts to design improved catalysts have been impeded by the lack of experimentally validated, quantitative structure-activity relationships. Here we show that CO reduction activity is directly correlated to the density of grain boundaries (GBs) in Cu nanoparticles (NPs). We prepared electrodes of Cu NPs on carbon nanotubes (Cu/CNT) with different average GB densities quantified by transmission electron microscopy. At potentials ranging from -0.3 V to -0.5 V vs the reversible hydrogen electrode, the specific activity for CO reduction to ethanol and acetate was linearly proportional to the fraction of NP surfaces comprised of GB surface terminations. Our results provide a design principle for CO reduction to ethanol and acetate on Cu. GB-rich Cu/CNT electrodes are the first NP catalysts with significant CO reduction activity at moderate overpotential, reaching a mass activity of up to ∼1.5 A per gram of Cu and a Faradaic efficiency >70% at -0.3 V.

Cobalt-embedded carbon nanofiber derived from a coordination polymer as a highly efficient heterogeneous catalyst for activating oxone in water.

PubMed

Lin, Kun-Yi Andrew; Tong, Wai-Chi; Du, Yunchen

2018-03-01

Carbon fiber (CF) supported cobalt nanoparticles (NPs) are promising catalysts for activating Oxone because carbon is non-metal and earth-abundant, and CF-based catalysts exhibit a high aspect ratio, which affords more accessible and dense catalytic sites. Nevertheless, most of CF-supported catalysts are fabricated by post-synthetic methods, which involve complicated preparations. More importantly, metallic NPs are attached to the outer surface of CF rather than embedded within CF. However, there is still a great demand for developing Co-bearing carbon fibers for Oxone activation via simple and effective methods. Thus, this study proposes to develop a cobalt NP-embedded carbon nanofiber (CCNF) by a simple hydrothermal reaction of Co and nitrilotriacetic acid (NA), followed by one-step carbonization. Owing to the coordinative structure of CoNA, the derivative CCNF exhibits a fibrous carbon matrix embedded with evenly distributed and densely packed Co 3 O 4 and magnetic Co 0 nanoparticles. The fibrous structure, magnetism and embedded Co NPs enable CCNF to be a promising catalyst for Oxone activation. As degradation of Rhodamine B (RhB) is selected as a model reaction, CCNF not only rapidly activates Oxone to fully degrade RhB but also shows a much higher catalytic activity than the most common Oxone activator, Co 3 O 4 . CCNF also exhibits the lowest activation energy than any reported catalysts for Oxone activation to degrade RhB. In addition, CCNF could be re-used to activate Oxone for RhB degradation. These results indicate that CCNF is a conveniently prepared and highly effective fibrous Co/C hybrid material for activating Oxone to oxidize contaminants in water. Copyright © 2017. Published by Elsevier Ltd.

Biodistribution of indocyanine green-loaded nanoparticles with surface modifications of PEG and folic acid.

PubMed

Ma, Ying; Sadoqi, Mostafa; Shao, Jun

2012-10-15

To establish the biodistribution profile of the PLGA nanoparticles with dual surface modifications of PEG and folic acid (FA) in mice xenografted with MDA-MB-231 human breast cancer cells with high expression of folate receptor (FR); and to illustrate that the modified nanoparticles can target the loaded indocyanine green (ICG) to the tumor with high FR expression. ICG-loaded nanoparticles were prepared with PLGA (non-modified nanoparticles, NM-NP) or mPEG-PLGA and FA-PLGA (dual modified nanoparticles, DM-NP). Biodistribution of the ICG-loaded nanoparticles (1.25 mg/kg) after i.v. injection was investigated on athymic mice transplanted with MDA-MB-231 tumor. ICG concentration in plasma from the DM-NP group was significantly (p<0.05) higher than the NM-NP group from 90 min to the end of the study (12 h). After 4 h, the drug concentration in the tumor tissue from the DM-NP started to be significantly (p<0.05) higher than the NM-NP until 12 h. Compared to the NM-NP, the DM-NP increased the AUC(0-12 h) in plasma by 245% and the AUC(0-12 h) in tumor by 194%, while decreased the AUC(0-12 h) in liver by 13%. The accumulation of DM-NP into the tumor was significantly higher than NM-NP due to the long circulation and FR-mediated uptake. Copyright © 2012 Elsevier B.V. All rights reserved.

Development of Molecular Catalysts to Bridge the Gap between Heterogeneous and Homogeneous Catalysts

NASA Astrophysics Data System (ADS)

Ye, Rong

Catalysts, heterogeneous, homogeneous, and enzymatic, are comprised of nanometer-sized inorganic and/or organic components. They share molecular factors including charge, coordination, interatomic distance, bonding, and orientation of catalytically active atoms. By controlling the governing catalytic components and molecular factors, catalytic processes of a multichannel and multiproduct nature could be run in all three catalytic platforms to create unique end-products. Unifying the fields of catalysis is the key to achieving the goal of 100% selectivity in catalysis. Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles - some without homogeneous analogues - for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence and structural uniformity, dendrimers have proven to

ZnO nanoparticles as an efficient, heterogeneous, reusable, and ecofriendly catalyst for four-component one-pot green synthesis of pyranopyrazole derivatives in water.

PubMed

Sachdeva, Harshita; Saroj, Rekha

2013-01-01

An extremely efficient catalytic protocol for the synthesis of a series of pyranopyrazole derivatives developed in a one-pot four-component approach in the presence of ZnO nanoparticles as heterogeneous catalyst using water as a green solvent is reported. Greenness of the process is well instituted as water is exploited both as reaction media and medium for synthesis of catalyst. The ZnO nanoparticles exhibited excellent catalytic activity, and the proposed methodology is capable of providing the desired products in good yield (85-90%) and short reaction time. After reaction course, ZnO nanoparticles can be recycled and reused without any apparent loss of activity which makes this process cost effective and hence ecofriendly. All the synthesized compounds have been characterized on the basis of elemental analysis, IR, ¹H NMR, and ¹³C NMR spectral studies.

Crumpled rGO-supported Pt-Ir bifunctional catalyst prepared by spray pyrolysis for unitized regenerative fuel cells

NASA Astrophysics Data System (ADS)

Kim, In Gyeom; Nah, In Wook; Oh, In-Hwan; Park, Sehkyu

2017-10-01

Three-dimensional (3D) crumpled reduced graphene oxide supported Pt-Ir alloys that served as bifunctional oxygen catalysts for use in untized regenerative fuel cells were synthesized by a facile spray pyrolysis method. Pt-Ir catalysts supported on rGO (Pt-Ir/rGOs) were physically characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) to observe change in composition by heat treatment, alloying, and morphological transition of the catalysts. Their catalytic activities and stabilities for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) conditions were electrochemically investigated using cyclic voltammetry (CV), linear sweep voltammetry (LSV), potential cycling and hold tests on the rotating disk electrode (RDE). Pt-Ir/rGO with no post heat-treatment (Pt-Ir/rGO_NP) showed a lower activity for ORR and OER although metal nanoparticles decorated on the support are relatively small. However, Pt-Ir/rGO showed remarkably enhanced activity following heat treatment, depending on temperature. Pt-Ir/rGO heat-treated at 600 °C after spray pyrolysis (Pt-Ir/rGO_P600) exhibited a higher activity and stability than a commercially available Pt/C catalyst kept under the ORR condition, and it also revealed a comparable OER activity and durability versus the commercial unsupported Ir catalyst.

Colloid Science of Metal Nanoparticle Catalysts in 2D and 3D Structures. Challenges of Nucleation, Growth, Composition, Particle Shape, Size Control and their Influence on Activity and Selectivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Somorjai, Gabor A.; Park, Jeong Y.

2008-02-13

Recent breakthroughs in synthesis in nanosciences have achieved control of size and shapes of nanoparticles that are relevant for catalyst design. In this article, we review the advance of synthesis of nanoparticles, fabrication of two and three dimensional model catalyst system, characterization, and studies of activity and selectivity. The ability to synthesize monodispersed platinum and rhodium nanoparticles in the 1-10 nm range permitted us to study the influence of composition, structure, and dynamic properties of monodispersed metal nanoparticle on chemical reactivity and selectivity. We review the importance of size and shape of nanoparticles to determine the reaction selectivity in multi-pathmore » reactions. The influence of metal-support interaction has been studied by probing the hot electron flows through the metal-oxide interface in catalytic nanodiodes. Novel designs of nanoparticle catalytic systems are discussed.« less

Extracellular synthesis of mycogenic silver nanoparticles by Cylindrocladium floridanum and its homogeneous catalytic degradation of 4-nitrophenol.

PubMed

Narayanan, Kannan Badri; Park, Hyun Ho; Sakthivel, Natarajan

2013-12-01

Green synthesis of extracellular mycogenic silver nanoparticles using the fungus, Cylindrocladium floridanum is reported. The synthesized mycogenic silver nanoparticles were characterized using UV-Vis absorption spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM) techniques. The nanoparticles exhibit fcc structure with Bragg's reflections of (111), (200), (220) and (311) was evidenced by XRD pattern, high-resolution TEM lattice fringes and circular rings in selected-area electron diffraction (SAED) pattern. The morphology of nanoparticles was roughly spherical in shape with an average size of ca. 25 nm. From FTIR spectrum, it was found that the biomolecules with amide I and II band were involved in the stabilization of nanoparticles. These mycogenic silver nanoparticles exhibited the homogeneous catalytic potential in the reduction of pollutant, 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) using sodium borohydride, which followed a pseudo-first-order kinetic model. Thus, the synthesis of metal nanoparticles using sustainable microbial approach opens up possibilities in the usage of mycogenic metal nanoparticles as catalysts in various chemical reactions. Copyright © 2013 Elsevier B.V. All rights reserved.

A nanoparticle catalyst for heterogeneous phase para-hydrogen-induced polarization in water.

PubMed

Glöggler, Stefan; Grunfeld, Alexander M; Ertas, Yavuz N; McCormick, Jeffrey; Wagner, Shawn; Schleker, P Philipp M; Bouchard, Louis-S

2015-02-16

Para-hydrogen-induced polarization (PHIP) is a technique capable of producing spin polarization at a magnitude far greater than state-of-the-art magnets. A significant application of PHIP is to generate contrast agents for biomedical imaging. Clinically viable and effective contrast agents not only require high levels of polarization but heterogeneous catalysts that can be used in water to eliminate the toxicity impact. Herein, we demonstrate the use of Pt nanoparticles capped with glutathione to induce heterogeneous PHIP in water. The ligand-inhibited surface diffusion on the nanoparticles resulted in a (1) H polarization of P=0.25% for hydroxyethyl propionate, a known contrast agent for magnetic resonance angiography. Transferring the (1) H polarization to a (13) C nucleus using a para-hydrogen polarizer yielded a polarization of 0.013%. The nuclear-spin polarizations achieved in these experiments are the first reported to date involving heterogeneous reactions in water. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Renewable Wood Pulp Paper Reactor with Hierarchical Micro/Nanopores for Continuous-Flow Nanocatalysis.

PubMed

Koga, Hirotaka; Namba, Naoko; Takahashi, Tsukasa; Nogi, Masaya; Nishina, Yuta

2017-06-22

Continuous-flow nanocatalysis based on metal nanoparticle catalyst-anchored flow reactors has recently provided an excellent platform for effective chemical manufacturing. However, there has been limited progress in porous structure design and recycling systems for metal nanoparticle-anchored flow reactors to create more efficient and sustainable catalytic processes. In this study, traditional paper is used for a highly efficient, recyclable, and even renewable flow reactor by tailoring the ultrastructures of wood pulp. The "paper reactor" offers hierarchically interconnected micro- and nanoscale pores, which can act as convective-flow and rapid-diffusion channels, respectively, for efficient access of reactants to metal nanoparticle catalysts. In continuous-flow, aqueous, room-temperature catalytic reduction of 4-nitrophenol to 4-aminophenol, a gold nanoparticle (AuNP)-anchored paper reactor with hierarchical micro/nanopores provided higher reaction efficiency than state-of-the-art AuNP-anchored flow reactors. Inspired by traditional paper materials, successful recycling and renewal of AuNP-anchored paper reactors were also demonstrated while high reaction efficiency was maintained. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Polymer- and dendrimer-coated magnetic nanoparticles as versatile supports for catalysts, scavengers, and reagents.

PubMed

Kainz, Quirin M; Reiser, Oliver

2014-02-18

The work-up of chemical reactions by standard techniques is often time consuming and energy demanding, especially when chemists have to guarantee low levels of metal contamination in the products. Therefore, scientists need new ideas to rapidly purify reaction mixtures that are both economically and environmentally benign. One intriguing approach is to tether functionalities that are required to perform organic reactions to magnetic nanoparticles, for example, catalysts, reagents, scavengers, or chelators. This strategy allows researchers to quickly separate active agents from reaction mixtures by exploiting the magnetic properties of the support. In this Account, we discuss the main attributes of magnetic supports and describe how we can make the different nanomagnets accessible by surface functionalization. Arguably the most prominent magnetic nanoparticles are superparamagnetic iron oxide nanoparticles (SPIONs) due to their biologically well-accepted constituents, their established size-selective synthesis methods, and their diminished agglomeration (no residual magnetic attraction in the absence of an external magnetic field). However, nanoparticles made of pure metal have a considerably higher magnetization level that is useful in applications where high loadings are needed. A few layers of carbon can efficiently shield such highly reactive metal nanoparticles and, equally important, enable facile covalent functionalization via diazonium chemistry or non-covalent functionalization through π-π interactions. We highlight carbon-coated cobalt (Co/C) and iron (Fe/C) nanoparticles in this Account and compare them to SPIONs stabilized with surfactants or silica shells. The graphene-like coating of these nanoparticles offers only low loadings with functional groups via direct surface modification, and the resulting nanomagnets are prone to agglomeration without effective steric stabilization. To overcome these restrictions and to tune the dispersibility of the

Catalyst design for enhanced sustainability through fundamental surface chemistry

DOE PAGES

Personick, Michelle L.; Montemore, Matthew M.; Kaxiras, Efthimios; ...

2016-01-11

Decreasing energy consumption in the production of platform chemicals is necessary to improve the sustainability of the chemical industry, which is the largest consumer of delivered energy. The majority of industrial chemical transformations rely on catalysts, and therefore designing new materials that catalyse the production of important chemicals via more selective and energy-efficient processes is a promising pathway to reducing energy use by the chemical industry. Efficiently designing new catalysts benefits from an integrated approach involving fundamental experimental studies and theoretical modelling in addition to evaluation of materials under working catalytic conditions. In this paper, we outline this approach inmore » the context of a particular catalyst—nanoporous gold (npAu)—which is an unsupported, dilute AgAu alloy catalyst that is highly active for the selective oxidative transformation of alcohols. Fundamental surface science studies on Au single crystals and AgAu thin-film alloys in combination with theoretical modelling were used to identify the principles which define the reactivity of npAu and subsequently enabled prediction of new reactive pathways on this material. Specifically, weak van der Waals interactions are key to the selectivity of Au materials, including npAu. Finally, we also briefly describe other systems in which this integrated approach was applied.« less

Concentration Dependence of Gold Nanoparticles for Fluorescence Enhancement

NASA Astrophysics Data System (ADS)

Solomon, Joel; Wittmershaus, Bruce

Noble metal nanoparticles possess a unique property known as surface plasmon resonance in which the conduction electrons oscillate due to incoming light, dramatically increasing their absorption and scattering of light. The oscillating electrons create a varying electric field that can affect nearby molecules. The fluorescence and photostability of fluorophores can be enhanced significantly when they are near plasmonic nanoparticles. This effect is called metal enhanced fluorescence (MEF). MEF from two fluorescence organic dyes, Lucifer Yellow CH and Riboflavin, was measured with different concentrations of 50-nm colloidal gold nanoparticles (Au-NP). The concentration range of Au-NP was varied from 2.5 to 250 pM. To maximize the interaction, the dyes were chosen so their emission spectra had considerable overlap with the absorption spectra of the Au-NP, which is common in MEF studies. If the dye molecules are too close to the surface of Au-NP, fluorescence quenching can occur instead of MEF. To try to observe this difference, silica-coated Au-NP were compared to citrate-based Au-NP; however, fluorescence quenching was observed with both Au-NP. This material is based upon work supported by the National Science Foundation under Grant Number NSF-ECCS-1306157.

Diameter control of vertically aligned carbon nanotubes using CoFe2O4 nanoparticle Langmuir-Blodgett films

NASA Astrophysics Data System (ADS)

Tamiya, Shuhei; Sato, Taiga; Kushida, Masahito

2018-03-01

Vertically aligned carbon nanotubes (VA-CNTs) are suggested for utilization as a new catalyst support of polymer electrolyte fuel cells (PEFCs). The independent control of the diameter and number density of VA-CNTs is essential for application in PEFCs. As the catalyst for VA-CNT growth, we fabricated CoFe2O4 nanoparticle (NP) films using the Langmuir-Blodgett (LB) technique. Using the LB technique, we were able to separately control the diameter and number density of VA-CNTs. The number density of VA-CNTs was changed by mixing with the filler moleculer, palmitic acid (C16). The VA-CNT diameter was changed by the adjusting the CoFe2O4 NP diameter. However, the heat-induced aggregation of CoFe2O4 NPs occurred in thermal chemical vapor deposition to synthesize VA-CNTs. Therefore, we examined how to minimize the effect of heat-induced aggregation of CoFe2O4 NPs. As a result, selection of the appropriate number density and diameter of CoFe2O4 NPs was found to be important for the control of VA-CNT diameter.

S-nitrosocaptopril nanoparticles as nitric oxide-liberating and transnitrosylating anti-infective technology.

PubMed

Mordorski, Breanne; Pelgrift, Robert; Adler, Brandon; Krausz, Aimee; da Costa Neto, Alexandre Batista; Liang, Hongying; Gunther, Leslie; Clendaniel, Alicea; Harper, Stacey; Friedman, Joel M; Nosanchuk, Joshua D; Nacharaju, Parimala; Friedman, Adam J

2015-02-01

Nitric oxide (NO), an essential agent of the innate immune system, exhibits multi-mechanistic antimicrobial activity. Previously, NO-releasing nanoparticles (NO-np) demonstrated increased antimicrobial activity when combined with glutathione (GSH) due to formation of S-nitrosoglutathione (GSNO), a transnitrosylating agent. To capitalize on this finding, we incorporated the thiol-containing ACE-inhibitor, captopril, with NO-np to form SNO-CAP-np, nanoparticles that both release NO and form S-nitrosocaptopril. In the presence of GSH, SNO-CAP-np demonstrated increased transnitrosylation activity compared to NO-np, as exhibited by increased GSNO formation. Escherichia coli and methicillin-resistant Staphylococcus aureus were highly susceptible to SNO-CAP-np in a dose-dependent fashion, with E. coli being most susceptible, and SNO-CAP-np were nontoxic in zebrafish embryos at translatable concentrations. Given SNO-CAP-np's increased transnitrosylation activity and increased E. coli susceptibility compared to NO-np, transnitrosylation rather than free NO is likely responsible for overcoming E. coli's resistance mechanisms and ultimately killing the pathogen. This team of authors incorporated the thiol-containing ACE-inhibitor, captopril, into a nitric oxide releasing nanoparticle system, generating nanoparticles that both release NO and form S-nitrosocaptopril, with pronounced toxic effects on MRSA and E. coli in the presented model system. Copyright © 2015 Elsevier Inc. All rights reserved.

A nanohybrid of platinum nanoparticles-porous ZnO-hemin with electrocatalytic activity to construct an amplified immunosensor for detection of influenza.

PubMed

Yang, Zhe-Han; Zhuo, Ying; Yuan, Ruo; Chai, Ya-Qin

2016-04-15

In this work, a nanohybrid of platinum nanoparticles-porous ZnO spheres-hemin (Pt-pZnO-hemin) was synthesized for construction of alkaline phosphatase-based immunosensor for detection of influenza. Briefly, porous ZnO spheres (pZnO) were prepared using soluble starches as the capping agent, followed by surface functionalization of platinum nanoparticles via a hydrothermal method (Pt-pZnO). Then, hemin with carboxylic functionality was spontaneously adsorbed onto Pt-pZnO by ester-like binding between carboxylic group of hemin and ZnO. Compared with platinum nanoparticles and hemin, the resulting Pt-pZnO-hemin nanohybrid showed more excellent electrocatalysis activity toward 1-naphthol (1-NP). Taking advantage of the Pt-pZnO-hemin, we have developed an amplified electrochemical immunosensor based on in situ generation of redox probe by alkaline phosphatase (ALP) and Pt-pZnO-hemin as signal enhancer. Herein, electrochemically active 1-NP was generated by enzymatic hydrolysis of inactive 1-naphthyl phosphate by ALP, then Pt-pZnO-hemin was used as catalyst to catalytically oxidize 1-NP, resulting in electrochemical signal amplification. Furthermore, in comparison with other nanomaterials including Au-pZnO, Pt-pZnO and Au-pZnO-hemin, the excellent catalytical property of Pt-pZnO-hemin make it a promising nanohybrid material for ALP-based immunosensor for signal amplification. Copyright © 2015. Published by Elsevier B.V.

Phytosynthesis of Iron Nanoparticle from Averrhoa Bilimbi Linn.

NASA Astrophysics Data System (ADS)

Rosli, I. R.; Zulhaimi, H. I.; Ibrahim, S. K. M.; Gopinath, S. C. B.; Kasim, K. F.; Akmal, H. M.; Nuradibah, M. A.; Sam, T. S.

2018-03-01

This paper demonstrates iron nanoparticles (FeNP) was synthesized from natural sources of Averrhoa bilimbi Linn. The plant extracts act as natural reducing agent in producing FeNP. There is no addition of any surfactants during the nanoparticles formation. Gravimetric analysis is used to calculate the percentage yield of plant extracts. TPC and DPPH assay method were used to evaluate antioxidant activity in different A. bilimbi extracts and synthesized FeNP. Based on the analyses, it showed that fruit has the highest percentage yield and antioxidant activity followed by leaf, twig and bark. Analysis from TPC, fruit contains 27.26 mg GAE/g and 39.46 mg GAE/g for FeNP. DPPH assay showed fruit extract has the highest free radical antioxidant activity with 61.93% in A. bilimbi and 80.00% in FeNP. Phytosynthesis of FeNP were examine by using UV-Vis spectrophotometer. Based on the spectra, it showed that FeNP recorded peak absorbance at 465 nm, 450 nm, 460 nm and 440 nm for UAE-F, UAE-L, UAE-T and UAE-B, respectively. FTIR analysis shows the presence of strong alcoholic bond, aldehyde, stretch amine and alkene that was responsible in reduction process to form FeNP. The result of UV-Vis and FTIR showed that the existance of FeNP and involvement of functional group that were responsible on the formation of nanoparticles.

Segregation Phenomena in Size-Selected Bimetallic CuNi Nanoparticle Catalysts

DOE PAGES

Pielsticker, Lukas; Zegkinoglou, Ioannis; Divins, Nuria J.; ...

2017-10-25

Surface segregation, restructuring, and sintering phenomena in size-selected copper–nickel nanoparticles (NPs) supported on silicon dioxide substrates were systematically investigated as a function of temperature, chemical state, and reactive gas environment. Using near-ambient pressure (NAP-XPS) and ultrahigh vacuum X-ray photoelectron spectroscopy (XPS), we showed that nickel tends to segregate to the surface of the NPs at elevated temperatures in oxygen- or hydrogen-containing atmospheres. It was found that the NP pretreatment, gaseous environment, and oxide formation free energy are the main driving forces of the restructuring and segregation trends observed, overshadowing the role of the surface free energy. The depth profile ofmore » the elemental composition of the particles was determined under operando CO 2 hydrogenation conditions by varying the energy of the X-ray beam. The temperature dependence of the chemical state of the two metals was systematically studied, revealing the high stability of nickel oxides on the NPs and the important role of high valence oxidation states in the segregation behavior. Atomic force microscopy (AFM) studies revealed a remarkable stability of the NPs against sintering at temperatures as high as 700 °C. The results provide new insights into the complex interplay of the various factors which affect alloy formation and segregation phenomena in bimetallic NP systems, often in ways different from those previously known for their bulk counterparts. In conclusion, this leads to new routes for tuning the surface composition of nanocatalysts, for example, through plasma and annealing pretreatments.« less

Dendrimer encapsulated Silver nanoparticles as novel catalysts for reduction of aromatic nitro compounds

NASA Astrophysics Data System (ADS)

Asharani, I. V.; Thirumalai, D.; Sivakumar, A.

2017-11-01

Polyethylene glycol (PEG) core dendrimer encapsulated silver nanoparticles (AgNPs) were synthesized through normal chemical reduction method, where dendrimer acts as reducing and stabilizing agent. The encapsulated AgNPs were well characterized using TEM, DLS and XPS techniques. The synthesized AgNPs showed excellent catalytic activity towards the reduction of aromatic nitro compounds with sodium borohydride as reducing agent and the results substantiate that dendrimer encapsulated AgNPs can be an effective catalyst for the substituted nitro aromatic reduction reactions. Also the kinetics of different nitro compounds reductions was studied and presented.

Effective rate constants for nanostructured heterogeneous catalysts

NASA Astrophysics Data System (ADS)

Hendy, Shaun; Gaston, Nicola; Zhang, Philip; Lund, Nat

2012-02-01

There is currently a high level of interest in the use of nanostructured materials for catalysis. For instance, gold, which is largely inert in the bulk, can exhibit strong catalytic activity when in nanoparticle form. With precious metal catalysts such as Pt and Pd in high demand, the use of these materials in nanoparticle form can also substantially reduce costs by exposure of more surface area for the same volume of material. When reactants are plentiful, the effective activity of a nanoparticulate catalyst will increase roughly with its surface area. However, under diffusion-limited conditions, the reactant must diffuse to active sites on the catalyst, so a high surface area and a high density of active sites may bring diminishing returns if reactant is consumed faster than it arrives. Here we apply a mathematical homogenisation approach to derive simple expressions for the effective reactivity of a nanostructured catalyst under diffusion limited conditions that relate the intrinsic rate constants of the surfaces presented by the catalyst to an effective rate constant. When highly active catalytic sites, such as step edges or other defects are present, we show that distinct limiting cases emerge depending on the degree of overlap of the reactant depletion zone about each site. In gases, the size of this depletion zone is approximately the mean free path, so the effective reactivity will depend on the structure of the catalyst on that scale. We discuss implications for the optimal design of nanoparticle catalysts.

Networks of connected Pt nanoparticles supported on carbon nanotubes as superior catalysts for methanol electrooxidation

NASA Astrophysics Data System (ADS)

Huang, Meihua; Zhang, Jianshuo; Wu, Chuxin; Guan, Lunhui

2017-02-01

The high cost and short lifetime of the Pt-based anode catalyst for methanol oxidation reaction (MOR) hamper the widespread commercialization of direct methanol fuel cell (DMFC). Therefore, improving the activity of Pt-based catalysts is necessary for their practical application. For the first time, we prepared networks of connected Pt nanoparticles supported on multi-walled carbon nanotubes with loading ratio as high as 91 wt% (Pt/MWCNTs). Thanks for the unique connected structure, the Pt mass activity of Pt/MWCNTs for methanol oxidation reaction is 4.4 times as active as that of the commercial Pt/C (20 wt%). When carbon support is considered, the total mass activity of Pt/MWCNTs is 20 times as active as that of the commercial Pt/C. The durability and anti-poisoning ability are also improved greatly.

Gold-nanoparticle-based catalysts for the oxidative esterification of 1,4-butanediol into dimethyl succinate.

PubMed

Brett, Gemma L; Miedziak, Peter J; He, Qian; Knight, David W; Edwards, Jennifer K; Taylor, Stuart H; Kiely, Christopher J; Hutchings, Graham J

2013-10-01

The oxidation of 1,4-butanediol and butyrolactone have been investigated by using supported gold, palladium and gold-palladium nanoparticles. The products of such reactions are valuable chemical intermediates and, for example, can present a viable pathway for the sustainable production of polymers. If both gold and palladium were present, a significant synergistic effect on the selective formation of dimethyl succinate was observed. The support played a significant role in the reaction, with magnesium hydroxide leading to the highest yield of dimethyl succinate. Based on structural characterisation of the fresh and used catalysts, it was determined that small gold-palladium nanoalloys supported on a basic Mg(OH)2 support provided the best catalysts for this reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalysts and methods of using the same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Slowing, Igor Ivan; Kandel, Kapil

2017-02-14

The present invention provides a catalyst including a mesoporous silica nanoparticle and a catalytic material comprising iron. In various embodiments, the present invention provides methods of using and making the catalyst. In some examples, the catalyst can be used to hydrotreat fatty acids or to selectively remove fatty acids from feedstocks.

Reduced Graphene Oxide-Based Silver Nanoparticle-Containing Composite Hydrogel as Highly Efficient Dye Catalysts for Wastewater Treatment

PubMed Central

Jiao, Tifeng; Guo, Haiying; Zhang, Qingrui; Peng, Qiuming; Tang, Yongfu; Yan, Xuehai; Li, Bingbing

2015-01-01

New reduced graphene oxide-based silver nanoparticle-containing composite hydrogels were successfully prepared in situ through the simultaneous reduction of GO and noble metal precursors within the GO gel matrix. The as-formed hydrogels are composed of a network structure of cross-linked nanosheets. The reported method is based on the in situ co-reduction of GO and silver acetate within the hydrogel matrix to form RGO-based composite gel. The stabilization of silver nanoparticles was also achieved simultaneously within the gel composite system. The as-formed silver nanoparticles were found to be homogeneously and uniformly dispersed on the surface of the RGO nanosheets within the composite gel. More importantly, this RGO-based silver nanoparticle-containing composite hydrogel matrix acts as a potential catalyst for removing organic dye pollutants from an aqueous environment. Interestingly, the as-prepared catalytic composite matrix structure can be conveniently separated from an aqueous environment after the reaction, suggesting the potentially large-scale applications of the reduced graphene oxide-based nanoparticle-containing composite hydrogels for organic dye removal and wastewater treatment. PMID:26183266

Plasmonic extinction in gold nanoparticle-polymer films as film thickness and nanoparticle separation decrease below resonant wavelength

NASA Astrophysics Data System (ADS)

Dunklin, Jeremy R.; Bodinger, Carter; Forcherio, Gregory T.; Keith Roper, D.

2017-01-01

Plasmonic nanoparticles embedded in polymer films enhance optoelectronic properties of photovoltaics, sensors, and interconnects. This work examined optical extinction of polymer films containing randomly dispersed gold nanoparticles (AuNP) with negligible Rayleigh scattering cross-sections at particle separations and film thicknesses less than (sub-) to greater than (super-) the localized surface plasmon resonant (LSPR) wavelength, λLSPR. Optical extinction followed opposite trends in sub- and superwavelength films on a per nanoparticle basis. In ˜70-nm-thick polyvinylpyrrolidone films containing 16 nm AuNP, measured resonant extinction per particle decreased as particle separation decreased from ˜130 to 76 nm, consistent with trends from Maxwell Garnett effective medium theory and coupled dipole approximation. In ˜1-mm-thick polydimethylsiloxane films containing 16-nm AuNP, resonant extinction per particle plateaued at particle separations ≥λLSPR, then increased as particle separation radius decreased from ˜514 to 408 nm. Contributions from isolated particles, interparticle interactions and heterogeneities in sub- and super-λLSPR films containing AuNP at sub-λLSPR separations were examined. Characterizing optoplasmonics of thin polymer films embedded with plasmonic NP supports rational development of optoelectronic, biomedical, and catalytic activity using these nanocomposites.

Nanoparticles-cell association predicted by protein corona fingerprints

NASA Astrophysics Data System (ADS)

Palchetti, S.; Digiacomo, L.; Pozzi, D.; Peruzzi, G.; Micarelli, E.; Mahmoudi, M.; Caracciolo, G.

2016-06-01

In a physiological environment (e.g., blood and interstitial fluids) nanoparticles (NPs) will bind proteins shaping a ``protein corona'' layer. The long-lived protein layer tightly bound to the NP surface is referred to as the hard corona (HC) and encodes information that controls NP bioactivity (e.g. cellular association, cellular signaling pathways, biodistribution, and toxicity). Decrypting this complex code has become a priority to predict the NP biological outcomes. Here, we use a library of 16 lipid NPs of varying size (Ø ~ 100-250 nm) and surface chemistry (unmodified and PEGylated) to investigate the relationships between NP physicochemical properties (nanoparticle size, aggregation state and surface charge), protein corona fingerprints (PCFs), and NP-cell association. We found out that none of the NPs' physicochemical properties alone was exclusively able to account for association with human cervical cancer cell line (HeLa). For the entire library of NPs, a total of 436 distinct serum proteins were detected. We developed a predictive-validation modeling that provides a means of assessing the relative significance of the identified corona proteins. Interestingly, a minor fraction of the HC, which consists of only 8 PCFs were identified as main promoters of NP association with HeLa cells. Remarkably, identified PCFs have several receptors with high level of expression on the plasma membrane of HeLa cells.In a physiological environment (e.g., blood and interstitial fluids) nanoparticles (NPs) will bind proteins shaping a ``protein corona'' layer. The long-lived protein layer tightly bound to the NP surface is referred to as the hard corona (HC) and encodes information that controls NP bioactivity (e.g. cellular association, cellular signaling pathways, biodistribution, and toxicity). Decrypting this complex code has become a priority to predict the NP biological outcomes. Here, we use a library of 16 lipid NPs of varying size (Ø ~ 100-250 nm) and surface

Drug Synergy of Tenofovir and Nanoparticle-Based Antiretrovirals for HIV Prophylaxis

PubMed Central

Chaowanachan, Thanyanan; Krogstad, Emily; Ball, Cameron; Woodrow, Kim A.

2013-01-01

Background The use of drug combinations has revolutionized the treatment of HIV but there is no equivalent combination product that exists for prevention, particularly for topical HIV prevention. Strategies to combine chemically incompatible agents may facilitate the discovery of unique drug-drug activities, particularly unexplored combination drug synergy. We fabricated two types of nanoparticles, each loaded with a single antiretroviral (ARV) that acts on a specific step of the viral replication cycle. Here we show unique combination drug activities mediated by our polymeric delivery systems when combined with free tenofovir (TFV). Methodology/Principal Findings Biodegradable poly(lactide-co-glycolide) nanoparticles loaded with efavirenz (NP-EFV) or saquinavir (NP-SQV) were individually prepared by emulsion or nanoprecipitation techniques. Nanoparticles had reproducible size (d ∼200 nm) and zeta potential (-25 mV). The drug loading of the nanoparticles was approximately 7% (w/w). NP-EFV and NP-SQV were nontoxic to TZM-bl cells and ectocervical explants. Both NP-EFV and NP-SQV exhibited potent protection against HIV-1 BaL infection in vitro. The HIV inhibitory effect of nanoparticle formulated ARVs showed up to a 50-fold reduction in the 50% inhibitory concentration (IC50) compared to free drug. To quantify the activity arising from delivery of drug combinations, we calculated combination indices (CI) according to the median-effect principle. NP-EFV combined with free TFV demonstrated strong synergistic effects (CI50 = 0.07) at a 1∶50 ratio of IC50 values and additive effects (CI50 = 1.05) at a 1∶1 ratio of IC50 values. TFV combined with NP-SQV at a 1∶1 ratio of IC50 values also showed strong synergy (CI50 = 0.07). Conclusions ARVs with different physicochemical properties can be encapsulated individually into nanoparticles to potently inhibit HIV. Our findings demonstrate for the first time that combining TFV with either NP-EFV or NP

Transport of silver nanoparticles in single fractured sandstone

NASA Astrophysics Data System (ADS)

Neukum, Christoph

2018-02-01

Silver nanoparticles (Ag-NP) are used in various consumer products and are one of the most prevalent metallic nanoparticle in commodities and are released into the environment. Transport behavior of Ag-NP in groundwater is one important aspect for the assessment of environmental impact and protection of drinking water resources in particular. Ag-NP transport processes in saturated single-fractured sandstones using triaxial flow cell experiments with different kind of sandstones is investigated. Ag-NP concentration and size are analyzed using flow field-flow fractionation and coupled SEM-EDX analysis. Results indicate that Ag-NP are more mobile and show generally lower attachment on rock surface compared to experiments in undisturbed sandstone matrix and partially fractured sandstones. Ag-NP transport is controlled by the characteristics of matrix porosity, time depending blocking of attachment sites and solute chemistry. Where Ag-NP attachment occur, it is heterogeneously distributed on the fracture surface.

Amino-functionalized silica nanoparticles with center-radially hierarchical mesopores as ideal catalyst carriers

NASA Astrophysics Data System (ADS)

Du, Xin; He, Junhui

2012-01-01

Our previously fabricated amino-functionalized silica nanoparticles (NPs) with center-radially hierarchical mesopores (NH2-HMSNs) were purified by a filtration membrane and used as catalyst carriers in the current article. Noble metal NPs (Au, Pd, Pt and Au & Pt) with small sizes (3-8 nm) were successfully immobilized into the NH2-HMSNs via the deposition-precipitation method. These noble metal NPs with readily adjusted small sizes have high density and well-dispersed distribution on the surface of large mesopores of NH2-HMSNs. Among them, Au-NH2-HMSNs were investigated as the composite catalyst in the catalytic reduction of 2-nitroaniline (2-NA) as a model reaction and exhibited excellent catalytic activity and stability. The presence of center-radially large mesopores in the NH2-HMSNs may favor the loading of noble metal NPs with high density and well-dispersed distribution on the surface of large mesopores of NH2-HMSNs. Metal-NH2-HMSNs may be more promising composite catalysts due to their superstructure of center-radially hierarchical mesopores that maybe significantly enhance and harmonize the diffusion of guest molecules of different sizes through the porous matrices.Our previously fabricated amino-functionalized silica nanoparticles (NPs) with center-radially hierarchical mesopores (NH2-HMSNs) were purified by a filtration membrane and used as catalyst carriers in the current article. Noble metal NPs (Au, Pd, Pt and Au & Pt) with small sizes (3-8 nm) were successfully immobilized into the NH2-HMSNs via the deposition-precipitation method. These noble metal NPs with readily adjusted small sizes have high density and well-dispersed distribution on the surface of large mesopores of NH2-HMSNs. Among them, Au-NH2-HMSNs were investigated as the composite catalyst in the catalytic reduction of 2-nitroaniline (2-NA) as a model reaction and exhibited excellent catalytic activity and stability. The presence of center-radially large mesopores in the NH2-HMSNs may favor

Anti-proliferative activity of silver nanoparticles

PubMed Central

AshaRani, PV; Hande, M Prakash; Valiyaveettil, Suresh

2009-01-01

Background Nanoparticles possess exceptional physical and chemical properties which led to rapid commercialisation. Silver nanoparticles (Ag-np) are among the most commercialised nanoparticles due to their antimicrobial potential. Ag-np based cosmetics, therapeutic agents and household products are in wide use, which raised a public concern regarding their safety associated with human and environmental use. No safety regulations are in practice for the use of these nanomaterials. The interactions of nanomaterials with cells, uptake mechanisms, distribution, excretion, toxicological endpoints and mechanism of action remain unanswered. Results Normal human lung fibroblasts (IMR-90) and human glioblastoma cells (U251) were exposed to different doses of Ag-nps in vitro. Uptake of Ag-nps occurred mainly through endocytosis (clathrin mediated process and macropinocytosis), accompanied by a time dependent increase in exocytosis rate. The electron micrographs revealed a uniform intracellular distribution of Ag-np both in cytoplasm and nucleus. Ag-np treated cells exhibited chromosome instability and mitotic arrest in human cells. There was efficient recovery from arrest in normal human fibroblasts whereas the cancer cells ceased to proliferate. Toxicity of Ag-np is mediated through intracellular calcium (Ca2+) transients along with significant alterations in cell morphology and spreading and surface ruffling. Down regulation of major actin binding protein, filamin was observed after Ag-np exposure. Ag-np induced stress resulted in the up regulation of metallothionein and heme oxygenase -1 genes. Conclusion Here, we demonstrate that uptake of Ag-np occurs mainly through clathrin mediated endocytosis and macropinocytosis. Our results suggest that cancer cells are susceptible to damage with lack of recovery from Ag-np-induced stress. Ag-np is found to be acting through intracellular calcium transients and chromosomal aberrations, either directly or through activation of

Magnetically retrievable catalysts for organic synthesis

EPA Science Inventory

The use of magnetic nanoparticles (MNPs) as a catalyst in organic synthesis has become a subject of intense investigation. The recovery of expensive catalysts after catalytic reaction and reusing it without losing its activity is an important feature in the sustainable process de...

Gold nanoparticles stabilized by poly(4-vinylpyridine) grafted cellulose nanocrystals as efficient and recyclable catalysts.

PubMed

Zhang, Zhen; Sèbe, Gilles; Wang, Xiaosong; Tam, Kam C

2018-02-15

pH-responsive poly(4-vinylpyridine) (P4VP) grafted cellulose nanocrystals (P4VP-g-CNC) were prepared by Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) and subsequently used to stabilize gold nanoparticles (Au NPs) as efficient and recyclable nanocatalysts for the reduction of 4-nitrophenol (4NP). The presence of P4VP brushes on the CNC surface controlled the growth of Au NPs yielding smaller averaged diameter compared to Au NPs deposited directly on pristine CNC. The catalytic performances of pristine Au NPs, Au@CNC and Au@P4VP-g-CNC were compared by measuring the turnover frequency (TOF) for the catalytic reduction of 4NP. Compared to pristine Au NPs, the catalytic activity of Au@CNC and Au@P4VP-g-CNC were 10 and 24 times better. Moreover, the Au@P4VP-g-CNC material could be recovered via flocculation at pH>5, and the recycled nanocatalyst remained highly active. Copyright © 2017 Elsevier Ltd. All rights reserved.

Cobalt-rhodium heterobimetallic nanoparticle-catalyzed reactions.

PubMed

Park, Ji Hoon; Chung, Young Keun

2008-05-14

Transition metal nanoparticles have attracted a great deal of attention. This review discusses the synthesis of heterobimetallic cobalt-rhodium nanoparticles and their use as catalysts in organic transformations. Co-Rh nanoparticles (Co2Rh2) with a fixed stoichiometry (2 : 2) were easily obtained from Co2Rh2(CO)12. These nanoparticles were quite effective catalysts for carbonylation reactions. Particularly, special focus is paid to the Pauson-Khand-type reaction.

Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water.

PubMed

Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

2016-06-22

Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m(2) g(-1) were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction.

Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water

NASA Astrophysics Data System (ADS)

Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

2016-06-01

Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m2 g-1 were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction.

Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water

PubMed Central

Chen, Xiufang; Zhang, Ligang; Zhang, Bo; Guo, Xingcui; Mu, Xindong

2016-01-01

Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m2 g−1 were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction. PMID:27328834

Tunable, biodegradable gold nanoparticles as contrast agents for computed tomography and photoacoustic imaging

PubMed Central

Cheheltani, Rabee; Ezzibdeh, Rami M.; Chhour, Peter; Pulaparthi, Kumidini; Kim, Johoon; Jurcova, Martina; Hsu, Jessica C.; Blundell, Cassidy; Litt, Harold I.; Ferrari, Victor A.; Allcock, Harry R.; Sehgal, Chandra M.; Cormode, David P.

2016-01-01

Gold nanoparticles (AuNP) have been proposed for many applications in medicine. Although large AuNP (>5.5 nm) are desirable for their longer blood circulation and accumulation in diseased tissues, small AuNP (<5.5 nm) are required for excretion via the kidneys. We present a novel platform where small, excretable AuNP are encapsulated into biodegradable poly di(carboxylatophenoxy)phosphazene (PCPP) nanospheres. These larger nanoparticles (Au-PCPP) can perform their function as contrast agents, then subsequently break down into harmless byproducts and release the AuNP for swift excretion. Homogeneous Au-PCPP were synthesized using a microfluidic device. The size of the Au-PCPP can be controlled by the amount of polyethylene glycol-polylysine (PEG-PLL) block co-polymer in the formulation. Synthesis of Au-PCPP nanoparticles and encapsulation of AuNP in PCPP were evaluated using transmission electron microscopy and their biocompatibility and biodegradability confirmed in vitro. The Au-PCPP nanoparticles were found to produce strong computed tomography contrast. The UV-Vis absorption peak of Au-PCPP can be tuned into the near infrared region via inclusion of varying amounts of AuNP and controlling the nanoparticle size. In vitro and in vivo experiments demonstrated the potential of Au-PCPP as contrast agents for photoacoustic imaging. Therefore, Au-PCPP nanoparticles have high potency as contrast agents for two imaging modalities, as well as being biocompatible and biodegradable, and thus represent a platform with potential for translation into the clinic. PMID:27322961

Nickel-doped cobalt ferrite nanoparticles: efficient catalysts for the reduction of nitroaromatic compounds and photo-oxidative degradation of toxic dyes.

PubMed

Singh, Charanjit; Goyal, Ankita; Singhal, Sonal

2014-07-21

This study deals with the exploration of NixCo₁-xFe₂O₄ (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) ferrite nanoparticles as catalysts for reduction of 4-nitrophenol and photo-oxidative degradation of Rhodamine B. The ferrite samples with uniform size distribution were synthesized using the reverse micelle technique. The structural investigation was performed using powder X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray and scanning tunneling microscopy. The spherical particles with ordered cubic spinel structure were found to have the crystallite size of 4-6 nm. Diffused UV-visible reflectance spectroscopy was employed to investigate the optical properties of the synthesized ferrite nanoparticles. The surface area calculated using BET method was found to be highest for Co₀.₄Ni₀.₆Fe₂O₄ (154.02 m(2) g(-1)). Co₀.₄Ni₀.₆Fe₂O₄ showed the best catalytic activity for reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4 as reducing agent, whereas CoFe₂O₄ was found to be catalytically inactive. The reduction reaction followed pseudo-first order kinetics. The effect of varying the concentration of catalyst and NaBH₄ on the reaction rates was also scrutinized. The photo-oxidative degradation of Rhodamine B, enhanced oxidation efficacy was observed with the introduction of Ni(2+) in to the cobalt ferrite lattice due to octahedral site preference of Ni(2+). Almost 99% degradation was achieved in 20 min using NiFe₂O₄ nanoparticles as catalyst.

Electrosprayed chitosan nanoparticles: facile and efficient approach for bacterial transformation

NASA Astrophysics Data System (ADS)

Abyadeh, Morteza; Sadroddiny, Esmaeil; Ebrahimi, Ammar; Esmaeili, Fariba; Landi, Farzaneh Saeedi; Amani, Amir

2017-12-01

A rapid and efficient procedure for DNA transformation is a key prerequisite for successful cloning and genomic studies. While there are efforts to develop a facile method, so far obtained efficiencies for alternative methods have been unsatisfactory (i.e. 105-106 CFU/μg plasmid) compared with conventional method (up to 108 CFU/μg plasmid). In this work, for the first time, we prepared chitosan/pDNA nanoparticles by electrospraying methods to improve transformation process. Electrospray method was used for chitosan/pDNA nanoparticles production to investigate the non-competent bacterial transformation efficiency; besides, the effect of chitosan molecular weight, N/P ratio and nanoparticle size on non-competent bacterial transformation efficiency was evaluated too. The results showed that transformation efficiency increased with decreasing the molecular weight, N/P ratio and nanoparticles size. In addition, transformation efficiency of 1.7 × 108 CFU/μg plasmid was obtained with chitosan molecular weight, N/P ratio and nanoparticles size values of 30 kDa, 1 and 125 nm. Chitosan/pDNA electrosprayed nanoparticles were produced and the effect of molecular weight, N/P and size of nanoparticles on transformation efficiency was evaluated. In total, we present a facile and rapid method for bacterial transformation, which has comparable efficiency with the common method.

Size-controllable APTS stabilized ruthenium(0) nanoparticles catalyst for the dehydrogenation of dimethylamine-borane at room temperature.

PubMed

Zahmakıran, Mehmet; Philippot, Karine; Özkar, Saim; Chaudret, Bruno

2012-01-14

Dimethylamine-borane, (CH(3))(2)NHBH(3), has been considered as one of the attractive materials for the efficient storage of hydrogen, which is still one of the key issues in the "Hydrogen Economy". In a recent communication we have reported the synthesis and characterization of 3-aminopropyltriethoxysilane stabilized ruthenium(0) nanoparticles with the preliminary results for their catalytic performance in the dehydrogenation of dimethylamine-borane at room temperature. Herein, we report a complete work including (i) effect of initial [APTS]/[Ru] molar ratio on both the size and the catalytic activity of ruthenium(0) nanoparticles, (ii) collection of extensive kinetic data under non-MTL conditions depending on the substrate and catalyst concentrations to define the rate law of Ru(0)/APTS-catalyzed dehydrogenation of dimethylamine-borane at room temperature, (iii) determination of activation parameters (E(a), ΔH(#) and ΔS(#)) for Ru(0)/APTS-catalyzed dehydrogenation of dimethylamine-borane; (iv) demonstration of the catalytic lifetime of Ru(0)/APTS nanoparticles in the dehydrogenation of dimethylamine-borane at room temperature, (v) testing the bottlability and reusability of Ru(0)/APTS nanocatalyst in the room-temperature dehydrogenation of dimethylamine-borane, (vi) quantitative carbon disulfide (CS(2)) poisoning experiments to find a corrected TTO and TOF values on a per-active-ruthenium-atom basis, (vii) a summary of extensive literature review for the catalysts tested in the catalytic dehydrogenation of dimethylamine-borane as part of the results and discussions.

Toxicity of silver nanoparticles in zebrafish models

NASA Astrophysics Data System (ADS)

Asharani, P. V.; Lian Wu, Yi; Gong, Zhiyuan; Valiyaveettil, Suresh

2008-06-01

This study was initiated to enhance our insight on the health and environmental impact of silver nanoparticles (Ag-np). Using starch and bovine serum albumin (BSA) as capping agents, silver nanoparticles were synthesized to study their deleterious effects and distribution pattern in zebrafish embryos (Danio rerio). Toxicological endpoints like mortality, hatching, pericardial edema and heart rate were recorded. A concentration-dependent increase in mortality and hatching delay was observed in Ag-np treated embryos. Additionally, nanoparticle treatments resulted in concentration-dependent toxicity, typified by phenotypes that had abnormal body axes, twisted notochord, slow blood flow, pericardial edema and cardiac arrhythmia. Ag+ ions and stabilizing agents showed no significant defects in developing embryos. Transmission electron microscopy (TEM) of the embryos demonstrated that nanoparticles were distributed in the brain, heart, yolk and blood of embryos as evident from the electron-dispersive x-ray analysis (EDS). Furthermore, the acridine orange staining showed an increased apoptosis in Ag-np treated embryos. These results suggest that silver nanoparticles induce a dose-dependent toxicity in embryos, which hinders normal development.

Transformation of Sodium Bicarbonate and CO2 into Sodium Formate over NiPd Nanoparticle Catalyst

NASA Astrophysics Data System (ADS)

Wang, Mengnan; Zhang, Jiaguang; Yan, Ning

2013-09-01

The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs). Ni NPs and eight NiM (M stands for a second metal) NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

Natrolite zeolite supported copper nanoparticles as an efficient heterogeneous catalyst for the 1,3-diploar cycloaddition and cyanation of aryl iodides under ligand-free conditions.

PubMed

Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Rostami-Vartooni, Akbar; Khalaj, Mehdi

2015-09-01

In this paper, we report the preparation of Natrolite zeolite supported copper nanoparticles as a heterogeneous catalyst for 1,3-diploar cycloaddition and synthesis aryl nitriles from aryl iodides under ligand-free conditions. The catalyst was characterized using XRD, SEM, TEM, EDS and TG-DTA. The experimental procedure is simple, the products are formed in high yields and the catalyst can be recycled and reused several times without any significant loss of catalytic activity. Copyright © 2015 Elsevier Inc. All rights reserved.

Electrochemistry at One Nanoparticle.

PubMed

Mirkin, Michael V; Sun, Tong; Yu, Yun; Zhou, Min

2016-10-18

Electrochemistry at metal nanoparticles (NPs) is of significant current interest because of its applications in catalysis, energy conversion and storage, and sensors. The electrocatalytic activity of NPs depends strongly on their size, shape, and surface attachment. The use of a large number of particles in most reported kinetic experiments obscured the effects of these factors because of polydispersity and different NP orientations. Recent efforts to probe electrochemistry at single NPs included recording of the catalytically amplified current produced by random collisions of particles with the electrode surface, immobilizing an NP on the surface of a small electrode, and delivering individual NPs to electrode surfaces. Although the signals recorded in such experiments were produced by single NPs, the characterization issues and problems with separating an individual particle from other NPs present in the system made it difficult to obtain spatially and/or temporally resolved information about heterogeneous processes occurring at a specific NP. To carry out electrochemical experiments involving only one NP and characterize such an NP in situ, one needs nanoelectrochemical tools with the characteristic dimension smaller than or comparable to those of the particle of interest. This Account presents fundamentals of two complementary approaches to studying NP electrochemistry, i.e., probing single immobilized NPs with the tip of a scanning electrochemical microscope (SECM) and monitoring the collisions between one catalytic NP and a carbon nanopipette. The former technique can provide spatially resolved information about NP geometry and measure its electron transfer properties and catalytic activity under steady-state conditions. The emphasis here is on the extraction of quantitative physicochemical information from nanoelectrochemical data. By employing a polished disk-type nanoelectrode as an SECM tip, one can characterize a specific nanoparticle in situ and then

Effects of cerium oxide nanoparticles on soil enzymatic activities and wheat grass nutrients uptake

NASA Astrophysics Data System (ADS)

Li, Biting; Chen, Yirui; Bai, Lingyun; Jacobson, Astrid; Darnault, Christophe

2015-04-01

The US National Science Foundation estimated that the use of nanomaterials and nanotechnology would reach a global market value of 1 million this year. Concomitant with the wide applications of nanoparticles is an increasing risk of adverse effects to the environment and human health. As a common nanomaterial used as a fuel catalyst and polish material, cerium (IV) oxide nanoparticles (CeO2 NP) were tested for their potential impact on soil health and plant growth. Through exposure by air, water, and solid deposition, nanoparticles may accumulate in soils and impact agricultural systems. The objectives of this research were to determine whether CeO2 NPs affect the growth of wheat grass and selected soil enzyme activities chose as indicators of soil health. Wheat grass was grown in plant boxes containing CeO2 NPs mixed with agricultural soil at different concentrations. Two control groups were included: one consisting of soil with plants but no CeO2 NPs, and one containing only soil, i.e., no NP or wheat plants added. The plants were grown for 10 weeks and harvested every two weeks in a laboratory under sodium growth lights. At the end of the each growing period, two weeks, soils were assayed for phosphatase, β-glucosidase, and urease activities, and NPK values. Spectrophotometer analyses were used to assess enzyme activities, and NPK values were tested by Clemson Agricultural Center. Wheat yields were estimated by shoot and root lengths and weights.

Bifunctional catalyst of graphite-encapsulated iron compound nanoparticle for magnetic carbon nanotubes growth by chemical vapor deposition

NASA Astrophysics Data System (ADS)

Saraswati, Teguh Endah; Prasiwi, Oktaviana Dewi Indah; Masykur, Abu; Anwar, Miftahul

2017-01-01

The carbon nanotube has widely taken great attractive in carbon nanomaterial research and application. One of its preparation methods is catalytic chemical vapor deposition (CCVD) using catalyst i.e. iron, nickel, etc. Generally, except the catalyst, carbon source gasses as the precursor are still required. Here, we report the use of the bifunctional material of Fe3O4/C which has an incorporated core/shell structures of carbon-encapsulated iron compound nanoparticles. The bifunctional catalyst was prepared by submerged arc discharge that simply performed using carbon and carbon/iron oxide electrodes in ethanol 50%. The prepared material was then used as a catalyst in thermal chemical vapor deposition at 800°C flown with ethanol vapor as the primer carbon source in a low-pressure condition. This catalyst might play a dual role as a catalyst and secondary carbon source for growing carbon nanotubes at the time. The synthesized products were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. The successful formation of carbon nanotubes was assigned by the shifted X-ray diffracted peak of carbon C(002), the iron oxides of Fe3O4 and γ-Fe2O3, and the other peaks which were highly considered to the other carbon allotropes with sp2 hybridization structures. The other assignment was studied by electron microscopy which successfully observed the presence of single-wall carbon nanotubes. In addition, the as-prepared carbon nanotubes have a magnetic property which was induced by the remaining of metal catalyst inside the CNT.

WE-FG-BRA-11: Theranostic Platinum Nanoparticle for Radiation Sensitization in Breast Cancer Radiotherapy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yue, Y; Wagner, S; Medina-Kauwe, L

Purpose: We have developed a novel receptor-targeted theranostic platinum nanoparticle (HER-PtNP) for enhanced radiation sensitization in HER2-positive breast cancer radiation treatment. This study aims to evaluate receptor-targeting specificity, and radiation sensitization of the nanoparticle. Methods: The platinum nanoparticle (PtNP) was synthesized with the diameter of 2nm, and capped with cysteine. The nanoparticle was tagged with a fluorescent dye (cy5) for the fluoresence detection, and conjuated with HER2/3 targeted protein (HerPBK10) for HER2-targeting specificity. We evaluated the theranostic features using in vitro breast cancer cell models: HER2-positive BT-474, and HER2-negative MDA-MB-231. The HER2-targeting specificity was evaluated using immunofluorescence and confocal microscopy.more » For each cell line, three sets of samples, including non-stained control, fluorescence stained PtNP-cy5 treated, and HER-PtNP treated, were imaged by confocal microscopy. Two breast cancer cell lineages were incubated with PtNP and HER-PtNP at 10 µg/mL, and then irradiated with X-rays for 2 Gy dose at 50 kVp. A colonogenic assay was used to determine cellular survival fractions by immediately reseeding 300 cells after irradiation in growth media and allowing colonies to grow for 2 weeks. Results: The results of confocal images show that no apparent nanoparticle cellular uptake was observed in the HER2-(MDA-MB-231) cells with 1% for PtNP-cy5 and 0.5% for HER-PtNP. Similarly no apparent PtNP-cy5 uptake (<1%) for BT474 cells was observed. However, there was significant HER-PtNP uptake (73%) for the HER2+(BT474) cells. The clonogenic assay showed that BT474 cells treated with HER-PtNP had significantly lower survival compared to those treated with PtNP (32% vs 81%, p=0.01). However, no significant radiosensitivity enhancement was observed for MDA-MB-231 cell treated with PtNP and HER-PtNP (89% vs 92%, p=0.78). Conclusion: Our studies suggest that the HER2-targeted

Mechanisms of resistance change under pressure for AgNP-based conducting wires

NASA Astrophysics Data System (ADS)

Qian, Zhentao; Liu, Liping; Huang, Han; Cheng, Xiong; Zhu, Xiaobo; Gu, Wenhua

2018-02-01

The silver nanoparticle (AgNP) based conducting wire is a fundamental element of flexible electronic devices, especially in the printing electronics area. Its resistance change mechanisms under pressure is of both scientific interest and practical importance. AgNP-based conducting wires were fabricated on flexible substrates by electrospraying printing technology, and three possible resistance change mechanisms were studied: vertical deformation (VD) of the AgNP wire due to vertical pressure, horizontal wire elongation (HWE) along with the flexible substrate due to vertical pressure, and local micro deformation (LMD) at the touching edge. Analysis of the experiment data revealed that the resistance change due to VD was negligible, the resistance change due to PWE was one order of magnitude smaller than the measured value, and the resistance change due to PWE was the dominating mechanism.

Albumin-based nanoparticle trehalose lyophilisation stress-down to preserve structure/function and enhanced binding.

PubMed

Siri, Macarena; Grasselli, Mariano; Alonso, Silvia Del V

2016-07-15

The aim of this study was to preserve albumin nanoparticle structure/function during the lyophilisation process. Bovine serum albumin nanoparticles were obtained by γ-irradiation. Nanoparticles were lyophilised in buffer, miliQ water or in trehalose/miliQ solution. The size and charge of the nanoparticles were tested after lyophilisation by light scattering and Z potential. The most relevant results in size of BSA nanoparticle were those lyophilised in PBS between 20 and 350nm, assembled in different aggregates, and negative Z potential obtained was 37±8mV in all, and those nanoparticles lyophilised with trehalose had a size range of 70±2nm and a negative Z potential of 20±5mV. Structure determination of surface aminoacids SH groups in the BSA NP lyophilised in PBS showed an increase in the free SH groups. Different aggregates had different amount of SH groups exposure from 55 to 938 (from smaller to bigger aggregates), whereas BSA NP lyophilised with trehalose showed no significant difference if compared with BSA NP. The binding properties of the BSA nanoparticle with a theragnostic probe (merocyanine 540) were studied after lyophilisation. Results showed more affinity between the BSA NP lyophilised with trehalose than that observed with non lyophilised BSA NP. As a result, the lyophilisation condition in trehalose 100μM solution is the best one to preserve the BSA NP structure/function and the one with the enhance binding affinity of the BSA NP. Copyright © 2016 Elsevier B.V. All rights reserved.

Operando chemistry of catalyst surfaces during catalysis.

PubMed

Dou, Jian; Sun, Zaicheng; Opalade, Adedamola A; Wang, Nan; Fu, Wensheng; Tao, Franklin Feng

2017-04-03

Chemistry of a catalyst surface during catalysis is crucial for a fundamental understanding of mechanism of a catalytic reaction performed on the catalyst in the gas or liquid phase. Due to the pressure- or molecular density-dependent entropy contribution of gas or liquid phase of the reactants and the potential formation of a catalyst surface during catalysis different from that observed in an ex situ condition, the characterization of the surface of a catalyst under reaction conditions and during catalysis can be significant and even necessary for understanding the catalytic mechanism at a molecular level. Electron-based analytical techniques are challenging for studying catalyst nanoparticles in the gas or liquid phase although they are necessary techniques to employ. Instrumentation and further development of these electron-based techniques have now made in situ/operando studies of catalysts possible. New insights into the chemistry and structure of catalyst nanoparticles have been uncovered over the last decades. Herein, the origin of the differences between ex situ and in situ/operando studies of catalysts, and the technical challenges faced as well as the corresponding instrumentation and innovations utilized for characterizing catalysts under reaction conditions and during catalysis, are discussed. The restructuring of catalyst surfaces driven by the pressure of reactant(s) around a catalyst, restructuring in reactant(s) driven by reaction temperature and restructuring during catalysis are also reviewed herein. The remaining challenges and possible solutions are briefly discussed.

Quantum and Classical Plasmonic Phenomena in Nanoparticle Arrays

NASA Astrophysics Data System (ADS)

Govorov, Alexander; Besteiro, Lucas; Khosravi Khorashad, Larousse; Kong, Xiang-Tian; Roller, Eva-Maria; Liedl, Tim

Using both classical and quantum approaches, we model plasmonic phenomena in nanoparticle (NP) dimers and trimers. Using a model of three nanoparticles, we propose a mechanism of non-dissipative and ultrafast plasmon passage assisted by hot spots. For this, the NP trimer should include two Au-NPs and one Ag-NP. In the Au-Ag-Au trimer, the two Au-plasmons become coupled via the virtual plasmon of the Ag-NP. The efficient and ultra-fast passage of the Au-plasmons assisted by the virtual Ag-plasmon only becomes possible when the inter-NP gaps in the trimer are small. In this coupling regime, the inter-NP gap regions become plasmonic hot spots that greatly enhance the plasmonic passage effect. At this moment, the plasmonic passage phenomenon was already observed experimentally using optical spectroscopy and the DNA-origami NP complexes. Other systems of our interest were a NP dimer and a nanostar with plasmonic hot spots. For those systems, we predict strong enhancement of the generation of energetic (hot) carriers.

The Dependence of CNT Aerogel Synthesis on Sulfur-driven Catalyst Nucleation Processes and a Critical Catalyst Particle Mass Concentration.

PubMed

Hoecker, Christian; Smail, Fiona; Pick, Martin; Weller, Lee; Boies, Adam M

2017-11-06

The floating catalyst chemical vapor deposition (FC-CVD) process permits macro-scale assembly of nanoscale materials, enabling continuous production of carbon nanotube (CNT) aerogels. Despite the intensive research in the field, fundamental uncertainties remain regarding how catalyst particle dynamics within the system influence the CNT aerogel formation, thus limiting effective scale-up. While aerogel formation in FC-CVD reactors requires a catalyst (typically iron, Fe) and a promotor (typically sulfur, S), their synergistic roles are not fully understood. This paper presents a paradigm shift in the understanding of the role of S in the process with new experimental studies identifying that S lowers the nucleation barrier of the catalyst nanoparticles. Furthermore, CNT aerogel formation requires a critical threshold of Fe x C y  > 160 mg/m 3 , but is surprisingly independent of the initial catalyst diameter or number concentration. The robustness of the critical catalyst mass concentration principle is proved further by producing CNTs using alternative catalyst systems; Fe nanoparticles from a plasma spark generator and cobaltocene and nickelocene precursors. This finding provides evidence that low-cost and high throughput CNT aerogel routes may be achieved by decoupled and enhanced catalyst production and control, opening up new possibilities for large-scale CNT synthesis.

Ameliorative role of nano-ceria against amine coated Ag-NP induced toxicity in Labeo rohita

NASA Astrophysics Data System (ADS)

Khan, Muhammad Saleem; Qureshi, Naureen Aziz; Jabeen, Farhat

2018-03-01

Silver nanoparticles (Ag-NPs) and its byproducts can spread pollution in aquatic habitat. Liver and gills are key target for toxicity. Oxidative stress, tissue alterations, and hemotoxicity are assumed to be associated with Ag-NPs in target animals. Cerium oxide nanoparticles (nano-ceria) show antioxidant potential in scavenging the free radicals generated in Ag-NP-induced oxidative stress. We determined ameliorated role of nano-ceria against Ag-NP-induced toxicity in fresh water Labeo rohita (L. rohita). Four groups were used in study including control, nano-ceria, Ag-NPs, and Ag-NPs + nano-ceria. Ag-NPs (30 mg l-1) and nano-ceria (50 µg kg-1) were given through water and prepared feed, respectively. The samples were taken after 28 days. Results demonstrated that pre-treatment of nano-ceria recovered L. rohita from Ag-NP-induced toxicity and oxidative stress. Nano-ceria pre-treatment actively mimics the activity of GST, GSH, CAT, and SOD. Furthermore, Ag-NPs' treatment caused severe inflammation and necrosis in hepatic parenchyma which leaded to congestion of blood in hepatic tissues. Accumulation of a yellow pigment in hepatic tissue was also seen due to necrosis of affected cells. In nano-ceria pre-treatment, there was no congestion in hepatic tissue. Vacuolization of cells and necrosis in some area was recorded in nano-ceria pre-treated group, but the gill and hepatic tissue showed improvement against Ag-NP-induced damage. Nano-ceria pre-treatment also improved hematological parameters in Ag-NP-treated fish. This study concluded that Ag-NP-induced toxicity in treated fish and pre-treatment of nano-ceria show ameliorative role.

Atomic scale deposition of Pt around Au nanoparticles to achieve much enhanced electrocatalysis of Pt

DOE PAGES

Xi, Zheng; Lv, Haifeng; Erdosy, Daniel P.; ...

2017-05-07

Here, we report an electrochemical method to deposit atomic scale Pt on a 5 nm Au nanoparticle (NP) surface in N 2-saturated 0.5 M H 2SO 4. Furthermore, Pt is provided by the Pt wire counter electrode via one-step Pt wire oxidation, dissolution, and deposition realized by controlled electrochemical scanning. Scanning from 0.6–1.0 V (vs. RHE) for 10 000 cycles gives Au 98.2Pt 1.8, which serves as an excellent catalyst for the formic acid oxidation reaction, showing 41 times higher specific activity (20.19 mA cm -2) and 25 times higher mass activity (10.80 A mg Pt -1) with much bettermore » CO-tolerance and stability than commercial Pt. This work demonstrates a unique strategy to minimize the use of Pt as a catalyst for electrochemical reactions.« less

Atomic scale deposition of Pt around Au nanoparticles to achieve much enhanced electrocatalysis of Pt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xi, Zheng; Lv, Haifeng; Erdosy, Daniel P.

Here, we report an electrochemical method to deposit atomic scale Pt on a 5 nm Au nanoparticle (NP) surface in N 2-saturated 0.5 M H 2SO 4. Furthermore, Pt is provided by the Pt wire counter electrode via one-step Pt wire oxidation, dissolution, and deposition realized by controlled electrochemical scanning. Scanning from 0.6–1.0 V (vs. RHE) for 10 000 cycles gives Au 98.2Pt 1.8, which serves as an excellent catalyst for the formic acid oxidation reaction, showing 41 times higher specific activity (20.19 mA cm -2) and 25 times higher mass activity (10.80 A mg Pt -1) with much bettermore » CO-tolerance and stability than commercial Pt. This work demonstrates a unique strategy to minimize the use of Pt as a catalyst for electrochemical reactions.« less

One-Pot Synthesis of Graphene-Supported Monodisperse Pd Nanoparticles as Catalyst for Formic Acid Electro-oxidation

PubMed Central

Yang, Sudong; Dong, Jing; Yao, Zhaohui; Shen, Chengmin; Shi, Xuezhao; Tian, Yuan; Lin, Shaoxiong; Zhang, Xiaogang

2014-01-01

To synthesize monodisperse palladium nanoparticles dispersed on reduced graphene oxide (RGO) sheets, we have developed an easy and scalable solvothermal reduction method from an organic solution system. The RGO-supported palladium nanoparticles with a diameter of 3.8 nm are synthesized in N-methyl-2-pyrrolidone (NMP) and in the presence of oleylamine and trioctylphosphine, which facilitates simultaneous reduction of graphene oxide and formation of Pd nanocrystals. So-produced Pd/RGO was tested for potential use as electrocatalyst for the electro-oxidation of formic acid. Pd/RGO catalyzes formic acid oxidation very well compared to Pd/Vulcan XC-72 catalyst. This synthesis method is a new way to prepare excellent electrocatalysts, which is of great significance in energy-related catalysis. PMID:24675779

Improved Oxygen Reduction Activity and Durability of Dealloyed PtCo x Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects.

PubMed

Jia, Qingying; Caldwell, Keegan; Strickland, Kara; Ziegelbauer, Joseph M; Liu, Zhongyi; Yu, Zhiqiang; Ramaker, David E; Mukerjee, Sanjeev

2015-01-02

The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Herein we report that the dealloyed PtCo/HSC and PtCo 3 /HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo 3 /HSC catalyst is dominated by NPs with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt-Pt and Pt-Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo 3 /HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling.

Green Silver Nanoparticles Based Dual Sensor for Toxic Hg (II) Ions.

PubMed

Sebastian, Maria; Aravind, Archana; Mathew, Beena

2018-06-11

The present study focuses on the utilization of green silver nanoparticles as they are more preferred for sensing applications due to their environment friendly nature. We have examined the optical and electrochemical sensing behavior of silver nanoparticles from Agaricus Bispores (AgNP-AB) towards Hg(II) ions. AgNP-AB was prepared by microwave reactor. The synthesized AgNPs have been used for the sensing of Hg(II) ions without the use of modifiers or further sophisticated instrumentation. The synthesized nanoparticles were successfully characterized by different techniques. AgNP-AB leads to aggregation with addition of Hg(II) ions in aqueous medium and developed a color change from brown to black which leads to the formation of AgNP-AB-Hg(II) complex. Moreover, the metal sensing ability of AgNPs has been explored using electrochemical studies. AgNP-AB modified platinum electrode (AgNP-AB/PE) was developed for the fast sensing of toxic Hg(II) ions. The sensor exhibits good limit of detection at 2.1x10-6M. The sensitivity of AgNP-AB/PE towards Hg(II) ion was analyzed with various metal ions. The sensing skill of developed system was successfully checked with real water sample from Vembanade Lake, Kumarakom, Kerala. The silver nanoparticles from Agaricus Bispoes are highly versatile and promising for different environmental applications. © 2018 IOP Publishing Ltd.

Improved delivery of magnetic nanoparticles with chemotherapy cancer treatment

NASA Astrophysics Data System (ADS)

Petryk, Alicia A.; Giustini, Andrew J.; Gottesman, Rachel E.; Hoopes, P. Jack

2013-02-01

Most nanoparticle-based cancer therapeutic strategies seek to develop an effective individual cancer cell or metastatic tumor treatment. Critical to the success of these therapies is to direct as much of the agent as possible to the targeted tissue while avoiding unacceptable normal tissue complications. In this light, three different cisplatinum/magnetic nanoparticle (mNP) administration regimens were investigated. The most important finding suggests that clinically relevant doses of cisplatinum result in a significant increase in the tumor uptake of systemically delivered mNP. This enhancement of mNP tumor uptake creates the potential for an even greater therapeutic ratio through the addition of mNP based, intracellular hyperthermia.

Nanoparticle-nanoparticle vs. nanoparticle-substrate hot spot contributions to the SERS signal: studying Raman labelled monomers, dimers and trimers.

PubMed

Sergiienko, Sergii; Moor, Kamila; Gudun, Kristina; Yelemessova, Zarina; Bukasov, Rostislav

2017-02-08

We used a combination of Raman microscopy, AFM and TEM to quantify the influence of dimerization on the surface enhanced Raman spectroscopy (SERS) signal for gold and silver nanoparticles (NPs) modified with Raman reporters and situated on gold, silver, and aluminum films and a silicon wafer. The overall increases in the mean SERS enhancement factor (EF) upon dimerization (up by 43% on average) and trimerisation (up by 96% on average) of AuNPs and AgNPs on the studied metal films are within a factor of two, which is moderate when compared to most theoretical models. However, the maximum ratio of EFs for some dimers to the mean EF of monomers can be as high as 5.5 for AgNPs on a gold substrate. In contrast, for dimerization and trimerization of gold and silver NPs on silicon, the mean EF increases by 1-2 orders of magnitude relative to the mean EF of single NPs. Therefore, hot spots in the interparticle gap between gold nanoparticles rather than hot spots between Au nanoparticles and the substrate dominate SERS enhancement for dimers and trimers on a silicon substrate. However, Raman labeled noble metal nanoparticles on plasmonic metal films generate on average SERS enhancement of the same order of magnitude for both types of hot spot zones (e.g. NP/NP and NP/metal film).

Identification of NpO2+x in the binary Np-O system

NASA Astrophysics Data System (ADS)

Tayal, Akhil; Conradson, Steven D.; Baldinozzi, Gianguido; Namdeo, Sonu; Roberts, Kevin E.; Allen, Patrick G.; Shuh, David K.

2017-07-01

In contrast to UO2 and PuO2, there is no consensus on the existence of mixed valence NpO2+x, resulting in a gap between NpO2 and Np2O5 (the highest binary oxide of Np) in the Np-O phase diagram. We now show NpO2+x via Np LIII Extended X-ray Absorption Fine Structure (EXAFS) spectra of three samples of NpO2 that, analogous to U and Pu, exhibit multisite Np-O distributions with varying numbers of oxygen atoms at 1.87-1.91 Å. This is supported by the diffraction pattern of the sample with the largest amount of this oxo-type species that can be refined with both the simple fluorite structure and a trigonal one related to α-U4O9. The implied Np(V)-bridging oxo moieties as well as possible indications of OHbar found by detailed EXAFS analysis suggest that NpO2+x more closely resembles PuO2+x than UO2+x. An additional common characteristic suggested by the EXAFS and X-Ray Diffraction (XRD) is the phase separation into NpO2 and what would be previously unreported Np4O9(-δ), indicative of O clustering.

Nickel-doped cobalt ferrite nanoparticles: efficient catalysts for the reduction of nitroaromatic compounds and photo-oxidative degradation of toxic dyes

NASA Astrophysics Data System (ADS)

Singh, Charanjit; Goyal, Ankita; Singhal, Sonal

2014-06-01

This study deals with the exploration of NixCo1-xFe2O4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) ferrite nanoparticles as catalysts for reduction of 4-nitrophenol and photo-oxidative degradation of Rhodamine B. The ferrite samples with uniform size distribution were synthesized using the reverse micelle technique. The structural investigation was performed using powder X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray and scanning tunneling microscopy. The spherical particles with ordered cubic spinel structure were found to have the crystallite size of 4-6 nm. Diffused UV-visible reflectance spectroscopy was employed to investigate the optical properties of the synthesized ferrite nanoparticles. The surface area calculated using BET method was found to be highest for Co0.4Ni0.6Fe2O4 (154.02 m2 g-1). Co0.4Ni0.6Fe2O4 showed the best catalytic activity for reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4 as reducing agent, whereas CoFe2O4 was found to be catalytically inactive. The reduction reaction followed pseudo-first order kinetics. The effect of varying the concentration of catalyst and NaBH4 on the reaction rates was also scrutinized. The photo-oxidative degradation of Rhodamine B, enhanced oxidation efficacy was observed with the introduction of Ni2+ in to the cobalt ferrite lattice due to octahedral site preference of Ni2+. Almost 99% degradation was achieved in 20 min using NiFe2O4 nanoparticles as catalyst.

An extracellular enzyme synthesizes narrow-sized silver nanoparticles in both water and methanol

NASA Astrophysics Data System (ADS)

Rai, Tripti; Panda, Debashis

2015-03-01

Cellulase reduces silver ions in both aqueous and methanolic media yielding stable narrow-sized silver nanoparticles (Ag-NP) at room temperature. The synthesized nanoparticles have been characterized by various spectroscopic, microscopic methods. The redox potentials of tyrosine residues and protein backbone play an instrumental role to reduce the metal ions. The average size of nanoparticles formed in aqueous medium is of 5.04 ± 3.50 nm. Post-synthesis of Ag-NP secondary structure of enzyme is completely lost whereas upon incubation with chemically synthesized Ag-NP a significant gain in secondary structure is observed. Cellulase as a capping ligand stabilizes the silver nanoparticles even in methanol.

Transformation of sodium bicarbonate and CO2 into sodium formate over NiPd nanoparticle catalyst

PubMed Central

Wang, Mengnan; Zhang, Jiaguang; Yan, Ning

2013-01-01

The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs). Ni NPs and eight NiM (M stands for a second metal) NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability. PMID:24790945

Self-Assembly Template Driven 3D Inverse Opal Microspheres Functionalized with Catalyst Nanoparticles Enabling a Highly Efficient Chemical Sensing Platform.

PubMed

Wang, Tianshuang; Can, Inci; Zhang, Sufang; He, Junming; Sun, Peng; Liu, Fangmeng; Lu, Geyu

2018-02-14

The design of semiconductor metal oxides (SMOs) with well-ordered porous structure has attracted tremendous attention owing to their larger specific surface area. Herein, three-dimensional inverse opal In 2 O 3 microspheres (3D-IO In 2 O 3 MSs) were fabricated through one-step ultrasonic spray pyrolysis (USP) which employed self-assembly sulfonated polystyrene (S-PS) spheres as a sacrificial template. The spherical pores observed in the 3D-IO In 2 O 3 MSs had diameters of about 4 and 80 nm. Subsequently, the catalytic palladium oxide nanoparticles (PdO NPs) were loaded on 3D-IO In 2 O 3 MSs via a simple impregnation method, and their gas sensing properties were investigated. In a comparison with pristine 3D-IO In 2 O 3 MSs, the 3D-IO PdO@In 2 O 3 MSs exhibited a 3.9 times higher response (R air /R gas = 50.9) to 100 ppm acetone at 250 °C and a good acetone selectivity. The detection limit for acetone could extend down to ppb level. Furthermore, the 3D-IO PdO@In 2 O 3 MSs-based sensor also possess good long-term stability. The extraordinary sensing performance can be attributed to the novel 3D periodic porous structure, highly three-dimensional interconnection, larger specific surface area, size-tunable (meso- and macroscale) bimodal pores, and PdO NP catalysts.

Effect of Gold Nanoparticles Addition to CuO–ZnO/A₂O₃ Catalyst in Conversion of Carbon Dioxide to Methanol.

PubMed

Kim, Ki-Joong; Ahn, Ho-Geun

2017-04-01

Hydrogenation of carbon dioxide (CO₂) into methanol (CH₃OH) was carried out in the CuO–ZnO based supported gold catalyst prepared by the co-precipitation method. When gold nanoparticles were added to the CuO–ZnO/Al2O₃ catalysts (CuO–ZnO/Au/Al₂O₃), the CO₂ conversion and CH₃OH yield were increased (two times higher than that of CuO–ZnO/Al₂O₃ catalyst) with increasing reaction pressure, but selectivity of CH3OH was decreased. The main reason of this result could suggest the importance gold-oxides interface in CH₃OH formation through hydrogenation of CO₂. Maximum selectivity and yield to CH₃OH over CuO–ZnO/Au/Al₂O₃ were obtained at 250°C and under 15–20 bars.

PHENANTHROLINE-STABILIZED PALLADIUM NANOPARTICLES IN POLYETHYLENE GLYCOL—AN ACTIVE AND RECYCLABLE CATALYST SYSTEM FOR THE SELECTIVE HYDROGENATION OF OLEFINS USING MOLECULAR HYDROGEN

EPA Science Inventory

1,10-Phenanthroline-stabilized palladium nanoparticles dispersed in a polyethylene glycol (PEG) matrix is synthesized which is found to be a stable and active catalyst for the selective hydrogenation of olefins using molecular hydrogen under mild reaction conditions. A variety of...

Synthesis of Vertically-Aligned Carbon Nanotubes from Langmuir-Blodgett Films Deposited Fe Nanoparticles on Al2O3/Al/SiO2/Si Substrate.

PubMed

Takagiwa, Shota; Kanasugi, Osamu; Nakamura, Kentaro; Kushida, Masahito

2016-04-01

In order to apply vertically-aligned carbon nanotubes (VA-CNTs) to a new Pt supporting material of polymer electrolyte fuel cell (PEFC), number density and outer diameter of CNTs must be controlled independently. So, we employed Langmuir-Blodgett (LB) technique for depositing CNT growth catalysts. A Fe nanoparticle (NP) was used as a CNT growth catalyst. In this study, we tried to thicken VA-CNT carpet height and inhibit thermal aggregation of Fe NPs by using Al2O3/Al/SiO2/Si substrate. Fe NP LB films were deposited on three typed of substrates, SiO2/Si, as-deposited Al2O3/Al/SiO2/Si and annealed Al2O3/Al/SiO2/Si at 923 K in Ar atmosphere of 16 Pa. It is known that Al2O3/Al catalyzes hydrocarbon reforming, inhibits thermal aggregation of CNT growth catalysts and reduces CNT growth catalysts. It was found that annealed Al2O3/Al/SiO2/Si exerted three effects more strongly than as-deposited Al2O3/Al/SiO2/Si. VA-CNTs were synthesized from Fe NPs-C16 LB films by thermal chemical vapor deposition (CVD) method. As a result, at the distance between two nearest CNTs 28 nm or less, VA-CNT carpet height on annealed Al2O3/Al/SiO2/Si was about twice and ten times thicker than that on SiO2/Si and that on as-deposited Al2O3/Al/SiO2/Si, respectively. Moreover, distribution of CNT outer diameter on annealed Al2O3/Al/SiO2/Si was inhibited compared to that on SiO2/Si. These results suggest that since thermal aggregation of Fe NPs is inhibited, catalyst activity increases and distribution of Fe NP size is inhibited.

Cobalt nanoparticles on charcoal: a versatile catalyst in the Pauson-Khand reaction, hydrogenation, and the reductive Pauson-Khand reaction.

PubMed

Son, Seung Uk; Park, Kang Hyun; Chung, Young Keun

2002-10-31

[formula: see text] Dispersions of nanometer-sized cobalt particles with very high stability were prepared in charcoal and analyzed by electron microscopy and X-ray analysis. The resulting cobalt nanoparticles on charcoal (CNC) were successfully used as a catalyst for the carbonylative cycloaddition of alkyne, alkene, and carbon monoxide (Pauson-Khand reaction), hydrogenation, and the reductive Pauson-Khand reaction.

Direct hydrogenation and one-pot reductive amidation of nitro compounds over Pd/ZnO nanoparticles as a recyclable and heterogeneous catalyst

NASA Astrophysics Data System (ADS)

Hosseini-Sarvari, Mona; Razmi, Zahra

2015-01-01

A novel Pd supported on ZnO nanoparticles was readily synthesized and characterized. The amount of palladium on ZnO is 9.84 wt% which was determined by ICP analysis and atomic absorption spectroscopy (AAS). Percentage of accessible Pd as active catalyst is also estimated to 2.72% based on the thermogravimetric (TG) analysis. This nano-sized Pd/ZnO with an average particle size of 20-25 nm and specific surface area 40.61 m2 g-1 was used as a new reusable heterogeneous catalyst for direct hydrogenation and one-pot reductive amidation of nitro compounds without the use of any ligands under atmospheric pressure. The catalyst can be recovered and recycled several times without marked loss of activity.

Cellular uptake and anticancer effects of mucoadhesive curcumin-containing chitosan nanoparticles.

PubMed

Chuah, Lay Hong; Roberts, Clive J; Billa, Nashiru; Abdullah, Syahril; Rosli, Rozita

2014-04-01

Curcumin, which is derived from turmeric has gained much attention in recent years for its anticancer activities against various cancers. However, due to its poor absorption, rapid metabolism and elimination, curcumin has a very low oral bioavailability. Therefore, we have formulated mucoadhesive nanoparticles to deliver curcumin to the colon, such that prolonged contact between the nanoparticles and the colon leads to a sustained level of curcumin in the colon, improving the anticancer effect of curcumin on colorectal cancer. The current work entails the ex vivo mucoadhesion study of the formulated nanoparticles and the in vitro effect of mucoadhesive interaction between the nanoparticles and colorectal cancer cells. The ex vivo study showed that curcumin-containing chitosan nanoparticles (CUR-CS-NP) have improved mucoadhesion compared to unloaded chitosan nanoparticles (CS-NP), suggesting that curcumin partly contributes to the mucoadhesion process. This may lead to an enhanced anticancer effect of curcumin when formulated in CUR-CS-NP. Our results show that CUR-CS-NP are taken up to a greater extent by colorectal cancer cells, compared to free curcumin. The prolonged contact offered by the mucoadhesion of CUR-CS-NP onto the cells resulted in a greater reduction in percentage cell viability as well as a lower IC50, indicating a potential improved treatment outcome. The formulation and free curcumin appeared to induce cell apoptosis in colorectal cancer cells, by arresting the cell cycle at G2/M phase. The superior anticancer effects exerted by CUR-CS-NP indicated that this could be a potential treatment for colorectal cancer. Copyright © 2014 Elsevier B.V. All rights reserved.

Water-soluble metal nanoparticles stabilized by plant polyphenols for improving the catalytic properties in oxidation of alcohols

NASA Astrophysics Data System (ADS)

Mao, H.; Liao, Y.; Ma, J.; Zhao, S. L.; Huo, F. W.

2015-12-01

Plant polyphenols extracted from plants are one of the most abundant biomasses in nature, which are typical water soluble natural polymers. Herein, we reported a facile approach for the synthesis of platinum nanoparticle (PtNP) aqueous colloid by utilizing black wattle tannin (BWT, a typical plant polyphenol) as amphiphilic stabilizer. The phenolic hydroxyls of BWT provide the PtNPs with enough hydrophilicity, and their reduction ability could protect the PtNPs from deactivation caused by oxygen atmosphere. Additionally, the hydrophilic nature of BWT could efficiently promote the oxidation of alcohols in water, meanwhile, the hydrophobic and rigid backbones of plant polyphenols are able to suppress the PtNPs from aggregating, thus ensuring the high dispersion of the PtNPs during reactions. Under mild aerobic conditions, the as-prepared BWT-Pt colloid catalyst exhibited high activity in a series of biphasic oxidation of aromatic alcohols and aliphatic alcohols. As for the cycling stability, the BWT-Pt catalyst showed no obvious decrease during the 7 cycles, revealing superior cycling stability as compared with the counterparts using PVP or PEG as the stabilizer.Plant polyphenols extracted from plants are one of the most abundant biomasses in nature, which are typical water soluble natural polymers. Herein, we reported a facile approach for the synthesis of platinum nanoparticle (PtNP) aqueous colloid by utilizing black wattle tannin (BWT, a typical plant polyphenol) as amphiphilic stabilizer. The phenolic hydroxyls of BWT provide the PtNPs with enough hydrophilicity, and their reduction ability could protect the PtNPs from deactivation caused by oxygen atmosphere. Additionally, the hydrophilic nature of BWT could efficiently promote the oxidation of alcohols in water, meanwhile, the hydrophobic and rigid backbones of plant polyphenols are able to suppress the PtNPs from aggregating, thus ensuring the high dispersion of the PtNPs during reactions. Under mild aerobic

The synthesis and characterization of iron nanoparticles

NASA Astrophysics Data System (ADS)

Bennett, Tyler

Nanoparticle synthesis has garnered attention for technological applications for catalysts, industrial processing, and medical applications. The size ranges for these is in the particles nanostructural domain. Pure iron nanoparticles have been of particular interest for their reactivity and relative biological inertness. Applications include cancer treatment and carrying medicine to a relevant site. Unfortunately, because of their reactivity, pure iron nanoparticles have been difficult to study. This is because of their accelerated tendency to form oxides in air, due to the increased surface area to volume ratio. Using synthesis processes with polyphenols or long chain amines, air stable iron nanoparticles have been produced with a diameter size range of ~ 2 to about ~10 nm, but apparently have transformed due to internal pressure and crystallographic defects to the FCC phase. The FCC crystals have been seen to form icosahedral and decahedral shapes. This size is within the range for use as a catalyst for the growth of both carbon nanotubes and boron nitride nanotubes as well for biomedical applications. The advantages of these kinds of catalysts are that nanotube growth can be for the first time separated from the catalyst formation. Additionally, the catalyst size can be preselected for a certain size nanotube to grow. In summary: (1) we found the size distributions of nanoparticles for various synthesis processes, (2) we discovered the right size range for growth of nanotubes from the iron nanoparticles, (3) the nanoparticles are under a very high internal pressure, (4) the nanoparticles are in the FCC phase, (5) they appear to be in icosahedral and decahedral structures, (6) they undergo room temperature twinning, (7) the FCC crystals are distorted due to carbon in octahedral sites, (8) the iron nanoparticles are stable in air, (9) adding small amounts of copper make the iron nanoparticles smaller.

Zwitterionic-surfactant-stabilized palladium nanoparticles as catalysts in the hydrogen transfer reductive amination of benzaldehydes.

PubMed

Drinkel, Emma E; Campedelli, Roberta R; Manfredi, Alex M; Fiedler, Haidi D; Nome, Faruk

2014-03-21

Palladium nanoparticles (NPs) stabilized by a zwitterionic surfactant are revealed here to be good catalysts for the reductive amination of benzaldehydes using formate salts as hydrogen donors in aqueous isopropanol. In terms of environmental impact and economy, metallic NPs offer several advantages over homogeneous and traditional heterogeneous catalysts. NPs usually display greater activity due to the increased metal surface area and sometimes exhibit enhanced selectivity. Thus, it is possible to use very low loadings of expensive metal. The methodology eliminates the use of a hydrogen gas atmosphere or toxic or expensive reagents. A range of aromatic aldehydes were converted to benzylamines when reacted with primary and secondary amines in the presence of the Pd NPs, which also displayed good activity when supported on alumina. In every case, the Pd NPs could be easily recovered and reused up to three more times, and at the end of the process, the product was metal-free.

A ship-in-a-bottle strategy to synthesize encapsulated intermetallic nanoparticle catalysts: Exemplified for furfural hydrogenation

DOE PAGES

Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; Goh, Tian Wei; ...

2016-01-28

In this paper, intermetallic compounds are garnering increasing attention as efficient catalysts for improved selectivity in chemical processes. Here, using a ship-in-a-bottle strategy, we synthesize single-phase platinum-based intermetallic nanoparticles (NPs) protected by a mesoporous silica (mSiO 2) shell by heterogeneous reduction and nucleation of Sn, Pb, or Zn in mSiO 2-encapsulated Pt NPs. For selective hydrogenation of furfural to furfuryl alcohol, a dramatic increase in activity and selectivity is observed when intermetallic NPs catalysts are used in comparison to Pt@mSiO 2. Among the intermetallic NPs, PtSn@mSiO 2 exhibits the best performance, requiring only one-tenth of the quantity of Pt usedmore » in Pt@mSiO 2 for similar activity and near 100% selectivity to furfuryl alcohol. A high-temperature oxidation–reduction treatment easily reverses any carbon deposition-induced catalyst deactivation. X-ray photoelectron spectroscopy shows the importance of surface composition to the activity, whereas density functional theory calculations reveal that the enhanced selectivity on PtSn compared to Pt is due to the different furfural adsorption configurations on the two surfaces.« less

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

DOE PAGES

Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; ...

2016-01-14

The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizesmore » the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.« less

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

PubMed Central

Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

2016-01-01

The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells. PMID:26762466

Evaluation of E. coli inhibition by plain and polymer-coated silver nanoparticles.

PubMed

Ashmore, D'Andrea; Chaudhari, Atul; Barlow, Brandi; Barlow, Brett; Harper, Talia; Vig, Komal; Miller, Michael; Singh, Shree; Nelson, Edward; Pillai, Shreekumar

2018-01-01

Escherichia coli causes various ailments such as septicemia, enteritis, foodborne illnesses, and urinary tract infections which are of concern in the public health field due to antibiotic resistance. Silver nanoparticles (AgNP) are known for their biocompatibility and antibacterial activity, and may prove to be an alternative method of treatment, especially as wound dressings. In this study, we compared the antibacterial efficacy of two polymer-coated silver nanoparticles either containing 10% Ag (Ag 10% + Polymer), or 99% Ag (AgPVP) in relation to plain uncoated silver nanoparticles (AgNP). Atomic force microscopy was used to characterize the nanoparticles, and their antibacterial efficacy was compared by the minimum inhibitory concentration (MIC) and bacterial growth curve assays, followed by molecular studies using scanning electron microscopy (SEM) and (qRT- PCR). AgNP inhibited the growth of E. coli only at 0.621 mg/mL, which was double the concentration required for both coated nanoparticles (0.312 mg/mL). Similarly, bacterial growth was impeded as early as 8 h at 0.156 mg/mL of both coated nanoparticles as compared to 0.312 mg/mL for plain AgNP. SEM data showed that nanoparticles damaged the cell membrane, resulting in bacterial cell lysis, expulsion of cellular contents, and complete disintegration of some cells. The expression of genes associated with the TCA cycle (aceF and frdB) and amino acid metabolism (gadB, metL, argC) were substantially downregulated in E. coli treated with nanoparticles. The reduction in the silver ion (Ag+) concentration of polymer-coated AgNP did not affect their antibacterial efficacy against E. coli.

Manganese porphyrin immobilized on magnetic MCM-41 nanoparticles as an efficient and reusable catalyst for alkene oxidations with sodium periodate

NASA Astrophysics Data System (ADS)

Hajian, Robabeh; Ehsanikhah, Amin

2018-01-01

This study describes the immobilization of tetraphenylporphyrinatomanganese(III) chloride, (MnPor), onto imidazole functionalized MCM-41 with magnetite nanoparticle core (Fe3O4@MCM-41-Im). The resultant material (Fe3O4@MCM-41-Im@MnPor) was characterized by X-ray diffractometry (XRD), Fourier transform infra-red (FT-IR), diffuse reflectance UV-Vis spectrophotometry (DR UV-Vis), field emission scanning electron microscopy (FESEM), Inductively coupled plasma (ICP), analyzer transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) surface area. This new heterogenized catalyst was applied as an efficient catalyst for the epoxidation of a variety of cyclic and linear olefins with NaIO4 under mild conditions. The prepared catalyst can be easily recovered through the application of an external magnet, and reused several times without any significant decrease in activity and magnetic properties.

Chitosan and silver nanoparticles as pudding with raisins with antimicrobial properties.

PubMed

Rodríguez-Argüelles, M Carmen; Sieiro, Carmen; Cao, Roberto; Nasi, Lucia

2011-12-01

Chitosan nanoparticles (CS-NP) containing small silver nanoparticles are reported (Ag@CS-NP). CS-NP was synthesized using tripolyphosphate (TPP) as a polyanionic template. TPP also served to electrostatically attract Ag(+) inside CS-NP, where it was reduced by the terminal glucosamine units of the biopolymer. This procedure is environmental friendly, inexpensive, and permits the synthesis of very small AgNP (0.93-1.7 nm), with only a discrete dependence from the amount of silver nitrate used (5-200mg). The obtained hybrid nanocomposites Ag@CS-NP were characterized by DLS, HRTEM, and HAADF-STEM presenting a mean hydrodynamic diameter of 78 nm. The antimicrobial activity of Ag@CS-NP against Candida glabrata, Sacharomyces cerevisiae, Escherichia coli, Klebsiella pneumoniae, Salmonella, Staphylococcus aureus, and Bacillus cereus corresponded to MIC values lower than for AgNO(3). Copyright © 2011 Elsevier Inc. All rights reserved.

Ultrasmall PdmMn1-mOx binary alloyed nanoparticles on graphene catalysts for ethanol oxidation in alkaline media

NASA Astrophysics Data System (ADS)

Ahmed, Mohammad Shamsuddin; Park, Dongchul; Jeon, Seungwon

2016-03-01

A rare combination of graphene (G)-supported palladium and manganese in mixed-oxides binary alloyed catalysts (BACs) have been synthesized with the addition of Pd and Mn metals in various ratios (G/PdmMn1-mOx) through a facile wet-chemical method and employed as an efficient anode catalyst for ethanol oxidation reaction (EOR) in alkaline fuel cells. The as prepared G/PdmMn1-mOx BACs have been characterized by several instrumental techniques; the transmission electron microscopy images show that the ultrafine alloyed nanoparticles (NPs) are excellently monodispersed onto the G. The Pd and Mn in G/PdmMn1-mOx BACs have been alloyed homogeneously, and Mn presents in mixed-oxidized form that resulted by X-ray diffraction. The electrochemical performances, kinetics and stability of these catalysts toward EOR have been evaluated using cyclic voltammetry in 1 M KOH electrolyte. Among all G/PdmMn1-mOx BACs, the G/Pd0.5Mn0.5Ox catalyst has shown much superior mass activity and incredible stability than that of pure Pd catalysts (G/Pd1Mn0Ox, Pd/C and Pt/C). The well dispersion, ultrafine size of NPs and higher degree of alloying are the key factor for enhanced and stable EOR electrocatalysis on G/Pd0.5Mn0.5Ox.

Carbon nanotube-supported Au-Pd alloy with cooperative effect of metal nanoparticles and organic ketone/quinone groups as a highly efficient catalyst for aerobic oxidation of amines.

PubMed

Deng, Weiping; Chen, Jiashu; Kang, Jincan; Zhang, Qinghong; Wang, Ye

2016-05-21

Functionalised carbon nanotube (CNT)-supported Au-Pd alloy nanoparticles were highly efficient catalysts for the aerobic oxidation of amines. We achieved the highest turnover frequencies (>1000 h(-1)) for the oxidative homocoupling of benzylamine and the oxidative dehydrogenation of dibenzylamine. We discovered a cooperative effect between Au-Pd nanoparticles and ketone/quinone groups on CNTs.

Improved Oxygen Reduction Activity and Durability of Dealloyed PtCo x Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects

DOE PAGES

Jia, Qingying; Caldwell, Keegan; Strickland, Kara; ...

2014-11-19

The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Here in this paper, we report that the dealloyed PtCo/HSC and PtCo 3/HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo 3/HSC catalyst is dominated by NPsmore » with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt–Pt and Pt–Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo 3/HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling.« less

In situ synthesis of silver-nanoparticles/bacterial cellulose composites for slow-released antimicrobial wound dressing.

PubMed

Wu, Jian; Zheng, Yudong; Song, Wenhui; Luan, Jiabin; Wen, Xiaoxiao; Wu, Zhigu; Chen, Xiaohua; Wang, Qi; Guo, Shaolin

2014-02-15

Bacterial cellulose has attracted increasing attention as a novel wound dressing material, but it has no antimicrobial activity, which is one of critical skin-barrier functions in wound healing. To overcome such deficiency, we developed a novel method to synthesize and impregnate silver nanoparticles on to bacterial cellulose nanofibres (AgNP-BC). Uniform spherical silver nano-particles (10-30 nm) were generated and self-assembled on the surface of BC nano-fibers, forming a stable and evenly distributed Ag nanoparticles coated BC nanofiber. Such hybrid nanostructure prevented Ag nanoparticles from dropping off BC network and thus minimized the toxicity of nanoparticles. Regardless the slow Ag(+) release, AgNP-BC still exhibited significant antibacterial activities with more than 99% reductions in Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa. Moreover, AgNP-BC allowed attachment and growth of epidermal cells with no cytotoxicity emerged. The results demonstrated that AgNP-BC could reduce inflammation and promote wound healing. Copyright © 2013 Elsevier Ltd. All rights reserved.

Conducting metal oxide and metal nitride nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

DiSalvo, Jr., Francis J.; Subban, Chinmayee V.

Conducting metal oxide and nitride nanoparticles that can be used in fuel cell applications. The metal oxide nanoparticles are comprised of for example, titanium, niobium, tantalum, tungsten and combinations thereof. The metal nitride nanoparticles are comprised of, for example, titanium, niobium, tantalum, tungsten, zirconium, and combinations thereof. The nanoparticles can be sintered to provide conducting porous agglomerates of the nanoparticles which can be used as a catalyst support in fuel cell applications. Further, platinum nanoparticles, for example, can be deposited on the agglomerates to provide a material that can be used as both an anode and a cathode catalyst supportmore » in a fuel cell.« less

Synthesis of nanoporous CuO/TiO2/Pd-NiO composite catalysts by chemical dealloying and their performance for methanol and ethanol electro-oxidation

NASA Astrophysics Data System (ADS)

Niu, Mengying; Xu, Wence; Zhu, Shengli; Liang, Yanqin; Cui, Zhenduo; Yang, Xianjin; Inoue, Akihisa

2017-09-01

Nanoporous CuO/TiO2/Pd-NiO-x (x = 0, 1, 3, 5, 7 at%) catalysts have been synthesized by dealloying Cu-Ti-Pd-Ni alloy ribbons in acid solution. The nanoporous structure and chemical composition of the catalysts distribute uniformly. Based on the electrochemical active area (EASA), electrocatalytic activity and stability, the np-CuO/TiO2/Pd-NiO-3 catalyst possesses the best performance for methanol and ethanol electro-oxidation. For methanol and ethanol electro-oxidation, the anodic current densities in forward scan of the np-CuO/TiO2/Pd-NiO-3 catalyst are about 5.6 times and 2.1 times larger than that of the np-CuO/TiO2/Pd catalyst, respectively. The introduction of NiO provides more electrochemical active sites due to the improved geometrical and bifunctional mechanism. NiO promotes the adsorption of oxygen-containing species (OHads) on the catalyst surface, and electron effect between Pd and Ni is favorable for charge transfer. This accelerates the removal of intermediate products during the oxidation process. The electrocatalytic processes of methanol and ethanol oxidation in alkaline solution are controlled by both charge transfer and diffusion.

Optical effects in artificial opals infiltrated with gold nanoparticles

NASA Astrophysics Data System (ADS)

Comoretto, Davide; Morandi, Valentina; Marabelli, Franco; Amendola, Vincenzo; Meneghetti, Moreno

2006-04-01

Polystyrene artificial opals are directly grown with embedded gold nanoparticles (NpAu) in their interstices. Reflectance spectra of samples having different sphere diameters and nanoparticles load clearly show a red shift of the photonic band gap as well as a reduction of its width without showing direct evidence of NpAu absorption. The case of transmission spectra is instead more complicated: here, overlapped to a broad NpAu absorption, a structure having unusual lineshape is detected. The infiltration of opal with NpAu removes the polarization dependence of the photonic band structure observed in bare opals. The lineshape of the absorption spectra suggest a spatial localization of the electromagnetic field in the volume where NpAu are confined thus enhancing its local intensity. This effect seems to be effective to stimulate optical nonlinearities of NpAu. Nanosecond transient absorption measurements on NpAu infiltrated opals indicate that a variation of transmission of about 10% is observed. Since this effect takes place within the pump pulse and since NpAu photoluminescence has been subtracted to the signal, we attribute it to an optical switching process.

SERS-barcoded colloidal gold NP assemblies as imaging agents for use in biodiagnostics

NASA Astrophysics Data System (ADS)

Dey, Priyanka; Olds, William; Blakey, Idriss; Thurecht, Kristofer J.; Izake, Emad L.; Fredericks, Peter M.

2014-03-01

There is a growing need for new biodiagnostics that combine high throughput with enhanced spatial resolution and sensitivity. Gold nanoparticle (NP) assemblies with sub-10 nm particle spacing have the benefits of improving detection sensitivity via Surface enhanced Raman scattering (SERS) and being of potential use in biomedicine due to their colloidal stability. A promising and versatile approach to form solution-stable NP assemblies involves the use of multi-branched molecular linkers which allows tailoring of the assembly size, hot-spot density and interparticle distance. We have shown that linkers with multiple anchoring end-groups can be successfully employed as a linker to assemble gold NPs into dimers, linear NP chains and clustered NP assemblies. These NP assemblies with diameters of 30-120 nm are stable in solution and perform better as SERS substrates compared with single gold NPs, due to an increased hot-spot density. Thus, tailored gold NP assemblies are potential candidates for use as biomedical imaging agents. We observed that the hot-spot density and in-turn the SERS enhancement is a function of the linker polymer concentration and polymer architecture. New deep Raman techniques like Spatially Offset Raman Spectroscopy (SORS) have emerged that allow detection from beneath diffusely scattering opaque materials, including biological media such as animal tissue. We have been able to demonstrate that the gold NP assemblies could be detected from within both proteinaceous and high lipid containing animal tissue by employing a SORS technique with a backscattered geometry.

Adsorption of Vanadium (V) from SCR Catalyst Leaching Solution and Application in Methyl Orange.

PubMed

Sha, Xuelong; Ma, Wei; Meng, Fanqing; Wang, Ren; Fuping, Tian; Wei, Linsen

2016-12-01

  In this study, we explored an effective and low-cost catalyst and its adsorption capacity and catalytic capacity for Methyl Orange Fenton oxidation degradation were investigated. The catalyst was directly prepared by reuse of magnetic iron oxide (Fe3O4) after saturated adsorption of vanadium (V) from waste SCR (Selective Catalytic Reduction) catalyst. The obtained catalyst was characterized by FTIR, XPS and the results showed that vanadium (V) adsorption process of Fe3O4 nanoparticles was non-redox reaction. The effects of pH, adsorption kinetics and equilibrium isotherms of adsorption were assessed. Adsorption of vanadium (V) ions by Fe3O4 nanoparticles could be well described by the Sips isotherm model which controlled by the mixed surface reaction and diffusion (MSRDC) adsorption kinetic model. The results show that vanadium (V) was mainly adsorbed on external surface of the Fe3O4 nanoparticles. The separation-recovering tungsten (VI) and vanadium (V) from waste SCR catalyst alkaline solution through pH adjustment was also investigated in this study. The results obtained from the experiments indicated that tungsten (VI) was selectively adsorbed from vanadium (V)/tungsten (VI) mixed solution in certain acidic condition by Fe3O4 nanoparticle to realize their recovery. Tungsten (V) with some impurity can be obtained by releasing from adsorbent, which can be confirmed by ICP-AES. The Methyl Orange degradation catalytic performance illustrated that the catalyst could improve Fenton reaction effectively at pH = 3.0 compare to Fe3O4 nanoparticles alone. Therefore, Fe3O4 nanoparticle adsorbed vanadium (V) has a potential to be employed as a heterogeneous Fenton-like catalyst in the present contribution, and its catalytic activity was mainly evaluated in terms of the decoloration efficiency of Methyl Orange.

Release profile and stability evaluation of optimized chitosan/alginate nanoparticles as EGFR antisense vector

PubMed Central

Azizi, Ebrahim; Namazi, Alireza; Haririan, Ismaeil; Fouladdel, Shamileh; Khoshayand, Mohammad R; Shotorbani, Parisa Y; Nomani, Alireza; Gazori, Taraneh

2010-01-01

Chitosan/alginate nanoparticles which had been optimized in our previous study using two different N/P ratios were chosen and their ability to release epidermal growth factor receptor (EGFR) antisense was investigated. In addition, the stability of these nanoparticles in aqueous medium and after freeze-drying was investigated. In the case of both N/P ratios (5, 25), nanoparticles started releasing EGFR antisense as soon as they were exposed to the medium and the release lasted for approximately 50 hours. Nanoparticle size, shape, zeta potential, and release profile did not show any significant change after the freeze-drying process (followed by reswelling). The nanoparticles were reswellable again after freeze-drying in phosphate buffer with a pH of 7.4 over a period of six hours. Agarose gel electrophoresis of the nanoparticles with the two different N/P ratios showed that these nanoparticles could protect EGFR antisense molecules for six hours. PMID:20957167

Nanoscale Catalysts for NMR Signal Enhancement by Reversible Exchange

PubMed Central

2015-01-01

Two types of nanoscale catalysts were created to explore NMR signal enhancement via reversible exchange (SABRE) at the interface between heterogeneous and homogeneous conditions. Nanoparticle and polymer comb variants were synthesized by covalently tethering Ir-based organometallic catalysts to support materials composed of TiO2/PMAA (poly(methacrylic acid)) and PVP (polyvinylpyridine), respectively, and characterized by AAS, NMR, and DLS. Following parahydrogen (pH2) gas delivery to mixtures containing one type of “nano-SABRE” catalyst particle, a target substrate, and ethanol, up to ∼(−)40-fold and ∼(−)7-fold 1H NMR signal enhancements were observed for pyridine substrates using the nanoparticle and polymer comb catalysts, respectively, following transfer to high field (9.4 T). These enhancements appear to result from intact particles and not from any catalyst molecules leaching from their supports; unlike the case with homogeneous SABRE catalysts, high-field (in situ) SABRE effects were generally not observed with the nanoscale catalysts. The potential for separation and reuse of such catalyst particles is also demonstrated. Taken together, these results support the potential utility of rational design at molecular, mesoscopic, and macroscopic/engineering levels for improving SABRE and HET-SABRE (heterogeneous-SABRE) for applications varying from fundamental studies of catalysis to biomedical imaging. PMID:26185545

High performance, high durability non-precious metal fuel cell catalysts

DOEpatents

Wood, Thomas E.; Atanasoski, Radoslav; Schmoeckel, Alison K.

2016-03-15

This invention relates to non-precious metal fuel cell cathode catalysts, fuel cells that contain these catalysts, and methods of making the same. The fuel cell cathode catalysts are highly nitrogenated carbon materials that can contain a transition metal. The highly nitrogenated carbon materials can be supported on a nanoparticle substrate.

An Efficient and Reusable Embedded Ru Catalyst for the Hydrogenolysis of Levulinic Acid to γ-Valerolactone.

PubMed

Wei, Zuojun; Lou, Jiongtao; Su, Chuanmin; Guo, Dechao; Liu, Yingxin; Deng, Shuguang

2017-04-22

To achieve a higher activity and reusability of a Ru-based catalyst, Ru nanoparticles were embedded in N-doped mesoporous carbon through a hard-template method. The catalyst showed excellent catalytic performance (314 h -1 turnover frequency) and recyclability (reusable five times with 3 % activity loss) for the hydrogenolysis of levulinic acid to γ-valerolactone. Compared with the mesoporous carbon without N-doping and conventional activated carbon, the introduction of N-dopant effectively improved the dispersion of Ru nanoparticles, decreased the average size of Ru nanoparticles to as small as 1.32 nm, and improved the adsorption of levulinic acid, which contributed to the increase in the activity of the catalyst. Additionally, the embedding method increased the interaction between Ru nanoparticles and carbon support in contrast with the conventional impregnation method, thus preventing the Ru nanoparticles from migration, aggregation, and leaching from the carbon surface and therefore increasing the reusability of the catalyst. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cytotoxicity of curcumin silica nanoparticle complexes conjugated with hyaluronic acid on colon cancer cells.

PubMed

Singh, Surya Prakash; Sharma, Mrinalini; Gupta, Pradeep Kumar

2015-03-01

We report results of our investigations on the cytotoxic efficacy of Organically modified silica nanoparticle (SiNp)-curcumin complex conjugated with hyaluronic acid (HA) (HA-SiNp-cur) and HA free SiNp-cur complex in human colon carcinoma (colo-205) cells. Curcumin was loaded in SiNp and resulting complexes were conjugated with HA, which has a strong affinity for cancer cells expressing CD44. After conjugation with HA, the average size of the SiNp-cur nanoparticles increased from 45 nm to 70 nm, and zeta potential changed to -33 mV from -26 mV. Compared to free curcumin and SiNp-cur, curcumin in HA-SiNp was more stable. The uptake and cytotoxicity of curcumin delivered through HA-SiNp-cur was significantly higher in monolayer and spheroids as compared to free curcumin and HA free SiNp-cur. Concomitantly, HA-SiNp-cur complex treatment resulted in higher inhibition of growth and migration of cells in spheroids. Further, incubation of colo-205 cancer cells with an excess of HA impaired the uptake of HA-SiNp-cur confirming the involvement of receptor mediated endocytosis in the uptake of HA conjugated nanocomplex. Time dependent increase in the fluorescence of curcumin observed in the release media when HA-SiNp-cur was incubated with hyaluronidase suggests involvement of enzyme in release of curcumin from nanoparticle. Copyright © 2014 Elsevier B.V. All rights reserved.

The catalytic behavior of precisely synthesized Pt–Pd bimetallic catalysts for use as diesel oxidation catalysts

DOE PAGES

Wong, Andrew P.; Kyriakidou, Eleni A.; Toops, Todd J.; ...

2016-04-17

The demands of stricter diesel engine emission regulations have created challenges for current exhaust systems. With advances in low-temperature internal combustion engines and their operations, advances must also be made in vehicle exhaust catalysts. Most current diesel oxidation catalysts use heavy amounts of precious group metals (PGMs) for hydrocarbon (HC), CO, and NO oxidation. These catalysts are expensive and are most often synthesized with poor bimetallic interaction and dispersion. In this paper, the goal was to study the effect of aging on diesel emission abatement of Pt–Pd bimetallic nanoparticles precisely prepared with different morphologies: well dispersed core–shell vs. well dispersedmore » homogeneously alloyed vs. poorly dispersed, poorly alloyed particles. Alumina and silica supports were studied. Particle morphology and dispersion were analyzed before and after hydrothermal treatments by XRD, EDX, and STEM. Reactivity as a function of aging was measured in simulated diesel engine exhaust. While carefully controlled bimetallic catalyst nanoparticle structure has a profound influence on initial or low temperature catalytic activity, the differences in behavior disappear with higher temperature aging as thermodynamic equilibrium is achieved. The metallic character of Pt-rich alumina-supported catalysts is such that behavior rather closely follows the Pt–Pd metal phase diagram. Nanoparticles disparately composed as well-dispersed core–shell (via seq-SEA), well-dispersed homogeneously alloyed (via co-SEA), and poorly dispersed, poorly alloyed (via co-DI) end up as well alloyed, large particles of almost the same size and activity. With Pd-rich systems, the oxidation of Pd also figures into the equilibrium, such that Pd-rich oxide phases appear in the high temperature forms along with alloyed metal cores. Finally, the small differences in activity after high temperature aging can be attributed to the synthesis methods, sequential SEA and co

Silver Nanoparticles: Technological Advances, Societal Impacts, and Metrological Challenges

PubMed Central

Calderón-Jiménez, Bryan; Johnson, Monique E.; Montoro Bustos, Antonio R.; Murphy, Karen E.; Winchester, Michael R.; Vega Baudrit, José R.

2017-01-01

Silver nanoparticles (AgNPs) show different physical and chemical properties compared to their macroscale analogs. This is primarily due to their small size and, consequently, the exceptional surface area of these materials. Presently, advances in the synthesis, stabilization, and production of AgNPs have fostered a new generation of commercial products and intensified scientific investigation within the nanotechnology field. The use of AgNPs in commercial products is increasing and impacts on the environment and human health are largely unknown. This article discusses advances in AgNP production and presents an overview of the commercial, societal, and environmental impacts of this emerging nanoparticle (NP), and nanomaterials in general. Finally, we examine the challenges associated with AgNP characterization, discuss the importance of the development of NP reference materials (RMs) and explore their role as a metrological mechanism to improve the quality and comparability of NP measurements. PMID:28271059

Silver nanoparticles: technological advances, societal impacts, and metrological challenges

NASA Astrophysics Data System (ADS)

Calderón-Jiménez, Bryan; Johnson, Monique E.; Montoro Bustos, Antonio R.; Murphy, Karen E.; Winchester, Michael R.; Vega Baudrit, José R.

2017-02-01

Silver nanoparticles (AgNPs) show different physical and chemical properties compared to their macroscale analogs. This is primarily due to their small size and, consequently, the exceptional surface area of these materials. Presently, advances in the synthesis, stabilization, and production of AgNPs have fostered a new generation of commercial products and intensified scientific investigation within the nanotechnology field. The use of AgNPs in commercial products is increasing and impacts on the environment and human health are largely unknown. This article discusses advances in AgNP production and presents an overview of the commercial, societal, and environmental impacts of this emerging nanoparticle (NP), and nanomaterials in general. Finally, we examine the challenges associated with AgNP characterization, discuss the importance of the development of NP reference materials (RMs) and explore their role as a metrological mechanism to improve the quality and comparability of NP measurements.

Silver Nanoparticles: Technological Advances, Societal Impacts, and Metrological Challenges.

PubMed

Calderón-Jiménez, Bryan; Johnson, Monique E; Montoro Bustos, Antonio R; Murphy, Karen E; Winchester, Michael R; Vega Baudrit, José R

2017-01-01

Silver nanoparticles (AgNPs) show different physical and chemical properties compared to their macroscale analogs. This is primarily due to their small size and, consequently, the exceptional surface area of these materials. Presently, advances in the synthesis, stabilization, and production of AgNPs have fostered a new generation of commercial products and intensified scientific investigation within the nanotechnology field. The use of AgNPs in commercial products is increasing and impacts on the environment and human health are largely unknown. This article discusses advances in AgNP production and presents an overview of the commercial, societal, and environmental impacts of this emerging nanoparticle (NP), and nanomaterials in general. Finally, we examine the challenges associated with AgNP characterization, discuss the importance of the development of NP reference materials (RMs) and explore their role as a metrological mechanism to improve the quality and comparability of NP measurements.

Biological Mechanism of Silver Nanoparticle Toxicity

NASA Astrophysics Data System (ADS)

Armstrong, Najealicka Nicole

Silver nanoparticles (AgNPs), like almost all nanoparticles, are potentially toxic beyond a certain concentration because the survival of the organism is compromised due to scores of pathophysiological abnormalities above that concentration. However, the mechanism of AgNP toxicity remains undetermined. Instead of applying a toxic dose, these investigations were attempted to monitor the effects of AgNPs at a non-lethal concentration on wild type Drosophila melanogaster by exposing them to nanoparticles throughout their development. All adult flies raised in AgNP doped food indicated that of not more than 50 mg/L had no negative influence on median survival; however, these flies appeared uniformly lighter in body color due to the loss of melanin pigments in their cuticle. Additionally, fertility and vertical movement ability were compromised after AgNP feeding. The determination of the amount of free ionic silver (Ag+) indicated that the observed biological effects had resulted from the AgNPs and not from Ag+. Biochemical analysis suggests that the activity of copper dependent enzymes, namely tyrosinase and Cu-Zn superoxide dismutase, were decreased significantly following the consumption of AgNPs, despite the constant level of copper present in the tissue. Furthermore, copper supplementation restored the loss of AgNP induced demelanization, and the reduction of functional Ctr1 in Ctr1 heterozygous mutants caused the flies to be resistant to demelanization. Consequently, these studies proposed a mechanism whereby consumption of excess AgNPs in association with membrane bound copper transporter proteins cause sequestration of copper, thus creating a condition that resembles copper starvation. This model also explained the cuticular demelanization effect resulting from AgNP since tyrosinase activity is essential for melanin biosynthesis. Finally, these investigations demonstrated that Drosophila, an established genetic model system, can be well utilized for further

Citrate coated silver nanoparticles with modulatory effects on aflatoxin biosynthesis in Aspergillus parasiticus

NASA Astrophysics Data System (ADS)

Mitra, Chandrani

The manufacture and usage of silver nanoparticles has drastically increased in recent years (Fabrega et al. 2011a). Hence, the levels of nanoparticles released into the environment through various routes have measurably increased and therefore are concern to the environment and to public health (Panyala, Pena-Mendez and Havel 2008). Previous studies have shown that silver nanoparticles are toxic to various organisms such as bacteria (Kim et al. 2007), fungi (Kim et al. 2008), aquatic plants (He, Dorantes-Aranda and Waite 2012a), arthropods (Khan et al. 2015), and mammalian cells (Asharani, Hande and Valiyaveettil 2009) etc. Most of the toxicity studies are carried out using higher concentrations or lethal doses of silver nanoparticles. However, there is no information available on how the fungal community reacts to the silver nanoparticles at nontoxic concentrations. In this study, we have investigated the effect of citrate coated silver nanoparticles (AgNp-cit) at a size of 20nm on Aspergillus parasiticus, a popular plant pathogen and well-studied model for secondary metabolism (natural product synthesis). A. parasiticus produces 4 major types of aflatoxins. Among other aflatoxins, aflatoxin B1 is considered to be one of most potent naturally occurring liver carcinogen, and is associated with an estimated 155,000 liver cancer cases globally (Liu and Wu 2010); therefore, contaminated food and feed are a significant risk factor for liver cancer in humans and animals (CAST 2003; Liu and Wu 2010). In this study, we have demonstrated the uptake of AgNp-cit (20nm) by A. parasiticus cells from the growth medium using a time course ICP-OES experiment. It was observed that the uptake of AgNp-cit had no effect on fungal growth and significantly decreased intracellular oxidative stress. It also down-regulated aflatoxin biosynthesis at the level of gene expression of aflatoxin pathway genes and the global regulatory genes of secondary metabolism. We also observed that the

Coiled-coil forming peptides for the induction of silver nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Božič Abram, Sabina; Graduate School of Biomedicine, University of Ljubljana, Ljubljana 1000; Aupič, Jana

Biopolymers with defined sequence patterns offer an attractive alternative for the formation of silver nanoparticle (AgNP). A set of coiled-coil dimer forming peptides was tested for their AgNP formation ability. Seventeen of those peptides mediated the formation of AgNPs in aqueous solution at neutral pH, while the formation of a coiled-coil dimer inhibited the nanoparticle generation. A QSAR regression model on the relationship between sequence and function suggests that in this peptide type the patterns KXQQ and KXEE are favorable, whereas Ala residues appear to have an inhibitory effect. UV–VIS spectra of the obtained nanoparticles gave a peak at aroundmore » 420 nm, typical for AgNPs in the size range around 40 nm, which was confirmed by dynamic light scattering and transmission electron microscopy. Peptide-induced AgNPs exhibited good antibacterial activity, even after a 15 min contact time, while they had low toxicity to human cells at the same concentrations. These results show that our designed peptides generate AgNPs with antibacterial activity at mild conditions and might be used for antibacterial coatings. - Highlights: • 17 of the 30 tested coiled-coil forming peptides induce AgNP formation. • Coiled-coil dimer formation suppresses AgNP generation of individual peptides. • Size of the peptide-induced silver nanoparticles is around 40 nm. • QSAR analysis points to the importance of KXQQ and KXEE motifs for AgNP generation. • Peptide-induced silver nanoparticles exhibit antibacterial activity.« less

T cells enhance gold nanoparticle delivery to tumors in vivo.

PubMed

Kennedy, Laura C; Bear, Adham S; Young, Joseph K; Lewinski, Nastassja A; Kim, Jean; Foster, Aaron E; Drezek, Rebekah A

2011-04-04

Gold nanoparticle-mediated photothermal therapy (PTT) has shown great potential for the treatment of cancer in mouse studies and is now being evaluated in clinical trials. For this therapy, gold nanoparticles (AuNPs) are injected intravenously and are allowed to accumulate within the tumor via the enhanced permeability and retention (EPR) effect. The tumor is then irradiated with a near infrared laser, whose energy is absorbed by the AuNPs and translated into heat. While reliance on the EPR effect for tumor targeting has proven adequate for vascularized tumors in small animal models, the efficiency and specificity of tumor delivery in vivo, particularly in tumors with poor blood supply, has proven challenging. In this study, we examine whether human T cells can be used as cellular delivery vehicles for AuNP transport into tumors. We first demonstrate that T cells can be efficiently loaded with 45 nm gold colloid nanoparticles without affecting viability or function (e.g. migration and cytokine production). Using a human tumor xenograft mouse model, we next demonstrate that AuNP-loaded T cells retain their capacity to migrate to tumor sites in vivo. In addition, the efficiency of AuNP delivery to tumors in vivo is increased by more than four-fold compared to injection of free PEGylated AuNPs and the use of the T cell delivery system also dramatically alters the overall nanoparticle biodistribution. Thus, the use of T cell chaperones for AuNP delivery could enhance the efficacy of nanoparticle-based therapies and imaging applications by increasing AuNP tumor accumulation.

T cells enhance gold nanoparticle delivery to tumors in vivo

NASA Astrophysics Data System (ADS)

Kennedy, Laura C.; Bear, Adham S.; Young, Joseph K.; Lewinski, Nastassja A.; Kim, Jean; Foster, Aaron E.; Drezek, Rebekah A.

2011-12-01

Gold nanoparticle-mediated photothermal therapy (PTT) has shown great potential for the treatment of cancer in mouse studies and is now being evaluated in clinical trials. For this therapy, gold nanoparticles (AuNPs) are injected intravenously and are allowed to accumulate within the tumor via the enhanced permeability and retention (EPR) effect. The tumor is then irradiated with a near infrared laser, whose energy is absorbed by the AuNPs and translated into heat. While reliance on the EPR effect for tumor targeting has proven adequate for vascularized tumors in small animal models, the efficiency and specificity of tumor delivery in vivo, particularly in tumors with poor blood supply, has proven challenging. In this study, we examine whether human T cells can be used as cellular delivery vehicles for AuNP transport into tumors. We first demonstrate that T cells can be efficiently loaded with 45 nm gold colloid nanoparticles without affecting viability or function (e.g. migration and cytokine production). Using a human tumor xenograft mouse model, we next demonstrate that AuNP-loaded T cells retain their capacity to migrate to tumor sites in vivo. In addition, the efficiency of AuNP delivery to tumors in vivo is increased by more than four-fold compared to injection of free PEGylated AuNPs and the use of the T cell delivery system also dramatically alters the overall nanoparticle biodistribution. Thus, the use of T cell chaperones for AuNP delivery could enhance the efficacy of nanoparticle-based therapies and imaging applications by increasing AuNP tumor accumulation.

Nano-catalysts: Bridging the gap between homogeneous and heterogeneous catalysis

EPA Science Inventory

Functionalized nanoparticles have emerged as sustainable alternatives to conventional materials, as robust, high-surface-area heterogeneous catalyst supports. We envisioned a catalyst system, which can bridge the homogenous and heterogeneous system. Postsynthetic surface modifica...

Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles

DOE PAGES

James, Trevor E.; Hemmingson, Stephanie L.; Campbell, Charles T.

2015-08-14

It is known that many catalysts consist of late transition metal nanoparticles dispersed across oxide supports. The chemical potential of the metal atoms in these particles correlate with their catalytic activity and long-term thermal stability. This chemical potential versus particle size across the full size range between the single isolated atom and bulklike limits is reported here for the first time for any metal on any oxide. The chemical potential of Cu atoms on CeO 2(111) surfaces, determined by single crystal adsorption calorimetry of gaseous Cu atoms onto slightly reduced CeO 2(111) at 100 and 300 K is shown tomore » decrease dramatically with increasing Cu cluster size. The Cu chemical potential is ~110 kJ/mol higher for isolated Cu adatoms on stoichometric terrace sites than for Cu in nanoparticles exceeding 2.5 nm diameter, where it reaches the bulk Cu(solid) limit. In Cu dimers, Cu’s chemical potential is ~57 kJ/mol lower at step edges than on stoichiometric terrace sites. Since Cu avoids oxygen vacancies, these monomer and dimer results are not strongly influenced by the 2.5% oxygen vacancies present on this CeO 2 surface and are thus considered representative of stoichiometric CeO 2(111) surfaces.« less

Green synthesis of the Cu/Fe3O4 nanoparticles using Morinda morindoides leaf aqueous extract: A highly efficient magnetically separable catalyst for the reduction of organic dyes in aqueous medium at room temperature

NASA Astrophysics Data System (ADS)

Nasrollahzadeh, Mahmoud; Atarod, Monireh; Sajadi, S. Mohammad

2016-02-01

This paper reports the green and in-situ preparation of the Cu/Fe3O4 magnetic nanocatalyst synthesized using Morinda morindoides leaf extract without stabilizers or surfactants. The catalyst was characterized by XRD, SEM, EDS, UV-visible, TEM, VSM and TGA-DTA. The catalytic performance of the resulting nanocatalyst was examined for the reduction of 4-nitrophenol (4-NP), Congo red (CR) and Rhodamine B (RhB) in an environmental friendly medium at room temperature. The catalyst was recovered using an external magnet and reused several times without appreciable loss of its catalytic activity. In addition, the stability of the recycled catalyst has been proved by SEM and EDS techniques.

Mesoporous silica nanoparticle supported PdIr bimetal catalyst for selective hydrogenation, and the significant promotional effect of Ir

NASA Astrophysics Data System (ADS)

Yang, Hui; Huang, Chao; Yang, Fan; Yang, Xu; Du, Li; Liao, Shijun

2015-12-01

A mesoporous silica nanoparticle (MSN) supported bimetal catalyst, PdIr/MSN, was prepared by a facile impregnation and hydrogen reduction method. The strong promotional effect of Ir was observed and thoroughly investigated. At the optimal molar ratio of Ir to Pd (NIr/NPd = 0.1), the activity of PdIr0.1/MSN was up to eight times and 28 times higher than that of monometallic Pd/MSN and Ir/MSN, respectively. The catalysts were characterized comprehensively by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and hydrogen temperature programmed reduction, which revealed that the promotional effect of Ir may be due to the enhanced dispersion of active components on the MSN, and to the intensified Pd-Ir electronic interaction caused by the addition of Ir.

Mesoporous carbon-supported Pd nanoparticles with high specific surface area for cyclohexene hydrogenation: Outstanding catalytic activity of NaOH-treated catalysts

NASA Astrophysics Data System (ADS)

Puskás, R.; Varga, T.; Grósz, A.; Sápi, A.; Oszkó, A.; Kukovecz, Á.; Kónya, Z.

2016-06-01

Extremely high specific surface area mesoporous carbon-supported Pd nanoparticle catalysts were prepared with both impregnation and polyol-based sol methods. The silica template used for the synthesis of mesoporous carbon was removed by both NaOH and HF etching. Pd/mesoporous carbon catalysts synthesized with the impregnation method has as high specific surface area as 2250 m2/g. In case of NaOH-etched impregnated samples, the turnover frequency of cyclohexene hydrogenation to cyclohexane at 313 K was obtained 14 molecules • site- 1 • s- 1. The specific surface area of HF-etched samples was higher compared to NaOH-etched samples. However, catalytic activity was 3-6 times higher on NaOH-etched samples compared to HF-etched samples, which can be attributed to the presence of sodium and surface hydroxylgroups of the catalysts etched with NaOH solution.

Polyelectrolyte induced formation of silver nanoparticles in copolymer hydrogel and their application as catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Yongqiang; Huang, Guanbo, E-mail: gbhuang2007@hotmail.com; Pan, Zeng

2015-10-15

Highlights: • A simple route for the in situ preparation of Ag nanoparticles has been developed. • The Ag loaded hydrogel showed catalytic activity for reduction of 4-nitrophenol. • The catalyst can be recovered by simple separation and showed good recyclability. - Abstract: A simple route for the in situ preparation of catalytically active Ag nanoparticles (NPs) in hydrogel networks has been developed. The electronegativity of the amide and carboxyl groups on the poly(acrylamide-co-acryl acid) chains caused strong binding of the Ag{sup +} ions which made the ions distribute uniformly inside the hydrogels. When the Ag{sup +} loaded hydrogels weremore » immersed in NaBH{sub 4} solution, the Ag{sup +} ions on the polymer networks were reduced to Ag NPs. The resultant hydrogel showed good catalytic activity for the reduction of a common organic pollutant, 4-nitrophenol, with sodium borohydride. A kinetic study of the catalytic reaction was carried out and a possible reason for the decline of the catalytic performance with reuse is proposed.« less

Hydrothermal synthesis of highly crystalline RuS{sub 2} nanoparticles as cathodic catalysts in the methanol fuel cell and hydrochloric acid electrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yanjuan; College of Material Science and Engineering, Key Laboratory of Automobile Materials of Ministry of Education, Jilin University, 2699 Qianjin Street, Changchun 130012; Li, Nan, E-mail: lin@jlu.edu.cn

2015-05-15

Highlights: • Highly crystalline RuS{sub 2} nanoparticles have been first synthesized by a “one-step” hydrothermal method. • The product presents a pure cubic phase of stoichiometric ratio RuS{sub 2} with average particle size of 14.8 nm. • RuS{sub 2} nanoparticles were used as cathodic catalysts in methanol fuel cell and hydrochloric acid electrolysis. • The catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl{sup −}. - Abstract: Highly crystalline ruthenium sulfide (RuS{sub 2}) nanoparticles have been first synthesized by a “one-step” hydrothermal method at 400 °C, using ruthenium chloride and thiourea as reactants. The products were characterized bymore » powder X-ray diffraction (XRD), scanning electron microscopy/energy disperse spectroscopy (SEM/EDS), thermo gravimetric-differential thermal analyze (TG-DTA), transmission electron microscopy equipped with selected area electron diffraction (TEM/SAED). Fourier transform infrared spectra (IR), and X-ray photoelectron spectroscopy (XPS). XRD result illustrates that the highly crystalline product presents a pure cubic phase of stoichiometric ratio RuS{sub 2} and the average particle size is 14.8 nm. SEM and TEM images display the products have irregular shape of 6–25 nm. XPS analyst indicates that the sulfur exists in the form of S{sub 2}{sup 2−}. Cyclic voltammetry (CV), rotating disk electrode (RDE), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) measurements are conducted to evaluate the electrocatalytic activity and stability of the highly crystalline RuS{sub 2} nanoparticles in oxygen reduction reaction (ORR) for methanol fuel cell and hydrochloric acid electrolysis. The results illustrate that RuS{sub 2} is active towards oxygen reduction reaction. Although the activity of RuS{sub 2} is lower than that of Pt/C, the RuS{sub 2} catalyst outperforms commercial Pt/C in methanol tolerance and stability towards Cl{sup −}.« less

Nickel(0) nanoparticles supported on bare or coated cobalt ferrite as highly active, magnetically isolable and reusable catalyst for hydrolytic dehydrogenation of ammonia borane.

PubMed

Manna, Joydev; Akbayrak, Serdar; Özkar, Saim

2017-12-15

Nickel(0) nanoparticles supported on cobalt ferrite (Ni 0 /CoFe 2 O 4 ), polydopamine coated cobalt ferrite (Ni 0 /PDA-CoFe 2 O 4 ) or silica coated cobalt ferrite (Ni 0 /SiO 2 -CoFe 2 O 4 ) are prepared and used as catalysts in hydrogen generation from the hydrolysis of ammonia borane at room temperature. Ni 0 /CoFe 2 O 4 (4.0% wt. Ni) shows the highest catalytic activity with a TOF value of 38.3min -1 in hydrogen generation from the hydrolysis of ammonia borane at 25.0±0.1°C. However, the initial catalytic activity of Ni 0 /CoFe 2 O 4 catalyst is not preserved in subsequent runs of hydrolysis. Coating the surface of cobalt ferrite support with polydopamine or silica leads to a significant improvement in the stability of catalysts. The TOF values of Ni 0 /PDA-CoFe 2 O 4 and Ni 0 /SiO 2 -CoFe 2 O 4 are found to be 7.6 and 5.3min -1 , respectively, at 25.0±0.1°C. Ni 0 /PDA-CoFe 2 O 4 catalyst shows high reusability as compared to the Ni 0 /CoFe 2 O 4 and Ni 0 /SiO 2 -CoFe 2 O 4 catalysts in hydrolytic dehydrogenation of ammonia borane at room temperature. All the catalysts are characterized by using a combination of various advanced analytical techniques. The results reveal that nickel nanoparticles with an average size of 12.3±0.7nm are well dispersed on the surface of PDA-CoFe 2 O 4 . . Copyright © 2017 Elsevier Inc. All rights reserved.

Nanoparticles That "Remember" Temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klajn, Rafal; Browne, Kevin P.; Siowling, Soh

2010-06-02

Photoresponsive gold nanoparticles dispersed in a solid/frozen matrix provide a basis for sensors that “remember” whether the sample has ever exceeded the melting temperature of the matrix. The operation of these sensors rests on the ability to photoinduce metastable electric dipoles on NP surfaces – upon melting, these dipoles drive NP aggregation, precipitation, and crosslinking. These events are manifested by a pronounced color change.

Monitoring nanoparticle-mediated cellular hyperthermia with a high-sensitivity biosensor

PubMed Central

Mukherjee, Amarnath; Castanares, Mark; Hedayati, Mohammad; Wabler, Michele; Trock, Bruce; Kulkarni, Prakash; Rodriguez, Ronald; Getzenberg, Robert H; DeWeese, Theodore L; Ivkov, Robert; Lupold, Shawn E

2014-01-01

Aim To develop and apply a heat-responsive and secreted reporter assay for comparing cellular response to nanoparticle (NP)- and macroscopic-mediated sublethal hyperthermia. Materials & methods Reporter cells were heated by water bath (macroscopic heating) or iron oxide NPs activated by alternating magnetic fields (nanoscopic heating). Cellular responses to these thermal stresses were measured in the conditioned media by secreted luciferase assay. Results & conclusion Reporter activity was responsive to macroscopic and nanoparticle heating and activity correlated with measured macroscopic thermal dose. Significant cellular responses were observed with NP heating under doses that were insufficient to measurably change the temperature of the system. Under these conditions, the reporter response correlated with proximity to cells loaded with heated nanoparticles. These results suggest that NP and macroscopic hyperthermia may be distinctive under conditions of mild hyperthermia. PMID:24547783

Parallel nano-assembling of a multifunctional GO/HapNP coating on ultrahigh-purity magnesium for biodegradable implants

NASA Astrophysics Data System (ADS)

Santos, C.; Piedade, C.; Uggowitzer, P. J.; Montemor, M. F.; Carmezim, M. J.

2015-08-01

This work reports the one-step fabrication of a novel coating on ultra high purity magnesium using a parallel nano assembling process. The multifunctional biodegradable surface was obtained by adding hydroxyapatite nanoparticles (HapNP) plus graphene oxide (GO). The coating was characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffractometer (XRD), micro-Raman spectroscopy. The thin phosphate coating (thickness of 1 μm) reveals a uniform coverage with cypress like structures. The incorporation of HapNP and GO promotes the hydrophilic behavior of the coating surface. The results revealed that the proposed coating can be used to tailor the surface properties such as wettability by adjusting the contents of HapNP and GO. The in vitro degradation rate of the coated magnesium suggests that the presence of HapNP and GO/HapNP in the phosphate coating decreased the current density compared to the single phosphate coating and uncoated magnesium. This study also reveals the HapNP/GO/phosphate coating induces apatite formation, showing suitable degradability that makes it a promising coating candidate for enhanced bone regeneration.

Tumor-associated macrophages are predominant carriers of cyclodextrin-based nanoparticles into gliomas.

PubMed

Alizadeh, Darya; Zhang, Leying; Hwang, Jungyeon; Schluep, Thomas; Badie, Behnam

2010-04-01

The goal of this study was to evaluate the mechanism of cyclodextrin-based nanoparticle (CDP-NP) uptake into a murine glioma model. Using mixed in vitro culture systems, we demonstrated that CDP-NPs were preferentially taken up by BV2 and N9 microglia (MG) cells compared with GL261 glioma cells. Fluorescent microscopy and flow cytometry analysis of intracranial GL261 gliomas confirmed these findings and demonstrated a predominant CDP-NP uptake by macrophages (MPs) and MG within and around the tumor site. Notably, in mice bearing bilateral intracranial tumor, MG and MPs carrying CDP-NPs were able to migrate to the contralateral tumors. In conclusion, these studies better characterize the cellular distribution of CDP-NPs in intracranial tumors and demonstrate that MPs and MG could potentially be used as nanoparticle drug carriers into malignant brain tumors. The goal of this study was to evaluate the mechanism of cyclodextrin-based nanoparticle (CDP-NP) uptake into a murine glioma model. CDP-NP was preferentially taken up microglia (MG) cells as compared to glioma cells. A predominant CDP-NP uptake by macrophages and MG was also shown in and around the tumor site. Macrophages and MG could potentially be used as nanoparticle drug carriers into malignant brain tumors. Copyright 2010 Elsevier Inc. All rights reserved.

Chemoenzymatic dynamic kinetic resolution of primary amines using a recyclable palladium nanoparticle catalyst together with lipases.

PubMed

Gustafson, Karl P J; Lihammar, Richard; Verho, Oscar; Engström, Karin; Bäckvall, Jan-E

2014-05-02

A catalyst consisting of palladium nanoparticles supported on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was used in chemoenzymatic dynamic kinetic resolution (DKR) to convert primary amines to amides in high yields and excellent ee's. The efficiency of the nanocatalyst at temperatures below 70 °C enables reaction conditions that are more suitable for enzymes. In the present study, this is exemplified by subjecting 1-phenylethylamine (1a) and analogous benzylic amines to DKR reactions using two commercially available lipases, Novozyme-435 (Candida antartica Lipase B) and Amano Lipase PS-C1 (lipase from Burkholderia cepacia) as biocatalysts. The latter enzyme has not previously been used in the DKR of amines because of its low stability at temperatures over 60 °C. The viability of the heterogeneous Pd-AmP-MCF was further demonstrated in a recycling study, which shows that the catalyst can be reused up to five times.

microcrystals as an efficient heterogeneous Fenton-like catalyst in degradation of rhodamine 6G

NASA Astrophysics Data System (ADS)

Li, Zhan Jun; Ali, Ghafar; Kim, Hyun Jin; Yoo, Seong Ho; Cho, Sung Oh

2014-05-01

We present a novel heterogeneous Fenton-like catalyst of LiFePO4 (LFP). LFP has been widely used as an electrode material of a lithium ion battery, but we observed that commercial LFP (LFP-C) could act as a good Fenton-like catalyst to decompose rhodamine 6G. The catalytic activity of LFP-C microparticles was much higher than a popular catalyst, magnetite nanoparticles. Furthermore, we found that the catalytic activity of LFP-C could be further increased by increasing the specific surface area. The reaction rate constant of the hydrothermally synthesized LFP microcrystals (LFP-H) is at least 18 times higher than that of magnetite nanoparticles even though the particle size of LFP is far larger than magnetite nanoparticles. The LFP catalysts also exhibited a good recycling behavior and high stability under an oxidizing environment. The effects of the experimental parameters such as the concentration of the catalysts, pH, and the concentration of hydrogen peroxide on the catalytic activity of LFP were also analyzed.

Selective Catalysis in Nanoparticle Metal-Organic Framework Composites

NASA Astrophysics Data System (ADS)

Stephenson, Casey Justin

The design of highly selective catalysts are becoming increasingly important, especially as chemical and pharmaceutical industries seek to improve atom economy and minimize energy intensive separations that are often required to separate side products from the desired product. Enzymes are among the most selective of all catalysts, generally operating through molecular recognition whereby an active site analogous to a lock and the substrate is analogous to a key. The assembly of a porous, crystalline material around a catalytically active metal particle could serve as an artificial enzyme. In this vein, we first synthesized the polyvinylpyrrolidone (PVP) coated nanoparticles of interest and then encapsulated them within zeolitic imidazolate framework 8 or ZIF-8. 2.8 nm Pt-PVP nanoparticles, which were encapsulated within ZIF-8 to form Pt ZIF-8 composite. Pt ZIF-8 was inactive for the hydrogenation of cyclic olefins such as cis-cyclooctene and cis-cyclohexene while the composite proved to be a highly selective catalyst for the hydrogenation of terminal olefins, hydrogenating trans-1,3-hexadiene to 3-hexene in 95% selectivity after 24 hours under 1 bar H2. We extended our encapsulation method to sub-2 nm Au nanoparticles to form Au ZIF-8. Au ZIF-8 served as a highly chemoselective catalyst for the hydrogenation of crotonaldehyde an alpha,beta-unsaturated aldehyde, to crotyl alcohol an alpha,beta-unsaturated alcohol, in 90-95% selectivity. In order to investigate nanoparticle size effects on selectivity, 6-10 nm Au nanoparticles were encapsulated within ZIF-8 to form Au6 ZIF-8. Control catalysts with nanoparticles supported on the surface of ZIF-8 were synthesized as well, Au/ZIF-8 and Au6/ZIF-8. Au6 ZIF-8 hydrogenated crotonaldehyde in 85% selectivity towards the unsaturated alcohol. Catalysts with nanoparticles supported on the exterior of ZIF-8 were far less selective towards the unsaturated alcohol. Post-catalysis transmission electron microscopy analysis of Au ZIF

Dynamic Nanoparticles Assemblies

PubMed Central

WANG, LIBING; XU, LIGUANG; KUANG, HUA; XU, CHUANLAI; KOTOV, NICHOLAS A.

2012-01-01

CONSPECTUS Importance Although nanoparticle (NP) assemblies are at the beginning of their development, their unique geometrical shapes and media-responsive optical, electronic and magnetic properties have attracted significant interest. Nanoscale assembly bridges multiple sizes of materials: individual nanoparticles, discrete molecule-like or virus-like nanoscale agglomerates, microscale devices, and macroscale materials. The capacity to self-assemble can greatly facilitate the integration of nanotechnology with other technologies and, in particular, with microscale fabrication. In this Account, we describe developments in the emerging field of dynamic NP assemblies, which are spontaneously formed superstructures containing more than two inorganic nanoscale particles that display ability to change their geometrical, physical, chemical, and other attributes. In many ways, dynamic assemblies can represent a bottleneck in the ‘bottom-up’ fabrication of NP-based devices because they can produce a much greater variety of assemblies, but they also provide a convenient tool for variation of geometries and dimensions of nanoparticle assemblies. Classification Superstructures of NPs (and those held together by similar intrinsic forces) are classified into two groups: Class 1 where media and external fields can alter shape, conformation, and order of stable superstructures with a nearly constant number same. The future development of successful dynamic assemblies requires understanding the equilibrium in dynamic NP systems. The dynamic nature of Class 1 assemblies is associated with the equilibrium between different conformations of a superstructure and is comparable to the isomerization in classical chemistry. Class 2 assemblies involve the formation and/or breakage of linkages between the NPs, which is analogous to the classical chemical equilibrium for the formation of a molecule from atoms. Finer classification of NP assemblies in accord with established conventions

Synthesis of Co3O4 nanoparticles with block and sphere morphology, and investigation into the influence of morphology on biological toxicity

PubMed Central

RAMAN, VENKATARAMANAN; SURESH, SHRUTHI; SAVARIMUTHU, PHILIP ANTHONY; RAMAN, THIAGARAJAN; TSATSAKIS, ARISTIDES MICHAEL; GOLOKHVAST, KIRIL SERGEEVICH; VADIVEL, VINOD KUMAR

2016-01-01

In the present study, cobalt oxide (Co3O4) magnetic nanoparticles with block and sphere morphologies were synthesized using various surfactants, and the toxicity of the particles was analyzed by monitoring biomarkers of nanoparticle toxicity in zebrafish. The use of tartarate as a surfactant produced highly crystalline blocks of Co3O4 nanoparticles with pores on the sides, whereas citrate lead to the formation of nanoparticles with a spherical morphology. Co3O4 structure, crystallinity, size and morphology were studied using X-ray diffractogram and field emission scanning electron microscopy. Following an increase in nanoparticle concentration from 1 to 200 ppm, there was a corresponding increase in nitric oxide (NO) generation, induced by both types of nanoparticles [Co3O4-NP-B (block), r=0.953; Co3O4-NP-S (sphere), r=1.140]. Comparative analyses indicated that both types of nanoparticle produced significant stimulation at ≥5 ppm (P<0.05) compared with a control. Upon analyzing the effect of nanoparticle morphology on NO generation, it was observed that Co3O4-NP-S was more effective compared with Co3O4-NP-B (5 and 100 ppm, P<0.05; 200 ppm, P<0.01). Exposure to both types of nanoparticles produced reduction in liver glutathione (GSH) activity with corresponding increase in dose (Co3O4-NP-B, r=−0.359; Co3O4-NP-S, r=−0.429). However, subsequent analyses indicated that Co3O4-NP-B was more potent in inhibiting liver GSH activity compared with Co3O4-NP-S. Co3O4-NP-B proved to be toxic at 5 ppm (P<0.05) and GSH activity was almost completely inhibited at 200 ppm. A similar toxicity was observed with both types of Co3O4-NPs against brain levels of acetylcholinesterase (AChE; Co3O4-NP-B, r=−0.180; Co3O4-NP-S, r=−0.230), indicating the ability of synthesized Co3O4-NPs to cross the blood-brain barrier and produce neuronal toxicity. Co3O4-NP-B showed increased inhibition of brain AChE activity compared with Co3O4-NP-S (1,5, and 10 ppm, P<0.05; 50, 100 and 200 ppm, P

Highly conductive ribbons prepared by stick-slip assembly of organosoluble gold nanoparticles.

PubMed

Lawrence, Jimmy; Pham, Jonathan T; Lee, Dong Yun; Liu, Yujie; Crosby, Alfred J; Emrick, Todd

2014-02-25

Precisely positioning and assembling nanoparticles (NPs) into hierarchical nanostructures is opening opportunities in a wide variety of applications. Many techniques employed to produce hierarchical micrometer and nanoscale structures are limited by complex fabrication of templates and difficulties with scalability. Here we describe the fabrication and characterization of conductive nanoparticle ribbons prepared from surfactant-free organosoluble gold nanoparticles (Au NPs). We used a flow-coating technique in a controlled, stick-slip assembly to regulate the deposition of Au NPs into densely packed, multilayered structures. This affords centimeter-scale long, high-resolution Au NP ribbons with precise periodic spacing in a rapid manner, up to 2 orders-of-magnitude finer and faster than previously reported methods. These Au NP ribbons exhibit linear ohmic response, with conductivity that varies by changing the binding headgroup of the ligands. Controlling NP percolation during sintering (e.g., by adding polymer to retard rapid NP coalescence) enables the formation of highly conductive ribbons, similar to thermally sintered conductive adhesives. Hierarchical, conductive Au NP ribbons represent a promising platform to enable opportunities in sensing, optoelectronics, and electromechanical devices.

Cobalt Nanoparticle-Embedded Porous Carbon Nanofibers with Inherent N- and F-Doping as Binder-Free Bifunctional Catalysts for Oxygen Reduction and Evolution Reactions.

PubMed

Singhal, Richa; Kalra, Vibha

2017-01-18

Efficient, low-cost, non-precious metal-based, and stable bifunctional electrocatalysts are key to various energy storage and conversion devices such as regenerative fuel cells and metal-air batteries. In this work, we report cobalt nanoparticle-embedded porous carbon nanofibers with inherent N- and F-doping as binder-free bifunctional electrocatalysts with excellent activity for both the oxygen reduction and oxygen evolution reaction (ORR/OER) in an alkaline medium. Single-step electrospinning of a solution of the polymer mixture (carbon precursor) and the cobalt precursor followed by controlled pyrolysis with an intermediate reduction step in H 2 (to reduce cobalt oxides to cobalt) was utilized to synthesize an integrated freestanding catalyst. The fabricated catalyst with effective structural and electronic interaction between the cobalt metal nanoparticles and the N- and F-doped carbon defect sites showed enhanced catalytic properties compared to the benchmark catalysts for ORR and OER (Pt, Ir, and Ru). The ORR potential at the current density of -3 mA cm -2 was 0.81 V RHE and the OER potential at a current density of 10 mA cm -2 was 1.595 V RHE , resulting in a ΔE of only 0.785 V. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rare Earth Oxide Fluoride Nanoparticles And Hydrothermal Method For Forming Nanoparticles

DOEpatents

Fulton, John L.; Hoffmann, Markus M.

2003-12-23

A hydrothermal method for forming nanoparticles of a rare earth element, oxygen and fluorine has been discovered. Nanoparticles comprising a rare earth element, oxygen and fluorine are also described. These nanoparticles can exhibit excellent refractory properties as well as remarkable stability in hydrothermal conditions. The nanoparticles can exhibit excellent properties for numerous applications including fiber reinforcement of ceramic composites, catalyst supports, and corrosion resistant coatings for high-temperature aqueous solutions.

Rare earth oxide fluoride nanoparticles and hydrothermal method for forming nanoparticles

DOEpatents

Fulton, John L [Richland, WA; Hoffmann, Markus M [Richland, WA

2001-11-13

A hydrothermal method for forming nanoparticles of a rare earth element, oxygen and fluorine has been discovered. Nanoparticles comprising a rare earth element, oxygen and fluorine are also described. These nanoparticles can exhibit excellent refractory properties as well as remarkable stability in hydrothermal conditions. The nanoparticles can exhibit excellent properties for numerous applications including fiber reinforcement of ceramic composites, catalyst supports, and corrosion resistant coatings for high-temperature aqueous solutions.

ICAM-1 Targeting of Doxorubicin-Loaded PLGA Nanoparticles to Lung Epithelial Cells

PubMed Central

Chuda, Chittasupho; Sheng-Xue, Xie; Abdulgader, Baoum; Tatyana, Yakovleva; Teruna, Siahaan J.; Cory, Berkland

2009-01-01

Interaction of leukocyte function associated antigen-1 (LFA-1) on T-lymphoctytes and intercellular adhesion molecule-1 (ICAM-1) on epithelial cells controls leukocyte adhesion, spreading, and extravasation. This process plays an important role in leukocyte recruitment to a specific site of inflammation and has been indentified as a biomarker for certain types of carcinomas. Cyclo-(1,12)-PenITDGEATDSGC (cLABL) has been shown to inhibit LFA-1 and ICAM-1 interaction via binding to ICAM-1. In addition, cLABL has been shown to internalize after binding ICAM-1. The possibility of using cLABL conjugated nanoparticles (cLABL-NP) as a targeted and controlled release drug delivery system has been investigated in this study. The cLABL peptide was conjugated to a modified Pluronic® surfactant on poly (DL-lactic-co-glycolic acid) (PLGA) nanoparticles. The cLABL-NP showed more rapid cellular uptake by A549 lung epithelial cells compared to nanoparticles without peptide. The specificity of ICAM-1 mediated internalization was confirmed by blocking the uptake of cLABL-NP to ICAM-1 using free cLABL peptide to block the binding of cLABL-NP to ICAM-1 on the cell surface. Cell studies suggested that cLABL-NPs targeted encapsulated doxorubicin to ICAM-1 expressing cells. Cytotoxicity assay confirmed the activity of the drug incorporated in nanoparticles. Sustained release of doxorubicin afforded by PLGA nanoparticles may enable cLABL-NP as a targeted, controlled release drug delivery system. PMID:19429421

Current advances in precious metal core-shell catalyst design.

PubMed

Wang, Xiaohong; He, Beibei; Hu, Zhiyu; Zeng, Zhigang; Han, Sheng

2014-08-01

Precious metal nanoparticles are commonly used as the main active components of various catalysts. Given their high cost, limited quantity, and easy loss of catalytic activity under severe conditions, precious metals should be used in catalysts at low volumes and be protected from damaging environments. Accordingly, reducing the amount of precious metals without compromising their catalytic performance is difficult, particularly under challenging conditions. As multifunctional materials, core-shell nanoparticles are highly important owing to their wide range of applications in chemistry, physics, biology, and environmental areas. Compared with their single-component counterparts and other composites, core-shell nanoparticles offer a new active interface and a potential synergistic effect between the core and shell, making these materials highly attractive in catalytic application. On one hand, when a precious metal is used as the shell material, the catalytic activity can be greatly improved because of the increased surface area and the closed interfacial interaction between the core and the shell. On the other hand, when a precious metal is applied as the core material, the catalytic stability can be remarkably improved because of the protection conferred by the shell material. Therefore, a reasonable design of the core-shell catalyst for target applications must be developed. We summarize the latest advances in the fabrications, properties, and applications of core-shell nanoparticles in this paper. The current research trends of these core-shell catalysts are also highlighted.

Biocatalytic Self-Assembly on Magnetic Nanoparticles.

PubMed

Conte, Maria P; Sahoo, Jugal Kishore; Abul-Haija, Yousef M; Lau, K H Aaron; Ulijn, Rein V

2018-01-24

Combining (bio)catalysis and molecular self-assembly provides an effective approach for the production and processing of self-assembled materials by exploiting catalysis to direct the assembly kinetics and hence controlling the formation of ordered nanostructures. Applications of (bio)catalytic self-assembly in biologically interfacing systems and in nanofabrication have recently been reported. Inspired by self-assembly in biological cells, efforts to confine catalysts on flat or patterned surfaces to exert spatial control over molecular gelator generation and nanostructure self-assembly have also emerged. Building on our previous work in the area, we demonstrate in this report the use of enzymes immobilized onto magnetic nanoparticles (NPs) to spatially localize the initiation of peptide self-assembly into nanofibers around NPs. The concept is generalized for both an equilibrium biocatalytic system that forms stable hydrogels and a nonequilibrium system that normally has a preset lifetime. Characterization of the hydrogels shows that self-assembly occurs at the site of enzyme immobilization on the NPs to give rise to gels with a "hub-and-spoke" morphology, where the nanofibers are linked through the enzyme-NP conjugates. This NP-controlled arrangement of self-assembled nanofibers enables both remarkable enhancements in the shear strength of hydrogel systems and a dramatic extension of the hydrogel stability in the nonequilibrium system. We are also able to show that the use of magnetic NPs enables the external control of both the formation of the hydrogel and its overall structure by application of an external magnetic field. We anticipate that the enhanced properties and stimuli-responsiveness of our NP-enzyme system will have applications ranging from nanomaterial fabrication to biomaterials and biosensing.

On-demand Hydrogen Production from Organosilanes at Ambient Temperature Using Heterogeneous Gold Catalysts

NASA Astrophysics Data System (ADS)

Mitsudome, Takato; Urayama, Teppei; Kiyohiro, Taizo; Maeno, Zen; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi

2016-11-01

An environmentally friendly (“green”), H2-generation system was developed that involved hydrolytic oxidation of inexpensive organosilanes as hydrogen storage materials with newly developed heterogeneous gold nanoparticle catalysts. The gold catalyst functioned well at ambient temperature under aerobic conditions, providing efficient production of pure H2. The newly developed size-selective gold nanoparticle catalysts could be separated easily from the reaction mixture containing organosilanes, allowing an on/off-switchable H2-production by the introduction and removal of the catalyst. This is the first report of an on/off-switchable H2-production system employing hydrolytic oxidation of inexpensive organosilanes without requiring additional energy.

Magnetic nanoparticle-enhanced PCR for the detection and identification of Staphylococcus aureus and Salmonella enteritidis.

PubMed

Houhoula, Dimitra; Papaparaskevas, Joseph; Zatsou, Katerina; Nikolaras, Nikolaos; Malkawi, Hanan I; Mingenot-Leclercq, Marie-Paule; Konteles, Spyros; Koussisis, Stamatis; Tsakris, Athanassios; Charvalos, Ekatherina

2017-07-01

This paper evaluated magnetic nanoparticle-enhanced PCR for the detection and identification of Staphylococcus aureus and Salmonella enteritidis. Two different types of magnetic nanoparticles designated MPIO (iron concentration 2.5 mg/ml, size 1 µm) and NP (iron concentration 8.7 mg/ml, size 60 nm), both conjugated with S. aureus or S. enteritidis antibodies were evaluated as an enrichment procedure for PCR-detection of the pathogens in Trypticase Soy Broth, milk, blood and meat broth. Bacterial suspensions (1.5x108 cfu/ml) were prepared and serial diluted 10-1. The MPIO and NP nanoparticles were added, followed by incubation for 1 hour at room temperature, magnetic separation of the pellet, DNA extraction and PCR, targeting the femA and invA sequences. The nanoparticle-free and the NP-supplemented dilutions were positive down to the 1.5x102 cfu/ml concentration for both bacteria. The MPIO-supplemented dilutions were positive down to approx. 2x100 cfu/ml concentration, respectively. Bacteria-free TSB was negative by PCR. MPIO nanoparticles (size 1 µm) enhanced the detection of S. aureus and S. enteritidis by PCR, whilst NP nanoparticles (size 60 nm) did not, thus indicating that the size of the magnetic nanoparticles play a significant role in the enrichment procedure.

Wet catalyst-support films for production of vertically aligned carbon nanotubes.

PubMed

Alvarez, Noe T; Hamilton, Christopher E; Pint, Cary L; Orbaek, Alvin; Yao, Jun; Frosinini, Aldo L; Barron, Andrew R; Tour, James M; Hauge, Robert H

2010-07-01

A procedure for vertically aligned carbon nanotube (VA-CNT) production has been developed through liquid-phase deposition of alumoxanes (aluminum oxide hydroxides, boehmite) as a catalyst support. Through a simple spin-coating of alumoxane nanoparticles, uniform centimer-square thin film surfaces were coated and used as supports for subsequent deposition of metal catalyst. Uniform VA-CNTs are observed to grow from this film following deposition of both conventional evaporated Fe catalyst, as well as premade Fe nanoparticles drop-dried from the liquid phase. The quality and uniformity of the VA-CNTs are comparable to growth from conventional evaporated layers of Al(2)O(3). The combined use of alumoxane and Fe nanoparticles to coat surfaces represents an inexpensive and scalable approach to large-scale VA-CNT production that makes chemical vapor deposition significantly more competitive when compared to other CNT production techniques.

Promising upshot of silver nanoparticles primed from Gracilaria crassa against bacterial pathogens.

PubMed

Lavakumar, V; Masilamani, K; Ravichandiran, V; Venkateshan, N; Saigopal, D V R; Ashok Kumar, C K; Sowmya, C

2015-01-01

The study on newer antimicrobial agent from metal based nano materials has augmented in recent years for the management of multidrug resistance microorganisms. In our present investigation, we synthesized silver nanoparticles (AgNP's) from red algae, Gracilaria crassa as beginning material which effectively condensed the silver ions to silver nanoparticles with less price tag and no risk. Silver nanoparticles were prepared by simple reaction of 1 mM AgNO3 with G. crassa extracts at room temperature. The fabricated AgNP's were subjected for characterization and screened against various microorganisms for antibacterial activity. UV-Vis spectroscopy (200-800 nm), XRD, FESEM and EDAX, were performed for AgNP's. UV-Vis spectroscopy demonstrated the absorption edge at 443 nm and EDAX pattern is purely due to the particle size and face centered cubic (fcc) symmetry of nanoparticles. Average size lays at 122.7 nm and zeta potential was found to be -34.9 mV. The antibacterial outcome of synthesized AgNP's (at the dose of 20 and 40 µg/ml) was evaluated against Escherichia coli, Proteus mirabilis, Bacillus subtilis and Pseudomonas aeruginosa. The mechanism of synthesized AgNP's bactericidal bustle is discussed in terms of interaction with the cell membrane of bacteria. The activity was found to be sky-scraping in a dose dependent manner. Thus, environmental friendly, cost effective, non hazardous stable nanoparticles were prepared by green synthesis using red algae, G. crassa. Synthesized G. crassa AgNP's were in acceptable size and shape. Further, it elicits better bactericidal activity against microorganism. This will assure the out put of superior antibacterial formulation for near future.

Synthesis of palladium nanoparticles with leaf extract of Chrysophyllum cainito (Star apple) and their applications as efficient catalyst for C-C coupling and reduction reactions

NASA Astrophysics Data System (ADS)

Majumdar, Rakhi; Tantayanon, Supawan; Bag, Braja Gopal

2017-10-01

A simple green chemical method for the one-step synthesis of palladium nanoparticles (PdNPs) has been described by reducing palladium (II) chloride with the leaf extract of Chrysophyllum cainito in aqueous medium. The synthesis of the palladium nanoparticles completed within 2-3 h at room temperature, whereas on heat treatment (70-80 °C), the synthesis of colloidal PdNPs completed almost instantly. The stabilized PdNPs have been characterized in detail by spectroscopic, electron microscopic and light scattering measurements. The synthesized PdNPs have been utilized as a green catalyst for C-C coupling reactions under aerobic and phosphine-free conditions in aqueous medium. In addition, the synthesized PdNPs have also been utilized as a catalyst for a very efficient sodium borohydride reduction of 3- and 4-nitrophenols. The synthesized PdNPs can retain their catalytic activity for several months.

Three dimensional spheroid cell culture for nanoparticle safety testing.

PubMed

Sambale, Franziska; Lavrentieva, Antonina; Stahl, Frank; Blume, Cornelia; Stiesch, Meike; Kasper, Cornelia; Bahnemann, Detlef; Scheper, Thomas

2015-07-10

Nanoparticles are widely employed for many applications and the number of consumer products, incorporating nanotechnology, is constantly increasing. A novel area of nanotechnology is the application in medical implants. The widespread use of nanoparticles leads to their higher prevalence in our environment. This, in turn, raises concerns regarding potential risks to humans. Previous studies have shown possible hazardous effects of some nanoparticles on mammalian cells grown in two-dimensional (2D) cultures. However, 2D in vitro cell cultures display several disadvantages such as changes in cell shape, cell function, cell responses and lack of cell-cell contacts. For this reason, the development of better models for mimicking in vivo conditions is essential. In the present work, we cultivated A549 cells and NIH-3T3 cells in three-dimensional (3D) spheroids and investigated the effects of zinc oxide (ZnO-NP) and titanium dioxide nanoparticles (TiO2-NP). The results were compared to cultivation in 2D monolayer culture. A549 cells in 3D cell culture formed loose aggregates which were more sensitive to the toxicity of ZnO-NP in comparison to cells grown in 2D monolayers. In contrast, NIH-3T3 cells showed a compact 3D spheroid structure and no differences in the sensitivity of the NIH-3T3 cells to ZnO-NP were observed between 2D and 3D cultures. TiO2-NP were non-toxic in 2D cultures but affected cell-cell interaction during 3D spheroid formation of A549 and NIH-3T3 cells. When TiO2-NP were directly added during spheroid formation in the cultures of the two cell lines tested, several smaller spheroids were formed instead of a single spheroid. This effect was not observed if the nanoparticles were added after spheroid formation. In this case, a slight decrease in cell viability was determined only for A549 3D spheroids. The obtained results demonstrate the importance of 3D cell culture studies for nanoparticle safety testing, since some effects cannot be revealed in 2D

Ammonia-modified graphene sheets decorated with magnetic Fe3O4 nanoparticles for the photocatalytic and photo-Fenton degradation of phenolic compounds under sunlight irradiation.

PubMed

Boruah, Purna K; Sharma, Bhagyasmeeta; Karbhal, Indrapal; Shelke, Manjusha V; Das, Manash R

2017-03-05

Synthesis of easily separable and eco-friendly efficient catalyst with both photocatalytic and photo-Fenton degradation properties is of great importance for environment remediation application. Herein, ammonia-modified graphene (AG) sheets decorated with Fe 3 O 4 nanoparticles (AG/Fe 3 O 4 ) as a magnetically recoverable photocatalyst by a simple in situ solution chemistry approach. First, we have functionalized graphene oxide (GO) sheets by amide functional group and then Fe 3 O 4 nanoparticles (NPs) are doped onto the functionalized GO surface. The AG/Fe 3 O 4 nanocomposite showed efficient photocatalytic activity towards degradation of phenol (92.43%), 2-nitrophenol (2-NP) (98%) and 2-chlorophenol (2-CP) (97.15%) within 70-120min. Consequently, in case of photo-Fenton degradation phenomenon, 93.56% phenol, 98.76% 2-NP and 98.06% of 2-CP degradation were achieved within 50-80min using AG/Fe 3 O 4 nanocomposite under sunlight irradiation. The synergistic effect between amide functionalized graphene and Fe 3 O 4 nanoparticles (NPs) enhances the photocatalytic activity by preventing the recombination rate of electron-hole-pair in Fe 3 O 4 NPs. Furthermore, the remarkable reusability of the AG/Fe 3 O 4 nanocomposite was observed up to ten cycles during the photocatalytic degradation of these phenolic compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Temozolomide nanoparticles for targeted glioblastoma therapy.

PubMed

Fang, Chen; Wang, Kui; Stephen, Zachary R; Mu, Qingxin; Kievit, Forrest M; Chiu, Daniel T; Press, Oliver W; Zhang, Miqin

2015-04-01

Glioblastoma (GBM) is a deadly and debilitating brain tumor with an abysmal prognosis. The standard therapy for GBM is surgery followed by radiation and chemotherapy with Temozolomide (TMZ). Treatment of GBMs remains a challenge, largely because of the fast degradation of TMZ, the inability to deliver an effective dose of TMZ to tumors, and a lack of target specificity that may cause systemic toxicity. Here, we present a simple method for synthesizing a nanoparticle-based carrier that can protect TMZ from rapid degradation in physiological solutions and can specifically deliver them to GBM cells through the mediation of a tumor-targeting peptide chlorotoxin (CTX). Our nanoparticle, namely NP-TMZ-CTX, had a hydrodynamic size of <100 nm, exhibited sustained stability in cell culture media for up to 2 weeks, and could accommodate stable drug loading. TMZ bound to nanoparticles showed a much higher stability at physiological pH, with a half-life 7-fold greater than that of free TMZ. NP-TMZ-CTX was able to target GBM cells and achieved 2-6-fold higher uptake and a 50-90% reduction of IC50 72 h post-treatment as compared to nontargeted NP-TMZ. NP-TMZ-CTX showed great promise in its ability to deliver a large therapeutic dose of TMZ to GBM cells and could serve as a template for targeted delivery of other therapeutics.

Characteristic time scales of coalescence of silver nanocomposite and nanoparticle films induced by continuous wave laser irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paeng, Dongwoo; Grigoropoulos, Costas P., E-mail: cgrigoro@berkeley.edu; Lee, Daeho

2014-08-18

In-situ optical probing has been performed to analyze and compare the characteristic coalescence time scales of silver ion-doped polyvinylalcohol nanocomposite (Ag-PVA NC) and polyvinylpyrrolidone-capped silver nanoparticle (Ag-PVP NP) films subjected to continuous wave laser irradiation. The Ag-PVA NC yielded conductive metallic patterns by photothermal reduction of PVA, formation of nanoparticles from silver ions and their subsequent coalescence. On the other hand, Ag-PVP NP thin films produced conductive patterns through only coalescence of nanoparticles. Upon laser irradiation, Ag-PVA NC and Ag-PVP NP films exhibited different coalescence characteristics.

Peptide-coated gold nanoparticles for modulation of angiogenesis in vivo.

PubMed

Roma-Rodrigues, Catarina; Heuer-Jungemann, Amelie; Fernandes, Alexandra R; Kanaras, Antonios G; Baptista, Pedro V

2016-01-01

In this work, peptides designed to selectively interact with cellular receptors involved in the regulation of angiogenesis were anchored to oligo-ethylene glycol-capped gold nanoparticles (AuNPs) and used to evaluate the modulation of vascular development using an ex ovo chick chorioallantoic membrane assay. These nanoparticles alter the balance between naturally secreted pro- and antiangiogenic factors, under various biological conditions, without causing toxicity. Exposure of chorioallantoic membranes to AuNP-peptide activators of angiogenesis accelerated the formation of new arterioles when compared to scrambled peptide-coated nanoparticles. On the other hand, antiangiogenic AuNP-peptide conjugates were able to selectively inhibit angiogenesis in vivo. We demonstrated that AuNP vectorization is crucial for enhancing the effect of active peptides. Our data showed for the first time the effective control of activation or inhibition of blood vessel formation in chick embryo via AuNP-based formulations suitable for the selective modulation of angiogenesis, which is of paramount importance in applications where promotion of vascular growth is desirable (eg, wound healing) or ought to be contravened, as in cancer development.

A Simple and Efficient Synthesis of 4-Arylacridinediones and 6-Aryldiindeno[1,2-b:2,1-e]pyridinediones using CuI Nanoparticles as Catalyst under Solvent-Free Conditions.

PubMed

Abdolmohammadi, Shahrzad; Dahi-Azar, Saman; Mohammadnejad, Mahdieh; Hosseinian, Akram

2017-01-01

The importance of acridine core structure and other heterocycles containing its framework is well known, as they are found in numerous compounds with a variety of biological effects. Pyridine is also an important solvent and heterocyclic nucleus for the design and synthesis of novel molecules with biological properties. It occurs in several natural compounds which are used as a precursor in agrochemicals and pharmaceuticals. The utility of nanostructured metal salts because of their small size and high surface area as catalysts in organic synthesis has drawn special attention due to their better properties such as slower reaction rate, reusability of the catalyst, and higher yields of products compared to the bulk size. Nanosized copper iodide is one reusable Lewis acid catalyst which has revealed several catalytic activities for the synthesis of organic compounds and others. As part of our recent study to develop heterocyclic syntheses using nanostructured catalysts, we now report an efficient and clean synthetic route to 4-arylacridinediones and 6-aryldiindeno[1,2-b:2,1-e]pyridinediones via a condensation reaction catalyzed by CuI nanoparticles under solvent-free conditions. The present work deals with the condensation reaction of aromatic aldehydes, ammonium acetate and active methylene compounds comprising dimedone or 1,3- indanedione in the presence of a catalytic amount of the synthesized CuI nanoparticles could be applied for the solvent-free preparation of 4-arylacridinediones and 6-aryldiindeno[1,2-b:2,1- e]pyridinediones at 70 °C within 60 min. A series of 9-aryl-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydro-1,8(2H,5H)-acridinediones and 6-aryldiindeno[1,2-b:2,1-e]pyridine-5,7-diones were synthesized in high to excellent yields via a simple one-pot three-component coupling reaction using the synthesized CuI nanoparticles as an efficient and recyclable catalyst. All synthesized compounds were well characterized by their satisfactory elemental analyses, IR, 1

Nickel nanoparticles-chitosan composite coated cellulose filter paper: An efficient and easily recoverable dip-catalyst for pollutants degradation.

PubMed

Kamal, Tahseen; Khan, Sher Bahadar; Asiri, Abdullah M

2016-11-01

In this report, we used cellulose filter paper (FP) as high surface area catalyst supporting green substrate for the synthesis of nickel (Ni) nanoparticles in thin chitosan (CS) coating layer and their easy separation was demonstrated for next use. In this work, FP was coated with a 1 wt% CS solution onto cellulose FP to prepare CS-FP as an economical and environment friendly host material. CS-FP was put into 0.2 M NiCl 2 aqueous solution for the adsorption of Ni 2+ ions by CS coating layer. The Ni 2+ adsorbed CS-FP was treated with 0.1 M NaBH 4 aqueous solution to convert the ions into nanoparticles. Thus, we achieved Ni nanoparticles-CS composite through water based in-situ preparation process. Successful Ni nanoparticles formations was assessed by FESEM and EDX analyses. FTIR used to track the interactions between nanoparticles and host material. Furthermore, we demonstrated that the nanocomposite displays an excellent catalytic activity and reusability in three reduction reactions of toxic compounds i.e. conversion of 4-nitrophenol to 4-aminophenol, 2-nitrophenol to 2-aminophenol, and methyl orange dye reduction by NaBH 4 . Such a fabrication process of Ni/CS-FP may be applicable for the immobilization of other metal nanoparticles onto FP for various applications in catalysis, sensing, and environmental sciences. Copyright © 2016 Elsevier Ltd. All rights reserved.

Catalytic Properties of Unsupported Palladium Nanoparticle Surfaces Capped with Small Organic Ligands

PubMed Central

Gavia, Diego J.

2015-01-01

This Minireview summarizes a variety of intriguing catalytic studies accomplished by employing unsupported, either solubilized or freely mobilized, and small organic ligand-capped palladium nanoparticles as catalysts. Small organic ligands are gaining more attention as nanoparticle stabilizers and alternates to larger organic supports, such as polymers and dendrimers, owing to their tremendous potential for a well-defined system with spatial control in surrounding environments of reactive surfaces. The nanoparticle catalysts are grouped depending on the type of surface stabilizers with reactive head groups, which include thiolate, phosphine, amine, and alkyl azide. Applications for the reactions such as hydrogenation, alkene isomerization, oxidation, and carbon-carbon cross coupling reactions are extensively discussed. The systems defined as “ligandless” Pd nanoparticle catalysts and solvent (e.g. ionic liquid)-stabilized Pd nanoparticle catalysts are not discussed in this review. PMID:25937846

Drug permeability and mucoadhesion properties of thiolated trimethyl chitosan nanoparticles in oral insulin delivery.

PubMed

Yin, Lichen; Ding, Jieying; He, Chunbai; Cui, Liming; Tang, Cui; Yin, Chunhua

2009-10-01

Trimethyl chitosan-cysteine conjugate (TMC-Cys) was synthesized in an attempt to combine the mucoadhesion and the permeation enhancing effects of TMC and thiolated polymers related to different mechanisms for oral absorption. TMC-Cys with various molecular weights (30, 200, and 500 kDa) and quaternization degrees (15 and 30%) was allowed to form polyelectrolyte nanoparticles with insulin through self-assembly, which demonstrated particle size of 100-200 nm, zeta potential of +12 to +18 mV, and high encapsulation efficiency. TMC-Cys/insulin nanoparticles (TMC-Cys NP) showed a 2.1-4.7-fold increase in mucoadhesion compared to TMC/insulin nanoparticles (TMC NP), which might be partly attributed to disulfide formation between TMC-Cys and mucin as evidenced by DSC measurement. Compared to insulin solution and TMC NP, TMC-Cys NP induced increased insulin transport through rat intestine by 3.3-11.7 and 1.7-2.6 folds, promoted Caco-2 cell internalization by 7.5-12.7 and 1.7-3.0 folds, and augmented uptake in Peyer's patches by 14.7-20.9 and 1.7-5.0 folds, respectively. Such results were further confirmed by in vivo experiment with the optimal TMC-Cys NP. Biocompatibility assessment revealed lack of toxicity of TMC-Cys NP. Therefore, self-assembled nanoparticles between TMC-Cys and protein drugs could be an effective and safe oral delivery system.

Silver nanoparticles coated with natural polysaccharides as models to study AgNP aggregation kinetics using UV-Visible spectrophotometry upon discharge in complex environments.

PubMed

Lodeiro, Pablo; Achterberg, Eric P; Pampín, Joaquín; Affatati, Alice; El-Shahawi, Mohammed S

2016-01-01

This study provides quantitative information on the aggregation and dissolution behaviour of silver nanoparticles (AgNPs) upon discharge in fresh and sea waters, represented here as NaCl solutions of increasing ionic strength (up to 1M) and natural fjord waters. Natural polysaccharides, sodium alginate (ALG) and gum Arabic (GA), were used as coatings to stabilize the AgNPs and the compounds acted as models to study AgNP aggregation kinetics. The DLVO theory was used to quantitatively describe the interactions between the AgNPs. The stability of AgNPs was established using UV-Visible spectrophotometry, including unique information collected during the first seconds of the aggregaton process. Alginate coating resulted in a moderate stabilization of AgNPs in terms of critical coagulation concentration (~82mM NaCl) and a low dissolution of <10% total Ag in NaCl solutions up to 1M. Gum Arabic coated AgNPs were more strongly stabilized, with ~7-30% size increase up to 77mM NaCl, but only when the silver ion content initially present in solution was low (<10% total Ag). The ALG and GA coated AgNPs showed a strongly enhanced stability in natural fjord waters (ca. 5h required to reduce the area of the surface plasmon resonance band (SPRB) by two fold) compared with NaCl at an equivalent ionic strength (1-2min period for a two fold SPRB reduction). This is ascribed to a stabilizing effect from dissolved organic matter present in natural fjord waters. Interestingly, for AgNP-GA solutions with 40% of total silver present as unreacted silver ions in the NP stock solution, fast aggregation kinetics were observed in NaCl solutions (SPRB area was reduced by ca. 50% within 40-150min), with even more rapid removal in fjord waters, attributed to the high amount of silver-chloride charged species, that interact with the NP coating and/or organic matter and reduce the NPs stabilization. Copyright © 2015 Elsevier B.V. All rights reserved.

Transition Metal Phosphide Nanoparticles Supported on SBA-15 as Highly Selective Hydrodeoxygenation Catalysts for the Production of Advanced Biofuels.

PubMed

Yang, Yongxing; Ochoa-Hernández, Cristina; de la Peña O'Shea, Víctor A; Pizarro, Patricia; Coronado, Juan M; Serrano, David P

2015-09-01

A series of catalysts constituted by nanoparticles of transition metal (M = Fe, Co, Ni and Mo) phosphides (TMP) dispersed on SBA-15 were synthesized by reduction of the corresponding metal phosphate precursors previously impregnated on the mesostructured support. All the samples contained a metal-loading of 20 wt% and with an initial M/P mole ratio of 1, and they were characterized by X-ray diffraction (XRD), N2 sorption, H2-TPR and transmission electron microscopy (TEM). Metal phosphide nanocatalysts were tested in a high pressure continuous flow reactor for the hydrodeoxygenation (HDO) of a methyl ester blend containing methyl oleate (C17H33-COO-CH3) as main component (70%). This mixture constitutes a convenient surrogate of triglycerides present in vegetable oils, and following catalytic hydrotreating yields mainly n-alkanes. The results of the catalytic assays indicate that Ni2P/SBA-15 catalyst presents the highest ester conversion, whereas the transformation rate is about 20% lower for MoP/SBA-15. In contrast, catalysts based on Fe and Co phosphides show a rather limited activity. Hydrocarbon distribution in the liquid product suggests that both hydrodeoxygenation and decarboxylation/decarbonylation reactions occur simultaneously over the different catalysts, although MoP/SBA-15 possess a selectivity towards hydrodeoxygenation exceeding 90%. Accordingly, the catalyst based on MoP affords the highest yield of n-octadecane, which is the preferred product in terms of carbon atom economy. Subsequently, in order to conjugate the advantages of both Ni and Mo phosphides, a series of catalysts containing variable proportions of both metals were prepared. The obtained results reveal that the mixed phosphides catalysts present a catalytic behavior intermediate between those of the monometallic phosphides. Accordingly, only marginal enhancement of the yield of n-octadecane is obtained for the catalysts with a Mo/Ni ratio of 3. Nevertheless, owing to this high selectivity

Nanoparticle diffusion in, and microrheology of, the bovine vitreous ex vivo

PubMed Central

Xu, Qingguo; Boylan, Nicholas J.; Suk, Jung Soo; Wang, Ying-Ying; Nance, Elizabeth; Yang, Jeh-Chang; McDonnell, Peter; Cone, Richard; Duh, Elia J.; Hanes, Justin

2013-01-01

Intravitreal injection of biodegradable nanoparticles (NP) holds promise for gene therapy and drug delivery to the back of the eye. In some cases, including gene therapy, NP need to diffuse rapidly from the site of injection in order to reach targeted cell types in the back of the eye, whereas in other cases it may be preferred for the particles to remain at the injection site and slowly release drugs that may then diffuse to the site of action. We studied the movements of polystyrene (PS) nanoparticles of various sizes and surface chemistries in fresh bovine vitreous. PS NP as large as 510 nm rapidly penetrated the vitreous gel when coated with polyethylene glycol (PEG), whereas the movements of NP 1190 nm in diameter or larger were highly restricted regardless of surface chemistry owing to steric obstruction. PS NP coated with primary amine groups (–NH2) possessed positively charged surfaces at the pH of bovine vitreous (pH = 7.2), and were immobilized within the vitreous gel. In comparison, PS NP coated with –COOH (possessing negatively charged surfaces) in the size range of 100–200 nm and at particle concentrations below 0.0025% (w/v) readily diffused through the vitreous meshwork; at higher concentrations (~0.1% w/v), these nanoparticles aggregated within vitreous. Based on the mobility of different sized PS-PEG NP, we estimated the average mesh size of fresh bovine vitreous to be ~550 ± 50 nm. The bovine vitreous behaved as an impermeable elastic barrier to objects sized 1190 nm and larger, but as a highly permeable viscoelastic liquid to non-adhesive objects smaller than 510 nm in diameter. Guided by these studies, we next sought to examine the transport of drug- and DNA-loaded nanoparticles in bovine vitreous. Biodegradable NP with diameter of 227 nm, composed of a poly(lactic-co-glycolic acid) (PLGA)-based core coated with poly(vinyl alcohol) rapidly penetrated vitreous. Rod-shaped, highly-compacted CK30PEG10k/DNA with PEG coating (neutral surface

Static and dynamic structural characterization of nanomaterial catalysts

NASA Astrophysics Data System (ADS)

Masiel, Daniel Joseph

Heterogeneous catalysts systems are pervasive in industry, technology and academia. These systems often involve nanostructured transition metal particles that have crucial interfaces with either their supports or solid products. Understanding the nature of these interfaces as well as the structure of the catalysts and support materials themselves is crucial for the advancement of catalysis in general. Recent developments in the field of transmission electron microscopy (TEM) including dynamic transmission electron microscopy (DTEM), electron tomography, and in situ techniques stand poised to provide fresh insight into nanostructured catalyst systems. Several electron microscopy techniques are applied in this study to elucidate the mechanism of silica nanocoil growth and to discern the role of the support material and catalyst size in carbon dioxide and steam reforming of methane. The growth of silica nanocoils by faceted cobalt nanoparticles is a process that was initially believed to take place via a vapor-liquid-solid growth mechanism similar to other nanowire growth techniques. The extensive TEM work described here suggests that the process may instead occur via transport of silicate and silica species over the nanoparticle surface. Electron tomography studies of the interface between the catalyst particles and the wire indicate that they grow from edges between facets. Studies on reduction of the Co 3O4 nanoparticle precursors to the faceted pure cobalt catalysts were carried out using DTEM and in situ heating. Supported catalyst systems for methane reforming were studied using dark field scanning TEM to better understand sintering effects and the increased activity of Ni/Co catalysts supported by carbon nanotubes. Several novel electron microscopy techniques are described including annular dark field DTEM and a metaheuristic algorithm for solving the phase problem of coherent diffractive imaging. By inserting an annular dark field aperture into the back focal

Preparation of Ru-doped SnO2-supported Pt catalysts and their electrocatalytic properties for methanol oxidation.

PubMed

Pang, H L; Zhang, X H; Zhong, X X; Liu, B; Wei, X G; Kuang, Y F; Chen, J H

2008-03-01

Ru-doped SnO2 nanoparticles were prepared by chemical precipitation and calcinations at 823 K. Due to high stability in diluted acidic solution, Ru-doped SnO2 nanoparticles were selected as the catalyst support and second catalyst for methanol electrooxidation. The micrograph, elemental composition, and structure of the Ru-doped SnO2 nanoparticles were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction, respectively. The electrocatalytic properties of the Ru-doped SnO2-supported Pt catalyst (Pt/Ru-doped SnO2) for methanol oxidation have been investigated by cyclic voltammetry. Under the same loading mass of Pt, the Pt/Ru-doped SnO2 catalyst shows better electrocatalytic performance than the Pt/SnO2 catalyst and the best atomic ratio of Ru to Sn in Ru-doped SnO2 is 1/75. Additionally, the Pt/Ru-doped SnO2 catalyst possesses good long-term cycle stability.

Monodisperse core/shell Ni/FePt nanoparticles and their con-version to Ni/Pt to catalyze oxygen reduction

DOE PAGES

Zhang, Sen; Hao, Yizhou; Su, Dong; ...

2014-10-28

We report a size-controllable synthesis of monodisperse core/shell Ni/FePt nanoparticles (NPs) via a seed-mediated growth and their subsequent conversion to Ni/Pt NPs. Preventing surface oxidation of the Ni seeds is essential for the growth of uniform FePt shells. These Ni/FePt NPs have a thin (≈ 1 nm) FePt shell, and can be converted to Ni/Pt by acetic acid wash to yield active catalysts for oxygen reduction reaction (ORR). Tuning the core size allow for optimization of their electrocatalytic activity. The specific activity and mass activity of 4.2 nm/0.8 nm core/shell Ni/FePt reach 1.95 mA/cm² and 490 mA/mg Pt at 0.9more » V ( vs. reversible hydrogen electrode, RHE), which are much higher than those of benchmark commercial Pt catalyst (0.34 mA/cm² and 92 mA/mg Pt at 0.9 V). Our studies provide a robust approach to monodisperse core/shell NPs with non-precious metal core, making it possible to develop advanced NP catalysts with ultralow Pt content for ORR and many other heterogeneous reactions.« less

Zirconium and silver co-doped TiO2 nanoparticles as visible light catalyst for reduction of 4-nitrophenol, degradation of methyl orange and methylene blue

NASA Astrophysics Data System (ADS)

Naraginti, Saraschandra; Stephen, Finian Bernard; Radhakrishnan, Adhithya; Sivakumar, A.

2015-01-01

Catalytic activity of Zr and Ag co-doped TiO2 nanoparticles on the reduction of 4-nitrophenol, degradation of methylene blue and methyl orange was studied using sodium borohydride as reducing agent. The nanoparticles were characterized using X-ray diffraction, energy dispersive X-ray, high resolution transmission electron microscopy, selected area electron diffraction and UV-Vis spectroscopy. The rate of the reduction/degradation was found to increase with increasing amount of the photocatalyst which could be attributed to higher dispersity and small size of the nanoparticles. The catalytic activity of Zr and Ag co-doped TiO2 nanoparticles showed no significant difference even after recycling the catalyst four times indicating a promising potential for industrial application of the prepared photocatalyst.

Photochemical generation of antimicrobial Ag-nanoparticles in intraocular lenses

NASA Astrophysics Data System (ADS)

Badur, Thorben; Kim, Hee-Cheol; Hampp, Norbert

2017-02-01

The antimicrobial properties of silver (Ag) nanoparticles (NP) have been investigated in depth during the last decades.[1] For cataract treatment minimal invasive surgery has become state-of-the-art. The physicians are still fighting against postoperative inflammations, such as endophthalmitis.[2] We present a novel approach to reduce these postoperative complications by equipping the hydrophilic intraocular lenses (IOL) with a Ag NP depot. As the Ag NP are completely entrapped inside the polymeric IOL no direct contact of the nanoparticles with epithelial cells may occur. Using 1-hydroxybenzotriazole (HOBt) or 7-hydroxycumarine (7HOCum) as photo reduction mediators (PRM) the formation of the Ag NP is accomplished in situ. PRM and Ag nitrate are diffused into the ready made IOL. By means of two-photon-absorption (TPA) photochemistry at λTPA = 532 nm the Ag NP generation is precisely controlled to occur inside the IOL only. At no point NP are directly exposed to the surface.[3] Interesting dependencies between the used PRM and the resulting particle size distribution or the effectiveness of the silver ion reduction inside the polymer matrix are reported. The Ag NP were prepared in the outer area of the IOL not to affect the optical properties of the ophthalmic implant. The amount of Ag ions released was determined and found to be sufficient to effectively reduce the counts of airborne germs. Besides HOBt and 7HOCum we also investigated the photo reductive properties of several other organic reagents, such as benzophenone (BP) and 4-hydroxybenzophenone (4HOBP) for the ability to produce even three-dimensional nanoparticle structures inside a polymer matrix.

IRON OXIDE NANOPARTICLE-INDUCED OXIDATIVE STRESS AND INFLAMMATION

EPA Science Inventory

1. Nanoparticle Physicochemical Characterizations

We first focused on creating NP systems that could be used to test our hypotheses and assessing their stability in aqueous media. The iron oxide NP systems were not stable in cell culture medium o...

2. Catalytic activity of Pd-doped Cu nanoparticles for hydrogenation as a single-atom-alloy catalyst.

   PubMed

   Cao, Xinrui; Fu, Qiang; Luo, Yi

   2014-05-14

   The single atom alloy of extended surfaces is known to provide remarkably enhanced catalytic performance toward heterogeneous hydrogenation. Here we demonstrate from first principles calculations that this approach can be extended to nanostructures, such as bimetallic nanoparticles. The catalytic properties of the single-Pd-doped Cu55 nanoparticles have been systemically examined for H2 dissociation as well as H atom adsorption and diffusion, following the concept of single atom alloy. It is found that doping a single Pd atom at the edge site of the Cu55 shell can considerably reduce the activation energy of H2 dissociation, while the single Pd atom doped at the top site or in the inner layers is much less effective. The H atom adsorption on Cu55 is slightly stronger than that on the Cu(111) surface; however, a larger nanoparticle that contains 147 atoms could effectively recover the weak binding of the H atoms. We have also investigated the H atom diffusion on the 55-atom nanoparticle and found that spillover of the produced H atoms could be a feasible process due to the low diffusion barriers. Our results have demonstrated that facile H2 dissociation and weak H atom adsorption could be combined at the nanoscale. Moreover, the effects of doping one more Pd atom on the H2 dissociation and H atom adsorption have also been investigated. We have found that both the doping Pd atoms in the most stable configuration could independently exhibit their catalytic activity, behaving as two single-atom-alloy catalysts.

3. Stability and dewetting of metal nanoparticle filled thin polymer films: control of instability length scale and dynamics.

   PubMed

   Mukherjee, Rabibrata; Das, Soma; Das, Anindya; Sharma, Satinder K; Raychaudhuri, Arup K; Sharma, Ashutosh

   2010-07-27

   We investigate the influence of gold nanoparticle addition on the stability, dewetting, and pattern formation in ultrathin polymer-nanoparticle (NP) composite films by examining the length and time scales of instability, morphology, and dynamics of dewetting. For these 10-50 nm thick (h) polystyrene (PS) thin films containing uncapped gold nanoparticles (diameter approximately 3-4 nm), transitions from complete dewetting to arrested dewetting to absolute stability were observed depending on the concentration of the particles. Experiments show the existence of three distinct stability regimes: regime 1, complete dewetting leading to droplet formation for nanoparticle concentration of 2% (w/w) or below; regime 2, partial dewetting leading to formation of arrested holes for NP concentrations in the range of 3-6%; and regime 3, complete inhibition of dewetting for NP concentrations of 7% and above. Major results are (a) length scale of instability, where lambdaH approximately hn remains unchanged with NP concentration in regime 1 (n approximately 2) but increases in regime 2 with a change in the scaling relation (n approximately 3-3.5); (b) dynamics of instability and dewetting becomes progressively sluggish with an increase in the NP concentration; (c) there are distinct regimes of dewetting velocity at low NP concentrations; (d) force modulation AFM, as well as micro-Raman analysis, shows phase separation and aggregation of the gold nanoparticles within each dewetted polymer droplet leading to the formation of a metal core-polymer shell morphology. The polymer shell could be removed by washing in a selective solvent, thus exposing an array of bare gold nanoparticle aggregates.

4. Pulmonary Cerium Dioxide Nanoparticles Exposure Differentially Impairs Coronary and Mesenteric Arteriolar Reactivity

   PubMed Central

   Minarchick, Valerie C; Stapleton, Phoebe A; Porter, Dale W; Wolfarth, Michael G; Çiftyürek, Engin; Barger, Mark; Sabolsky, Edward M.; Nurkiewicz, Timothy R

   2013-01-01

   Cerium dioxide nanoparticles (CeO2 NPs) are an engineered nanomaterial that possesses unique catalytic, oxidative and reductive properties. Currently, CeO2 NPs are being used as a fuel catalyst but these properties are also utilized in the development of potential drug treatments for radiation and stroke protection. These uses of CeO2 NPs present a risk for human exposure; however, to date no studies have investigated the effects of CeO2 NPs on the microcirculation following pulmonary exposure. Previous studies in our laboratory with other nanomaterials have shown impairments in normal microvascular function after pulmonary exposures. Therefore, we predicted that CeO2 NP exposure would cause microvascular dysfunction that is dependent on the tissue bed and dose. Twenty-four hour post exposure to CeO2 NPs (0–400 μg), mesenteric and coronary arterioles were isolated and microvascular function was assessed. Our results provided evidence that pulmonary CeO2 NP exposure impairs endothelium-dependent and -independent arteriolar dilation in a dose-dependent manner. The CeO2 NP exposure dose which causes a 50% impairment in arteriolar function (EC50) was calculated and ranged from 15 – 100 μg depending on the chemical agonist and microvascular bed. Microvascular assessments with acetylcholine revealed a 33–75% reduction in function following exposure. Additionally, there was a greater sensitivity to CeO2 NP exposure in the mesenteric microvasculature due to the 40% decrease in the calculated EC50 compared to the coronary microvasculature EC50. CeO2 NP exposure increased mean arterial pressure in some groups. Taken together these observed microvascular changes may likely have detrimental effects on local blood flow regulation and contribute to cardiovascular dysfunction associated with particle exposure. PMID:23645470

RuO 2 nanoparticles supported on MnO 2 nanorods as high efficient bifunctional electrocatalyst of lithium-oxygen battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Yue-Feng; Chen, Yuan; Xu, Gui-Liang

RuO2 nanoparticles supported on MnO2 nanorods (denoted as np-RuO2/nr-MnO2) were synthesized via a two-step hydrothermal reaction. SEM and TEM images both illustrated that RuO2 nanoparticles are well dispersed on the surface of MnO2 nanorods in the as-prepared np-RuO2/nr-MnO2 material. Electrochemical results demonstrated that the np-RuO2/nr-MnO2 as oxygen cathode of Li-O-2 batteries could maintain a reversible capacity of 500 mA h g(-1) within 75 cycles at a rate of 50 mA g(-1), and a higher capacity of 4000 mA h g(-1) within 20 cycles at a rate as high as 200 mA g(-1). Moreover, the cell with the np-RuO2/nr-MnO2 catalyst presentedmore » much lower voltage polarization (about 0.58 V at a rate of 50 mA g(-1)) than that measured with only MnO2 nanorods during charge/discharge processes. The catalytic property of the np-RuO2/nr-MnO2 and MnO2 nanorods were further compared by conducting studies of using rotating disk electrode (RDE), chronoamperommetry and linear sweep voltammetry. The results illustrated that the np-RuO2/nr-MnO2 exhibited excellent bifunctional electrocatalytic activities towards both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, in-situ high-energy X-ray diffraction was employed to trace evolution of species on the np-RuO2/nr-MnO2 cathode during the discharge processes. In-situ XRD patterns demonstrated the formation process of the discharge products that consisted of mainly Li2O2. Ex-situ SEM images were recorded to investigate the morphology and decomposition of the sphere-like Li2O2, which could be observed clearly after discharge process, while are decomposed almost after charge process. The excellent electrochemical performances of the np-RuO2/nr-MnO2 as cathode of Li-O-2 battery could be contributed to the excellent bifunctional electrocatalytic activities for both the ORR and OER, and to the one-dimensional structure which would benefit the diffusion of oxygen and the storage of Li2O2 in the discharge

Structural rearrangement of mesostructured silica nanoparticles incorporated with ZnO catalyst and its photoactivity: Effect of alkaline aqueous electrolyte concentration

NASA Astrophysics Data System (ADS)

Jusoh, N. W. C.; Jalil, A. A.; Triwahyono, S.; Karim, A. H.; Salleh, N. F.; Annuar, N. H. R.; Jaafar, N. F.; Firmansyah, M. L.; Mukti, R. R.; Ali, M. W.

2015-03-01

ZnO-incorporated mesostructured silica nanoparticles (MSN) catalysts (ZM) were prepared by the introduction of Zn ions into the framework of MSN via a simple electrochemical system in the presence of various concentrations of NH4OH aqueous solution. The physicochemical properties of the catalysts were studied by XRD, 29Si MAS NMR, nitrogen adsorption-desorption, FE-SEM, TEM, FTIR, and photoluminescence spectroscopy. Characterization results demonstrated that the alkaline aqueous electrolyte simply generated abundant silanol groups on the surface of the catalysts as a consequence of desilication to form the hierarchical-like structure of the MSN. Subsequent restructuring of the silica network by the creation of oxygen vacancies and formation of Si-O-Zn during the electrolysis, as well as formation of new Si-O-Si bonds during calcination seemed to be the main factors that enhanced the catalytic performance of photodecolorization of methyl orange. A ZM prepared in the presence of 1.0 M NH4OH (ZM-1.0) was determined to be the most effective catalyst. The catalyst displays a higher first-order kinetics rate of 3.87 × 10-1 h-1 than unsupported ZnO (1.13 × 10-1 h-1) that prepared under the same conditions in the absence of MSN. The experiment on effect of scavengers showed that hydroxyl radicals generated from the three main sources; reduced O2 at the conduction band, decomposed water at the valence band and irradiated H2O2 in the solution, are key factors that influenced the reaction. It is also noted that the recycled ZM-1.0 catalyst maintained its activity up to five runs without serious catalyst deactivation.

Effect of Phenolic Compounds on the Synthesis of Gold Nanoparticles and its Catalytic Activity in the Reduction of Nitro Compounds.

PubMed

Alegria, Elisabete C B A; Ribeiro, Ana P C; Mendes, Marta; Ferraria, Ana M; do Rego, Ana M Botelho; Pombeiro, Armando J L

2018-05-10

Gold nanoparticles (AuNPs) were prepared using an eco-friendly approach in a single step by reduction of HAuCl₄ with polyphenols from tea extracts, which act as both reducing and capping agents. The obtained AuNPs were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet⁻visible spectroscopy (UV⁻vis), and X-ray photoelectron spectroscopy (XPS). They act as highly efficient catalysts in the reduction of various aromatic nitro compounds in aqueous solution. The effects of a variety of factors (e.g., reaction time, type and amount of reducing agent, shape, size, or amount of AuNPs) were studied towards the optimization of the processes. The total polyphenol content (TPC) was determined before and after the catalytic reaction and the results are discussed in terms of the tea extract percentage, the size of the AuNPs, and their catalytic activity. The reusability of the AuNP catalyst in the reduction of 4-nitrophenol was also tested. The reactions follow pseudo first-order kinetics.

pH-Triggered Molecular Alignment for Reproducible SERS Detection via an AuNP/Nanocellulose Platform

PubMed Central

Wei, Haoran; Vikesland, Peter J.

2015-01-01

The low affinity of neutral and hydrophobic molecules towards noble metal surfaces hinders their detection by surface-enhanced Raman spectroscopy (SERS). Herein, we present a method to enhance gold nanoparticle (AuNP) surface affinity by lowering the suspension pH below the analyte pKa. We developed an AuNP/bacterial cellulose (BC) nanocomposite platform and applied it to two common pollutants, carbamazepine (CBZ) and atrazine (ATZ) with pKa values of 2.3 and 1.7, respectively. Simple mixing of the analytes with AuNP/BC at pH < pKa resulted in consistent electrostatic alignment of the CBZ and ATZ molecules across the nanocomposite and highly reproducible SERS spectra. Limits of detection of 3 nM and 11 nM for CBZ and ATZ, respectively, were attained. Tests with additional analytes (melamine, 2,4-dichloroaniline, 4-chloroaniline, 3-bromoaniline, and 3-nitroaniline) further illustrate that the AuNP/BC platform provides reproducible analyte detection and quantification while avoiding the uncontrolled aggregation and flocculation of AuNPs that often hinder low pH detection. PMID:26658696

pH-Triggered Molecular Alignment for Reproducible SERS Detection via an AuNP/Nanocellulose Platform

NASA Astrophysics Data System (ADS)

Wei, Haoran; Vikesland, Peter J.

2015-12-01

The low affinity of neutral and hydrophobic molecules towards noble metal surfaces hinders their detection by surface-enhanced Raman spectroscopy (SERS). Herein, we present a method to enhance gold nanoparticle (AuNP) surface affinity by lowering the suspension pH below the analyte pKa. We developed an AuNP/bacterial cellulose (BC) nanocomposite platform and applied it to two common pollutants, carbamazepine (CBZ) and atrazine (ATZ) with pKa values of 2.3 and 1.7, respectively. Simple mixing of the analytes with AuNP/BC at pH < pKa resulted in consistent electrostatic alignment of the CBZ and ATZ molecules across the nanocomposite and highly reproducible SERS spectra. Limits of detection of 3 nM and 11 nM for CBZ and ATZ, respectively, were attained. Tests with additional analytes (melamine, 2,4-dichloroaniline, 4-chloroaniline, 3-bromoaniline, and 3-nitroaniline) further illustrate that the AuNP/BC platform provides reproducible analyte detection and quantification while avoiding the uncontrolled aggregation and flocculation of AuNPs that often hinder low pH detection.

Hyperspectral Imaging, Flow cytometry and Microscopic Morphology of Silver Nanoparticle within Cells

EPA Science Inventory

The ability to detect and track silver nanoparticles (AgNP) that enter cells is important to understand the potential biological and toxicological actions of AgNP. The uptake and fate in cells of four different types of AgNP was studied in a retinal pigment epithelial cell line ...

Role of surface charge and oxidative stress in cytotoxicity of organic monolayer-coated silicon nanoparticles towards macrophage NR8383 cells

PubMed Central

2010-01-01

Background Surface charge and oxidative stress are often hypothesized to be important factors in cytotoxicity of nanoparticles. However, the role of these factors is not well understood. Hence, the aim of this study was to systematically investigate the role of surface charge, oxidative stress and possible involvement of mitochondria in the production of intracellular reactive oxygen species (ROS) upon exposure of rat macrophage NR8383 cells to silicon nanoparticles. For this aim highly monodisperse (size 1.6 ± 0.2 nm) and well-characterized Si core nanoparticles (Si NP) were used with a surface charge that depends on the specific covalently bound organic monolayers: positively charged Si NP-NH2, neutral Si NP-N3 and negatively charged Si NP-COOH. Results Positively charged Si NP-NH2 proved to be more cytotoxic in terms of reducing mitochondrial metabolic activity and effects on phagocytosis than neutral Si NP-N3, while negatively charged Si NP-COOH showed very little or no cytotoxicity. Si NP-NH2 produced the highest level of intracellular ROS, followed by Si NP-N3 and Si NP-COOH; the latter did not induce any intracellular ROS production. A similar trend in ROS production was observed in incubations with an isolated mitochondrial fraction from rat liver tissue in the presence of Si NP. Finally, vitamin E and vitamin C induced protection against the cytotoxicity of the Si NP-NH2 and Si NP-N3, corroborating the role of oxidative stress in the mechanism underlying the cytotoxicity of these Si NP. Conclusion Surface charge of Si-core nanoparticles plays an important role in determining their cytotoxicity. Production of intracellular ROS, with probable involvement of mitochondria, is an important mechanism for this cytotoxicity. PMID:20831820

Effect of mucoadhesive polymers on the in vitro performance of insulin-loaded silica nanoparticles: Interactions with mucin and biomembrane models.

PubMed

Andreani, Tatiana; Miziara, Leonardo; Lorenzón, Esteban N; de Souza, Ana Luiza R; Kiill, Charlene P; Fangueiro, Joana F; Garcia, Maria L; Gremião, Palmira D; Silva, Amélia M; Souto, Eliana B

2015-06-01

The present paper focuses on the development and characterization of silica nanoparticles (SiNP) coated with hydrophilic polymers as mucoadhesive carriers for oral administration of insulin. SiNP were prepared by sol-gel technology under mild conditions and coated with different hydrophilic polymers, namely, chitosan, sodium alginate or poly(ethylene glycol) (PEG) with low and high molecular weight (PEG 6000 and PEG 20000) to increase the residence time at intestinal mucosa. The mean size and size distribution, association efficiency, insulin structure and insulin thermal denaturation have been determined. The mean nanoparticle diameter ranged from 289 nm to 625 nm with a PI between 0.251 and 0.580. The insulin association efficiency in SiNP was recorded above 70%. After coating, the association efficiency of insulin increased up to 90%, showing the high affinity of the protein to the hydrophilic polymer chains. Circular dichroism (CD) indicated that no conformation changes of insulin structure occurred after loading the peptide into SiNP. Nano-differential scanning calorimetry (nDSC) showed that SiNP shifted the insulin endothermic peak to higher temperatures. The influence of coating on the interaction of nanoparticles with dipalmitoylphosphatidylcholine (DPPC) biomembrane models was also evaluated by nDSC. The increase of ΔH values suggested a strong association of non-coated SiNP and those PEGylated nanoparticles coated with DPPC polar heads by forming hydrogen bonds and/or by electrostatic interaction. The mucoadhesive properties of nanoparticles were examined by studying the interaction with mucin in aqueous solution. SiNP coated with alginate or chitosan showed high contact with mucin. On the other hand, non-coated SiNP and PEGylated SiNP showed lower interaction with mucin, indicating that these nanoparticles can interdiffuse across mucus network. The results of the present work provide valuable data in assessing the in vitro performance of insulin

Metallic nanoparticle deposition techniques for enhanced organic photovoltaic cells

NASA Astrophysics Data System (ADS)

Cacha, Brian Joseph Gonda

Energy generation via organic photovoltaic (OPV) cells provide many advantages over alternative processes including flexibility and price. However, more efficient OPVs are required in order to be competitive for applications. One way to enhance efficiency is through manipulation of exciton mechanisms within the OPV, for example by inserting a thin film of bathocuproine (BCP) and gold nanoparticles between the C60/Al and ZnPc/ITO interfaces, respectively. We find that BCP increases efficiencies by 330% due to gains of open circuit voltage (Voc) by 160% and short circuit current (Jsc) by 130%. However, these gains are complicated by the anomalous photovoltaic effect and an internal chemical potential. Exploration in the tuning of metallic nanoparticle deposition on ITO was done through four techniques. Drop casting Ag nanoparticle solution showed arduous control on deposited morphology. Spin-coating deposited very low densities of nanoparticles. Drop casting and spin-coating methods showed arduous control on Ag nanoparticle morphology due to clustering and low deposition density, respectively. Sputtered gold on glass was initially created to aid the adherence of Ag nanoparticles but instead showed a quick way to deposit aggregated gold nanoparticles. Electrodeposition of gold nanoparticles (AuNP) proved a quick method to tune nanoparticle morphology on ITO substrates. Control of deposition parameters affected AuNP size and distribution. AFM images of electrodeposited AuNPs showed sizes ranging from 39 to 58 nm. UV-Vis spectroscopy showed the presence of localized plasmon resonance through absorption peaks ranging from 503 to 614 nm. A linear correlation between electrodeposited AuNP size and peak absorbance was seen with a slope of 3.26 wavelength(nm)/diameter(nm).

Finely controlled multimetallic nanocluster catalysts for solvent-free aerobic oxidation of hydrocarbons

PubMed Central

Takahashi, Masaki; Koizumi, Hiromu; Chun, Wang-Jae; Kori, Makoto; Imaoka, Takane; Yamamoto, Kimihisa

2017-01-01

The catalytic activity of alloy nanoparticles depends on the particle size and composition ratio of different metals. Alloy nanoparticles composed of Pd, Pt, and Au are widely used as catalysts for oxidation reactions. The catalytic activities of Pt and Au nanoparticles in oxidation reactions are known to increase as the particle size decreases and to increase on the metal-metal interface of alloy nanoparticles. Therefore, multimetallic nanoclusters (MNCs) around 1 nm in diameter have potential as catalysts for oxidation reactions. However, there have been few reports describing the preparation of uniform alloy nanoclusters. We report the synthesis of finely controlled MNCs (around 1 nm) using a macromolecular template with coordination sites arranged in a gradient of basicity. We reveal that Cu-Pt-Au MNCs supported on graphitized mesoporous carbon show catalytic activity that is 24 times greater than that of a commercially available Pt catalyst for aerobic oxidation of hydrocarbons. In addition, solvent-free aerobic oxidation of hydrocarbons to ketones at room temperature, using small amounts of a radical initiator, was achieved as a heterogeneous catalytic reaction for the first time. PMID:28782020

Flower-Like ZnO-Assisted One-Pot Encapsulation of Noble Metal Nanoparticles Supported Catalysts with ZIFs

NASA Astrophysics Data System (ADS)

Lin, Lu; Liu, Haiou; Zhang, Xiongfu

2018-03-01

Rational design of efficient approaches to fabricate MOFs-coated core-shell composites is promising but challenging. We report here the encapsulation of Pd nanoparticles (Pd NPs) supported flower-like ZnO (F-ZnO) microspheres with ZIF-8 shell through a facile strategy, in which the formation and immobilization of Pd NPs on F-ZnO supports and the subsequent growth of ZIF-8 shells over them are effectively integrated into one-pot synthetic route. Importantly, the utilization of ZnO both as support of Pd NPs and Zn2+ source of ZIF-8 is favorable for the implement of one-pot synthesis, due to its functions in anchoring Pd NPs and inducing ZIF-8 formation. Further insights into the morphological influence of zinc oxide particles on the resulting materials indicate that the flower-like microspheres with 2D nanosheets as subunits also benefit the coating of Pd NPs supported cores with ZIF-8, resulting in a well-defined core-shell catalyst. The achieved catalyst deliveries remarkable performance in terms of selectivity, anti-poisoning and recyclability in the liquid hydrogenations of alkenes.

Enhanced room-temperature catalytic decomposition of formaldehyde on magnesium-aluminum hydrotalcite/boehmite supported platinum nanoparticles catalyst.

PubMed

Yan, Zhaoxiong; Yang, Zhihua; Xu, Zhihua; An, Liang; Xie, Fang; Liu, Jiyan

2018-08-15

Magnesium-aluminum hydrotalcite (Mg-Al HT)/boehmite (AlOOH) composite supported Pt catalysts were obtained via one-pot microemulsion synthesis of Mg-Al HT/AlOOH composite and NaBH 4 -reduction of Pt precursor processes. The catalytic performances of the catalysts were evaluated for formaldehyde (HCHO) removal at room temperature. The performance tests showed that the catalyst obtained by immobilizing Pt nanoparticles (NPs) on Mg-Al HT/AlOOH support with Al/Mg molar ratio equivalent to 9:1 (Pt/Al 9 Mg 1 ) displayed a superior catalytic activity and stability for HCHO removal. In order to find out the causes of its higher activity, X-ray diffraction, transmission electron microscopy, N 2 adsorption/desorption, X-ray photoelectron spectroscopy, temperature programmed desorption of CO 2 and reduction of H 2 were used to analyze the physicochemical properties of Pt/Al 9 Mg 1 and Pt/AlOOH. The remarkable catalytic performance of Pt/Al 9 Mg 1 is mainly attributed to the relatively larger amount of surface oxygen species, and more reactive oxygen species led by the interaction of Mg-Al HT and AlOOH/Pt, and relatively larger number of weak base sites caused by Mg-Al HT. The formate species are the main reaction intermediate over Pt/Al 9 Mg 1 during HCHO oxidation at room temperature, which could be further oxidized into CO 2 and H 2 O in the presence of O 2 . This study might shed some light on further improving the catalytic performance of the catalyst for indoor air purification at room temperature. Copyright © 2018 Elsevier Inc. All rights reserved.

Preparation of metallic Pd nanoparticles using supercritical CO2 deposition: An efficient catalyst for Suzuki cross-coupling reaction

NASA Astrophysics Data System (ADS)

Tezcan, Burcu; Ulusal, Fatma; Egitmen, Asım; Guzel, Bilgehan

2018-05-01

Ligand-free palladium nanoparticles supported on multi-walled carbon nanotubes (Pd/MWCNT) were prepared by the supercritical carbon dioxide (scCO2) deposition method using a novel scCO2-soluble Pd organometallic complex as a precursor. The precursor with the perfluoroalkyl chain group was synthesized and identified by microanalytic methods. The deposition was carried out at the temperature of 363.15 K and pressure of 27.6 MPa CO2. The prepared metallic nanoparticles were obtained with an average size of 2 nm. Pd/MWCNT was utilized as a heterogeneous catalyst in Suzuki cross-coupling reaction. The nanocatalyst was found very effective in Suzuki reaction and it could also be recovered easily from the reaction media and reused over several cycles without significant loss of catalytic activity under mild conditions. [Figure not available: see fulltext.

Porous nanocrystalline silicon supported bimetallic Pd-Au catalysts: preparation, characterization and direct hydrogen peroxide synthesis

NASA Astrophysics Data System (ADS)

Potemkin, Dmitriy I.; Maslov, Dmitry K.; Loponov, Konstantin; Snytnikov, Pavel V.; Shubin, Yuri V.; Plyusnin, Pavel E.; Svintsitskiy, Dmitry A.; Sobyanin, Vladimir A.; Lapkin, Alexei A.

2018-03-01

Bimetallic Pd-Au catalysts were prepared on the porous nanocrystalline silicon (PSi) for the first time. The catalysts were tested in the reaction of direct hydrogen peroxide synthesis and characterised by standard structural and chemical techniques. It was shown that the Pd-Au/PSi catalyst prepared from conventional H2[PdCl4] and H[AuCl4] precursors contains monometallic Pd and a range of different Pd-Au alloy nanoparticles over the oxidized PSi surface. The PdAu2/PSi catalyst prepared from the [Pd(NH3)4][AuCl4]2 double complex salt single-source precursor predominantly contains bimetallic Pd-Au alloy nanoparticles. For both catalysts the surface of bimetallic nanoparticles is Pd-enriched and contains palladium in Pd0 and Pd2+ states. Among the catalysts studied, the PdAu2/PSi catalyst was the most active and selective in the direct H2O2 synthesis with H2O2 productivity of 0.5 at selectivity of 50 % and H2O2 concentration of 0.023 M in 0.03 M H2SO4-methanol solution after 5 h on stream at -10 °C and atmospheric pressure. This performance is due to high activity in the H2O2 synthesis reaction and low activities in the undesirable H2O2 decomposition and hydrogenation reactions. Good performance of the PdAu2/PSi catalyst was associated with the major part of Pd in the catalyst being in the form of the bimetallic Pd-Au nanoparticles. Porous silicon was concluded to be a promising catalytic support for direct hydrogen peroxide synthesis due to its inertness with respect to undesirable side reactions, high thermal stability and conductivity, possibility of safe operation at high temperatures and pressures and a well-established manufacturing process.

Multifunctional iron oxide nanoparticles for biomedical applications

NASA Astrophysics Data System (ADS)

Bloemen, M.; Denis, C.; Van Stappen, T.; De Meester, L.; Geukens, N.; Gils, A.; Verbiest, T.

2015-03-01

Multifunctional nanoparticles have attracted a lot of attention since they can combine interesting properties like magnetism, fluorescence or plasmonic effects. As a core material, iron oxide nanoparticles have been the subject of intensive research. These cost-effective and non-toxic particles are used nowadays in many applications. We developed a heterobifunctional PEG ligand that can be used to introduce functional groups (carboxylic acids) onto the surface of the NP. Via click chemistry, a siloxane functionality was added to this ligand, for a subsequent covalent ligand exchange reaction. The functionalized nanoparticles have an excellent colloidal stability in complex environments like buffers and serum or plasma. Antibodies were coupled to the introduced carboxylic acids and these NP-antibody bioconjugates were brought into contact with Legionella bacteria for magnetic separation experiments.

Hybrid Nanomaterials with Single-Site Catalysts by Spatially Controllable Immobilization of Nickel Complexes via Photoclick Chemistry for Alkene Epoxidation.

PubMed

Ghosh, Dwaipayan; Febriansyah, Benny; Gupta, Disha; Ng, Leonard Kia-Sheun; Xi, Shibo; Du, Yonghua; Baikie, Tom; Dong, ZhiLi; Soo, Han Sen

2018-05-22

Catalyst deactivation is a persistent problem not only for the scientific community but also in industry. Isolated single-site heterogeneous catalysts have shown great promise to overcome these problems. Here, a versatile anchoring strategy for molecular complex immobilization on a broad range of semiconducting or insulating metal oxide ( e. g., titanium dioxide, mesoporous silica, cerium oxide, and tungsten oxide) nanoparticles to synthesize isolated single-site catalysts has been studied systematically. An oxidatively stable anchoring group, maleimide, is shown to form covalent linkages with surface hydroxyl functionalities of metal oxide nanoparticles by photoclick chemistry. The nanocomposites have been thoroughly characterized by techniques including UV-visible diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and X-ray absorption spectroscopy (XAS). The IR spectroscopic studies confirm the covalent linkages between the maleimide group and surface hydroxyl functionalities of the oxide nanoparticles. The hybrid nanomaterials function as highly efficient catalysts for essentially quantitative oxidations of terminal and internal alkenes and show molecular catalyst product selectivities even in more eco-friendly solvents. XAS studies verify the robustness of the catalysts after several catalytic cycles. We have applied the photoclick anchoring methodology to precisely control the deposition of a luminescent variant of our catalyst on the metal oxide nanoparticles. Overall, we demonstrate a general approach to use irradiation to anchor molecular complexes on oxide nanoparticles to create recyclable, hybrid, single-site catalysts that function with high selectivity in a broad range of solvents. We have achieved a facile, spatially and temporally controllable photoclick method that can potentially be extended to other ligands, catalysts, functional molecules, and surfaces.

Microwave assisted green synthesis and characterizations of noble metal nanoparticles and their roles as catalysts in organic reduction reactions and anticancer agent

NASA Astrophysics Data System (ADS)

Francis, Sijo; Koshy, Ebey P.; Mathew, Beena

2018-04-01

Nanomaterials are interesting chemicals that uncover the explorations and expectations of decades. The report suggests environmentally benevolent and easy route for the synthesis of noble metal nanoparticles. Personnel, laboratory and ecological benefits of the synthesized nanoparticles are demonstrated herein. The aqueous extract from the leaves of Litchi chinensis Sonn is performed as the alternative reducing agent. The microwave activated silver and gold nanoparticles have spherical geometries with crystalline essence. X-ray diffraction technique witnessed the face centered cubic lattice for the nano silver and gold particles that preferentially oriented towards the (111) plane. The reduction of nitro anilines is performed to elucidate the heterogeneous catalytic power of the nanoparticles. The nano catalyst is a potential candidate to meet the challenges raised from organic pollutant dye that cause environmental contamination. The chemical stability, low-cost factor and plant based origin of the new nanoparticles are admired. The multitudes of health hazards especially human carcinoma can be effectively inhibited by the silver and gold nanoparticles. The leaf extract, silver and gold nanoparticles showed IC50 values 66.56 ± 0.80, 23.55 ± 0.43 and 20.38 ± 0.41 μg ml‑1 respectively against the human lung adenocarcinoma cell lines A549 determined using the MTT dye conversion assay.

Toxicity, Bioaccumulation and Biotransformation of Silver Nanoparticles in Marine Organisms.

EPA Science Inventory

The toxicity, bioaccumulation and biotransformation of citrate and polyvinylpyrrolidone (PVP) coated silver nanoparticles (NPs) (AgNP-citrate and AgNP-PVP) in marine organisms via marine sediment exposure was investigated. Results from 7-d sediment toxicity tests indicate that Ag...

Adjuvant effect of Gantrez®AN nanoparticles during oral vaccination of piglets against F4+enterotoxigenic Escherichia coli.

PubMed

Vandamme, Katrien; Melkebeek, Vesna; Vesna, Melkebeek; Cox, Eric; Eric, Cox; Remon, Jean Paul; Paul, Remon Jean; Vervaet, Chris; Chris, Vervaet

2011-02-15

In this study, the adjuvanticity of methylvinylether-co-maleic anhydride (Gantrez(®)AN) nanoparticles (NP) was investigated in an oral immunisation experiment of pigs against F4+enterotoxigenic Escherichia coli (F4+ETEC). In addition, Wheat Germ Agglutinin (WGA)-coating of the nanoparticles was tested for enterocyte-targeting. Pigs were either vaccinated with F4 fimbriae, F4 encapsulated in Gantrez(®)AN NP, F4 encapsulated in Gantrez(®)AN NP coated with WGA or F4 fimbriae mixed with empty Gantrez(®)AN NP. Only vaccination with the combination of F4 mixed with empty Gantrez(®)AN NP improved protection against F4+ETEC infection. In addition, vaccination with this formulation also resulted in an F4-specific serum antibody response prior to F4+ETEC challenge. Encapsulation of F4 in Gantrez(®)AN NP only raised the serum antibody response after F4+ETEC challenge compared to soluble F4, but did not improve protection, whereas WGA-coating almost completely abolished the serum antibody response. These data indicate that nanoparticle effects after F4 encapsulation were of lesser importance for the adjuvant effect of Gantrez(®)AN NP, contrarily to the reactivity of the Gantrez(®)AN polymer used to prepare the nanoparticles. Copyright © 2010 Elsevier B.V. All rights reserved.

Synthesis and redox activity of "clicked" triazolylbiferrocenyl polymers, network encapsulation of gold and silver nanoparticles and anion sensing.

PubMed

Rapakousiou, Amalia; Deraedt, Christophe; Irigoyen, Joseba; Wang, Yanlan; Pinaud, Noël; Salmon, Lionel; Ruiz, Jaime; Moya, Sergio; Astruc, Didier

2015-03-02

The design of redox-robust polymers is called for in view of interactions with nanoparticles and surfaces toward applications in nanonetwork design, sensing, and catalysis. Redox-robust triazolylbiferrocenyl (trzBiFc) polymers have been synthesized with the organometallic group in the side chain by ring-opening metathesis polymerization using Grubbs-III catalyst or radical polymerization and with the organometallic group in the main chain by Cu(I) azide alkyne cycloaddition (CuAAC) catalyzed by [Cu(I)(hexabenzyltren)]Br. Oxidation of the trzBiFc polymers with ferricenium hexafluorophosphate yields the stable 35-electron class-II mixed-valent biferrocenium polymer. Oxidation of these polymers with Au(III) or Ag(I) gives nanosnake-shaped networks (observed by transmission electron microscopy and atomic force microscopy) of this mixed-valent Fe(II)Fe(III) polymer with encapsulated metal nanoparticles (NPs) when the organoiron group is located on the side chain. The factors that are suggested to be synergistically responsible for the NP stabilization and network formation are the polymer bulk, the trz coordination, the nearby cationic charge of trzBiFc, and the inter-BiFc distance. For instance, reduction of such an oxidized trzBiFc-AuNP polymer to the neutral trzBiFc-AuNP polymer with NaBH4 destroys the network, and the product flocculates. The polymers easily provide modified electrodes that sense, via the oxidized Fe(II)Fe(III) and Fe(III)Fe(III) polymer states, respectively, ATP(2-) via the outer ferrocenyl units of the polymer and Pd(II) via the inner Fc units; this recognition works well in dichloromethane, but also to a lesser extent in water with NaCl as the electrolyte.

Resistive-pulse measurements with nanopipettes: detection of Au nanoparticles and nanoparticle-bound anti-peanut IgY.

PubMed

Wang, Yixian; Kececi, Kaan; Mirkin, Michael V; Mani, Vigneshwaran; Sardesai, Naimish; Rusling, James F

2013-02-01

Solid-state nanopores have been widely employed in sensing applications from Coulter counters to DNA sequencing devices. The analytical signal in such experiments is the change in ionic current flowing through the orifice caused by the large molecule or nanoparticle translocation through the pore. Conceptually similar nanopipette-based sensors can offer several advantages including the ease of fabrication and small physical size essential for local measurements and experiments in small spaces. This paper describes the first evaluation of nanopipettes with well characterized geometry for resistive-pulse sensing of Au nanoparticles (AuNP), nanoparticles coated with an allergen epitope peptide layer, and AuNP-peptide particles with bound antipeanut antibodies (IgY) on the peptide layer. The label-free signal produced by IgY-conjugated particles was strikingly different from those obtained with other analytes, thus suggesting the possibility of selective and sensitive resistive-pulse sensing of antibodies.

Tumor-Associated Macrophages Are Predominant Carriers of Cyclodextrin-Based Nanoparticles into Gliomas

PubMed Central

Alizadeh, Darya; Zhang, Leying; Hwang, Jungyeon; Schluep, Thomas; Badie, Behnam

2009-01-01

The goal of this study was to evaluate the mechanism of cyclodextrin-based nanoparticle (CDP-NP) uptake into a murine glioma model. Using mixed in vitro culture systems, we demonstrated that CDP-NP was preferentially taken up by BV2 and N9 microglia (MG) cells as compared to GL261 glioma cells. Fluorescent microscopy and flow cytometry analysis of intracranial (i.c.) GL261 gliomas confirmed these findings and demonstrated a predominant CDP-NP uptake by macrophages (MP) and MG within and around the tumor site. Interestingly, in mice bearing bilateral i.c. tumor, MG and MP carrying CDP-NP were able to migrate to the contralateral tumors. In conclusion, these studies better characterize the cellular distribution of CDP-NP in i.c. tumors and demonstrate that MP and MG could potentially be used as nanoparticle drug carriers into malignant brain tumors. PMID:19836468

Biotransformation of magnetic nanoparticles as a function of coating in a rat model

NASA Astrophysics Data System (ADS)

Ruiz, A.; Gutiérrez, L.; Cáceres-Vélez, P. R.; Santos, D.; Chaves, S. B.; Fascineli, M. L.; Garcia, M. P.; Azevedo, R. B.; Morales, M. P.

2015-10-01

Long-term in vivo studies in murine models have shown that DMSA-coated nanoparticles accumulate in spleen, liver and lung tissues during extended periods of time (at least up to 3 months) without any significant signs of toxicity detected. During that time, nanoparticles undergo a process of biotransformation either by reducing the size or the particle aggregation or both. Using a rat model, we have evaluated the transformations of magnetic nanoparticles injected at low doses. Particles with two different coatings, dimercaptosuccinic acid (NP-DMSA) and polyethylene glycol (NP-PEG-(NH2)2) have been administered to animals, to evaluate the role of coating in the degradation of the particles. We have found that low doses of magnetic nanoparticles are quickly metabolized by the animals. In fact, using a nanoparticle dose four times lower than in previous experiments, NP-DMSA were not observed 24 h after the administration either in the liver or in the lungs. Interestingly, an increased amount of ferritin, the iron storage protein, was observed in liver tissues from rats that were treated with the low dose of NP-DMSA in comparison with the control ones, suggesting a rapid metabolization of the particles into ferritin iron. On the other side we have found that, NP-PEG-(NH2)2 are still detectable in several organs 24 h after their administration at low doses. Probably, due to the longer circulation times of the NP-PEG-(NH2)2, there is a delay in the arrival of the particles to the tissue and this is the reason why we are able to see the particles 24 h post-administration. PEG coating could also be protecting the nanoparticles from rapid degradation of the reticuloendothelial system. Knowledge on the biodistribution, circulation time and degradation processes is required to gain a better understanding of the safety evaluation of this kind of nanomaterial for biomedical applications.

Colloidal stability of carbonate-coated silver nanoparticles in synthetic and natural freshwater.

PubMed

Piccapietra, Flavio; Sigg, Laura; Behra, Renata

2012-01-17

To gain important information on fate, mobility, and bioavailability of silver nanoparticles (AgNP) in aquatic systems, the influence of pH, ionic strength, and humic substances on the stability of carbonate-coated AgNP (average diameter 29 nm) was systematically investigated in 10 mM carbonate and 10 mM MOPS buffer, and in filtered natural freshwater. Changes in the physicochemical properties of AgNP were measured using nanoparticle tracking analysis, dynamic light scattering, and ultraviolet-visible spectroscopy. According to the pH-dependent carbonate speciation, below pH 4 the negatively charged surface of AgNP became positive and increased agglomeration was observed. Electrolyte concentrations above 2 mM Ca(2+) and 100 mM Na(+) enhanced AgNP agglomeration in the synthetic media. In the considered concentration range of humic substances, no relevant changes in the AgNP agglomeration state were measured. Agglomeration of AgNP exposed in filtered natural freshwater was observed to be primarily controlled by the electrolyte type and concentration. Moreover, agglomerated AgNP were still detected after 7 days of exposure. Consequently, slow sedimentation and high mobility of agglomerated AgNP could be expected under the considered natural conditions. A critical evaluation of the different methods used is presented as well.

Preparation of Silica Nanoparticles Through Microwave-assisted Acid-catalysis

PubMed Central

Lovingood, Derek D.; Owens, Jeffrey R.; Seeber, Michael; Kornev, Konstantin G.; Luzinov, Igor

2013-01-01

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle diameters ranging from 30-250 nm by varying the reaction conditions. Through the selection of a microwave compatible solvent, silicic acid precursor, catalyst, and microwave irradiation time, these microwave-assisted methods were capable of overcoming the previously reported shortcomings associated with synthesis of silica nanoparticles using microwave reactors. The siloxane precursor was hydrolyzed using the acid catalyst, HCl. Acetone, a low-tan δ solvent, mediates the condensation reactions and has minimal interaction with the electromagnetic field. Condensation reactions begin when the silicic acid precursor couples with the microwave radiation, leading to silica nanoparticle sol formation. The silica nanoparticles were characterized by dynamic light scattering data and scanning electron microscopy, which show the materials' morphology and size to be dependent on the reaction conditions. Microwave-assisted reactions produce silica nanoparticles with roughened textured surfaces that are atypical for silica sols produced by Stöber's methods, which have smooth surfaces. PMID:24379052

Functionalized magnetic nanoparticles for the decontamination of water polluted with cesium

NASA Astrophysics Data System (ADS)

Helal, Ahmed S.; Decorse, Philippe; Perruchot, Christian; Novak, Sophie; Lion, Claude; Ammar, Souad; El Hage Chahine, Jean-Michel; Hémadi, Miryana

2016-05-01

Magnetic nanoparticles are attracting considerable interest because of their potential applications in practically all fields of science and technology, including the removal of heavy metals from contaminated waters. It is, therefore, of great importance to adapt the surfaces of these nanoparticles according to the application. In this work advanced nanoparticles (NPs) with well-tailored surface functionalities were synthesized using the polyol method. The efficiency of a chelating agent, succinyl-β-cyclodextrin (SBCD), was first investigated spectrophotometrically and by Isothermal Titration Calorimetry (ITC). SBCD was then grafted onto nanoparticles previously functionalized with 3-aminopropyl triethoxsilane (NP-APTES). The resulting NP-SBCD system was then incubated with a solution of cesium. After magnetic separation, the solid residue was removed from the supernatant and characterized by X-Ray Photoelectron spectrometry (XPS), X-Ray Fluorescence spectrometry (XRF) and Superconducting QUantum Interference Device (SQUID) magnetometry. These characterizations show the presence of cesium in the solid residue, which indicates Cs uptake by the NP-SBCD system. This nanohybrid system constitutes a promising model for heavy metal decontamination.

Synthesis of liquid crystal silane-functionalized gold nanoparticles and their effects on the optical and electro-optic properties of a structurally related nematic liquid crystal.

PubMed

Mirzaei, Javad; Urbanski, Martin; Kitzerow, Heinz-S; Hegmann, Torsten

2014-05-19

Chemically and thermally robust liquid crystal silane-functionalized gold nanoparticles (i.e. AuNP1-AuNP3) were synthesized through silane conjugation. Colloidal dispersions of these particles with mesogenic ligands that are structurally identical (as in AuNP1, AuNP2) or compatible (as in AuNP3) with molecules of the nematic liquid crystal (N-LC) host showed superior colloidal stability and dispersibility. The thermal, optical, and electro-optic behaviors of the N-LC composites at different concentrations of each gold nanoparticle were investigated. All dispersions showed lower values for the rotational viscosity and elastic constant, but only AuNP3 with a dissimilar structure between the nanoparticle ligand and the host displayed the most drastic thermal effects and overall strongest impact on the electro-optic properties of the host. The observed results were explained considering both the structure and the density of the surface ligands of each gold nanoparticle. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Minocycline encapsulated chitosan nanoparticles for central antinociceptive activity.

PubMed

Nagpal, Kalpana; Singh, S K; Mishra, D N

2015-01-01

The purpose of the study is to explore the central anti-nociceptive activity of brain targeted nanoparticles (NP) of minocycline hydrochloride (MH). The NP were formulated using the modified ionotropic gelation method (MHNP) and were coated with Tween 80 (T80) to target them to brain (cMHNP). The formulated nanoparticles have already been characterized for particle size, zeta potential, drug entrapment efficiency and in vitro drug release. The nanoparticles were then evaluated for pharmacodynamic activity using thermal methods. The pure drug and the formulation, MHNP were not able to show a statistically significant central analgesic activity. cMHNP on the other hand evidenced a significant central analgesic activity. Animal models evidenced that brain targeted nanoparticles may be utilized for effective delivery of central anti-nociceptive effect of MH. Further clinical studies are required to explore the activity for mankind. Copyright © 2014 Elsevier B.V. All rights reserved.

Antimicrobial activity of silver nanoparticles encapsulated in poly-N-isopropylacrylamide-based polymeric nanoparticles.

PubMed

Qasim, Muhammad; Udomluck, Nopphadol; Chang, Jihyun; Park, Hansoo; Kim, Kyobum

2018-01-01

In this study, we analyzed the antimicrobial activities of poly- N -isopropylacrylamide (pNIPAM)-based polymeric nanoparticles encapsulating silver nanoparticles (AgNPs). Three sizes of AgNP-encapsulating pNIPAM- and pNIPAM-NH 2 -based polymeric nanoparticles were fabricated. Highly stable and uniformly distributed AgNPs were encapsulated within polymeric nanoparticles via in situ reduction of AgNO 3 using NaBH 4 as the reducing agent. The formation and distribution of AgNPs was confirmed by UV-visible spectroscopy, transmission electron microscopy, and inductively coupled plasma optical emission spectrometry, respectively. Both polymeric nanoparticles showed significant bacteriostatic activities against Gram-negative ( Escherichia coli ) and Gram-positive ( Staphylococcus aureus ) bacteria depending on the nanoparticle size and amount of AgNO 3 used during fabrication.

Antimicrobial activity of silver nanoparticles encapsulated in poly-N-isopropylacrylamide-based polymeric nanoparticles

PubMed Central

Qasim, Muhammad; Udomluck, Nopphadol; Chang, Jihyun; Park, Hansoo; Kim, Kyobum

2018-01-01

In this study, we analyzed the antimicrobial activities of poly-N-isopropylacrylamide (pNIPAM)-based polymeric nanoparticles encapsulating silver nanoparticles (AgNPs). Three sizes of AgNP-encapsulating pNIPAM- and pNIPAM-NH2-based polymeric nanoparticles were fabricated. Highly stable and uniformly distributed AgNPs were encapsulated within polymeric nanoparticles via in situ reduction of AgNO3 using NaBH4 as the reducing agent. The formation and distribution of AgNPs was confirmed by UV-visible spectroscopy, transmission electron microscopy, and inductively coupled plasma optical emission spectrometry, respectively. Both polymeric nanoparticles showed significant bacteriostatic activities against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria depending on the nanoparticle size and amount of AgNO3 used during fabrication. PMID:29379284

Toxicity, Bioaccumulation and Biotransformation of Silver Nanoparticles in Marine Organisms

EPA Science Inventory

The toxicity, bioaccumulation and biotransformation of citrate and polyvinylpyrrolidone (PVP) capped silver nanoparticles (NPs) (AgNP-citrate and AgNP-PVP) and titanium dioxide (TiO2) NPs in marine organisms via marine sediment exposure were investigated. Results from 7-d sedimen...

Gold nanoparticles: role of size and surface chemistry on blood protein adsorption

NASA Astrophysics Data System (ADS)

Benetti, F.; Fedel, M.; Minati, L.; Speranza, G.; Migliaresi, C.

2013-06-01

Material interaction with blood proteins is a critical issue, since it could influence the biological processes taking place in the body following implantation/injection. This is particularly important in the case of nanoparticles, where innovative properties, such as size and high surface to volume ratio can lead to a behavioral change with respect to bulk macroscopic materials and could be responsible for a potential risk for human health. The aim of this work was to compare gold nanoparticles (AuNP) and planar surfaces to study the role of surface curvature moving from the macro- to the nano-size in the process of blood protein adsorption. In the course of the study, different protocols were tested to optimize the analysis of protein adsorption on gold nanoparticles. AuNP with different size (10, 60 and 200 nm diameter) and surface coatings (citrate and polyethylene glycol) were carefully characterized. The stabilizing action of blood proteins adsorbed on AuNP was studied measuring the variation of size and solubility of the nanoparticles following incubation with single protein solutions (human serum albumin and fibrinogen) and whole blood plasma. In addition, we developed a method to elute proteins from AuNP to study the propensity of gold materials to adsorb plasma proteins in function of dimensional characteristics and surface chemistry. We showed a different efficacy of the various eluting media tested, proving that even the most aggressive agent cannot provide a complete detachment of the protein corona. Enhanced protein adsorption was evidenced on AuNP if compared to gold laminae (bare and PEGylated) used as macroscopic control, probably due to the superior AuNP surface reactivity.

Immunomodulatory properties of silver nanoparticles contribute to anticancer strategy for murine fibrosarcoma

PubMed Central

Chakraborty, Biswajit; Pal, Ramkrishna; Ali, Mohammed; Singh, Leichombam Mohindro; Shahidur Rahman, Dewan; Kumar Ghosh, Sujit; Sengupta, Mahuya

2016-01-01

The use of nanotechnology in nanoparticle-based cancer therapeutics is gaining impetus due to the unique biophysical properties of nanoparticles at the quantum level. Silver nanoparticles (AgNPs) have been reported as one type of potent therapeutic nanoparticles. The present study is aimed to determine the effect of AgNPs in arresting the growth of a murine fibrosarcoma by a reductive mechanism. Initially, a bioavailability study showed that mouse serum albumin (MSA)-coated AgNPs have enhanced uptake; therefore, toxicity studies of AgNP-MSA at 10 different doses (1–10 mg/kg b.w.) were performed in LACA mice by measuring the complete blood count, lipid profile and histological parameters. The complete blood count, lipid profile and histological parameter results showed that the doses from 2 to 8 mg (IC50: 6.15 mg/kg b.w.) sequentially increased the count of leukocytes, lymphocytes and granulocytes, whereas the 9- and 10-mg doses showed conclusive toxicity. In an antitumor study, the incidence and size of fibrosarcoma were reduced or delayed when murine fibrosarcoma groups were treated by AgNP-MSA. Transmission electron micrographs showed that considerable uptake of AgNP-MSA by the sentinel immune cells associated with tumor tissue and a morphologically buckled structure of the immune cells containing AgNP-MSA. Because the toxicity studies revealed a relationship between AgNPs and immune function, the protumorigenic cytokines TNF-α, IL-6 and IL-1β were also assayed in AgNP-MSA-treated and non-treated fibrosarcoma groups, and these cytokines were found to be downregulated after treatment with AgNP-MSA. PMID:25938978

Transition-Metal Nitride Core@Noble-Metal Shell Nanoparticles as Highly CO Tolerant Catalysts

DOE PAGES

Garg, Aaron; Milina, Maria; Ball, Madelyn; ...

2017-05-25

Core–shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. In conclusion, the ability to control shell coveragemore » and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties.« less

Transition-Metal Nitride Core@Noble-Metal Shell Nanoparticles as Highly CO Tolerant Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garg, Aaron; Milina, Maria; Ball, Madelyn

Core–shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. In conclusion, the ability to control shell coveragemore » and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties.« less

Sol-Gel Synthesis, Electrochemical Characterization, and Stability Testing of Ti0.7W0.3O2 Nanoparticles for Catalyst Support Applications in Proton-Exchange Membrane Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Subban, Chinmayee V.; Zhou, Qin; Hu, Anthony

2010-11-19

The materials currently used in proton-exchange membrane fuel cells (PEMFCs) require complex control of operating conditions to make them sufficiently durable to permit commercial deployment. One of the major materials challenges to allow simplification of fuel cell operating strategies is the discovery of catalyst supports that are much more stable to oxidative decomposition than currently used carbon blacks. Here we report the synthesis and characterization of Ti 0.7W 0.3O 2 nanoparticles (approximately 50 nm diameter), a promising doped metal oxide that is a candidate for such a durable catalyst support. The synthesized nanoparticles were platinized, characterized by electrochemical testing, andmore » evaluated for stability under PEMFC and other oxidizing acidic conditions. Ti 0.7W 0.3O 2 nanoparticles show no evidence of decomposition when heated in a Nafion solution for 3 weeks at 80 °C. In contrast, when heated in sulfuric, nitric, perchloric, or hydrochloric acid, the oxide reacts to form salts such as titanylsulfatehydrate from sulfuric acid. Electrochemical tests show that rates of hydrogen oxidation and oxygen reduction by platinum nanoparticles supported on Ti 0.7W 0.3O 2 are comparable to those of commercial Pt on carbon black.« less

Synthesis and Characterization of Cluster-Derived Supported Bimetallic Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adams, Richard D; Amiridis, Michael D

2008-10-10

New procedures have been developed for synthesizing di- and tri-metallic cluster complexes. The chemical properties of the new complexes have been investigated, particularly toward the activation of molecular hydrogen. These complexes were then converted into bi- and tri-metallic nanoparticles on silica and alumina supports. These nanoparticles were characterized by electron microscopy and were then tested for their ability to produce catalytic hydrogenation of unsaturated hydrocarbons and for the preferential oxidation of CO in the presence of hydrogen. The bi- and tri-metallic nanoparticles exhibited far superior activity and selectivity as hydrogenation catalysts when compared to the individual metallic components. It wasmore » found that the addition of tin greatly improved the selectivity of the catalysts for the hydrogenation of polyolefins. The addition of iron improves the catalysts for the selective oxidation of CO by platinum in the presence of hydrogen. The observations should lead to the development of lower cost routes to molecules that can be used to produce polymers and plastics for use by the general public and for procedures to purify hydrogen for use as an alternative energy in the hydrogen economy of the future.« less

Impact of water chemistry on the particle-specific toxicity of copper nanoparticles to Daphnia magna.

PubMed

Xiao, Yinlong; Peijnenburg, Willie J G M; Chen, Guangchao; Vijver, Martina G

2018-01-01

Toxicity of metallic nanoparticle suspensions (NP (total) ) is generally assumed to result from the combined effect of the particles present in suspensions (NP (particle) ) and their released ions (NP (ion) ). Evaluation and consideration of how water chemistry affects the particle-specific toxicity of NP (total) are critical for environmental risk assessment of nanoparticles. In this study, it was found that the toxicity of Cu NP (particle) to Daphnia magna, in line with the trends in toxicity for Cu NP (ion) , decreased with increasing pH and with increasing concentrations of divalent cations and dissolved organic carbon (DOC). Without the addition of DOC, the toxicity of Cu NP (total) to D. magna at the LC50 was driven mainly by Cu NP (ion) (accounting for ≥53% of the observed toxicity). However, toxicity of Cu NP (total) in the presence of DOC at a concentration ranging from 5 to 50mg C/L largely resulted from the NP (particle) (57%-85%), which could be attributable to the large reduction of the concentration of Cu NP (ion) and the enhancement of the stability of Cu NP (particle) when DOC was added. Our results indicate that water chemistry needs to be explicitly taken into consideration when evaluating the role of NP (particle) and NP (ion) in the observed toxicity of NP (total) . Copyright © 2017 Elsevier B.V. All rights reserved.

Nanoparticle Assemblies at Fluid Interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Russell, Thomas P.

2015-03-10

A systematic study of the structure and dynamics of nanoparticles (NP) and NP-surfactants was performed. The ligands attached to both the NPs and NP-surfactants dictate the manner in which the nanoscopic materials assemble at fluid interfaces. Studies have shown that a single layer of the nanoscpic materials form at the interface to reduce the interactions between the two immiscible fluids. The shape of the NP is, also, important, where for spherical particles, a disordered, liquid-like monolayer forms, and, for nanorods, ordered domains at the interface is found and, if the monolayers are compressed, the orientation of the nanorods with respectmore » to the interface can change. By associating end-functionalized polymers to the NPs assembled at the interface, NP-surfactants are formed that increase the energetic gain in segregating each NP at the interface which allows the NP-surfactants to jam at the interface when compressed. This has opened the possibility of structuring the two liquids by freezing in shape changes of the liquids.« less

An ultrastable conjugate of silver nanoparticles and protein formed through weak interactions

NASA Astrophysics Data System (ADS)

Brahmkhatri, Varsha P.; Chandra, Kousik; Dubey, Abhinav; Atreya, Hanudatta S.

2015-07-01

In recent years, silver nanoparticles (AgNPs) have attracted significant attention owing to their unique physicochemical, optical, conductive and antimicrobial properties. One of the properties of AgNPs which is crucial for all applications is their stability. In the present study we unravel a mechanism through which silver nanoparticles are rendered ultrastable in an aqueous solution in complex with the protein ubiquitin (Ubq). This involves a dynamic and reversible association and dissociation of ubiquitin from the surface of AgNP. The exchange occurs at a rate much greater than 25 s-1 implying a residence time of <40 ms for the protein. The AgNP-Ubq complex remains stable for months due to steric stabilization over a wide pH range compared to unconjugated AgNPs. NMR studies reveal that the protein molecules bind reversibly to AgNP with an approximate dissociation constant of 55 μM and undergo fast exchange. At pH > 4 the positively charged surface of the protein comes in contact with the citrate capped AgNP surface. Further, NMR relaxation-based experiments suggest that in addition to the dynamic exchange, a conformational rearrangement of the protein takes place upon binding to AgNP. The ultrastability of the AgNP-Ubq complex was found to be useful for its anti-microbial activity, which allowed the recycling of this complex multiple times without the loss of stability. Altogether, the study provides new insights into the mechanism of protein-silver nanoparticle interactions and opens up new avenues for its application in a wide range of systems.In recent years, silver nanoparticles (AgNPs) have attracted significant attention owing to their unique physicochemical, optical, conductive and antimicrobial properties. One of the properties of AgNPs which is crucial for all applications is their stability. In the present study we unravel a mechanism through which silver nanoparticles are rendered ultrastable in an aqueous solution in complex with the protein

Optical properties of metal nanoparticles embedded in amorphous silicon analysed using discrete dipole approximation

NASA Astrophysics Data System (ADS)

Fantoni, Alessandro; Fernandes, Miguel; Vygranenko, Yuri; Vieira, Manuela; Oliveira-Silva, Rui P.; Prazeres, D. M. F.; Ribeiro, Ana P. C.; Alegria, Elisabete C. B. A.

2018-02-01

Localized surface plasmons (LSP) can be excited in metal nanoparticles (NP) by UV, visible or NIR light and are described as coherent oscillation of conduction electrons. Taking advantage of the tunable optical properties of NPs, we propose the realization of a plasmonic structure, based on the LSP interaction of NP with an embedding matrix of amorphous silicon. This study is directed to define the characteristics of NP and substrate necessary to the development of a LSP proteomics sensor that, once provided immobilized antibodies on its surface, will screen the concentration of selected antigens through the determination of LSPR spectra and peaks of light absorption. Metals of interest for NP composition are: Aluminium and Gold. Recent advances in nanoparticle production techniques allow almost full control over shapes and size, permitting full control over their optical and plasmonic properties and, above all, over their responsive spectra. Analytical solution is only possible for simple NP geometries, therefore our analysis, is realized recurring to computer simulation using the Discrete Dipole Approximation method (DDA). In this work we use the free software DDSCAT to study the optical properties of metal nanoparticles embedded in an amorphous silicon matrix, as a function of size, shape, aspect-ratio and metal type. Experimental measurements realized with arrays of metal nanoparticles are compared with the simulations.

Photophysical insights on effect of gold nanoparticles over fullerene-porphyrin interaction in solution.

PubMed

Mitra, Ratul; Bauri, Ajoy K; Banerjee, Shrabanti; Bhattacharya, Sumanta

2014-11-11

The present article reports the role of gold nanoparticles, i.e., AuNp (having diameter ∼2-4nm), in non-covalent interaction between fullerenes (C60 and C70) and a monoporphyrin (1) in toluene. Both UV-vis and fluorescence measurements reveal considerable reduction in the average value of binding constant (Kav) for the C70-1 system (KC70-1(av)=19,300 dm3 mol(-1)) in presence of AuNp, i.e., KC70-1-AuNp(av)=13,515 dm3 mol(-1) although no such phenomenon is observed in case of C60-1 system, viz., KC60-1(av)=1445 dm3 mol(-1) and KC60-1-AuNp(av)=1210 dm3 mol(-1). DLS study reveals sizeable amount of increase in the particle size of C70-1-AuNp nanocomposite, i.e., ∼105 nm, compared to C60-1-AgNp system, e.g., ∼5.5 nm which gives very good support in favor of decrease in the value of Kav for the former system. SEM study reveals that nanoparticles are dispersed in larger extent in case of C70-1-AuNp system. Time-resolved fluorescence study envisages that deactivation of the excited singlet state of 1 by C70 takes place at a faster rate in comparison to C60 in presence of gold nanoparticles. Copyright © 2014 Elsevier B.V. All rights reserved.

Biogenic platinum and palladium nanoparticles as new catalysts for the removal of pharmaceutical compounds.

PubMed

Martins, Mónica; Mourato, Cláudia; Sanches, Sandra; Noronha, João Paulo; Crespo, M T Barreto; Pereira, Inês A C

2017-01-01

Pharmaceutical products (PhP) are one of the most alarming emergent pollutants in the environment. Therefore, it is of extreme importance to investigate efficient PhP removal processes. Biologic synthesis of platinum nanoparticles (Bio-Pt) has been reported, but their catalytic activity was never investigated. In this work, we explored the potential of cell-supported platinum (Bio-Pt) and palladium (Bio-Pd) nanoparticles synthesized with Desulfovibrio vulgaris as biocatalysts for removal of four PhP: ciprofloxacin, sulfamethoxazole, ibuprofen and 17β-estradiol. The catalytic activity of the biological nanoparticles was compared with the PhP removal efficiency of D. vulgaris whole-cells. In contrast with Bio-Pd, Bio-Pt has a high catalytic activity in PhP removal, with 94, 85 and 70% removal of 17β-estradiol, sulfamethoxazole and ciprofloxacin, respectively. In addition, the estrogenic activity of 17β-estradiol was strongly reduced after the reaction with Bio-Pt, showing that this biocatalyst produces less toxic effluents. Bio-Pt or Bio-Pd did not act on ibuprofen, but this could be completely removed by D. vulgaris whole-cells, demonstrating that sulfate-reducing bacteria are among the microorganisms capable of biotransformation of ibuprofen in anaerobic environments. This study demonstrates for the first time that Bio-Pt has a high catalytic activity, and is a promising catalyst to be used in water treatment processes for the removal of antibiotics and endocrine disrupting compounds, the most problematic PhP. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis of Self-Assembled Multifunctional Nanocomposite Catalysts with Highly Stabilized Reactivity and Magnetic Recyclability

NASA Astrophysics Data System (ADS)

Yu, Xu; Cheng, Gong; Zheng, Si-Yang

2016-05-01

In this paper, a multifunctional Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite catalyst with highly stabilized reactivity and magnetic recyclability was synthesized by a self-assembled method. The magnetic Fe3O4 nanoparticles were coated with a thin layer of the SiO2 to obtain a negatively charged surface. Then positively charged poly(ethyleneimine) polymer (PEI) was self-assembled onto the Fe3O4@SiO2 by electrostatic interaction. Next, negatively charged glutathione capped gold nanoparticles (GSH-AuNPs) were electrostatically self-assembled onto the Fe3O4@SiO2@PEI. After that, silver was grown on the surface of the nanocomposite due to the reduction of the dopamine in the alkaline solution. An about 5 nm thick layer of polydopamine (PDA) was observed to form the Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite was carefully characterized by the SEM, TEM, FT-IR, XRD and so on. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite shows a high saturation magnetization (Ms) of 48.9 emu/g, which allows it to be attracted rapidly to a magnet. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite was used to catalyze the reduction of p-nitrophenol (4-NP) to p-aminophenol (4-AP) as a model system. The reaction kinetic constant k was measured to be about 0.56 min-1 (R2 = 0.974). Furthermore, the as-prepared catalyst can be easily recovered and reused for 8 times, which didn’t show much decrease of the catalytic capability.

Enhanced activity of Pt/CNTs anode catalyst for direct methanol fuel cells using Ni2P as co-catalyst

NASA Astrophysics Data System (ADS)

Li, Xiang; Luo, Lanping; Peng, Feng; Wang, Hongjuan; Yu, Hao

2018-03-01

The direct methanol fuel cell is a promising energy conversion device because of the utilization of the state-of-the-art platinum (Pt) anode catalyst. In this work, novel Pt/Ni2P/CNTs catalysts were prepared by the H2 reduction method. It was found that the activity and stability of Pt for methanol oxidation reaction (MOR) could be significantly enhanced while using nickel phosphide (Ni2P) nanoparticles as co-catalyst. X-ray photoelectron spectroscopy revealed that the existence of Ni2P affected the particle size and electronic distribution of Pt obviously. Pt/CNTs catalyst, Pt/Ni2P/CNTs catalysts with different Ni2P amount were synthesized, among which Pt/6%Ni2P/CNTs catalyst exhibited the best MOR activity of 1400 mAmg-1Pt, which was almost 2.5 times of the commercial Pt/C-JM catalyst. Moreover, compared to other Pt-based catalysts, this novel Pt/Ni2P/CNTs catalyst also exhibited higher onset current density and better steady current density. The result of this work may provide positive guidance to the research on high efficiency and stability of Pt-based catalyst for direct methanol fuel cells.

A Synthetic Pseudo-Rh: NOx Reduction Activity and Electronic Structure of Pd-Ru Solid-solution Alloy Nanoparticles

NASA Astrophysics Data System (ADS)

Sato, Katsutoshi; Tomonaga, Hiroyuki; Yamamoto, Tomokazu; Matsumura, Syo; Zulkifli, Nor Diana Binti; Ishimoto, Takayoshi; Koyama, Michihisa; Kusada, Kohei; Kobayashi, Hirokazu; Kitagawa, Hiroshi; Nagaoka, Katsutoshi

2016-06-01

Rh is one of the most important noble metals for industrial applications. A major fraction of Rh is used as a catalyst for emission control in automotive catalytic converters because of its unparalleled activity toward NOx reduction. However, Rh is a rare and extremely expensive element; thus, the development of Rh alternative composed of abundant elements is desirable. Pd and Ru are located at the right and left of Rh in the periodic table, respectively, nevertheless this combination of elements is immiscible in the bulk state. Here, we report a Pd-Ru solid-solution-alloy nanoparticle (PdxRu1-x NP) catalyst exhibiting better NOx reduction activity than Rh. Theoretical calculations show that the electronic structure of Pd0.5Ru0.5 is similar to that of Rh, indicating that Pd0.5Ru0.5 can be regarded as a pseudo-Rh. Pd0.5Ru0.5 exhibits better activity than natural Rh, which implies promising applications not only for exhaust-gas cleaning but also for various chemical reactions.

Electron flow in large metallomacromolecules and electronic switch of nanoparticle stabilization: new click ferrocenyl dentromers that reduce Au(III) to Au nanoparticles.

PubMed

Astruc, Didier; Wang, Qi; Fu, Fangyu; Martinez-Villacorta, Angel M; Moya, Sergio; Salmon, Lionel; Ruiz, Jaime; Hunel, Julien; Vax, Amélie

2018-06-04

Click ferrocenyl-terminal dentromers, a family of arene-cored dendrimers with triple branching (9-Fc, 27-Fc, 81-Fc and 243-Fc) reduce Au(III) to ferricinium dentromer-stabilized Au nanoparticles (AuNPs). Cyclic voltammetry studies in CH2Cl2 show reversible CV waves with some adsorption for the 243-Fc dentromer and a number of redox groups found, 255 ± 25, using the Bard-Anson method, close to the theoretical number of 243. The dentromers reduce aqueous HAuCl4 to water-soluble ferricinium chloride dentromer-stabilized gold nanoparticles (AuNPs) with core sizes between 30 and 47 nm. These triazolylferricinium dentromer-stabilized AuNPs are reduced by cobaltocene to cobalticinium chloride and ferrocene dentromer-weakly stabilized AuNPs together with red shift of the AuNP plasmon. The weakness of the AuNP stabilization is characterized by dentromer extraction with CH2Cl2 along with irreversible AuNP agglomeration for the 9, 27 and 81-ferrocenyl dentromer, only the 243-ferrocenyl dentromer-AuNP withstanding this process. Altogether this demonstrates the electronic switch of the dentromer-mediated AuNP stabilization. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalyst design with atomic layer deposition

DOE PAGES

O'Neill, Brandon J.; Jackson, David H. K.; Lee, Jechan; ...

2015-02-06

Atomic layer deposition (ALD) has emerged as an interesting tool for the atomically precise design and synthesis of catalytic materials. Herein, we discuss examples in which the atomic precision has been used to elucidate reaction mechanisms and catalyst structure-property relationships by creating materials with a controlled distribution of size, composition, and active site. We highlight ways ALD has been utilized to design catalysts with improved activity, selectivity, and stability under a variety of conditions (e.g., high temperature, gas and liquid phase, and corrosive environments). In addition, due to the flexibility and control of structure and composition, ALD can create myriadmore » catalytic structures (e.g., high surface area oxides, metal nanoparticles, bimetallic nanoparticles, bifunctional catalysts, controlled microenvironments, etc.) that consequently possess applicability for a wide range of chemical reactions (e.g., CO 2 conversion, electrocatalysis, photocatalytic and thermal water splitting, methane conversion, ethane and propane dehydrogenation, and biomass conversion). Lastly, the outlook for ALD-derived catalytic materials is discussed, with emphasis on the pending challenges as well as areas of significant potential for building scientific insight and achieving practical impacts.« less

Catalyst design with atomic layer deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

O'Neill, Brandon J.; Jackson, David H. K.; Lee, Jechan

Atomic layer deposition (ALD) has emerged as an interesting tool for the atomically precise design and synthesis of catalytic materials. Herein, we discuss examples in which the atomic precision has been used to elucidate reaction mechanisms and catalyst structure-property relationships by creating materials with a controlled distribution of size, composition, and active site. We highlight ways ALD has been utilized to design catalysts with improved activity, selectivity, and stability under a variety of conditions (e.g., high temperature, gas and liquid phase, and corrosive environments). In addition, due to the flexibility and control of structure and composition, ALD can create myriadmore » catalytic structures (e.g., high surface area oxides, metal nanoparticles, bimetallic nanoparticles, bifunctional catalysts, controlled microenvironments, etc.) that consequently possess applicability for a wide range of chemical reactions (e.g., CO 2 conversion, electrocatalysis, photocatalytic and thermal water splitting, methane conversion, ethane and propane dehydrogenation, and biomass conversion). Lastly, the outlook for ALD-derived catalytic materials is discussed, with emphasis on the pending challenges as well as areas of significant potential for building scientific insight and achieving practical impacts.« less

Understanding and Interpreting Japanese NP1 "wa" NP2 "da" Sentences: Mechanism and Contextual Factors

ERIC Educational Resources Information Center

Yoshida, Megumi

2013-01-01

This dissertation investigates the contextual factors that affect the understanding and interpretation of one Japanese topicalized construction, NP[subscript 1] wa NP[subscript 2] da sentences, by native speakers of Japanese. The construction allows two possibilities in the relation between the NP[subscript 1] and the NP[subscript 2]. When the two…

Enzyme and Cancer Cell Selectivity of Nanoparticles: Inhibition of 3D Metastatic Phenotype and Experimental Melanoma by Zinc Oxide.

PubMed

DeLong, Robert K; Mitchell, Jennifer A; Morris, R Tyler; Comer, Jeffrey; Hurst, Miranda N; Ghosh, Kartik; Wanekaya, Adam; Mudge, Miranda; Schaeffer, Ashley; Washington, Laurie L; Risor-Marhanka, Azure; Thomas, Spencer; Marroquin, Shanna; Lekey, Amber; Smith, Joshua J; Garrad, Richard; Aryal, Santosh; Abdelhakiem, Mohamed; Glaspell, Garry P

2017-02-01

Biomedical applications for metal and metal oxide nanoparticles are rapidly increasing. Here their functional impact on two well-characterized model enzymes, Luciferase (Luc) or β-galactosidase (β-Gal) was quantitatively compared. Nickel oxide nanoparticle (NiO-NP) activated β-Gal (>400% control) and boron carbide nanoparticle (B4C-NP) inhibited Luc(<10% control), whereas zinc oxide (ZnO-NP) and cobalt oxide (Co3O4-NP) activated β-Gal to a lesser extent and magnesium oxide (MgO) moderately inhibited both enzymes. Melanoma specific killing was in the order; ZnO > B4C ≥ Cu > MgO > Co3O4 > Fe2O3 > NiO, ZnO-NP inhibiting B16F10 and A375 cells as well as ERK enzyme (>90%) and several other cancer-associated kinases (AKT, CREB, p70S6K). ZnO-NP or nanobelt (NB) serve as photoluminescence (PL) cell labels and inhibit 3-D multi-cellular tumor spheroid (MCTS) growth and were tested in a mouse melanoma model. These results demonstrate nanoparticle and enzyme specific biochemical activity and suggest their utility as new tools to explore the important model metastatic foci 3-D environment and their chemotherapeutic potential.

Hardness and Elastic Modulus on Six-Fold Symmetry Gold Nanoparticles

PubMed Central

Ramos, Manuel; Ortiz-Jordan, Luis; Hurtado-Macias, Abel; Flores, Sergio; Elizalde-Galindo, José T.; Rocha, Carmen; Torres, Brenda; Zarei-Chaleshtori, Maryam; Chianelli, Russell R.

2013-01-01

The chemical synthesis of gold nanoparticles (NP) by using gold (III) chloride trihydrate (HAuCl∙3H2O) and sodium citrate as a reducing agent in aqueous conditions at 100 °C is presented here. Gold nanoparticles areformed by a galvanic replacement mechanism as described by Lee and Messiel. Morphology of gold-NP was analyzed by way of high-resolution transmission electron microscopy; results indicate a six-fold icosahedral symmetry with an average size distribution of 22 nm. In order to understand the mechanical behaviors, like hardness and elastic moduli, gold-NP were subjected to nanoindentation measurements—obtaining a hardness value of 1.72 GPa and elastic modulus of 100 GPa in a 3–5 nm of displacement at the nanoparticle’s surface. PMID:28809302

Magnetic multi-metal co-doped magnesium ferrite nanoparticles: An efficient visible light-assisted heterogeneous Fenton-like catalyst synthesized from saprolite laterite ore.

PubMed

Diao, Yifei; Yan, Zhikai; Guo, Min; Wang, Xidong

2018-02-15

Magnetic nanoparticles of multi-metal co-doped magnesium ferrite (MgFe 2 O 4 ) were synthesized from saprolite laterite ore by a hydrothermal method, and firstly proposed as a heterogeneous photon-Fenton-like catalyst for degradation of Rhodamine B (RhB). The factors that influence the degradation reaction including pH value, the concentration of H 2 O 2 and the amount of catalyst, were systematically investigated. The doped MgFe 2 O 4 exhibited a degradation efficiency up to 96.8%, and the chemical oxygen demand (COD) and total organic carbon (TOC) removal efficiencies about 85.6% and 68.3%, respectively, under visible light illumination for 180min. The high activity is mainly attributed to the high specific surface area of the catalyst and the synergistic interaction between photo-catalytic oxidation and Fenton-like oxidation. Moreover, the catalyst also showed good stability and recycling performance for degrading RhB. After five consecutive degradation cycles, the activity decayed no more than 10%. Compared to other catalysts prepared from pure chemical agents, the multi-metal co-doped MgFe 2 O 4 is more competitive due to its high activity, good stability, ease of recollection, and especially the use of saprolite laterite ore as precursor. This work may provide a new avenue to synthesize efficient ferrite catalysts for degrading organic pollutants in wastewater by using natural minerals. Copyright © 2017 Elsevier B.V. All rights reserved.

Method of making chalcogen catalysts for polymer electrolyte fuel cells

DOEpatents

Choi, Jong-Ho; Zelenay, Piotr; Wieckowski, Andrzej; Cao, Dianxue

2010-12-14

A method of making an electrode catalyst material using aqueous solutions. The electrode catalyst material includes a support comprising at least one transition metal and at least one chalcogen disposed on a surface of the transition metal. The method includes reducing a metal powder, mixing the metal powder with an aqueous solution containing at least one inorganic compound of the chalcogen to form a mixture, and providing a reducing agent to the mixture to form nanoparticles of the electrode catalyst. The electrode catalyst may be used in a membrane electrode assembly for a fuel cell.

The interplay of lung surfactant proteins and lipids assimilates the macrophage clearance of nanoparticles.

PubMed

Ruge, Christian A; Schaefer, Ulrich F; Herrmann, Jennifer; Kirch, Julian; Cañadas, Olga; Echaide, Mercedes; Pérez-Gil, Jesús; Casals, Cristina; Müller, Rolf; Lehr, Claus-Michael

2012-01-01

The peripheral lungs are a potential entrance portal for nanoparticles into the human body due to their large surface area. The fact that nanoparticles can be deposited in the alveolar region of the lungs is of interest for pulmonary drug delivery strategies and is of equal importance for toxicological considerations. Therefore, a detailed understanding of nanoparticle interaction with the structures of this largest and most sensitive part of the lungs is important for both nanomedicine and nanotoxicology. Astonishingly, there is still little known about the bio-nano interactions that occur after nanoparticle deposition in the alveoli. In this study, we compared the effects of surfactant-associated protein A (SP-A) and D (SP-D) on the clearance of magnetite nanoparticles (mNP) with either more hydrophilic (starch) or hydrophobic (phosphatidylcholine) surface modification by an alveolar macrophage (AM) cell line (MH-S) using flow cytometry and confocal microscopy. Both proteins enhanced the AM uptake of mNP compared with pristine nanoparticles; for the hydrophilic ST-mNP, this effect was strongest with SP-D, whereas for the hydrophobic PL-mNP it was most pronounced with SP-A. Using gel electrophoretic and dynamic light scattering methods, we were able to demonstrate that the observed cellular effects were related to protein adsorption and to protein-mediated interference with the colloidal stability. Next, we investigated the influence of various surfactant lipids on nanoparticle uptake by AM because lipids are the major surfactant component. Synthetic surfactant lipid and isolated native surfactant preparations significantly modulated the effects exerted by SP-A and SP-D, respectively, resulting in comparable levels of macrophage interaction for both hydrophilic and hydrophobic nanoparticles. Our findings suggest that because of the interplay of both surfactant lipids and proteins, the AM clearance of nanoparticles is essentially the same, regardless of different

237Np analytical method using 239Np tracers and application to a contaminated nuclear disposal facility

DOE PAGES

Snow, Mathew S.; Morrison, Samuel S.; Clark, Sue B.; ...

2017-03-21

In this study, environmental 237Np analyses are challenged by low 237Np concentrations and lack of an available yield tracer; we report a rapid, inexpensive 237Np analytical approach employing the short lived 239Np (t1/2 = 2.3 days) as a chemical yield tracer followed by 237Np quantification using inductively coupled plasma-mass spectrometry. 239Np tracer is obtained via separation from a 243Am stock solution and standardized using gamma spectrometry immediately prior to sample processing. Rapid digestions using a commercial, 900 W "Walmart" microwave and Parr microwave vessels result in 99.8 ± 0.1% digestion yields, while chromatographic separations enable Np/U separation factors on themore » order of 10 6 and total Np yields of 95 ± 4% (2σ). Application of this method to legacy soil samples surrounding a radioactive disposal facility (the Subsurface Disposal Area at Idaho National Laboratory) reveal the presence of low level 237Np contamination within 600 m of this site, with maximum 237Np concentrations on the order of 10 3 times greater than nuclear weapons testing fallout levels.« less

237 Np analytical method using 239 Np tracers and application to a contaminated nuclear disposal facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snow, Mathew S.; Morrison, Samuel S.; Clark, Sue B.

2017-06-01

Environmental 237Np analyses are challenged by low 237Np concentrations and lack of an available yield tracer; we report a rapid, inexpensive 237Np analytical approach employing the short lived 239Np (t1/2 = 2.3 days) as a chemical yield tracer followed by 237Np quantification using inductively coupled plasma-mass spectrometry. 239Np tracer is obtained via separation from a 243Am stock solution and standardized using gamma spectrometry immediately prior to sample processing. Rapid digestions using a commercial, 900 watt “Walmart” microwave and Parr microwave vessels result in 99.8 ± 0.1% digestion yields, while chromatographic separations enable Np/U separation factors on the order of 106more » and total Np yields of 95 ± 4% (2σ). Application of this method to legacy soil samples surrounding a radioactive disposal facility (the Subsurface Disposal Area at Idaho National Laboratory) reveal the presence of low level 237Np contamination within 600 meters of this site, with maximum 237Np concentrations on the order of 103 times greater than nuclear weapons testing fallout levels.« less

237Np analytical method using 239Np tracers and application to a contaminated nuclear disposal facility.

PubMed

Snow, Mathew S; Morrison, Samuel S; Clark, Sue B; Olson, John E; Watrous, Matthew G

2017-06-01

Environmental 237 Np analyses are challenged by low 237 Np concentrations and lack of an available yield tracer; we report a rapid, inexpensive 237 Np analytical approach employing the short lived 239 Np (t 1/2  = 2.3 days) as a chemical yield tracer followed by 237 Np quantification using inductively coupled plasma-mass spectrometry. 239 Np tracer is obtained via separation from a 243 Am stock solution and standardized using gamma spectrometry immediately prior to sample processing. Rapid digestions using a commercial, 900 W "Walmart" microwave and Parr microwave vessels result in 99.8 ± 0.1% digestion yields, while chromatographic separations enable Np/U separation factors on the order of 10 6 and total Np yields of 95 ± 4% (2σ). Application of this method to legacy soil samples surrounding a radioactive disposal facility (the Subsurface Disposal Area at Idaho National Laboratory) reveal the presence of low level 237 Np contamination within 600 m of this site, with maximum 237 Np concentrations on the order of 10 3 times greater than nuclear weapons testing fallout levels. Copyright © 2017 Elsevier Ltd. All rights reserved.

Noble-metal-free bimetallic alloy nanoparticle-catalytic gasification of phenol in supercritical water

DOE PAGES

Jia, Lijuan; Yu, Jiangdong; Chen, Yuan; ...

2017-08-01

The exploration of non-noble-metal catalysts for high efficiency gasification of biomass in supercritical water (SCW) is of great significance for the sustainable development. A series of Ni–M (M = Co or Zn) bimetallic nanoparticles supported on graphitized carbon black were synthesized and examined as catalysts for gasification of phenol in SCW. We found that a nearly complete gasification of phenol can be achieved even at a low temperature of 450 °C with the bimetallic nanoparticles catalysts. Kinetic study indicated the activation energy for phenol gasification were 20.4 ± 2.6 and 43.6 ± 2.6 kJ/mol for Ni20Zn15 and Ni20Co15 catalyst, respectively.more » Furthermore, XRD, XPS and TEM were performed to characterize the catalysts and the results showed the formation of NiCo and NiZn alloy phase. Catalyst recycling experiments were also conducted to evaluate the stability of the catalysts. The characterization of used catalysts suggest that the severe agglomeration of nanoparticles leads to the decrease in catalytic activity.« less

Noble-metal-free bimetallic alloy nanoparticle-catalytic gasification of phenol in supercritical water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia, Lijuan; Yu, Jiangdong; Chen, Yuan

The exploration of non-noble-metal catalysts for high efficiency gasification of biomass in supercritical water (SCW) is of great significance for the sustainable development. A series of Ni–M (M = Co or Zn) bimetallic nanoparticles supported on graphitized carbon black were synthesized and examined as catalysts for gasification of phenol in SCW. We found that a nearly complete gasification of phenol can be achieved even at a low temperature of 450 °C with the bimetallic nanoparticles catalysts. Kinetic study indicated the activation energy for phenol gasification were 20.4 ± 2.6 and 43.6 ± 2.6 kJ/mol for Ni20Zn15 and Ni20Co15 catalyst, respectively.more » Furthermore, XRD, XPS and TEM were performed to characterize the catalysts and the results showed the formation of NiCo and NiZn alloy phase. Catalyst recycling experiments were also conducted to evaluate the stability of the catalysts. The characterization of used catalysts suggest that the severe agglomeration of nanoparticles leads to the decrease in catalytic activity.« less

A durable PtRu/C catalyst with a thin protective layer for direct methanol fuel cells.

PubMed

Shimazaki, Yuzuru; Hayasaka, Sho; Koyama, Tsubasa; Nagao, Daisuke; Kobayashi, Yoshio; Konno, Mikio

2010-11-15

A methanol oxidation catalyst with improved durability in acidic environments is reported. The catalyst consists of PtRu alloy nanoparticles on a carbon support that were stabilized with a silane-coupling agent. The catalyst was prepared by reducing ions of Pt and Ru in the presence of a carbon support and the silane-coupling agent. The careful choice of preparatory conditions such as the concentration of the silane-coupling agent and solution pH resulted in the preparation of catalyst in which the PtRu nanoparticles were dispersively adsorbed onto the carbon support. The catalytic activity was similar to that of a commercial catalyst and was unchanged after immersion in sulfuric acid solution for 1000 h, suggesting the high durability of the PtRu catalyst for the anode of direct methanol fuel cells. Copyright © 2010 Elsevier Inc. All rights reserved.

Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamamoto, Umi; Carrillo, Jan-Michael Y.; Bocharova, Vera

We theoretically study the diffusion of a single attractive nanoparticle (NP) in unentangled and entangled polymer melts based on combining microscopic “core–shell” and “vehicle” mechanisms in a dynamic bond percolation theory framework. A physical picture is constructed which addresses the role of chain length (N), degree of entanglement, nanoparticle size, and NP–polymer attraction strength. The nanoparticle diffusion constant is predicted to initially decrease with N due to the dominance of the core–shell mechanism, then to cross over to the vehicle diffusion regime with a weaker N dependence, and eventually plateau at large enough N. This behavior corresponds to decoupling ofmore » NP diffusivity from the macroscopic melt viscosity, which is reminiscent of repulsive NPs in entangled melts, but here it occurs for a distinct physical reason. Specifically, it reflects a crossover to a transport mechanism whereby nanoparticles adsorb on polymer chains and diffuse using them as “vehicles” over a characteristic desorption time scale. Repetition of random desorption events then leads to Fickian long time NP diffusion. Complementary simulations for a range of chain lengths and low to moderate NP–polymer attraction strengths are also performed. They allow testing of the proposed diffusion mechanisms and qualitatively support the theoretically predicted dynamic crossover behavior. In conclusion, when the desorption time is smaller than or comparable to the onset of entangled polymer dynamics, the NP diffusivity becomes almost chain length independent.« less

Theory and Simulation of Attractive Nanoparticle Transport in Polymer Melts

DOE PAGES

Yamamoto, Umi; Carrillo, Jan-Michael Y.; Bocharova, Vera; ...

2018-03-06

We theoretically study the diffusion of a single attractive nanoparticle (NP) in unentangled and entangled polymer melts based on combining microscopic “core–shell” and “vehicle” mechanisms in a dynamic bond percolation theory framework. A physical picture is constructed which addresses the role of chain length (N), degree of entanglement, nanoparticle size, and NP–polymer attraction strength. The nanoparticle diffusion constant is predicted to initially decrease with N due to the dominance of the core–shell mechanism, then to cross over to the vehicle diffusion regime with a weaker N dependence, and eventually plateau at large enough N. This behavior corresponds to decoupling ofmore » NP diffusivity from the macroscopic melt viscosity, which is reminiscent of repulsive NPs in entangled melts, but here it occurs for a distinct physical reason. Specifically, it reflects a crossover to a transport mechanism whereby nanoparticles adsorb on polymer chains and diffuse using them as “vehicles” over a characteristic desorption time scale. Repetition of random desorption events then leads to Fickian long time NP diffusion. Complementary simulations for a range of chain lengths and low to moderate NP–polymer attraction strengths are also performed. They allow testing of the proposed diffusion mechanisms and qualitatively support the theoretically predicted dynamic crossover behavior. In conclusion, when the desorption time is smaller than or comparable to the onset of entangled polymer dynamics, the NP diffusivity becomes almost chain length independent.« less

LiFePO4 microcrystals as an efficient heterogeneous Fenton-like catalyst in degradation of rhodamine 6G.

PubMed

Li, Zhan Jun; Ali, Ghafar; Kim, Hyun Jin; Yoo, Seong Ho; Cho, Sung Oh

2014-01-01

We present a novel heterogeneous Fenton-like catalyst of LiFePO4 (LFP). LFP has been widely used as an electrode material of a lithium ion battery, but we observed that commercial LFP (LFP-C) could act as a good Fenton-like catalyst to decompose rhodamine 6G. The catalytic activity of LFP-C microparticles was much higher than a popular catalyst, magnetite nanoparticles. Furthermore, we found that the catalytic activity of LFP-C could be further increased by increasing the specific surface area. The reaction rate constant of the hydrothermally synthesized LFP microcrystals (LFP-H) is at least 18 times higher than that of magnetite nanoparticles even though the particle size of LFP is far larger than magnetite nanoparticles. The LFP catalysts also exhibited a good recycling behavior and high stability under an oxidizing environment. The effects of the experimental parameters such as the concentration of the catalysts, pH, and the concentration of hydrogen peroxide on the catalytic activity of LFP were also analyzed.

Synthesis of platinum nanoparticle electrocatalysts by atomic layer deposition

NASA Astrophysics Data System (ADS)

Lubers, Alia Marie

Demand for energy continues to increase, and without alternatives to fossil fuel combustion the effects on our environment will become increasingly severe. Fuel cells offer a promising improvement on current methods of energy generation; they are able to convert hydrogen fuel into electricity with a theoretical efficiency of up to 83% and interface smoothly with renewable hydrogen production. Fuel cells can replace internal combustion engines in vehicles and are used in stationary applications to power homes and businesses. The efficiency of a fuel cell is maximized by its catalyst, which is often composed of platinum nanoparticles supported on carbon. Economical production of fuel cell catalysts will promote adoption of this technology. Atomic layer deposition (ALD) is a possible method for producing catalysts at a large scale when employed in a fluidized bed. ALD relies on sequential dosing of gas-phase precursors to grow a material layer by layer. We have synthesized platinum nanoparticles on a carbon particle support (Pt/C) by ALD for use in proton exchange membrane fuel cells (PEMFCs) and electrochemical hydrogen pumps. Platinum nanoparticles with different characteristics were deposited by changing two chemistries: the carbon substrate through functionalization; and the deposition process by use of either oxygen or hydrogen as ligand removing reactants. The metal depositing reactant was trimethyl(methylcyclopentadienyl)platinum(IV). Functionalizing the carbon substrate increased nucleation during deposition resulting in smaller and more dispersed nanoparticles. Use of hydrogen produced smaller nanoparticles than oxygen, due to a gentler hydrogenation reaction compared to using oxygen's destructive combustion reaction. Synthesized Pt/C materials were used as catalysts in an electrochemical hydrogen pump, a device used to separate hydrogen fuel from contaminants. Catalysts deposited by ALD on functionalized carbon using a hydrogen chemistry were the most

Collisions of Ir Oxide Nanoparticles with Carbon Nanopipettes: Experiments with One Nanoparticle.

PubMed

Zhou, Min; Yu, Yun; Hu, Keke; Xin, Huolin L; Mirkin, Michael V

2017-03-07

Investigating the collisions of individual metal nanoparticles (NPs) with electrodes can provide new insights into their electrocatalytic behavior, mass transport, and interactions with surfaces. Here we report a new experimental setup for studying NP collisions based on the use of carbon nanopipettes to enable monitoring multiple collision events involving the same NP captured inside the pipet cavity. A patch clamp amplifier capable of measuring pA-range currents on the microsecond time scale with a very low noise and stable background was used to record the collision transients. The analysis of current transients produced by oxidation of hydrogen peroxide at one IrO x NP provided information about the origins of deactivation of catalytic NPs and the effects of various experimental conditions on the collision dynamics. High-resolution TEM of carbon pipettes was used to attain better understanding of the NP capture and collisions.

Collisions of Ir oxide nanoparticles with carbon nanopipettes: Experiments with one nanoparticle

DOE PAGES

Zhou, Min; Yu, Yun; Hu, Keke; ...

2017-02-03

Investigating the collisions of individual metal nanoparticles (NPs) with electrodes can provide new insights into their electrocatalytic behavior, mass transport, and interactions with surfaces. Here we report a new experimental setup for studying NP collisions based on the use of carbon nanopipettes to enable monitoring multiple collision events involving the same NP captured inside the pipet cavity. A patch clamp amplifier capable of measuring pA-range currents on the microsecond time scale with a very low noise and stable background was used to record the collision transients. The analysis of current transients produced by oxidation of hydrogen peroxide at one IrOxmore » NP provided information about the origins of deactivation of catalytic NPs and the effects of various experimental conditions on the collision dynamics. Lastly, high-resolution TEM of carbon pipettes was used to attain better understanding of the NP capture and collisions.« less

PLGA nanoparticles loaded with beta-lactoglobulin-derived peptides modulate mucosal immunity and may facilitate cow's milk allergy prevention.

PubMed

Kostadinova, Atanaska I; Middelburg, Jim; Ciulla, Michele; Garssen, Johan; Hennink, Wim E; Knippels, Leon M J; van Nostrum, Cornelus F; Willemsen, Linette E M

2018-01-05

Beta-lactoglobulin (BLG)-derived peptides may facilitate oral tolerance to whey and prevent cow's milk allergy (CMA). Loading of BLG-peptides in poly(lactic-co-glycolic acid) (PLGA) nanoparticles (Pep-NP) may improve this. Here we studied the uptake of NP and the capacity of NP and Pep-NP to activate bone marrow dendritic cells (BMDC). Furthermore, CMA prevention was evaluated by orally exposing three-week-old female C3H/HeOuJ mice to Pep-NP, NP or free peptides (PepMix) for 6 days before oral sensitization with whole whey protein and effects on the spleen and small intestine lamina propria (SI-LP) were studied. In BMDC, NP and Pep-NP enhanced CD40 expression and IL-6 and TNF-α secretion, while tended to decrease CD80 expression and prevented PepMix-induced IL-12 secretion. In vivo, oral exposure to Pep-NP, but not NP or PepMix, prior to whey sensitization tended to partially prevent the acute allergic skin response to whole whey protein. Splenocytes of NP-pre-exposed mice secreted increased levels of whey-specific IL-6, but this was silenced in Pep-NP-pre-exposed mice which also showed reduced TNF-α and IFN-γ secretion. In the SI-LP, Pep-NP pre-exposure reduced the CD4 + T cell frequency in CMA mice compared to PBS pre-exposure. In addition, while NP increased whey-specific IL-6 secretion in the SI-LP, Pep-NP did not and maintained regulatory TGF-β secretion. This study presents a proof-of-concept that PLGA nanoparticles facilitate the capacity of BLG peptides to suppress the allergic response to whole whey protein. Hence, PLGA nanoparticles may be further developed as an adjunct strategy for BLG-peptide-based oral tolerance induction and CMA prevention. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Single plasmonic nanoparticles for ultrasensitive DNA sensing: From invisible to visible.

PubMed

Guo, Longhua; Chen, Lichan; Hong, Seungpyo; Kim, Dong-Hwan

2016-05-15

The background signal is a major factor that restricts the limit of detection of biosensors. Herein, we present a zero-background DNA-sensing approach that utilizes enzyme-guided gold nanoparticle (AuNP) enlargement. This sensing strategy is based on the finding that small nanoparticles are invisible under a darkfield optical microscope, thus completely eliminating the background signal. In the event of target binding, Ag deposition is triggered and enlarges the AuNP beyond its optical diffraction limit, thereby making the invisible AuNP visible. Because the plasmon scattering of Ag is stronger than that of Au, only a thin layer of Ag is required to greatly enhance the scattering intensity of the AuNPs. Our investigation revealed that a target DNA concentration as low as 5.0×10(-21)M can transform the darkfield image of the nanoparticle from completely dark (invisible) to a blue dot (visible). Copyright © 2015 Elsevier B.V. All rights reserved.

Enzymatic functionalization of cork surface with antimicrobial hybrid biopolymer/silver nanoparticles.

PubMed

Francesko, Antonio; Blandón, Lucas; Vázquez, Mario; Petkova, Petya; Morató, Jordi; Pfeifer, Annett; Heinze, Thomas; Mendoza, Ernest; Tzanov, Tzanko

2015-05-13

Laccase-assisted assembling of hybrid biopolymer-silver nanoparticles and cork matrices into an antimicrobial material with potential for water remediation is herein described. Amino-functional biopolymers were first used as doping agents to stabilize concentrated colloidal dispersions of silver nanoparticles (AgNP), additionally providing the particles with functionalities for covalent immobilization onto cork to impart a durable antibacterial effect. The solvent-free AgNP synthesis by chemical reduction was carried out in the presence of chitosan (CS) or 6-deoxy-6-(ω-aminoethyl) aminocellulose (AC), leading to simultaneous AgNP biofunctionalization. This approach resulted in concentrated hybrid NP dispersion stable to aggregation and with hydrodynamic radius of particles of about 250 nm. Moreover, laccase enabled coupling between the phenolic groups in cork and amino moieties in the biopolymer-doped AgNP for permanent modification of the material. The antibacterial efficiency of the functionalized cork matrices, aimed as adsorbents for wastewater treatment, was evaluated against Escherichia coli and Staphylococcus aureus during 5 days in conditions mimicking those in constructed wetlands. Both intrinsically antimicrobial CS and AC contributed to the bactericidal effect of the enzymatically grafted on cork AgNP. In contrast, unmodified AgNP were easily washed off from the material, confirming that the biopolymers potentiated a durable antibacterial functionalization of the cork matrices.

In vitro studies on radiosensitization effect of glucose capped gold nanoparticles in photon and ion irradiation of HeLa cells

NASA Astrophysics Data System (ADS)

Kaur, Harminder; Pujari, Geetanjali; Semwal, Manoj K.; Sarma, Asitikantha; Avasthi, Devesh Kumar

2013-04-01

Noble metal nanoparticles are of great interest due to their potential applications in diagnostics and therapeutics. In the present work, we synthesized glucose capped gold nanoparticle (Glu-AuNP) for internalization in the HeLa cell line (human cervix cancer cells). The capping of glucose on Au nanoparticle was confirmed by Raman spectroscopy. The Glu-AuNP did not show any toxicity to the HeLa cell. The γ-radiation and carbon ion irradiation of HeLa cell with and without Glu-AuNP were performed to evaluate radiosensitization effects. The study revealed a significant reduction in radiation dose for killing the HeLa cells with internalized Glu-AuNPs as compared to the HeLa cells without Glu-AuNP. The Glu-AuNP treatment resulted in enhancement of radiation effect as evident from increase in relative biological effectiveness (RBE) values for carbon ion irradiated HeLa cells.

A surfactant free preparation of ultradispersed surface-clean Pt catalyst with highly stable electrocatalytic performance

NASA Astrophysics Data System (ADS)

Tao, Lu; Zhao, Yueping; Zhao, Yufeng; Huang, Shifei; Yang, Yunxia; Tong, Qi; Gao, Faming

2018-02-01

High efficiency platinum-based catalyst demands the ultrafine size and well dispersion of Pt nanoparticles (NPs), with clean surface and strong interactions between the supports. In this work, we demonstrate a simple strategy for the preparation of ultra-dispersed surface-clean Pt catalyst with high stability, in which the Pt nanoparticles (NPs) with 1.8 ± 0.6 nm in size are anchored tightly on a 3D hierarchical porous graphitized carbon (3D-HPG) through galvanic replacement reaction. The as-obtained catalyst can undergo 2000 voltage cycles with negligible activity decay and no apparent structure and size changes for MOR during the durability test, and its mass activity for ORR only reduce 18.3% after 5000 cycles. The excellent performance is attributed to strong anchoring effect between carbon support and Pt nanoparticles.

Study of serum interaction with a cationic nanoparticle: Implications for in vitro endocytosis, cytotoxicity and genotoxicity.

PubMed

Merhi, Maysaloun; Dombu, Christophe Youta; Brient, Alizée; Chang, Jiang; Platel, Anne; Le Curieux, Frank; Marzin, Daniel; Nesslany, Fabrice; Betbeder, Didier

2012-02-14

We used well-characterized and positively charged nanoparticles (NP(+)) to investigate the importance of cell culture conditions, specifically the presence of serum and proteins, on NP(+) physicochemical characteristics, and the consequences for their endocytosis and genotoxicity in bronchial epithelial cells (16HBE14o-). NP(+) surface charge was significantly reduced, proportionally to NP(+)/serum and NP(+)/BSA ratios, while NP(+) size was not modified. Microscopy studies showed high endocytosis of NP(+) in 16HBE14o-, and serum/proteins impaired this internalization in a dose-dependent manner. Toxicity studies showed no cytotoxicity, even for very high doses of NP(+). No genotoxicity was observed with classic comet assay while primary oxidative DNA damage was observed when using the lesion-specific repair enzyme, formamidopyrimidine DNA-glycosylase (FPG). The micronucleus test showed NP(+) genotoxicity only for very high doses that cannot be attained in vivo. The low toxicity of these NP(+) might be explained by their high exocytosis from 16HBE14o- cells. Our results confirm the importance of serum and proteins on nanoparticles endocytosis and genotoxicity. Copyright © 2011 Elsevier B.V. All rights reserved.

Recognition-mediated activation of therapeutic gold nanoparticles inside living cells

NASA Astrophysics Data System (ADS)

Kim, Chaekyu; Agasti, Sarit S.; Zhu, Zhengjiang; Isaacs, Lyle; Rotello, Vincent M.

2010-11-01

Supramolecular chemistry provides a versatile tool for the organization of molecular systems into functional structures and the actuation of these assemblies for applications through the reversible association between complementary components. Use of this methodology in living systems, however, represents a significant challenge owing to the chemical complexity of cellular environments and lack of selectivity of conventional supramolecular interactions. Herein, we present a host-guest system featuring diaminohexane-terminated gold nanoparticles (AuNP-NH2) and complementary cucurbit[7]uril (CB[7]). In this system, threading of CB[7] on the particle surface reduces the cytotoxicity of AuNP-NH2 through sequestration of the particle in endosomes. Intracellular triggering of the therapeutic effect of AuNP-NH2 was then achieved through the administration of 1-adamantylamine (ADA), removing CB[7] from the nanoparticle surface, causing the endosomal release and concomitant in situ cytotoxicity of AuNP-NH2. This supramolecular strategy for intracellular activation provides a new tool for potential therapeutic applications.

Nanoparticle-Based Topical Ophthalmic Gel Formulation for Sustained Release of Hydrocortisone Butyrate.

PubMed

Yang, Xiaoyan; Trinh, Hoang M; Agrahari, Vibhuti; Sheng, Ye; Pal, Dhananjay; Mitra, Ashim K

2016-04-01

This study was conducted to develop formulations of hydrocortisone butyrate (HB)-loaded poly(D,L-lactic-co-glycolic acid) nanoparticles (PLGA NP) suspended in thermosensitive gel to improve ocular bioavailability of HB for the treatment of bacterial corneal keratitis. PLGA NP with different surfactants such as polyvinyl alcohol (PVA), pluronic F-108, and chitosan were prepared using oil-in-water (O/W) emulsion evaporation technique. NP were characterized with respect to particle size, entrapment efficiency, polydispersity, drug loading, surface morphology, zeta potential, and crystallinity. In vitro release of HB from NP showed a biphasic release pattern with an initial burst phase followed by a sustained phase. Such burst effect was completely eliminated when nanoparticles were suspended in thermosensitive gels and zero-order release kinetics was observed. In HCEC cell line, chitosan-emulsified NP showed the highest cellular uptake efficiency over PVA- and pluronic-emulsified NP (59.09 ± 6.21%, 55.74 ± 6.26%, and 62.54 ± 3.30%, respectively) after 4 h. However, chitosan-emulsified NP indicated significant cytotoxicity of 200 and 500 μg/mL after 48 h, while PVA- and pluronic-emulsified NP exhibited no significant cytotoxicity. PLGA NP dispersed in thermosensitive gels can be considered as a promising drug delivery system for the treatment of anterior eye diseases.

A hierarchical flower-like hollow alumina supported bimetallic AuPd nanoparticle catalyst for enhanced solvent-free ethylbenzene oxidation.

PubMed

Dong, Huijuan; Xie, Renfeng; Yang, Lan; Li, Feng

2018-06-12

Currently, oxidation of alkylaromatics is considered as one of the most crucial chemical technologies to produce high added-value alcohols, ketones and carboxylic acids, due to its significant importance both in fine synthetic chemistry and in the academic field. In this work, a novel hierarchical marigold-like hollow alumina supported bimetallic AuPd nanoparticle catalyst was successfully fabricated and employed for highly efficient solvent-free ethylbenzene oxidation to produce acetophenone with the coexistence of both molecular oxygen and tert-butyl hydroperoxide as the oxidant and the initiator. The as-fabricated bimetallic AuPd nanocatalyst conferred a superior catalytic performance to the corresponding monometallic counterparts and commercial Al2O3 or solid Al2O3 microsphere supported AuPd ones, along with a high acetophenone selectivity of 88.2% at a conversion of 50.9% under mild reaction conditions (120 °C and oxygen pressure of 1.0 MPa), as well as an unprecedentedly high turnover frequency value of 46 768 h-1. Such exceptional efficiency of the catalyst was related to both the significant synergy between the Au-Pd atoms and strong metal-support interactions, and the unique hierarchical micro/nanostructure of the support being beneficial to the close contact of reactants with surface adsorption and reaction sites and easy product diffusion. Moreover, the present bimetallic AuPd catalyst was recyclable and stable. The developed approach is expected to offer exciting opportunities for designing other supported monometallic or bimetallic catalysts with various active components applied in heterogeneous catalysis.

Nanoparticle-Hydrogel: A Hybrid Biomaterial System for Localized Drug Delivery

PubMed Central

Gao, Weiwei; Zhang, Yue; Zhang, Qiangzhe; Zhang, Liangfang

2016-01-01

Nanoparticles have offered a unique set of properties for drug delivery including high drug loading capacity, combinatorial delivery, controlled and sustained drug release, prolonged stability and lifetime, and targeted delivery. To further enhance therapeutic index, especially for localized application, nanoparticles have been increasingly combined with hydrogels to form a hybrid biomaterial system for controlled drug delivery. Herein, we review recent progresses in engineering such nanoparticle-hydrogel hybrid system (namely ‘NP-gel’) with a particular focus on its application for localized drug delivery. Specifically, we highlight four research areas where NP-gel has shown great promises, including (1) passively controlled drug release, (2) stimuli-responsive drug delivery, (3) site-specific drug delivery, and (4) detoxification. Overall, integrating therapeutic nanoparticles with hydrogel technologies creates a unique and robust hybrid biomaterial system that enables effective localized drug delivery. PMID:26951462

Porous Nanocrystalline Silicon Supported Bimetallic Pd-Au Catalysts: Preparation, Characterization, and Direct Hydrogen Peroxide Synthesis

PubMed Central

Potemkin, Dmitriy I.; Maslov, Dmitry K.; Loponov, Konstantin; Snytnikov, Pavel V.; Shubin, Yuri V.; Plyusnin, Pavel E.; Svintsitskiy, Dmitry A.; Sobyanin, Vladimir A.; Lapkin, Alexei A.

2018-01-01

Bimetallic Pd-Au catalysts were prepared on the porous nanocrystalline silicon (PSi) for the first time. The catalysts were tested in the reaction of direct hydrogen peroxide synthesis and characterized by standard structural and chemical techniques. It was shown that the Pd-Au/PSi catalyst prepared from conventional H2[PdCl4] and H[AuCl4] precursors contains monometallic Pd and a range of different Pd-Au alloy nanoparticles over the oxidized PSi surface. The PdAu2/PSi catalyst prepared from the [Pd(NH3)4][AuCl4]2 double complex salt (DCS) single-source precursor predominantly contains bimetallic Pd-Au alloy nanoparticles. For both catalysts the surface of bimetallic nanoparticles is Pd-enriched and contains palladium in Pd0 and Pd2+ states. Among the catalysts studied, the PdAu2/PSi catalyst was the most active and selective in the direct H2O2 synthesis with H2O2 productivity of 0.5 mol gPd-1 h-1 at selectivity of 50% and H2O2 concentration of 0.023 M in 0.03 M H2SO4-methanol solution after 5 h on stream at −10°C and atmospheric pressure. This performance is due to high activity in the H2O2 synthesis reaction and low activities in the undesirable H2O2 decomposition and hydrogenation reactions. Good performance of the PdAu2/PSi catalyst was associated with the major part of Pd in the catalyst being in the form of the bimetallic Pd-Au nanoparticles. Porous silicon was concluded to be a promising catalytic support for direct hydrogen peroxide synthesis due to its inertness with respect to undesirable side reactions, high thermal stability, and conductivity, possibility of safe operation at high temperatures and pressures and a well-established manufacturing process. PMID:29637068

Controlled evaluation of silver nanoparticle dissolution using atomic force microscopy.

PubMed

Kent, Ronald D; Vikesland, Peter J

2012-07-03

Incorporation of silver nanoparticles (AgNPs) into an increasing number of consumer products has led to concern over the potential ecological impacts of their unintended release to the environment. Dissolution is an important environmental transformation that affects the form and concentration of AgNPs in natural waters; however, studies on AgNP dissolution kinetics are complicated by nanoparticle aggregation. Herein, nanosphere lithography (NSL) was used to fabricate uniform arrays of AgNPs immobilized on glass substrates. Nanoparticle immobilization enabled controlled evaluation of AgNP dissolution in an air-saturated phosphate buffer (pH 7.0, 25 °C) under variable NaCl concentrations in the absence of aggregation. Atomic force microscopy (AFM) was used to monitor changes in particle morphology and dissolution. Over the first day of exposure to ≥10 mM NaCl, the in-plane AgNP shape changed from triangular to circular, the sidewalls steepened, the in-plane radius decreased by 5-11 nm, and the height increased by 6-12 nm. Subsequently, particle height and in-plane radius decreased at a constant rate over a 2-week period. Dissolution rates varied linearly from 0.4 to 2.2 nm/d over the 10-550 mM NaCl concentration range tested. NaCl-catalyzed dissolution of AgNPs may play an important role in AgNP fate in saline waters and biological media. This study demonstrates the utility of NSL and AFM for the direct investigation of unaggregated AgNP dissolution.

Acid-functionalized nanoparticles for biomass hydrolysis

NASA Astrophysics Data System (ADS)

Pena Duque, Leidy Eugenia

Cellulosic ethanol is a renewable source of energy. Lignocellulosic biomass is a complex material composed mainly of cellulose, hemicellulose, and lignin. Biomass pretreatment is a required step to make sugar polymers liable to hydrolysis. Mineral acids are commonly used for biomass pretreatment. Using acid catalysts that can be recovered and reused could make the process economically more attractive. The overall goal of this dissertation is the development of a recyclable nanocatalyst for the hydrolysis of biomass sugars. Cobalt iron oxide nanoparticles (CoFe2O4) were synthesized to provide a magnetic core that could be separated from reaction using a magnetic field and modified to carry acid functional groups. X-ray diffraction (XRD) confirmed the crystal structure was that of cobalt spinel ferrite. CoFe2O4 were covered with silica which served as linker for the acid functions. Silica-coated nanoparticles were functionalized with three different acid functions: perfluoropropyl-sulfonic acid, carboxylic acid, and propyl-sulfonic acid. Transmission electron microscope (TEM) images were analyzed to obtain particle size distributions of the nanoparticles. Total carbon, nitrogen, and sulfur were quantified using an elemental analyzer. Fourier transform infra-red spectra confirmed the presence of sulfonic and carboxylic acid functions and ion-exchange titrations accounted for the total amount of catalytic acid sites per nanoparticle mass. These nanoparticles were evaluated for their performance to hydrolyze the beta-1,4 glycosidic bond of the cellobiose molecule. Propyl-sulfonic (PS) and perfluoropropyl-sulfonic (PFS) acid functionalized nanoparticles catalyzed the hydrolysis of cellobiose significantly better than the control. PS and PFS were also evaluated for their capacity to solubilize wheat straw hemicelluloses and performed better than the control. Although PFS nanoparticles were stronger acid catalysts, the acid functions leached out of the nanoparticle during

Novel catalysts and photoelectrochemical system for solar fuel production

NASA Astrophysics Data System (ADS)

Zhang, Yan