Size-tunable drug-delivery capsules composed of a magnetic nanoshell.

PubMed

Fuchigami, Teruaki; Kitamoto, Yoshitaka; Namiki, Yoshihisa

2012-01-01

Nano-sized FePt capsules with two types of ultrathin shell were fabricated using a template method for use in a nano-scale drug delivery system. One capsule was composed of an inorganic-organic hybrid shell of a water-soluble polymer and FePt nanoparticles, and the other capsule was composed of a network of fused FePt nanoparticles. We demonstrated that FePt nanoparticles selectively accumulated on the polymer molecules adsorbed on the template silica particles, and investigated the morphologies of the particle accumulation by changing the concentration of the polymer solution with which the template particles were treated. Capsular size was reduced from 340 to less than 90 nm by changing the size of the silica template particles, and the shell thickness was controlled by changing the amount of FePt nanoparticles adsorbed on the template particles. The hybrid shell was maintained by the connection of FePt nanoparticles and polymer molecules, and the shell thickness was 10 nm at the maximum. The FePt network shell was fabricated by hydrothermal treatment of the FePt/polymer-modified silica composite particles. The FePt network shell was produced from only the FePt alloy, and the shell thickness was 3 nm. Water-soluble anti-cancer drugs could be loaded into the hollow space of FePt network capsules, and lipid-coated FePt network capsules loaded with anti-cancer drugs showed cellular toxicity. The nano-sized capsular structure and the ultrathin shell suggest applicability as a drug carrier in magnetically guided drug delivery systems.

Size-tunable drug-delivery capsules composed of a magnetic nanoshell

PubMed Central

Fuchigami, Teruaki; Kitamoto, Yoshitaka; Namiki, Yoshihisa

2012-01-01

Nano-sized FePt capsules with two types of ultrathin shell were fabricated using a template method for use in a nano-scale drug delivery system. One capsule was composed of an inorganic-organic hybrid shell of a water-soluble polymer and FePt nanoparticles, and the other capsule was composed of a network of fused FePt nanoparticles. We demonstrated that FePt nanoparticles selectively accumulated on the polymer molecules adsorbed on the template silica particles, and investigated the morphologies of the particle accumulation by changing the concentration of the polymer solution with which the template particles were treated. Capsular size was reduced from 340 to less than 90 nm by changing the size of the silica template particles, and the shell thickness was controlled by changing the amount of FePt nanoparticles adsorbed on the template particles. The hybrid shell was maintained by the connection of FePt nanoparticles and polymer molecules, and the shell thickness was 10 nm at the maximum. The FePt network shell was fabricated by hydrothermal treatment of the FePt/polymer-modified silica composite particles. The FePt network shell was produced from only the FePt alloy, and the shell thickness was 3 nm. Water-soluble anti-cancer drugs could be loaded into the hollow space of FePt network capsules, and lipid-coated FePt network capsules loaded with anti-cancer drugs showed cellular toxicity. The nano-sized capsular structure and the ultrathin shell suggest applicability as a drug carrier in magnetically guided drug delivery systems. PMID:23507895

Amperometric biosensors based on deposition of gold and platinum nanoparticles on polyvinylferrocene modified electrode for xanthine detection.

PubMed

Baş, Salih Zeki; Gülce, Handan; Yıldız, Salih; Gülce, Ahmet

2011-12-15

In this study, new xanthine biosensors, XO/Au/PVF/Pt and XO/Pt/PVF/Pt, based on electroless deposition of gold(Au) and platinum(Pt) nanoparticles on polyvinylferrocene(PVF) coated Pt electrode for detection of xanthine were presented. The amperometric responses of the enzyme electrodes were measured at the constant potential, which was due to the electrooxidation of enzymatically produced H(2)O(2). Compared with XO/PVF/Pt electrode, XO/Au/PVF/Pt and XO/Pt/PVF/Pt exhibited excellent electrocatalytic activity towards the oxidation of the analyte. Effect of Au and Pt nanoparticles was investigated by monitoring the response currents at the different deposition times and the different concentrations of KAuCl(4) and PtBr(2). Under the optimal conditions, the calibration curves of XO/Au/PVF/Pt and XO/Pt/PVF/Pt were obtained over the range of 2.5 × 10(-3) to 0.56 mM and 2.0 × 10(-3) to 0.66 mM, respectively. The detection limits were 7.5 × 10(-4)mM for XO/Au/PVF/Pt and 6.0 × 10(-4)mM for XO/Pt/PVF/Pt. The effects of interferents, the operational and the storage stabilities of the biosensors and the applicabilities of the proposed biosensors to the drug samples analysis were also evaluated. Copyright © 2011 Elsevier B.V. All rights reserved.

A novel enzymatic glucose sensor based on Pt nanoparticles-decorated hollow carbon spheres-modified glassy carbon electrode

NASA Astrophysics Data System (ADS)

Luhana, Charles; Bo, Xiang-Jie; Ju, Jian; Guo, Li-Ping

2012-10-01

A new glucose biosensor was developed based on hollow carbon spheres decorated with platinum nanoparticles (Pt/HCSs)-modified glassy carbon electrode immobilized with glucose oxidase (GOx) with the help of Nafion. The Pt nanoparticles were well dispersed on the HCSs with an average size of 2.29 nm. The detection of glucose was achieved via electrochemical detection of the enzymatically liberated H2O2 at +0.5 V versus Ag/AgCl at physiologic pH of 7.4. The Pt/HCSs-modified electrode exhibited excellent electrocatalytic activities toward both the oxidation and reduction of H2O2. The glucose biosensor showed good electrocatalytic performance in terms of high sensitivity (4.1 μA mM-1), low detection limit (1.8 μM), fast response time <3 s, and wide linear range (0.04-8.62 mM). The apparent Michaelis-Menten constant ( K m) and the maximum current density ( i max) values for the biosensor were 10.94 mM and 887 μA cm-2 respectively. Furthermore, this biosensor showed an acceptable reproducibility and high stability. The interfering signals from ascorbic acid and uric acid at concentration levels normally found in human blood were not much compared with the response to glucose. Blood serum samples were also tested with this biosensor and a good recovery was achieved for the two spiked serum samples.

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.

Fabrication of sensitive enzymatic biosensor based on multi-layered reduced graphene oxide added PtAu nanoparticles-modified hybrid electrode

PubMed Central

Hossain, Md Faruk; Park, Jae Y.

2017-01-01

A highly sensitive amperometric glucose sensor was developed by immobilization of glucose oxidase (GOx) onto multi-layer reduced graphene oxide (MRGO) sheets decorated with platinum and gold flower-like nanoparticles (PtAuNPs) modified Au substrate electrode. The fabricated MRGO/PtAuNPs modified hybrid electrode demonstrated high electrocatalytic activities toward oxidation of H2O2, to which it had a wide linear response that ranged from 0.5 to 8 mM (R2 = 0.997), and high sensitivity of 506.25 μA/mMcm2. Furthermore, glucose oxidase-chitosan composite and cationic polydiallyldimethylammonium chloride (PDDA) were assembled by a casting method on the surface of MRGO/PtAuNPs modified electrode. This as-fabricated hybrid biosensor electrode exhibited high electrocatalytic activity for the detection of glucose in PBS. It demonstrated good analytical properties in terms of a low detection limit of 1 μM (signal-to-noise ratio of 3), short response time (3 s), high sensitivity (17.85 μA/mMcm2), and a wide linear range (0.01–8 mM) for glucose sensing. These results reveal that the newly developed sensing electrode offers great promise for new type enzymatic biosensor applications. PMID:28333943

Construction of an electrochemical sensor based on the electrodeposition of Au-Pt nanoparticles mixtures on multi-walled carbon nanotubes film for voltammetric determination of cefotaxime.

PubMed

Shahrokhian, Saeed; Rastgar, Shokoufeh

2012-06-07

Mixtures of gold-platinum nanoparticles (Au-PtNPs) are fabricated consecutively on a multi-walled carbon nanotubes (MWNT) coated glassy carbon electrode (GCE) by the electrodeposition method. The surface morphology and nature of the hybrid film (Au-PtNPs/MWCNT) deposited on glassy carbon electrodes is characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. The modified electrode is used as a new and sensitive electrochemical sensor for the voltammetric determination of cefotaxime (CFX). The electrochemical behavior of CFX is investigated on the surface of the modified electrode using linear sweep voltammetry (LSV). The results of voltammetric studies exhibited a considerable improvement in the oxidation peak current of CFX compared to glassy carbon electrodes individually coated with MWCNT or Au-PtNPs. Under the optimized conditions, the modified electrode showed a wide linear dynamic range of 0.004-10.0 μM with a detection limit of 1.0 nM for the voltammetric determination of CFX. The modified electrode was successfully applied for the accurate determination of trace amounts of CFX in pharmaceutical and clinical preparations.

Direct electron transfer of Phanerochaete chrysosporium cellobiose dehydrogenase at platinum and palladium nanoparticles decorated carbon nanotubes modified electrodes.

PubMed

Bozorgzadeh, Somayyeh; Hamidi, Hassan; Ortiz, Roberto; Ludwig, Roland; Gorton, Lo

2015-10-07

In the present work, platinum and palladium nanoparticles (PtNPs and PdNPs) were decorated on the surface of multi-walled carbon nanotubes (MWCNTs) by a simple thermal decomposition method. The prepared nanohybrids, PtNPs-MWCNTs and PdNPs-MWCNTs, were cast on the surface of spectrographic graphite electrodes and then Phanerochaete chrysosporium cellobiose dehydrogenase (PcCDH) was adsorbed on the modified layer. Direct electron transfer between PcCDH and the nanostructured modified electrodes was studied using flow injection amperometry and cyclic voltammetry. The maximum current responses (Imax) and the apparent Michaelis-Menten constants (K) for the different PcCDH modified electrodes were calculated by fitting the data to the Michaelis-Menten equation and compared. The sensitivity towards lactose was 3.07 and 3.28 μA mM(-1) at the PcCDH/PtNPs-MWCNTs/SPGE and PcCDH/PdNPs-MWCNTs/SPGE electrodes, respectively, which were higher than those measured at the PcCDH/MWCNTs/SPGE (2.60 μA mM(-1)) and PcCDH/SPGE (0.92 μA mM(-1)). The modified electrodes were additionally tested as bioanodes for biofuel cell applications.

The simultaneous electrochemical detection of ascorbic acid, dopamine, and uric acid using graphene/size-selected Pt nanocomposites.

PubMed

Sun, Chia-Liang; Lee, Hsin-Hsien; Yang, Jen-Ming; Wu, Ching-Chou

2011-04-15

In this study, a graphene/Pt-modified glassy carbon (GC) electrode was created to simultaneously characterize ascorbic acid (AA), dopamine (DA), and uric acid (UA) levels via cyclic voltammetry (CV) and differential pulse voltammetry (DPV). During the preparation of the nanocomposite, size-selected Pt nanoparticles with a mean diameter of 1.7 nm were self-assembled onto the graphene surface. In the simultaneous detection of the three aforementioned analytes using CV, the electrochemical potential differences among the three detected peaks were 185 mV (AA to DA), 144 mV (DA to UA), and 329 mV (AA and UA), respectively. In comparison to the CV results of bare GC and graphene-modified GC electrodes, the large electrochemical potential difference that is achieved via the use of the graphene/Pt nanocomposites is essential to the distinguishing of these three analytes. An optimized adsorption of size-selected Pt colloidal nanoparticles onto the graphene surface results in a graphene/Pt nanocomposite that can provide a good platform for the routine analysis of AA, DA, and UA. Copyright © 2011 Elsevier B.V. All rights reserved.

Fabrication of Metal Nanoparticle-Modified Screen Printed Carbon Electrodes for the Evaluation of Hydrogen Peroxide Content in Teeth Whitening Strips

ERIC Educational Resources Information Center

Popa, Adriana; Abenojar, Eric C.; Vianna, Adam; Buenviaje, Czarina Y. A.; Yang, Jiahua; Pascual, Cherrie B.; Samia, Anna Cristina S.

2015-01-01

A laboratory experiment in which students synthesize Ag, Au, and Pt nanoparticles (NPs) and use them to modify screen printed carbon electrodes for the electroanalysis of the hydrogen peroxide content in commercially available teeth whitening strips is described. This experiment is designed for two 3-h laboratory periods and can be adapted for…

Hemispherical platinum : silver core : shell nanoparticles for miRNA detection.

PubMed

Spain, Elaine; Adamson, Kellie; Elshahawy, Mohammad; Bray, Isabella; Keyes, Tia E; Stallings, Raymond L; Forster, Robert J

2017-02-27

Defects within a self-assembled monolayer (SAM) of dodecanethiol on gold have been used as nucleation sites for the electrodeposition of mushroom shaped platinum nanoparticles (PtNPs). The top surfaces of these PtNPs were then decorated with a layer of silver creating a hemispherical - platinum : silver core : shell nanoparticle (Pt-AgNP). Thiolated probe strand miRNA was then immobilised onto the upper silver surface. These regioselectively modified particles were desorbed by applying a current jump to yield nanoparticles capable of hybridising to a complementary miRNA target with electrocatalysis occurring on the non-functionalized lower surface. A second electrode was functionalized with single stranded capture miRNA that has a sequence that is complementary to an miRNA, miR-132, associated with the childhood cancer, Neuroblastoma but leaves a section of the target available to bind the nucleic acid sequence on the core : shell Pt-AgNPs. Following hybridization of the target and capture strands the surface was exposed to the miRNA labelled electrocatalytic Pt-AgNPs. The concentration of the target was then determined by monitoring the current associated with the reduction of hydrogen peroxide in a solution of H 2 SO 4 . Calibration plots of the log[miRNA] vs. faradaic current were linear from 1 aM to 1 μM and aM concentrations could be detected without the need for chemical amplification of the target, e.g., using PCR or NASBA. The regioselectively modified particles were also immobilised within the interior of gold microcavity arrays via miRNA hybridisation and their Raman properties investigated.

Fabrication of Pt nanoparticles decorated Gd-doped Bi2MoO6 nanosheets: Design, radicals regulating and mechanism of Gd/Pt-Bi2MoO6 photocatalyst

NASA Astrophysics Data System (ADS)

Li, Hongda; Li, Wenjun; Wang, Fangzhi; Liu, Xintong; Ren, Chaojun; Miao, Xiao

2018-01-01

A new Pt nanoparticles decorated Gd-doped Bi2MoO6 photocatalyst was synthesized by the hydrothermal process and in-situ reduction method. The crystal structure, morphology, chemical state and optical property of the obtained photocatalysts were investigated. The activities of photocatalysts were also evaluated by the degradation of Rhodamine B, Tetracyclines and 4-Chlorophenol under visible light irradiation, and the results indicated that the Gd/Pt co-modified Bi2MoO6 sample shows better photocatalytic activity. Meanwhile, the results of trapping experiments and Electron Spin Resonance (ESR) spectra demonstrated that the rad OH radicals can be formed by doping of Gd3+ ions, and the addition of Pt was conducive to the producing of more • O2- and rad OH radicals. Also the results from the degradation of 4-chlorophenol implied that the formed rad OH radicals in the system of Gd/Pt-BMO possess stronger oxidizability than • O2- radicals for degrading the special organics which are difficult to be mineralized. Additionally, the mechanism about the excellent photocatalytic activity of Gd/Pt co-modified Bi2MoO6 was also discussed.

Soft landing of bare PtRu nanoparticles for electrochemical reduction of oxygen.

PubMed

Johnson, Grant E; Colby, Robert; Engelhard, Mark; Moon, Daewon; Laskin, Julia

2015-08-07

Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 × 10(4) ions μm(-2) and that their average height is centered at 4.5 nm. Scanning transmission electron microscopy images obtained in the high-angle annular dark field mode (HAADF-STEM) further confirm that the soft-landed PtRu nanoparticles are uniform in size. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in atomic concentrations of ∼9% and ∼33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt 4f and Ru 3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He(+) and O(+) ions. The activity of electrodes containing 7 × 10(4) ions μm(-2) of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the nanoparticles supported on glassy carbon. The reproducibility of the nanoparticle synthesis and deposition was evaluated by employing the same experimental parameters to prepare nanoparticles on glassy carbon electrodes on three occasions separated by several days. Surfaces with almost identical electrochemical behavior were observed with CV, demonstrating the highly reproducible preparation of bare nanoparticles using physical synthesis in the gas-phase combined with soft landing of mass-selected ions.

Morphology controlled synthesis of platinum nanoparticles performed on the surface of graphene oxide using a gas-liquid interfacial reaction and its application for high-performance electrochemical sensing.

PubMed

Bai, Wushuang; Sheng, Qinglin; Zheng, Jianbin

2016-07-21

In this paper, we report a novel morphology-controlled synthetic method. Platinum (Pt) nanoparticles with three kinds of morphology (aggregation-like, cube-like and globular) were grown on the surface of graphene oxide (GO) using a simple gas-liquid interfacial reaction and Pt/GO nanocomposites were obtained successfully. According to the experimental results, the morphology of the Pt nanoparticles can be controlled by adjusting the reaction temperature with the protection of chitosan. The obtained Pt/GO nanocomposites were characterized using transmission electron microscopy (TEM), X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FTIR). Then the Pt/GO nanocomposites with the three kinds of morphology were all used to fabricate electrochemical sensors. The electrochemical experimental results indicated that compared with various reported electrochemical sensors, the Pt/GO modified sensors in this work exhibit a low detection limit, high sensitivity and an extra wide linear range for the detection of nitrite. In addition, the synthesis of Pt particles based on a gas-liquid interfacial reaction provides a new platform for the controllable synthesis of nanomaterials.

Green synthesis of platinum nanoparticles that induce cell death and G2/M-phase cell cycle arrest in human cervical cancer cells.

PubMed

Alshatwi, Ali A; Athinarayanan, Jegan; Vaiyapuri Subbarayan, Periasamy

2015-01-01

Platinum-based chemotherapeutic drugs, including cisplatin, carboplatin, and oxaliplatin, have been used to manage cancer in spite of dose-dependent side effects, including nephrotoxicity, neurotoxicity and ototoxicity. These disadvantages have prompted the development of new strategies for cancer therapy that utilize functionalized nanoparticles as nanomedicines. In the present investigation, we have synthesized platinum nanoparticles using tea polyphenol (TPP) as both a reducing and surface modifying agent. The crystalline nature and morphology of the prepared TPP-functionalized platinum nanoparticles (TPP@Pt) were analyzed using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD results revealed that the TPP@Pt had a crystalline nature with a face-centered cubic structure. TEM imaging suggested that the TTP@Pt are flower shaped with a well-dispersed 30-60 nm-sized TPP@Pt formation. Cervical cancer cells (SiHa) were then treated with different concentrations of TPP@Pt. The effects of TPP@Pt on cell viability, nuclear morphology and cell cycle distribution were investigated. A cell viability assay revealed that the proliferation of SiHa cells was inhibited by TPP@Pt. Propidium iodide nuclear staining indicated that TPP@Pt induced nuclear fragmentation and chromatin condensation. Treatment with TPP@Pt significantly increased the percentage of cells in the G2/M phase, which indicates induced cell cycle arrest in the G2/M phase and an increased number of cells in the subG0 cell death phase. These findings highlight a potential use of TPP@Pt in cervical cancer treatment.

UV-Vis-Induced Degradation of Phenol over Magnetic Photocatalysts Modified with Pt, Pd, Cu and Au Nanoparticles

PubMed Central

Wysocka, Izabela; Trzciński, Konrad; Łapiński, Marcin; Nowaczyk, Grzegorz; Zielińska-Jurek, Anna

2018-01-01

The combination of TiO2 photocatalyst and magnetic oxide nanoparticles enhances the separation and recoverable properties of nanosized TiO2 photocatalyst. Metal-modified (Me = Pd, Au, Pt, Cu) TiO2/SiO2@Fe3O4 nanocomposites were prepared by an ultrasonic-assisted sol-gel method. All prepared samples were characterized by X-ray powder diffraction (XRD) analysis, Brunauer-Emmett-Teller (BET) method, X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), Mott-Schottky analysis and photoluminescence spectroscopy (PL). Phenol oxidation pathways of magnetic photocatalysts modified with Pt, Pd, Cu and Au nanoparticles proceeded by generation of reactive oxygen species, which oxidized phenol to benzoquinone, hydroquinone and catechol. Benzoquinone and maleic acid were products, which were determined in the hydroquinone oxidation pathway. The highest mineralization rate was observed for Pd-TiO2/SiO2@Fe3O4 and Cu-TiO2/SiO2@Fe3O4 photocatalysts, which produced the highest concentration of catechol during photocatalytic reaction. For Pt-TiO2/SiO2@Fe3O4 nanocomposite, a lack of catechol after 60 min of irradiation resulted in low mineralization rate (CO2 formation). It is proposed that the enhanced photocatalytic activity of palladium and copper-modified photocatalysts is related to an increase in the amount of adsorption sites and efficient charge carrier separation, whereas the keto-enol tautomeric equilibrium retards the rate of phenol photomineralization on Au-TiO2/SiO2@Fe3O4. The magnetization hysteresis loop indicated that the obtained hybrid photocatalyst showed magnetic properties and therefore could be easily separated after treatment process. PMID:29316667

Soft Landing of Bare PtRu Nanoparticles for Electrochemical Reduction of Oxygen

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

Johnson, Grant E.; Colby, Robert J.; Engelhard, Mark H.

2015-08-07

Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu alloy nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 x 104 ions µm-2 and that their average height is centered at 4 nm. Scanning transmission electron microscopy images obtained in themore » high-angle annular dark field mode (STEM-HAADF) further confirm that the soft-landed PtRu alloy nanoparticles are uniform in size and have a Ru core decorated with small regions of Pt on the surface. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in relative atomic concentrations of ~9% and ~33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt4f and Ru3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the alloy nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He+ and O+ ions. The activity of electrodes containing 7 x 104 ions µm-2 of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the alloy nanoparticles supported on glassy carbon. The reproducibility of the nanoparticle synthesis and deposition was evaluated by employing the same experimental parameters to prepare nanoparticles on glassy carbon electrodes on three occasions separated by several days. Surfaces with almost identical electrochemical behavior were observed with CV, demonstrating the highly reproducible preparation of bare alloy nanoparticles using physical synthesis in the gas-phase combined with soft landing of mass-selected ions« less

Controlled Synthesis of Pd/Pt Core Shell Nanoparticles Using Area-selective Atomic Layer Deposition

PubMed Central

Cao, Kun; Zhu, Qianqian; Shan, Bin; Chen, Rong

2015-01-01

We report an atomic scale controllable synthesis of Pd/Pt core shell nanoparticles (NPs) via area-selective atomic layer deposition (ALD) on a modified surface. The method involves utilizing octadecyltrichlorosilane (ODTS) self-assembled monolayers (SAMs) to modify the surface. Take the usage of pinholes on SAMs as active sites for the initial core nucleation, and subsequent selective deposition of the second metal as the shell layer. Since new nucleation sites can be effectively blocked by surface ODTS SAMs in the second deposition stage, we demonstrate the successful growth of Pd/Pt and Pt/Pd NPs with uniform core shell structures and narrow size distribution. The size, shell thickness and composition of the NPs can be controlled precisely by varying the ALD cycles. Such core shell structures can be realized by using regular ALD recipes without special adjustment. This SAMs assisted area-selective ALD method of core shell structure fabrication greatly expands the applicability of ALD in fabricating novel structures and can be readily applied to the growth of NPs with other compositions. PMID:25683469

Electrochemical Co-Reduction Synthesis of AuPt Bimetallic Nanoparticles-Graphene Nanocomposites for Selective Detection of Dopamine in the Presence of Ascorbic Acid and Uric Acid

PubMed Central

Zhao, Zongya; Zhang, Mingming; Chen, Xiang; Li, Youjun; Wang, Jue

2015-01-01

In this paper, AuPt bimetallic nanoparticles-graphene nanocomposites were obtained by electrochemical co-reduction of graphene oxide (GO), HAuCl4 and H2PtCl6. The as-prepared AuPt bimetallic nanoparticles-graphene nanocomposites were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and other electrochemical methods. The morphology and composition of the nanocomposite could be easily controlled by adjusting the HAuCl4/H2PtCl6 concentration ratio. The electrochemical experiments showed that when the concentration ratio of HAuCl4/H2PtCl6 was 1:1, the obtained AuPt bimetallic nanoparticles-graphene nanocomposite (denoted as Au1Pt1NPs-GR) possessed the highest electrocatalytic activity toward dopamine (DA). As such, Au1Pt1NPs-GR nanocomposites were used to detect DA in the presence of ascorbic acid (AA) and uric acid (UA) using the differential pulse voltammetry (DPV) technique and on the modified electrode, there were three separate DPV oxidation peaks with the peak potential separations of 177 mV, 130 mV and 307 mV for DA and AA, DA and UA, AA and UA, respectively. The linear range of the constructed DA sensor was from 1.6 μM to 39.7 μM with a detection limit of 0.1 μM (S/N = 3). The obtained DA sensor with good stability, high reproducibility and excellent selectivity made it possible to detect DA in human urine samples. PMID:26184200

Electrochemical Co-Reduction Synthesis of AuPt Bimetallic Nanoparticles-Graphene Nanocomposites for Selective Detection of Dopamine in the Presence of Ascorbic Acid and Uric Acid.

PubMed

Zhao, Zongya; Zhang, Mingming; Chen, Xiang; Li, Youjun; Wang, Jue

2015-07-09

In this paper, AuPt bimetallic nanoparticles-graphene nanocomposites were obtained by electrochemical co-reduction of graphene oxide (GO), HAuCl4 and H2PtCl6. The as-prepared AuPt bimetallic nanoparticles-graphene nanocomposites were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and other electrochemical methods. The morphology and composition of the nanocomposite could be easily controlled by adjusting the HAuCl4/H2PtCl6 concentration ratio. The electrochemical experiments showed that when the concentration ratio of HAuCl4/H2PtCl6 was 1:1, the obtained AuPt bimetallic nanoparticles-graphene nanocomposite (denoted as Au1Pt1NPs-GR) possessed the highest electrocatalytic activity toward dopamine (DA). As such, Au1Pt1NPs-GR nanocomposites were used to detect DA in the presence of ascorbic acid (AA) and uric acid (UA) using the differential pulse voltammetry (DPV) technique and on the modified electrode, there were three separate DPV oxidation peaks with the peak potential separations of 177 mV, 130 mV and 307 mV for DA and AA, DA and UA, AA and UA, respectively. The linear range of the constructed DA sensor was from 1.6 μM to 39.7 μM with a detection limit of 0.1 μM (S/N = 3). The obtained DA sensor with good stability, high reproducibility and excellent selectivity made it possible to detect DA in human urine samples.

Synthesis and comparative photocatalytic activity of Pt/WO 3 and Au/WO 3 nanocomposites under sunlight-type excitation

NASA Astrophysics Data System (ADS)

Qamar, M.; Yamani, Z. H.; Gondal, M. A.; Alhooshani, K.

2011-09-01

The article deals with the synthesis of highly active visible-light-driven nanocomposite for the decontamination of water hazards under sunlight-type excitation. The surface of visible-light-active nanostructured photocatalyst tungsten oxide (WO 3) was modified with noble metals, such as platinum (Pt) and gold (Au) nanoparticles, and the resulting photocatalytic activity of the nanocomposites was investigated by studying the removal of Methyl Orange and 2,4-Dichlorophenoxyacetic acid (2,4-D) under sunlight-type excitation. The study revealed that the deposited noble metals are not always favorable for the enhancement of photocatalytic response of catalysts; the activity of WO 3 was enhanced manyfold (˜8 times) by depositing an optimum amount of Pt nanoparticles after certain photodeposition time whereas the presence of Au nanoparticles onto the WO 3 surface, under identical experimental conditions, affected the removal process negatively. The variation in the photocatalytic activity of nanocomposites was attributed to the size of the deposited metals; Pt nanoparticles were uniformly dispersed with narrow size distribution (2-4 nm) while the size distribution of Au nanoparticles was found to be 10-15 nm for similar preparation conditions. The effects of critical parameters, such as metal deposition time and metal contents, on the photocatalytic activity of WO 3 were investigated. Furthermore, Pt/WO 3 nanocomposites showed good stability and recyclability under the conditions studied.

An Investigation of Methyl Viologen Functionalized Reduced Graphene Oxide: Chitosan as a Support for Pt Nanoparticles Towards Ethanol Electrooxidation

NASA Astrophysics Data System (ADS)

Ekrami-Kakhki, Mehri-Saddat; Farzaneh, Nahid; Abbasi, Sedigheh; Beitollahi, Hadi; Ekrami-Kakhki, Seyed Ali

2018-05-01

In this research, graphene oxide was prepared by a modified Hummers' method, and then functionalized with 1, 1'-dimethyl-4, 4'-bipyridinium dichloride (MV), and chitosan (CH) to get a MV-RGO-CH support. Pt nanoparticles were prepared on this support to get Pt/MV-RGO-CH catalyst. The morphology and microstructure of Pt/MV-RGO-CH catalyst were characterized with transmission electron microscopy image and X-ray diffraction analysis. The electrocatalytic activity of the prepared catalyst towards ethanol oxidation was investigated by carbon monoxide stripping voltammetry, cyclic voltammetry, and electrochemical impedance spectroscopy techniques. The effects of some experimental parameters such as scan rate, ethanol concentration, and temperature were investigated for ethanol electrooxidation at Pt/MV-RGO-CH catalyst. Durability of the catalyst was also investigated. The electrocatalytic performance of Pt/MV-RGO-CH catalyst for ethanol oxidation was compared with those of Pt/CH and Pt/MV-RGO catalysts. The higher electrocatalytic performance of Pt/MV-RGO-CH than Pt/CH and Pt/MV-RGO catalysts towards ethanol electrooxidation indicated that Pt/MV-RGO-CH could be a promising catalyst for application in direct ethanol fuel cells.

Mesoporous Aluminosilicate Catalysts for the Selective Isomerization of n-Hexane: The Roles of Surface Acidity and Platinum Metal.

PubMed

Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2015-08-19

Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brönsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed.

Colorimetric assay of heparin in plasma based on the inhibition of oxidase-like activity of citrate-capped platinum nanoparticles.

PubMed

You, Jyun-Guo; Liu, Yao-Wen; Lu, Chi-Yu; Tseng, Wei-Lung; Yu, Cheng-Ju

2017-06-15

We report citrate-capped platinum nanoparticles (Pt NPs) as oxidase mimetics for effectively catalyzing the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB), 2,2'-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid), dopamine, and methylene blue in the presence of O 2 . To confirm oxidase-like activity of citrate-capped Pt NPs, their activity toward oxygen reduction reaction was studied using cyclic voltammetry and rotating ring-disk electrode method. The results obtained showed that Pt NP NPs can catalyze the oxidation of organic substrates to the colored product and the reduction of oxygen to water through a four-electron exchange process. Because the aggregation of Pt NPs can inhibit their oxidase-like activity and protamine can recognize heparin, we prepared the protamine-modified Pt NPs through direct adsorption on the surface of citrate-capped Pt NPs. The electrostatic attraction between heparin and protamine-stabilized Pt NPs induced nanoparticle aggregation, inhibiting their catalytic activity. Therefore, the lowest detectable heparin concentrations through UV-vis absorption and by the naked eye were estimated to be 0.3 and 60nM, respectively. Moreover, the proposed system enabled the determination of the therapeutic heparin concentration in a single drop of blood. Copyright © 2016 Elsevier B.V. All rights reserved.

Fabrication of aligned magnetic nanoparticles using tobamoviruses.

PubMed

Kobayashi, Mime; Seki, Munetoshi; Tabata, Hitoshi; Watanabe, Yuichiro; Yamashita, Ichiro

2010-03-10

We used genetically modified tube-shaped tobamoviruses to produce 3 nm aligned magnetic nanoparticles. Amino acid residues facing the central channel of the virus were modified to increase the number of nucleation sites. Energy dispersive X-ray spectroscopy and superconducting quantum interference device analysis suggest that the particles consisted of Co-Pt alloy. The use of tobamovirus mutants is a promising approach to making a variety of components that can be applied to fabricate nanometer-scaled electronic devices.

Citric acid functionalized carbon materials for fuel cell applications

NASA Astrophysics Data System (ADS)

Poh, Chee Kok; Lim, San Hua; Pan, Hui; Lin, Jianyi; Lee, Jim Yang

Carbon materials can be easily functionalized using citric acid (CA) treatment. The CA modification of carbon materials is both simple and effective. It requires no prolonged heating, filtration and washing, and produces more functional groups such as carboxyl and hydroxide on CA-modified carbon nanotubes and XC72 carbon blacks than on HNO 3-H 2SO 4 oxidized carbon nanotubes and as-purchased XC72. Platinum nanoparticles are deposited on these functionalized carbon materials by means of a microwave-assisted polyol process. The investigations using TEM, XRD, FTIR and TGA indicate that CA modification creates more functional groups and thus deposits more Pt nanoparticles with smaller average particle size on the surface of carbon materials. Electrochemical studies of the Pt/C samples for methanol oxidation reveal higher activity for Pt on CA-modified carbon materials. It is therefore considered that this method can find important applications in reducing the cost and improving performance of proton-exchange membrane fuel cells.

Plasma modified nanofibres based on gum kondagogu and their use for collection of nanoparticulate silver, gold and platinum.

PubMed

Padil, Vinod Vellora Thekkae; Stuchlík, Martin; Černík, Miroslav

2015-05-05

Electrospun nanofibre membranes from blend solutions of deacetylated gum kondagogu and polyvinyl alcohol of various weight proportions were prepared. The electrospun membrane was cross linked by heating at 150°C for 6h and later modified by methane plasma treatment. Membranes were successively used for the removal of nanoparticles (Ag, Au and Pt) from water. Pt nanoparticles with the smallest size (2.4 ± 0.7 nm) has a higher adsorption capacity (270.4 mg/g and 327.2mg/g) compared to Au and Ag nanoparticles with particle sizes 7.8 ± 2.3 nm and 10.5 ± 3.5 nm onto nanofibre membrane (NFM) and methane plasma treated membrane (P-NFM). The extraction efficiency of P-NFM for the removal of nanoparticles in water is higher compared to untreated membranes. The adsorption kinetics were evaluated by pseudo-first order and pseudo-second order models for the extraction of nanoparticles from water, with the pseudo-second order model providing a better fit. The reusability and regeneration of the P-NFM for consecutive adsorption was also established. Copyright © 2015 Elsevier Ltd. All rights reserved.

Platinum and palladium nano-structured catalysts for polymer electrolyte fuel cells and direct methanol fuel cells.

PubMed

Long, Nguyen Viet; Thi, Cao Minh; Yong, Yang; Nogami, Masayuki; Ohtaki, Michitaka

2013-07-01

In this review, we present the synthesis and characterization of Pt, Pd, Pt based bimetallic and multi-metallic nanoparticles with mixture, alloy and core-shell structure for nano-catalysis, energy conversion, and fuel cells. Here, Pt and Pd nanoparticles with modified nanostructures can be controllably synthesized via chemistry and physics for their uses as electro-catalysts. The cheap base metal catalysts can be studied in the relationship of crystal structure, size, morphology, shape, and composition for new catalysts with low cost. Thus, Pt based alloy and core-shell catalysts can be prepared with the thin Pt and Pt-Pd shell, which are proposed in low and high temperature proton exchange membrane fuel cells (PEMFCs), and direct methanol fuel cells (DMFCs). We also present the survey of the preparation of Pt and Pd based catalysts for the better catalytic activity, high durability, and stability. The structural transformations, quantum-size effects, and characterization of Pt and Pd based catalysts in the size ranges of 30 nm (1-30 nm) are presented in electro-catalysis. In the size range of 10 nm (1-10 nm), the pure Pt catalyst shows very large surface area for electro-catalysis. To achieve homogeneous size distribution, the shaped synthesis of the polyhedral Pt nanoparticles is presented. The new concept of shaping specific shapes and morphologies in the entire nano-scale from nano to micro, such as polyhedral, cube, octahedra, tetrahedra, bar, rod, and others of the nanoparticles is proposed, especially for noble and cheap metals. The uniform Pt based nanosystems of surface structure, internal structure, shape, and morphology in the nanosized ranges are very crucial to next fuel cells. Finally, the modifications of Pt and Pd based catalysts of alloy, core-shell, and mixture structures lead to find high catalytic activity, durability, and stability for nano-catalysis, energy conversion, fuel cells, especially the next large-scale commercialization of next PEMFCs, and DMFCs.

Catalytic activity of platinum on ruthenium electrodes with modified (electro)chemical states.

PubMed

Park, Kyung-Won; Sung, Yung-Eun

2005-07-21

Using Pt on Ru thin-film electrodes with various (electro)chemical states designed by the sputtering method, the effect of Ru states on the catalytic activity of Pt was investigated. The chemical and electrochemical properties of Pt/Ru thin-film samples were confirmed by X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry. In addition, Pt nanoparticles on Ru metal or oxide for an actual fuel cell system showed an effect of Ru states on the catalytic activity of Pt in methanol electrooxidation. Finally, it was concluded that such an enhancement of methanol electrooxidation on the Pt is responsible for Ru metallic and/or oxidation sites compared to pure Pt without any Ru state.

Novel synthesis of highly durable and active Pt catalyst encapsulated in nitrogen containing carbon for polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Lee, Hyunjoon; Sung, Yung-Eun; Choi, Insoo; Lim, Taeho; Kwon, Oh Joong

2017-09-01

Novel synthesis of a Pt catalyst encapsulated in a N-containing carbon layer for use in a polymer electrolyte membrane fuel cell is described in this study. A Pt-aniline complex, formed by mixing Pt precursor and aniline monomer, was used as the source of Pt, C, and N. Heat treatment of the Pt-aniline complex with carbon black yielded 5 nm Pt nanoparticles encapsulated by a N-containing carbon layer originating from aniline carbonization. The synthesized Pt catalyst exhibited higher mass specific activity to oxygen reduction reaction than that shown by conventional Pt/C catalyst because pyridinic N with graphitic carbon in the carbon layer provided active sites for oxygen reduction reaction in addition to those provided by Pt. In single cell testing, initial performance of the synthesized catalyst was limited because the thick catalyst layer increased resistance related to mass transfer. However, it was observed that the carbon layer successfully prevented Pt nanoparticles from growing via agglomeration and Ostwald ripening under fuel cell operation, thereby improving durability. Furthermore, a mass specific performance of the synthesized catalyst higher than that of a conventional Pt/C catalyst was achieved by modifying the synthesized catalyst's layer thickness.

Fabrication of Highly Sensitive Nonenzymatic Electrochemical H₂O₂ Sensor Based on Pt Nanoparticles Anchored Reduced Graphene Oxide.

PubMed

Dhara, Keerthy; Ramachandran, T; Nair, Bipin G; Babu, T G Satheesh

2018-06-01

A highly sensitive nonenzymatic hydrogen peroxide (H2O2) sensor was fabricated using platinum nanoparticles decorated reduced graphene oxide (Pt/rGO) nanocomposite. The Pt/rGO nanocomposite was prepared by single-step chemical reduction method. Nanocomposite was characterized by various analytical techniques including Raman spectroscopy, X-ray diffraction, field emission scanning electron microscope and high-resolution transmission electron microscopy. Screen printed electrodes (SPEs) were fabricated and the nanocomposite was cast on the working area of the SPE. Cyclic voltammetry and amperometry demonstrated that the Pt/rGO/SPE displayed much higher electrocatalytic activity towards the reduction of H2O2 than the other modified electrodes. The sensor exhibited wide linear detection range (from 10 μM to 8 mM), very high sensitivity of 1848 μA mM-1 cm-2 and a lower limit of detection of 0.06 μM. The excellent performance of Pt/rGO/SPE sensor were attributed to the reduced graphene oxide being used as an effective matrix to load a number of Pt nanoparticles and the synergistic amplification effect of the two kinds of nanomaterials. Moreover, the sensor showed remarkable features such as good reproducibility, repeatability, long-term stability, and selectivity.

Preparation of carbon paste electrodes including poly(styrene) attached glycine-Pt(IV) for amperometric detection of glucose.

PubMed

Dönmez, Soner; Arslan, Fatma; Sarı, Nurşen; Kurnaz Yetim, Nurdan; Arslan, Halit

2014-04-15

In this study, a novel carbon paste electrode that is sensitive to glucose was prepared using the nanoparticles modified (4-Formyl-3-methoxyphenoxymethyl) with polystyren (FMPS) with L-Glycine-Pt(IV) complexes. Polymeric nanoparticles having Pt(IV) ion were prepared from (4-Formyl-3-methoxyphenoxymethyl) polystyren, glycine and PtCl4 by template method. Glucose oxidase enzyme was immobilized to a modified carbon paste electrode (MCPE) by cross-linking with glutaraldehyde. Determination of glucose was carried out by oxidation of enzymatically produced H2O2 at 0.5 V vs. Ag/AgCl. Effects of pH and temperature were investigated, and optimum parameters were found to be 8.0 and 55°C, respectively. Linear working range of the electrode was 5.0×10(-6)-1.0×10(-3) M, R(2)=0.997. Storage stability and operational stability of the enzyme electrode were also studied. Glucose biosensor gave perfect reproducible results after 10 measurements with 2.3% relative standard deviation. Also, it had good storage stability (gave 53.57% of the initial amperometric response at the end of 33th day). © 2013 Published by Elsevier B.V.

Modified WO3 nanorod with Pt nanoparticle as retrievable materials in catalytic and photocatalytic aerobic oxidation of alcohols

NASA Astrophysics Data System (ADS)

Hosseini, Farnaz; Safaei, Elham; Mohebbi, Sajjad

2017-07-01

This study has focused on catalytic and photocatalytic oxidation of aromatic alcohols using WO3 nanorod and a series of Pt/WO3 nanocomposite Pt nanoparticles was loaded on WO3 nanorod with several mass ratios 0.1, 0.2, and 0.3 via a photoreduction process (PRP) and characterized by TEM, FE-SEM imaging, EDAX, XRD, DRS, ICP, and XPS. WO3 nanorods were obtained monodispersed with average 40-nm diameter and square cross section without significant size change by the loading of platinum nanoparticles on it. Progress of oxidation reaction was monitored by GC and the yield of aerobic photocatalytic oxidation of alcohols reached up to 98% for Pt/WO3 and 69% for WO3 while, no oxidation was detected in the absence of light. The highest photocatalytic performance was obtained for mass ratio 0.2 with the selectivity >99%. So, this nanocomposite has potentials to be used as high-performance heterogeneous catalyst and photocatalyst under visible light irradiation with advantages of high activity, high selectivity, and reusability.

Preparation of platinum modified titanium dioxide nanoparticles with the use of laser ablation in water.

PubMed

Siuzdak, K; Sawczak, M; Klein, M; Nowaczyk, G; Jurga, S; Cenian, A

2014-08-07

We report on the preparation method of nanocrystalline titanium dioxide modified with platinum by using nanosecond laser ablation in liquid (LAL). Titania in the form of anatase crystals has been prepared in a two-stage process. Initially, irradiation by laser beam of a titanium metal plate fixed in a glass container filled with deionized water was conducted. After that, the ablation process was continued, with the use of a platinum target placed in a freshly obtained titania colloid. In this work, characterization of the obtained nanoparticles, based on spectroscopic techniques--Raman, X-ray photoelectron and UV-vis reflectance spectroscopy--is given. High resolution transmission electron microscopy was used to describe particle morphology. On the basis of photocatalytic studies we observed the rate of degradation process of methylene blue (MB) (a model organic pollution) in the presence of Pt modified titania in comparison to pure TiO2--as a reference case. Physical and chemical mechanisms of the formation of platinum modified titania are also discussed here. Stable colloidal suspensions containing Pt modified titanium dioxide crystalline anatase particles show an almost perfect spherical shape with diameters ranging from 5 to 30 nm. The TiO2 nanoparticles decorated with platinum exhibit much higher (up to 30%) photocatalytic activity towards the degradation of MB under UV illumination than pure titania.

Facile and one-pot synthesis of uniform PtRu nanoparticles on polydopamine-modified multiwalled carbon nanotubes for direct methanol fuel cell application.

PubMed

Chen, Fengxia; Ren, Junkai; He, Qian; Liu, Jun; Song, Rui

2017-07-01

A facile, environment-friendly and one-pot synthesis method for the preparation of high performance PtRu electrocatalysts on the multiwalled carbon nanotubes (MWCNTs) is reported. Herein, bimetallic PtRu electrocatalysts are deposited onto polydopamine (Pdop) - functionalized MWCNTs by mildly stirring at room temperature. Without the use of expensive chemicals or corrosive acids, this noncovalent functionalization of MWCNTs by Pdop is simple, facile and eco-friendly, and thus preserving the integrity and electronic structure of MWCNTs. Due to the well improved dispersion and the decreased size of alloy nanoparticles, the PtRu electrocatalysts on Pdop-functionalized MWCNTs show much better dispersion, higher electrochemically active surface area, and higher electrocatalytic activity for the electrooxidation of methanol in direct methanol fuel cells, compared with the conventional acid-treated MWCNTs. Copyright © 2017 Elsevier Inc. All rights reserved.

Enhancement of catalytic activity of platinum-based nanoparticles towards electrooxidation of ethanol through interfacial modification with heteropolymolybdates

NASA Astrophysics Data System (ADS)

Barczuk, Piotr J.; Lewera, Adam; Miecznikowski, Krzysztof; Zurowski, Artur; Kulesza, Pawel J.

As evidenced from the increase of electrocatalytic currents measured under voltammetric and chronoamperometric conditions, the activity of bimetallic Pt-Ru and Pt-Sn nanoparticles towards oxidation of ethanol is increased by modification of their surfaces with ultra-thin films of phosphododecamolybdic acid (H 3PMo 12O 40). The enhancement effect has been most pronounced in a case of heteropolymolybdate-modified carbon-supported Pt-Sn catalysts. Independent high-resolution XPS measurements indicate the ability of heteropolymolybdates to stabilize tin (in bimetallic Pt-Sn particles) at higher oxidation states (presumably as tin oxo species). The overall activation effect may also be ascribed to changes in the morphology of catalytic films following modification with heteropolymolybdates. Presence of the polyoxometallate is also likely to increase of the interfacial population of reactive oxo groups in the vicinity of platinum centers.

Preparation of ternary Pt/Rh/SnO2 anode catalysts for use in direct ethanol fuel cells and their electrocatalytic activity for ethanol oxidation reaction

NASA Astrophysics Data System (ADS)

Higuchi, Eiji; Takase, Tomonori; Chiku, Masanobu; Inoue, Hiroshi

2014-10-01

Pt, Rh and SnO2 nanoparticle-loaded carbon black (Pt/Rh/SnO2/CB) catalysts with different contents of Pt and Rh were prepared by the modified Bönnemann method. The mean size and size distribution of Pt, Rh and SnO2 for Pt-71/Rh-4/SnO2/CB (Pt : Rh : Sn = 71 at.%: 4 at.%: 25 at.%) were 3.8 ± 0.7, 3.2 ± 0.7 and 2.6 ± 0.5 nm, respectively, indicating that Pt, Rh and SnO2 were all nanoparticles. The onset potential of ethanol oxidation current for the Pt-65/Rh-10/SnO2/CB and Pt-56/Rh-19/SnO2/CB electrodes was ca. 0.2 V vs. RHE which was ca. 0.2 V less positive than that for the Pt/CB electrode. The oxidation current at 0.6 V for the Pt/Rh/SnO2/CB electrode (ca. 2% h-1) decayed more slowly than that at the Pt/SnO2/CB electrode (ca. 5% h-1), indicating that the former was superior in durability to the latter. The main product of EOR in potentiostatic electrolysis at 0.6 V for the Pt-71/Rh-4/SnO2/CB electrode was acetic acid.

Gelatin-encapsulated iron oxide nanoparticles for platinum (IV) prodrug delivery, enzyme-stimulated release and MRI.

PubMed

Cheng, Ziyong; Dai, Yunlu; Kang, Xiaojiao; Li, Chunxia; Huang, Shanshan; Lian, Hongzhou; Hou, Zhiyao; Ma, Pingan; Lin, Jun

2014-08-01

A facile method for transferring hydrophobic iron oxide nanoparticles (IONPs) from chloroform to aqueous solution via encapsulation of FITC-modified gelatin based on the hydrophobic-hydrophobic interaction is described in this report. Due to the existence of large amount of active groups such as amine groups in gelatin, the fluorescent labeling molecules of fluorescein isothiocyanate (FITC) and platinum (IV) prodrug functionalized with carboxylic groups can be conveniently conjugated on the IONPs. The nanoparticles carrying Pt(IV) prodrug exhibit good anticancer activities when the Pt(IV) complexes are reduced to Pt(II) in the intracellular environment, while the pure Pt(IV) prodrug only presents lower cytotoxicity on cancer cells. Meanwhile, fluorescence of FITC on the surface of nanoparticles was completely quenched due to the possible Förster Resonance Energy Transfer (FRET) mechanism and showed a fluorescence recovery after gelatin release and detachment from IONPs. Therefore FITC as a fluorescence probe can be used for identification, tracking and monitoring the drug release. In addition, adding pancreatic enzyme can effectively promote the gelatin release from IONPs owing to the degradation of gelatin. Noticeable darkening in magnetic resonance image (MRI) was observed at the tumor site after in situ injection of nanoparticles, indicating the IONPs-enhanced T2-weighted imaging. Our results suggest that the gelatin encapsulated Fe3O4 nanoparticles have potential applications in multi-functional drug delivery system for disease therapy, MR imaging and fluorescence sensor. Copyright © 2014 Elsevier Ltd. All rights reserved.

Characterization and bacterial anti-adherent effect on modified PMMA denture acrylic resin containing platinum nanoparticles

PubMed Central

2014-01-01

PURPOSE This study characterized the synthesis of a modified PMMA (Polymethyl methacrylate) denture acrylic loading platinum nanoparticles (PtN) and assessed its bacterial inhibitory efficacy to produce novel antimicrobial denture base material. MATERIALS AND METHODS Polymerized PMMA denture acrylic disc (20 mm × 2 mm) specimens containing 0 (control), 10, 50, 100 and 200 mg/L of PtN were fabricated respectively. The obtained platinum-PMMA nanocomposite (PtNC) was characterized by TEM (transmission electron microscopy), SEM/EDX (scanning electron microscope/energy dispersive X-ray spectroscopy), thermogravimetric and atomic absorption spectrophotometer analysis. In antimicrobial assay, specimens were placed on the cell culture plate, and 100 µL of microbial suspensions of S. mutans (Streptococcus mutans) and S. sobrinus (Streptococcus sobrinus) were inoculated then incubated at 37℃ for 24 hours. The bacterial attachment was tested by FACS (fluorescence-activated cell sorting) analysis after staining with fluorescent probe. RESULTS PtN were successfully loaded and uniformly immobilized into PMMA denture acrylic with a proper thermal stability and similar surface morphology as compared to control. PtNC expressed significant bacterial anti-adherent effect rather than bactericidal effect above 50 mg/L PtN loaded when compared to pristine PMMA (P=.01) with no or extremely small amounts of Pt ion eluted. CONCLUSION This is the first report on the synthesis and its antibacterial activity of Pt-PMMA nanocomposite. PMMA denture acrylic loading PtN could be a possible intrinsic antimicrobial denture material with proper mechanical characteristics, meeting those specified for denture bases. For clinical application, future studies including biocompatibility, color stability and warranting the long-term effect were still required. PMID:25006385

Platinum and Palladium Overlayers Dramatically Enhance the Activity of Ruthenium Nanotubes for Alkaline Hydrogen Oxidation

DOE PAGES

St. John, Samuel; Atkinson, Robert W.; Unocic, Kinga A.; ...

2015-10-18

Templated vapor synthesis and thermal annealing were used to synthesize unsupported metallic Ru nanotubes with Pt or Pd overlayers. By controlling the elemental composition and thickness of these overlayers, we obtain nanostructures with very high alkaline hydrogen oxidation activity. For nanotubes with a nominal atomic composition of Ru 0.90Pt 0.10 display a surface-specific activity (2.4 mA/cm 2) that is 35 times greater than that of pure Ru nanotubes at a 50 mV overpotential and 2.5 times greater than that of pure Pt nanotubes (0.98 mA/cm 2). The surface-segregated structure also confers dramatically increased Pt utilization efficiency. We find a platinum-mass-specificmore » activity of 1240 A/gPt for the optimized nanotube versus 280 A/gPt for carbon-supported Pt nanoparticles and 109 A/gPt for monometallic Pt nanotubes. Here, we attribute the enhancement of both area- and platinum-mass-specific activity to the atomic-scale homeomorphism of the nanotube form factor with adlayer-modified polycrystals. Subsurface ligand and bifunctional effects previously observed on segregated, adlayer-modified polycrystals are translated to nanoscale catalysts.« less

Probing the formation mechanism and chemical states of carbon-supported Pt-Ru nanoparticles by in situ X-ray absorption spectroscopy.

PubMed

Hwang, Bing Joe; Chen, Ching-Hsiang; Sarma, Loka Subramanyam; Chen, Jiun-Ming; Wang, Guo-Rung; Tang, Mau-Tsu; Liu, Din-Goa; Lee, Jyh-Fu

2006-04-06

The understanding of the formation mechanism of nanoparticles is essential for the successful particle design and scaling-up process. This paper reports findings of an X-ray absorption spectroscopy (XAS) investigation, comprised of X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions, to understand the mechanism of the carbon-supported Pt-Ru nanoparticles (NPs) formation process. We have utilized Watanabe's colloidal reduction method to synthesize Pt-Ru/C NPs. We slightly modified the Watanabe method by introducing a mixing and heat treatment step of Pt and Ru oxidic species at 100 degrees C for 8 h with a view to enhance the mixing efficiency of the precursor species, thereby one can achieve improved homogeneity and atomic distribution in the resultant Pt-Ru/C NPs. During the reduction process, in situ XAS measurements allowed us to follow the evolution of Pt and Ru environments and their chemical states. The Pt LIII-edge XAS indicates that when H2PtCl6 is treated with NaHSO3, the platinum compound is found to be reduced to a Pt(II) form corresponding to the anionic complex [Pt(SO3)4]6-. Further oxidation of this anionic complex with hydrogen peroxide forms dispersed [Pt(OH)6]2- species. Analysis of Ru K-edge XAS results confirms the reduction of RuIIICl3 to [RuII(OH)4]2- species upon addition of NaHSO3. Addition of hydrogen peroxide to [RuII(OH)4]2- causes dehydrogenation and forms RuOx species. Mixing of [Pt(OH)6]2- and RuOx species and heat treatment at 100 degrees C for 8 h produced a colloidal sol containing both Pt and Ru metallic as well as ionic contributions. The reduction of this colloidal mixture at 300 degrees C in hydrogen atmosphere for 2 h forms Pt-Ru nanoparticles as indicated by the presence of Pt and Ru atoms in the first coordination shell. Determination of the alloying extent or atomic distribution of Pt and Ru atoms in the resulting Pt-Ru/C NPs reveals that the alloying extent of Ru (JRu) is greater than that of the alloying extent of Pt (JPt). The XAS results support the Pt-rich core and Ru-rich shell structure with a considerable amount of segregation in the Pt region and with less segregation in the Ru region for the obtained Pt-Ru/C NPs.

To alloy or not to alloy? Cr modified Pt/C cathode catalysts for PEM fuel cells.

PubMed

Wells, Peter P; Qian, Yangdong; King, Colin R; Wiltshire, Richard J K; Crabb, Eleanor M; Smart, Lesley E; Thompsett, David; Russell, Andrea E

2008-01-01

The cathode electrocatalysts for proton exchange membrane (PEM) fuel cells are commonly platinum and platinum based alloy nanoparticles dispersed on a carbon support. Control over the particle size and composition has, historically, been attained empirically, making systematic studies of the effects of various structural parameters difficult. The controlled surface modification methodology used in this work has enabled the controlled modification of carbon supported Pt nanoparticles by Cr so as to yield nanoalloy particles with defined compositions. Subsequent heat treatment in 5% H2 in N2 resulted in the formation of a distinct Pt3Cr alloy phase which was either restricted to the surface of the particles or present throughout the bulk of the particle structure. Measurement of the oxygen reduction activity of the catalysts was accomplished using the rotating thin film electrode method and the activities obtained were related to the structure of the nanoalloy catalyst particles, largely determined using Cr K edge and Pt L3 edge XAS.

Shape-dependent surface magnetism of Co-Pt and Fe-Pt nanoparticles from first principles

NASA Astrophysics Data System (ADS)

Liu, Zhenyu; Wang, Guofeng

2017-12-01

In this paper, we have performed the first-principles density functional theory calculations to predict the magnetic properties of the CoPt and FePt nanoparticles in cuboctahedral, decahedral, and icosahedral shapes. The modeled alloy nanoparticles have a diameter of 1.1 nm and consist of 31 5 d Pt atoms and 24 3 d Co (or Fe) atoms. For both CoPt and FePt, we found that the decahedral nanoparticles had appreciably lower surface magnetic moments than the cuboctahedral and icosahedral nanoparticles. Our analysis indicated that this reduction in the surface magnetism was related to a large contraction of atomic spacing and high local Co (or Fe) concentration in the surface of the decahedral nanoparticles. More interestingly, we predicted that the CoPt and FePt cuboctahedral nanoparticles exhibited dramatically different surface spin structures when noncollinear magnetism was taken into account. Our calculation results revealed that surface anisotropy energy decided the fashion of surface spin canting in the CoPt and FePt nanoparticles, confirming previous predictions from atomistic Monte Carlo simulations.

Elastomeric nanoparticle composites covalently bound to Al2O3/GaAs surfaces.

PubMed

Song, Hyon Min; Ye, Peide D; Ivanisevic, Albena

2007-08-28

This article reports the modification of Al2O3/GaAs surfaces with multifunctional soft materials. Siloxane elastomers were covalently bound to dopamine-modified Al2O3/GaAs semiconductor surfaces using MPt (M = Fe, Ni) nanoparticles. The sizes of the monodisperse FePt and NiPt nanoparticles were less than 5 nm. The surfaces of the nanoparticles as well as the Al2O3/GaAs substrates were modified with allyl-functionalized dopamine that utilized a dihydroxy group as a strong ligand. The immobilization of the elastomers was performed via a hydrosilation reaction of the allyl-functionalized dopamines with the siloxane backbones. X-ray photoelectron spectroscopy (XPS) experiments confirmed the covalent bonding of the siloxane elastomers to the oxide layer on the semiconductor surface. Fourier transform-infrared reflection absorption spectroscopy (FT-IRRAS) measurements revealed that the allyl functional groups are bonded to the siloxane backbones. The FT-IRRAS data also showed that the density of the allyl groups on the surface was lower than that of the siloxane backbones. The mechanical properties of the surface-bound nanocomposites were tested using nanoindentation experiments. The nanoindentation data showed that the soft matrix composed of the elastomeric coating on the surfaces behaves differently from the inner, hard Al2O3/GaAs substrate.

Hybrid nanocatalysts containing enzymes and metallic nanoparticles for ethanol/O2 biofuel cell

NASA Astrophysics Data System (ADS)

Aquino Neto, S.; Almeida, T. S.; Palma, L. M.; Minteer, S. D.; de Andrade, A. R.

2014-08-01

We report the preparation of hybrid nanostructured bioanodes containing the enzyme alcohol dehydrogenase (ADH) with either Au, Pt, or Pt0.75Sn0.25 nanoparticles for use in ethanol/O2 hybrid biofuel cells. We describe two different methodologies for the preparation of the bioanodes: in a first case, multi walled carbon nanotubes (MWCNTs) were employed as a support for the metallic nanoparticles and TBAB-modified Nafion® aided enzyme immobilization. In the second case, we immobilized the enzymes using dendrimers-encapsulated nanoparticles as the agent for enzyme anchoring. The biofuel cell tests showed that the addition of metallic nanoparticles to the bioanode structure enhanced the overall biofuel cell performance. The bioelectrode containing Au nanoparticles displaying the best performance, with an open circuit potential of 0.61 ± 0.05 V and a maximum power density of 155 ± 11 μW cm-2. NADH cyclic voltammetric experiments indicated that Au nanoparticles behaved as a catalyst toward NADH oxidation. Comparing the two protocols we used to synthetized nanoparticles, the sample containing the Au nanoparticles supported on MWCNTs furnished fourfold higher values. Therefore, from the satisfactory results obtained, it can be inferred that the combination of small amounts of metallic nanoparticles with enzymes improve bioanode performance.

Fuel blends: Enhanced electro-oxidation of formic acid in its blend with methanol at platinum nanoparticles modified glassy carbon electrodes

NASA Astrophysics Data System (ADS)

El-Deab, Mohamed S.; El-Nagar, Gumaa A.; Mohammad, Ahmad M.; El-Anadouli, Bahgat E.

2015-07-01

The current study addresses, for the first time, the enhanced direct electro-oxidation of formic acid (FA) at platinum-nanoparticles modified glassy carbon (nano-Pt/GC) electrode in the presence of methanol (MeOH) as a blending fuel. This enhancement is probed by: (i) the increase of the direct oxidation current of FA to CO2 (Ipd, dehydrogenation pathway), (ii) suppressing the dehydration pathway (Ipind, producing the poisoning intermediate CO) and (iii) a favorable negative shift of the onset potential of Ipd with increasing the mole fraction of MeOH in the blend. Furthermore, the charge of the direct FA oxidation in 0.3 M FA + 0.3 M MeOH blend is by 14 and 21times higher than that observed for 0.3 M FA and 0.3 M MeOH, respectively. MeOH is believed to adsorb at the Pt surface sites and thus disfavor the "non-faradaic" dissociation of FA (which produces the poisoning CO intermediate), i.e., MeOH induces a high CO tolerance of the Pt catalyst. The enhanced oxidation activity indicates that FA/MeOH blend is a promising fuel system.

Polyamidoamine dendrimers-assisted electrodeposition of gold-platinum bimetallic nanoflowers.

PubMed

Qian, Lei; Yang, Xiurong

2006-08-24

Novel Au-Pt bimetallic flower nanostructures fabricated on a polyamidoamine dendrimers-modified surface by electrodeposition are reported. These polyamidoamine dendrimers were stable, and they assisted the formation of Au-Pt bimetallic nanoflowers during the electrodeposition process. These nanoflowers were characterized by field-emitted scanning electron microscopy (FE-SEM), energy-dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction, and electrochemical methods. FE-SEM images showed that the bimetallic nanoflower included two parts: the "light" and the "pale" part. The two parts consisted of many small bimetallic nanoparticles, which was attributed to the progressive nucleation process. Moreover, the "light" part contained more bimetallic nanoparticles. The morphologies of bimetallic nanoflowers depended on the electrodeposition time and potential and the layer number of assembled dendrimers. The average size of nanoflowers increased with the increase in electrodeposition time. The layer number of assembled dendrimers obviously affected the size and morphologies of the "pale" parts of deposited nanoflowers. EDS and XPS indicated that the content of Au element was higher than that of Pt element in the nanoflowers. The bimetallic nanoflowers-modified electrode had electrochemical properties similar to those of bare gold and platinum electrodes. It also exhibited significant electrocatalytic activities toward oxygen reduction.

Structural evolution and mechanical behaviour of Pt nanoparticle superlattices at high pressure

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

Zhu, Jinlong; Quan, Zewei; Wang, Chenyu

High pressure is an effective means for tuning the interparticle distances of nanoparticle (NP) superlattice and thus for modifying their physical properties and functionalities. In this work, we determined the evolutio of inter-NP distances of a Pt NP superlattice with increasing pressure using an in situ synchrotro small-angle X-ray scattering (SAXS) technique in a diamond-anvil cell (DAC). Transmission electro microscopy (TEM) was used to characterize the microstructures of pre- and post-compression samples Our results demonstrate that the evolution of Pt NP assemblies with increasing pressure consists of fou stages: (1) ligand elastic response, (2) uniform compression, (3) ligand detachment frommore » NP surfaces, an (4) deviatoric compression of ligands between neighboring NPs. Lastly, by controlling the magnitudes of applie pressure and deviatoric stress, one can sinter NPs into novel architectures such as nanowires an nanoceramics.« less

Structural evolution and mechanical behaviour of Pt nanoparticle superlattices at high pressure

DOE PAGES

Zhu, Jinlong; Quan, Zewei; Wang, Chenyu; ...

2016-02-05

High pressure is an effective means for tuning the interparticle distances of nanoparticle (NP) superlattice and thus for modifying their physical properties and functionalities. In this work, we determined the evolutio of inter-NP distances of a Pt NP superlattice with increasing pressure using an in situ synchrotro small-angle X-ray scattering (SAXS) technique in a diamond-anvil cell (DAC). Transmission electro microscopy (TEM) was used to characterize the microstructures of pre- and post-compression samples Our results demonstrate that the evolution of Pt NP assemblies with increasing pressure consists of fou stages: (1) ligand elastic response, (2) uniform compression, (3) ligand detachment frommore » NP surfaces, an (4) deviatoric compression of ligands between neighboring NPs. Lastly, by controlling the magnitudes of applie pressure and deviatoric stress, one can sinter NPs into novel architectures such as nanowires an nanoceramics.« less

Synthesis and hydrogenation application of Pt-Pd bimetallic nanocatalysts stabilized by macrocycle-modified dendrimer.

PubMed

Jin, Zhijun; Xiao, Haiyan; Zhou, Wei; Zhang, Dongqiao; Peng, Xiaohong

2017-12-01

Different generations of poly(propylene imine) (G n -PPI) terminated with N-containing 15-membered triolefinic macrocycle (G n M) ( n  = 2, 3, 4, 5) were prepared. The bimetallic nanoparticle catalysts G n M-(Pt x /Pd 10- x ) ( x  = 0, 3, 5, 7, 10) were prepared by the synchronous ligand-exchange reaction between G n M and the complexes of Pt(PPh 3 ) 4 and Pd(PPh 3 ) 4 . The structure and catalytic properties of G n M-(Pt x /Pd 10- x ) were characterized via Fourier transform infrared spectroscopy, 1 H nuclear magnetic resonance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy-dispersive spectroscopy and inductively coupled plasma atomic emission spectroscopy. The novel bimetallic Pd-Pt nanoparticle catalysts stabilized by dendrimers (DSNs) present higher catalytic activities for the hydrogenation of dimeric acid (DA) than that of nitrile butadiene rubber (NBR). It can be concluded that bimetallic Pd-Pt DSNs possess alloying and synergistic electronic effects on account of the hydrogenation degree (HD) of DA and NBR. Furthermore, the HD of DA and NBR shows a remarkable decrease with the incremental generations ( n ) of G n M-(Pt 3 /Pd 7 ) ( n  = 2, 3, 4, 5).

Influence of hot carriers on catalytic reaction; Pt nanoparticles on GaN substrates under light irradiation.

PubMed

Kim, Sun Mi; Park, Dahee; Yuk, Youngji; Kim, Sang Hoon; Park, Jeong Young

2013-01-01

We report the hot carrier-driven catalytic activity of two-dimensional arrays of Pt nanoparticles on GaN substrate under light irradiation. In order to elucidate the effect of a hot carrier in a catalytic chemical reaction, the CO oxidation reaction was carried out on Pt nanoparticles on p- and n-type GaN under light irradiation. Metal catalysts composed of Pt nanoparticles were prepared using two different preparation methods: the one-pot polyol reduction and are plasma deposition methods. Under light irradiation, the catalytic activity of the Pt nanoparticles supported on GaN exhibited a distinct change depending on the doping type. The catalytic activity of the Pt nanoparticles on the n-doped GaN wafer decreased by 8-28% under light irradiation, compared to no irradiation (i.e., in the dark), while the Pt nanoparticles on the p-doped GaN wafer increased by 11-33% under light irradiation, compared to no irradiation. The catalytic activity increased on the smaller Pt nanoparticles, compared to the larger nanoparticles, presumably due to the mean free path of hot carriers. Based on these results, we conclude that the flow of hot carriers generated at the Pt-GaN interface during light irradiation is responsible for the change in catalytic activity on the Pt nanoparticles.

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides.

PubMed

Kulesza, Pawel J; Pieta, Izabela S; Rutkowska, Iwona A; Wadas, Anna; Marks, Diana; Klak, Karolina; Stobinski, Leszek; Cox, James A

2013-11-01

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO 3 , MoO 3 , TiO 2 , ZrO 2 , V 2 O 5 , and CeO 2 ) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems.

Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides

PubMed Central

Kulesza, Pawel J.; Pieta, Izabela S.; Rutkowska, Iwona A.; Wadas, Anna; Marks, Diana; Klak, Karolina; Stobinski, Leszek; Cox, James A.

2013-01-01

Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO3, MoO3, TiO2, ZrO2, V2O5, and CeO2) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems. PMID:24443590

Nonenzymatic free-cholesterol detection via a modified highly sensitive macroporous gold electrode with platinum nanoparticles.

PubMed

Lee, Yi-Jae; Park, Jae-Yeong

2010-12-15

A sensitive macroporous Au electrode with a highly rough surface obtained through the use of with Pt nanoparticles (macroporous Au-/nPts) is reported. It has been designed for nonenzymatic free-cholesterol biosensor applications. A macroporous Au-/nPts electrode was fabricated by electroplating Pt nanoparticles onto a coral-like shaped macroporous Au electrode structure. The macroporous Au-/nPts electrode was physically characterized by field emission scanning electron microscopy (FESEM). It was confirmed that the Pt nanoparticles were well deposited on the surface of the macroporous Au electrode. The porosity and window pore size of the macroporous Au electrode were 50% and 100-300 nm, respectively. The electroplated Pt nanoparticle size was approximately 10-20 nm. Electrochemical experiments showed that the macroporous Au-/nPts exhibited a much larger surface activation area (roughness factor (RF)=2024.7) than the macroporous Au electrode (RF=46.07). The macroporous Au-/nPts also presented a much stronger electrocatalytic activity towards cholesterol oxidation than does the macroporous Au electrode. At 0.2 V, the electrode responded linearly up to a 5 mM cholesterol concentration in a neutral media, with a detection limit of 0.015 mM and detection sensitivity of 226.2 μA mM(-1) cm(-2). Meanwhile, interfering species such as ascorbic acid (AA), acetaminophen (AP), and uric acid (UA), were effectively avoided. This novel nonenzymatic detection electrode has strong applications as an electrochemically based cholesterol biosensor. Copyright © 2010 Elsevier B.V. All rights reserved.

Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles

DOE PAGES

Jia, Qingying; Zhao, Zipeng; Cao, Liang; ...

2017-12-22

Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo–PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shapemore » enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution. Consequently, the favorable Pt 3Ni(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δμ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Lastly, our studies point out a possible way to stabilize the favorable shape and composition established on conceptual catalytic models in practical nanoscale catalysts.« less

Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles

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

Jia, Qingying; Zhao, Zipeng; Cao, Liang

Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo–PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shapemore » enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution. Consequently, the favorable Pt 3Ni(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δμ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Lastly, our studies point out a possible way to stabilize the favorable shape and composition established on conceptual catalytic models in practical nanoscale catalysts.« less

An electrochemical immunoassay for Escherichia coli O157:H7 using double functionalized Au@Pt/SiO2 nanocomposites and immune magnetic nanoparticles.

PubMed

Ye, Lingxian; Zhao, Guangying; Dou, Wenchao

2018-05-15

A sensitive Point-of-Care Testing (POCT) with Au-Pt bimetallic nanoparticles (Au@Pt) functionalized silica nanoparticle (SiO 2 NPs) and Fe 3 O 4 magnetic nanoparticles (Fe 3 O 4 NPs) was designed for the quantitative detection of Escherichia coli O157:H7 (E. coli O157:H7). The poly-(4-styrenesulfonic acid-co-maleic acid) (PSSMA) as a negatively charged polyelectrolyte can be easily coated on surface of the amino group modified SiO 2 NPs via electrostatic force. PSSMA is also a good stabilizer for water-soluble bimetallic nanostructures. The PSSMA is first time used as a "bridge" to connect the negative charge Au@Pt NPs to the SiO 2 NPs, forming Au@Pt/SiO 2 NPs. Antibody and invertase conjugated Au@Pt/SiO 2 NPs (denoted as Ab/invertase-Au@Pt/SiO 2 NPs) were used as signal labels. Monoclonal antibody against E. coli O157:H7 (Ab) functionalized magnetic nanoparticles (denoted as Ab-Fe 3 O 4 @SiO 2 NPs) were used to enrich and capture the E. coli O157:H7 in positive sample. The immunosensing platform also composed of a personal glucometer (PGM) using for signal readout. Based on this sandwich-type immunoassay, the invertase in the final formed sandwich immunocomplex catalyzed the hydrolysis of sucrose to produce a large amount of glucose for quantitative readout by the PGM. Under optimal conditions, a linear relationship between the glucose concentration and the logarithm of E. coli O157:H7 concentration was obtained in the concentration range from 3.5 × 10 2 to 3.5 × 10 8 CFU mL -1 with a detection limit of 1.83 × 10 2 CFU mL -1 (3σ). This method was used to detect E. coli O157:H7 in spiked milk samples, indicating its potential practical application. This protocol can be applied in various fields of study. Copyright © 2018 Elsevier B.V. All rights reserved.

A high efficiency microreactor with Pt/ZnO nanorod arrays on the inner wall for photodegradation of phenol.

PubMed

Zhang, Quan; Zhang, Qinghong; Wang, Hongzhi; Li, Yaogang

2013-06-15

A high efficiency microreactor with Pt coated ZnO (Pt/ZnO) nanorod arrays on the inner wall was successfully fabricated by pumping a Pt sol into the microchannel containing preformed ZnO nanorod arrays. Phenol was selected as a persistent organic pollutant to evaluate the photocatalytic performance of the microreactors. The microreactor which was coated by Pt sol for 5 min showed the best photocatalytic performance compared with other Pt/ZnO nanorod array-modified microreactors. The presence of Pt nanoparticles on the surfaces of ZnO nanorods promoted the separation of photoinduced electron-hole pairs and thus enhanced the photocatalytic activity. In addition, the recyclable property of the microcreator was investigated. It was found that the microreactor displayed higher durability during the continuous photocatalytic process. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis and hydrogenation application of Pt-Pd bimetallic nanocatalysts stabilized by macrocycle-modified dendrimer

NASA Astrophysics Data System (ADS)

Jin, Zhijun; Xiao, Haiyan; Zhou, Wei; Zhang, Dongqiao; Peng, Xiaohong

2017-12-01

Different generations of poly(propylene imine) (Gn-PPI) terminated with N-containing 15-membered triolefinic macrocycle (GnM) (n = 2, 3, 4, 5) were prepared. The bimetallic nanoparticle catalysts GnM-(Ptx/Pd10-x) (x = 0, 3, 5, 7, 10) were prepared by the synchronous ligand-exchange reaction between GnM and the complexes of Pt(PPh3)4 and Pd(PPh3)4. The structure and catalytic properties of GnM-(Ptx/Pd10-x) were characterized via Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy-dispersive spectroscopy and inductively coupled plasma atomic emission spectroscopy. The novel bimetallic Pd-Pt nanoparticle catalysts stabilized by dendrimers (DSNs) present higher catalytic activities for the hydrogenation of dimeric acid (DA) than that of nitrile butadiene rubber (NBR). It can be concluded that bimetallic Pd-Pt DSNs possess alloying and synergistic electronic effects on account of the hydrogenation degree (HD) of DA and NBR. Furthermore, the HD of DA and NBR shows a remarkable decrease with the incremental generations (n) of GnM-(Pt3/Pd7) (n = 2, 3, 4, 5).

Enhancement of the catalytic activity of Pt nanoparticles toward methanol electro-oxidation using doped-SnO2 supporting materials

NASA Astrophysics Data System (ADS)

Merati, Zohreh; Basiri Parsa, Jalal

2018-03-01

Catalyst supports play important role in governing overall catalyst activity and durability. In this study metal oxides (SnO2, Sb and Nb doped SnO2) were electrochemically deposited on titanium substrate (Ti) as a new support material for Pt catalyst in order to electro-oxidation of methanol. Afterward platinum nanoparticles were deposited on metal oxide film via electro reduction of platinum salt in an acidic solution. The surface morphology of modified electrodes were evaluated by field-emission scanning electron microscopy (FESEM) and energy dispersive X-ray analysis (EDX) techniques. The electro-catalytic activities of prepared electrodes for methanol oxidation reaction (MOR) and oxidation of carbon monoxide (CO) absorbed on Pt was considered with cyclic voltammetry. The results showed high catalytic activity for Pt/Nb-SnO2/Ti electrode. The electrochemical surface area (ECSA) of a platinum electro-catalyst was determined by hydrogen adsorption. Pt/Nb-SnO2/Ti electrode has highest ECSA compared to other electrode resulting in high activity toward methanol electro-oxidation and CO stripping experiments. The doping of SnO2 with Sb and Nb improved ECSA and MOR activity, which act as electronic donors to increase electronic conductivity.

Monolayer-directed Assembly and Magnetic Properties of FePt Nanoparticles on Patterned Aluminum Oxide

PubMed Central

Yildirim, Oktay; Gang, Tian; Kinge, Sachin; Reinhoudt, David N.; Blank, Dave H.A.; van der Wiel, Wilfred G.; Rijnders, Guus; Huskens, Jurriaan

2010-01-01

FePt nanoparticles (NPs) were assembled on aluminum oxide substrates, and their ferromagnetic properties were studied before and after thermal annealing. For the first time, phosph(on)ates were used as an adsorbate to form self-assembled monolayers (SAMs) on alumina to direct the assembly of NPs onto the surface. The Al2O3 substrates were functionalized with aminobutylphosphonic acid (ABP) or phosphonoundecanoic acid (PNDA) SAMs or with poly(ethyleneimine) (PEI) as a reference. FePt NPs assembled on all of these monolayers, but much less on unmodified Al2O3, which shows that ligand exchange at the NPs is the most likely mechanism of attachment. Proper modification of the Al2O3 surface and controlling the immersion time of the modified Al2O3 substrates into the FePt NP solution resulted in FePt NPs assembly with controlled NP density. Alumina substrates were patterned by microcontact printing using aminobutylphosphonic acid as the ink, allowing local NP assembly. Thermal annealing under reducing conditions (96%N2/4%H2) led to a phase change of the FePt NPs from the disordered FCC phase to the ordered FCT phase. This resulted in ferromagnetic behavior at room temperature. Such a process can potentially be applied in the fabrication of spintronic devices. PMID:20480007

A pathway for the growth of core-shell Pt-Pd nanoparticles

DOE PAGES

Narula, Chaitanya Kumar; Yang, Xiaofan; Li, Chen; ...

2015-10-12

In this study, the aging of both Pt-Pd nanoparticles and core-shell Pt-Pd nanoparticles has been reported to result in alloying of Pt with Pd. In comparison to monometallic Pt catalysts, the growth of Pd-Pt bimetallics is slower; however, the mechanism of growth of particles and the mechanism by which Pd improves the hydrothermal durability of bimetallic Pd-Pt particles remains uncertain. In our work on hydrothermal aging of core-shell Pt-Pd nanoparticles, synthesized by solution methods, with varying Pd:Pt ratio of 1:4, 1:1, and 4:1, we compare the growth of core-shell Pt-Pd nanoparticles and find that particles grow by migrating and joiningmore » together. The unique feature of the observed growth is that Pd shells from both particles open up and join, allowing the cores to merge. At high temperatures, alloying occurs in good agreement with reports by other workers.« less

New electrocatalysts for unitized regenerative fuel cell: Pt-Ir alloy deposited on the proton exchange membrane surface by impregnation-reduction method.

PubMed

Wan, Chieh-Hao; Wu, Chun-Lin; Lin, Meng-Tsun; Shih, Chihhsiong

2010-07-01

In this paper, a modified technique to prepare Pt-Ir catalyst layer on the proton exchange membrane (PEM) surface using the impregnation-reduction (IR) method is proposed to improve the electrocatalytic activity as well as the life cycle of the bifunctional oxygen electrode (BOE). The resulted electrocatalysts were characterized by the Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Electron Probe Micro-Analysis (EPMA), and Transmission Electron Microscope (TEM). The electrocatalytic properties of the Pt-Ir layer on PEM surface for the oxygen reduction and water oxidation reactions as well as the life cycle of MEA were investigated. Experimental results showed that the Ir particles were dispersed densely in the platinum layer through the modified IR technique. The atomic ratio of Pt over Ir elements was 9:1, and the resulted thickness of the obtained Pt-Ir catalyst layer was about 1.0 microm. The Pt-Ir catalyst layer was composed of Pt layer doped with Ir nano-particles comprising nano Pt-Ir alloy phase. The large surface area of Ir core with Pt shell particles and the presence of nano Pt-Ir alloy phase led to a higher electrocatalytic activity of BOE. Due to the good binding between the Nafion membrane and the Pt-Ir alloy catalyst, as well as the composite structure of the resulted Pt-Ir, the life cycle of Unitized Regenerative Fuel Cell (URFC) is improved through this novel BOE.

Electrodeposition of gold-platinum alloy nanoparticles on ionic liquid-chitosan composite film and its application in fabricating an amperometric cholesterol biosensor.

PubMed

Safavi, Afsaneh; Farjami, Fatemeh

2011-01-15

An electrodeposition method was applied to form gold-platinum (AuPt) alloy nanoparticles on the glassy carbon electrode (GCE) modified with a mixture of an ionic liquid (IL) and chitosan (Ch) (AuPt-Ch-IL/GCE). AuPt nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical methods. AuPt-Ch-IL/GCE electrocatalyzed the reduction of H(2)O(2) and thus was suitable for the preparation of biosensors. Cholesterol oxidase (ChOx) was then, immobilized on the surface of the electrode by cross-linking ChOx and chitosan through addition of glutaraldehyde (ChOx/AuPt-Ch-IL/GCE). The fabricated biosensor exhibited two wide linear ranges of responses to cholesterol in the concentration ranges of 0.05-6.2 mM and 6.2-11.2 mM. The sensitivity of the biosensor was 90.7 μA mM(-1) cm(-2) and the limit of detection was 10 μM of cholesterol. The response time was less than 7 s. The Michaelis-Menten constant (K(m)) was found as 0.24 mM. The effect of the addition of 1 mM ascorbic acid and glucose was tested on the amperometric response of 0.5 mM cholesterol and no change in response current of cholesterol was observed. Copyright © 2010 Elsevier B.V. All rights reserved.

DNA-templated synthesis of PtAu bimetallic nanoparticle/graphene nanocomposites and their application in glucose biosensor

PubMed Central

2014-01-01

In this paper, single-stranded DNA (ss-DNA) is demonstrated to functionalize graphene (GR) and to further guide the growth of PtAu bimetallic nanoparticles (PtAuNPs) on GR with high densities and dispersion. The obtained nanocomposites (PtAuNPs/ss-DNA/GR) were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectrometer (EDS), and electrochemical techniques. Then, an enzyme nanoassembly was prepared by self-assembling glucose oxidase (GOD) on PtAuNP/ss-DNA/GR nanocomposites (GOD/PtAuNPs/ss-DNA/GR). The nanocomposites provided a suitable microenvironment for GOD to retain its biological activity. The direct and reversible electron transfer process between the active site of GOD and the modified electrode was realized without any extra electron mediator. Thus, the prepared GOD/PtAuNP/ss-DNA/GR electrode was proposed as a biosensor for the quantification of glucose. The effects of pH, applied potential, and temperature on the performance of the biosensor were discussed in detail and were optimized. Under optimal conditions, the biosensor showed a linearity with glucose concentration in the range of 1.0 to 1,800 μM with a detection limit of 0.3 μM (S/N = 3). The results demonstrate that the developed approach provides a promising strategy to improve the sensitivity and enzyme activity of electrochemical biosensors. PMID:24572068

Highly exposed Pt nanoparticles supported on porous graphene for electrochemical detection of hydrogen peroxide in living cells.

PubMed

Liu, Jian; Bo, Xiangjie; Zhao, Zheng; Guo, Liping

2015-12-15

In this study, we developed a novel biosensor based on highly exposed Pt nanoparticles (Pt NPs) decorated porous graphene (PG) for the reliable detection of extracellular hydrogen peroxide (H2O2) released from living cells. The commercially available low-cost hydrophilic CaCO3 spheres were used as template for preparing PG. The porous structure provided larger surface area and more active sites. Due to the porous structure of PG, the Pt NPs supported on PG were not secluded by aggregated graphene layers and were highly exposed to target molecules. Ultrafine Pt NPs were well dispersed and loaded on PG by a method of microwave assistance. Electrochemical performances of the Pt/PG nanocomposites modified glassy carbon electrode (GCE) were investigated. The electrocatalytic reduction of H2O2 showed a wide linear range from 1 to 1477 μM, with a high sensitivity of 341.14 μA mM(-1) cm(-2) and a limit of detection (LOD) as low as 0.50 μM. Moreover, the Pt/PG/GCE exhibited excellent anti-interference property, reproducibility and long-term storage stability. Because of these remarkable analytical advantages, the constructed sensor was used to determine H2O2 released from living cells with satisfactory results. The superior catalytic activity makes Pt/PG nanocomposites a promising candidate for electrochemical sensors and biosensors design. Copyright © 2015 Elsevier B.V. All rights reserved.

Novel ferrocene-anchored ZnO nanoparticle/carbon nanotube assembly for glucose oxidase wiring: application to a glucose/air fuel cell.

PubMed

Haddad, Raoudha; Mattei, Jean-Gabriel; Thery, Jessica; Auger, Aurélien

2015-06-28

Glucose oxidase (GOx) is immobilized on ZnO nanoparticle-modified electrodes. The immobilized glucose oxidase shows efficient mediated electron transfer with ZnO nanoparticles to which the ferrocenyl moiety is π-stacked into a supramolecular architecture. The constructed ZnO-Fc/CNT modified electrode exhibits high ferrocene surface coverage, preventing any leakage of the π-stacked ferrocene from the newly described ZnO hybrid nanoparticles. The use of the new architecture of ZnO supported electron mediators to shuttle electrons from the redox centre of the enzyme to the surface of the working electrode can effectively bring about successful glucose oxidation. These modified electrodes evaluated as a highly efficient architecture provide a catalytic current for glucose oxidation and are integrated in a specially designed glucose/air fuel cell prototype using a conventional platinum-carbon (Pt/C) cathode at physiological pH (7.0). The obtained architecture leads to a peak power density of 53 μW cm(-2) at 300 mV for the Nafion® based biofuel cell under "air breathing" conditions at room temperature.

Negative differential resistance effect induced by metal ion implantation in SiO2 film for multilevel RRAM application

NASA Astrophysics Data System (ADS)

Wu, Facai; Si, Shuyao; Shi, Tuo; Zhao, Xiaolong; Liu, Qi; Liao, Lei; Lv, Hangbing; Long, Shibing; Liu, Ming

2018-02-01

Pt/SiO2:metal nanoparticles/Pt sandwich structure is fabricated with the method of metal ion (Ag) implantation. The device exhibits multilevel storage with appropriate R off/R on ratio, good endurance and retention properties. Based on transmission electron microscopy and energy dispersive spectrometer analysis, we confirm that Pt nanoparticles are spurted into SiO2 film from Pt bottom electrode by Ag implantation; during electroforming, the local electric field can be enhanced by these Pt nanoparticles, meanwhile the Ag nanoparticles constantly migrate toward the Pt nanoparticles. The implantation induced nanoparticles act as trap sites in the resistive switching layer and play critical roles in the multilevel storage, which is evidenced by the negative differential resistance effect in the current-voltage (I-V) measurements.

In situ SAXS study on size changes of platinum nanoparticles with temperature

NASA Astrophysics Data System (ADS)

Wang, W.; Chen, X.; Cai, Q.; Mo, G.; Jiang, L. S.; Zhang, K.; Chen, Z. J.; Wu, Z. H.; Pan, W.

2008-09-01

Poly(vinylpyrrolidone) (PVP)-coated platinum (Pt) nanoparticles were prepared in methanol-water reduction method. In situ small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD) techniques were used to probe the size change of particles and crystallites with temperature. Tangent-by-tangent (TBT) method of SAXS data analysis was improved and used to get the particle size distribution (PSD) from SAXS intensity. Scherrer’s equation was used to derive the crystallite size from XRD pattern. Combining SAXS and XRD results, a step-like characteristic of the Pt nanoparticle growth has been found. Three stages (diffusion, aggregation, and agglomeration) can be used to describe the growth of the Pt nanoparticles and nanocrystallites. Aggregation was found to be the main growth mode of the Pt nanoparticles during heating. The maximum growth rates of Pt nanoparticles and Pt nanocrystallites, as well as the maximum aggregation degree of Pt nanocrystallites were found, respectively, at 250 °C, 350 °C and 300 °C. These results are helpful to understanding the growth mode of nanoparticles, as well as controlling the nanoparticle size.

Electrochemical sensor based on gold nanoparticles fabricated molecularly imprinted polymer film at chitosan-platinum nanoparticles/graphene-gold nanoparticles double nanocomposites modified electrode for detection of erythromycin.

PubMed

Lian, Wenjing; Liu, Su; Yu, Jinghua; Xing, Xianrong; Li, Jie; Cui, Min; Huang, Jiadong

2012-01-01

A molecularly imprinted electrochemical sensor was fabricated based on gold electrode decorated by chitosan-platinum nanoparticles (CS-PtNPs) and graphene-gold nanoparticles (GR-AuNPs) nanocomposites for convenient and sensitive determination of erythromycin. The synergistic effects of CS-PtNPs and GR-AuNPs nanocomposites improved the electrochemical response and the sensitivity of the sensor. The molecularly imprinted polymers (MIPs) were prepared by HAuCl(4), 2-mercaptonicotinic acid (MNA) and erythromycin. Erythromycin and MNA were used as template molecule and functional monomer, respectively. They were first assembled on the surface of GR-AuNPs/CS-PtNPs/gold electrode by the formation of Au-S bonds and hydrogen-bonding interactions. Then the MIPs were formed by electropolymerization of HAuCl(4), MNA and erythromycin. The sensor was characterized by cyclic voltammetry (CV), scanning electron microscope (SEM), UV-visible (UV-vis) absorption speactra and amperometry. The linear range of the sensor was from 7.0 × 10(-8)mol/L-9.0 × 10(-5)mol/L, with the limit of detection (LOD) of 2.3 × 10(-8)mol/L (S/N=3). The sensor showed high selectivity, excellent stability and good reproducibility for the determination of erythromycin, and it was successfully applied to the detection of erythromycin in real spiked samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Biobutanol as Fuel for Direct Alcohol Fuel Cells-Investigation of Sn-Modified Pt Catalyst for Butanol Electro-oxidation.

PubMed

Puthiyapura, Vinod Kumar; Brett, Dan J L; Russell, Andrea E; Lin, Wen-Feng; Hardacre, Christopher

2016-05-25

Direct alcohol fuel cells (DAFCs) mostly use low molecular weight alcohols such as methanol and ethanol as fuels. However, short-chain alcohol molecules have a relative high membrane crossover rate in DAFCs and a low energy density. Long chain alcohols such as butanol have a higher energy density, as well as a lower membrane crossover rate compared to methanol and ethanol. Although a significant number of studies have been dedicated to low molecular weight alcohols in DAFCs, very few studies are available for longer chain alcohols such as butanol. A significant development in the production of biobutanol and its proposed application as an alternative fuel to gasoline in the past decade makes butanol an interesting candidate fuel for fuel cells. Different butanol isomers were compared in this study on various Pt and PtSn bimetallic catalysts for their electro-oxidation activities in acidic media. Clear distinctive behaviors were observed for each of the different butanol isomers using cyclic voltammetry (CV), indicating a difference in activity and the mechanism of oxidation. The voltammograms of both n-butanol and iso-butanol showed similar characteristic features, indicating a similar reaction mechanism, whereas 2-butanol showed completely different features; for example, it did not show any indication of poisoning. Ter-butanol was found to be inactive for oxidation on Pt. In situ FTIR and CV analysis showed that OHads was essential for the oxidation of primary butanol isomers which only forms at high potentials on Pt. In order to enhance the water oxidation and produce OHads at lower potentials, Pt was modified by the oxophilic metal Sn and the bimetallic PtSn was studied for the oxidation of butanol isomers. A significant enhancement in the oxidation of the 1° butanol isomers was observed on addition of Sn to the Pt, resulting in an oxidation peak at a potential ∼520 mV lower than that found on pure Pt. The higher activity of PtSn was attributed to the bifunctional mechanism on PtSn catalyst. The positive influence of Sn was also confirmed in the PtSn nanoparticle catalyst prepared by the modification of commercial Pt/C nanoparticle and a higher activity was observed for PtSn (3:1) composition. The temperature-dependent data showed that the activation energy for butanol oxidation reaction over PtSn/C is lower than that over Pt/C.

Natural diatomite modified as novel hydrogen storage material

NASA Astrophysics Data System (ADS)

Jin, Jiao; Zheng, Chenghui; Yang, Huaming

2014-03-01

Natural diatomite, subjected to different modifications, is investigated for hydrogen adsorption capacities at room temperature. An effective metal-modified strategy is developed to disperse platinum (Pt) and palladium (Pd) nanoparticles on the surface of diatomite. Hydrogen adsorption capacity of pristine diatomite (diatomite) is 0.463 wt.% at 2.63 MPa and 298 K, among the highest of the known sorbents, while that of acid-thermally activated diatomite (A-diatomite) could reach up to 0.833 wt.% due to the appropriate pore properties by activation. By incorporation with a small amount of Pt and Pd ( 0.5 wt.%), hydrogen adsorption capacities are enhanced to 0.696 wt.% and 0.980 wt.%, respectively, indicating that activated diatomite shows interesting application in the field of hydrogen storage at room temperature.

Effect of platinum dispersion on photocatalytic performance of Pt-TiO2

NASA Astrophysics Data System (ADS)

Hou, Lili; Zhang, Min; Guan, Zhongjie; Li, Qiuye; Yang, Jianjun

2018-03-01

Noble metal Pt nanoparticles have been considered as the most effective co-catalyst to improve the photocatalytic hydrogen production activity of TiO2. In this study, the effect of the dispersion of Pt nanoparticles on the photoactivity of TiO2 nanotubes was investigated. Compared with the samples that the co-catalyst of Pt nanoparticles agglomerated or freely dispersed, the sample with the uniformly dispersion of Pt nanoparticles showed a higher performance for photocatalytic hydrogen production. The photocatalysts were characterized systematically by TEM, BET, UV-Vis, XPS, and PL techniques, and the relationship between the structure and the photoactivity was investigated in detail. The results demonstrated that the dispersion status of Pt nanoparticles had a crucial effect on the photocatalytic activity.

Study the Polyol Process of Preparing the ru Doped FePt Nanoparticles

NASA Astrophysics Data System (ADS)

Lee, Chih-Hao; Hsu, Jen-Ho; Su, Hui-Chia; Huang, Tzu Wen

The structure of Ru doped FePt nanoparticles using polyol process was studied. The particle size grown is around 5 nm, and a shell structure might be formed. By selecting the time and temperature of adding the Ru precursors into solution, three different processes to synthesize the FePtRu particles were studied resulting in different growing mechanics. The possible models during the reaction process are also discussed. The phase transition temperature for the as-grown FCC FePt nanoparticle to transform into L10 FePt nanoparticle is about 823 K which is about the same as the one without doping Ru atoms. From the XAS study of each element, the possible scenario is that: although Ru atoms with the size close to the Pt, they do not totally replace the Pt sites in the FePt alloy. Instead, most of Ru formed a shell outside the FePt nanoparticles and Fe atoms are replaced.

Evaluation of Alkylamine Modified Pt Nanoparticles as Oxygen Reduction Reaction Electrocatalyst for Fuel Cells via Electrochemical Impedance Spectroscopy.

PubMed

Joshi, Prerna; Okada, Toshihiko; Miyabayashi, Keiko; Miyake, Mikio

2018-05-15

Organically (octyl amine, OA) surface modified electrocatalyst (OA-Pt/CB) was studied for its oxygen reduction reaction (ORR) activity via dc methods and its charge and mass transfer properties were studied via electrochemical impedance spectroscopy (EIS). Comparison with a commercial catalyst (TEC10V30E) with similar Pt content was also carried out. In EIS, both the catalysts showed a single time-constant with an emerging high-frequency semicircle of very small diameter which was fitted using suitable equivalent circuits. The organically modified catalyst showed lower charge-transfer resistance and hence, low polarization resistance in high potential region as compared to the commercial catalyst. The dominance of kinetic processes was observed at 0.925-1.000 V, whereas domination of diffusion based processes was observed at lower potential region for the organic catalyst. No effect due to the presence of carbon was observed in the EIS spectra. Using the hydrodynamic method, higher current penetration depth was obtained for the organically modified catalyst at 1600 rpm. Exchange current density and Tafel slopes for both the electrocatalysts were calculated from the polarization resistance obtained from EIS which was in correlation with the results obtained from dc methods.

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.

Characterization of Platinum Nanoparticles Deposited on Functionalized Graphene Sheets

PubMed Central

Chiang, Yu-Chun; Liang, Chia-Chun; Chung, Chun-Ping

2015-01-01

Due to its special electronic and ballistic transport properties, graphene has attracted much interest from researchers. In this study, platinum (Pt) nanoparticles were deposited on oxidized graphene sheets (cG). The graphene sheets were applied to overcome the corrosion problems of carbon black at operating conditions of proton exchange membrane fuel cells. To enhance the interfacial interactions between the graphene sheets and the Pt nanoparticles, the oxygen-containing functional groups were introduced onto the surface of graphene sheets. The results showed the Pt nanoparticles were uniformly dispersed on the surface of graphene sheets with a mean Pt particle size of 2.08 nm. The Pt nanoparticles deposited on graphene sheets exhibited better crystallinity and higher oxygen resistance. The metal Pt was the predominant Pt chemical state on Pt/cG (60.4%). The results from the cyclic voltammetry analysis showed the value of the electrochemical surface area (ECSA) was 88 m2/g (Pt/cG), much higher than that of Pt/C (46 m2/g). The long-term test illustrated the degradation in ECSA exhibited the order of Pt/C (33%) > Pt/cG (7%). The values of the utilization efficiency were calculated to be 64% for Pt/cG and 32% for Pt/C. PMID:28793577

Mobility and Oxidation of Adsorbed CO on Shape-Controlled Pt Nanoparticles in Acidic Medium.

PubMed

Farias, Manuel J S; Busó-Rogero, Carlos; Vidal-Iglesias, Francisco J; Solla-Gullón, José; Camara, Giuseppe A; Feliu, Juan M

2017-01-31

The knowledge about how CO occupies and detaches from specific surface sites on well-structured Pt surfaces provides outstanding information on both dynamics/mobility of CO ads and oxidation of this molecule under electrochemical conditions. This work reports how the potentiostatic growth of different coverage CO adlayers evolves with time on both cubic and octahedral Pt nanoparticles in acidic medium. Data suggest that during the growth of the CO adlayer, CO ads molecules slightly shift toward low coordination sites only on octahedral Pt nanoparticles, so that these undercoordinated sites are the first filled on octahedral Pt nanoparticles. Conversely, on cubic Pt nanoparticles, adsorbed CO behaves as an immobile species, and low coordinated sites as well as (100) terraces are apparently filled uniformly and simultaneously. However, once the adlayer is complete, irrespectively of whether the CO is oxidized in a single step or in a sequence of different potential steps, results suggest that CO ads behaves as an immobile species during its oxidation on both octahedral and cubic Pt nanoparticles.

Facile synthesis of hollow dendritic Ag/Pt alloy nanoparticles for enhanced methanol oxidation efficiency.

PubMed

Sui, Ning; Wang, Ke; Shan, Xinyao; Bai, Qiang; Wang, Lina; Xiao, Hailian; Liu, Manhong; Colvin, Vicki L; Yu, William W

2017-11-14

Hollow dendritic Ag/Pt alloy nanoparticles were synthesized by a double template method: Ag nanoparticles as the hard template to obtain hollow spheres by a galvanic replacement reaction between PtCl 6 2- and metallic Ag and surfactant micelles (Brij58) as the soft template to generate porous dendrites. The formation of a Ag/Pt alloy phase was confirmed by XRD and HRTEM. Elemental mapping and line scanning revealed the formation of the hollow architecture. We studied the effects of the Ag/Pt ratio, surfactant and reaction temperature on the morphology. In addition, we explored the formation process of hollow dendritic Ag/Pt nanoparticles by tracking the morphologies of the nanostructures formed at different stages. In order to improve the electrocatalytic property, we controlled the size of the nanoparticles and the thickness of the shell by adjusting the amount of the precursor. We found that these Ag/Pt alloy nanoparticles exhibited high activity (440 mA mg -1 ) and stability as an electrocatalyst for catalyzing methanol oxidation.

Insight into nanoparticle charging mechanism in nonpolar solvents to control the formation of Pt nanoparticle monolayers by electrophoretic deposition

DOE PAGES

Cernohorsky, Ondrej; Grym, Jan; Yatskiv, Roman; ...

2016-08-13

We report on the formation of Pt nanoparticle monolayers by electrophoretic deposition from nonpolar solvents. First, the growth kinetics of Pt nanoparticles prepared by the reverse micelle technique are described in detail. Second, a model of nanoparticle charging in nonpolar media is discussed and methods to control the nanoparticle charging are proposed. Lastly, essential parameters of the electrophoretic deposition process to control the deposition of nanoparticle monolayers are discussed and mechanisms of their formation are analyzed.

Insight into nanoparticle charging mechanism in nonpolar solvents to control the formation of Pt nanoparticle monolayers by electrophoretic deposition

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

Cernohorsky, Ondrej; Grym, Jan; Yatskiv, Roman

We report on the formation of Pt nanoparticle monolayers by electrophoretic deposition from nonpolar solvents. First, the growth kinetics of Pt nanoparticles prepared by the reverse micelle technique are described in detail. Second, a model of nanoparticle charging in nonpolar media is discussed and methods to control the nanoparticle charging are proposed. Lastly, essential parameters of the electrophoretic deposition process to control the deposition of nanoparticle monolayers are discussed and mechanisms of their formation are analyzed.

Two dimensional visible-light-active Pt-BiOI photoelectrocatalyst for efficient ethanol oxidation reaction in alkaline media

NASA Astrophysics Data System (ADS)

Zhai, Chunyang; Hu, Jiayue; Sun, Mingjuan; Zhu, Mingshan

2018-02-01

Two dimensional (2D) BiOI nanoplates were synthesized and used as support for the deposition of Pt nanoparticles. Owing to broad visible light absorption (up to 660 nm), the as-obtained Pt-BiOI electrode was used as effective photoelectrocatalyst in the application of catalytic ethanol oxidation in alkaline media under visible light irradiation. Compared to dark condition, the Pt-BiOI modified electrode displayed 3 times improved catalytic activity towards ethanol oxidation under visible light irradiation. The synergistic effect of electrocatalytic and photocatalytic, and the unique of 2D structures contribute to the improvement of catalytic activity. The mechanism of enhanced photoelectrocatalytic process is proposed. The present results suggest that 2D visible-light-activated BiOI can be served as promising support for the decoration of Pt and applied in the fields of photoelectrochemical and photo-assisted fuel cell applications

Exploring the Efficacy of Platinum and Palladium Nanostructures for Organic Molecule Detection via Raman Spectroscopy

PubMed Central

Tran, Minh; Whale, Alison

2018-01-01

Noble transition metals, like palladium (Pd) and platinum (Pt), have been well-known for their excellent catalytic and electrochemical properties. However, they have been considered non-active for surface enhanced Raman spectroscopy (SERS). In this work, we explore the scattering contributions of Pd and Pt for the detection of organic molecules. The Pd and Pt nanostructures were synthesized on silicon substrate using a modified galvanic displacement method. The results show Pt nanoparticles and dendritic Pd nanostructures with controlled density and size. The influence of surfactants, including sodium dodecyl sulfate and cetyltrimethylammonium bromide, on the size and morphology of the nanostructures was investigated. The Pd and Pt nanostructures with a combination of large size and high density were then used to explore their applicability for the detection of 10−5 M Rhodamine 6G and 10−2 M paraoxon. PMID:29316659

Sintering behavior of spin-coated FePt and FePtAu nanoparticles

NASA Astrophysics Data System (ADS)

Kang, Shishou; Jia, Zhiyong; Zoto, I.; Reed, D.; Nikles, David E.; Harrell, J. W.; Thompson, Gregory; Mankey, Gary; Krishnamurthy, Vemuru V.; Porcar, L.

2006-04-01

FePt and [FePt]95Au5 nanoparticles with an average size of about 4 nm were chemically synthesized and spin coated onto silicon substrates. Samples were subsequently thermally annealed at temperatures ranging from 250 to 500 °C for 30 min. Three-dimensional structural characterization was carried out with small-angle neutron scattering (SANS) and small-angle x-ray diffraction (SAXRD) measurements. For both FePt and [FePt]95Au5 particles before annealing, SANS measurements gave an in-plane coherence length parameter a=7.3 nm, while SAXRD measurements gave a perpendicular coherence length parameter c=12.0 nm. The ratio of c/a is about 1.64, indicating the as-made particle array has a hexagonal close-packed superstructure. For both FePt and FePtAu nanoparticles, the diffraction peaks shifted to higher angles and broadened with increasing annealing temperature. This effect corresponds to a shrinking of the nanoparticle array, followed by agglomeration and sintering of the nanoparticles, resulting in the eventual loss of positional order with increasing annealing temperature. The effect is more pronounced for FePtAu than for FePt. Dynamic coercivity measurements show that the FePtAu nanoparticles have both higher intrinsic coercivity and higher switching volume at the same annealing temperature. These results are consistent with previous studies that show that additive Au both lowers the chemical ordering temperature and promotes sintering.

Effect of counterpart metals in carbon-supported Pt-based catalysts prepared using radiation chemical method

NASA Astrophysics Data System (ADS)

Okazaki, Tomohisa; Seino, Satoshi; Matsuura, Yoshiyuki; Otake, Hiroaki; Kugai, Junichiro; Ohkubo, Yuji; Nitani, Hiroaki; Nakagawa, Takashi; Yamamoto, Takao A.

2017-04-01

The process of nanoparticle formation by radiation chemical synthesis in a heterogeneous system has been investigated. Carbon-supported Pt-based bimetallic nanoparticles were synthesized using a high-energy electron beam. Rh, Cu, Ru, and Sn were used as counterpart metals. The nanoparticles were characterized by inductively coupled plasma atomic emission spectrometry, transmission electron microscopy, X-ray diffraction, and X-ray absorption spectroscopy. PtRh formed a uniform random alloy nanoparticle, while Cu partially formed an alloy with Pt and the remaining Cu existed as CuO. PtRu formed an alloy structure with a composition distribution of a Pt-rich core and Ru-rich shell. No alloying was observed in PtSn, which had a Pt-SnO2 structure. The alloy and oxide formation mechanisms are discussed considering the redox potentials, the standard enthalpy of oxide formation, and the solid solubilities of Pt and the counterpart metals.

Tuning the synthesis of platinum-copper nanoparticles with a hollow core and porous shell for the selective hydrogenation of furfural to furfuryl alcohol

NASA Astrophysics Data System (ADS)

Huang, Shuangshuang; Yang, Nating; Wang, Shibin; Sun, Yuhan; Zhu, Yan

2016-07-01

Pt-Cu nanoparticles constructed with a hollow core and porous shell have been synthesized in which Pt-Cu cages with multiporous outermost shells are formed at the initial stage and then the Pt and Cu atoms in solution continuously fed these hollow-core of cages by passing through the porous tunnels of the outermost shells, finally leading to the formation of hollow structures with different sizes. Furthermore, these hollow-core Pt-Cu nanoparticles are more effective than the solid-core Pt-Cu nanoparticles for the catalytic hydrogenation of furfural toward furfuryl alcohol. The former can achieve almost 100% conversion of furfural with 100% selectivity toward the alcohol.Pt-Cu nanoparticles constructed with a hollow core and porous shell have been synthesized in which Pt-Cu cages with multiporous outermost shells are formed at the initial stage and then the Pt and Cu atoms in solution continuously fed these hollow-core of cages by passing through the porous tunnels of the outermost shells, finally leading to the formation of hollow structures with different sizes. Furthermore, these hollow-core Pt-Cu nanoparticles are more effective than the solid-core Pt-Cu nanoparticles for the catalytic hydrogenation of furfural toward furfuryl alcohol. The former can achieve almost 100% conversion of furfural with 100% selectivity toward the alcohol. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03894h

Fabrication of NiS modified CdS nanorod p-n junction photocatalysts with enhanced visible-light photocatalytic H2-production activity.

PubMed

Zhang, Jun; Qiao, Shi Zhang; Qi, Lifang; Yu, Jiaguo

2013-08-07

Production of hydrogen from photocatalytic water splitting has become an attractive research area due to the possibility of converting solar energy into green chemical energy. In this study, novel NiS nanoparticle (NP) modified CdS nanorod (NR) p-n junction photocatalysts were prepared by a simple two-step hydrothermal method. Even without the Pt co-catalyst, the as-prepared NiS NP-CdS NR samples exhibited enhanced visible-light photocatalytic activity and good stability for H2-production. The optimal NiS loading content was determined to be 5 mol%, and the corresponding H2-production rate reached 1131 μmol h(-1) g(-1), which is even higher than that of the optimized Pt-CdS NRs. It is believed that the assembly of p-type NiS NPs on the surface of n-type CdS NRs could form a large number of p-n junctions, which could effectively reduce the recombination rates of electrons and holes, thus greatly enhancing the photocatalytic activity. This work not only shows a possibility for the utilization of low cost NiS nanoparticles as a substitute for noble metals (such as Pt) in the photocatalytic H2-production but also provides a new insight into the design and fabrication of other new p-n junction photocatalysts for enhancing H2-production activity.

From well-defined Pt(II) surface species to the controlled growth of silica supported Pt nanoparticles.

PubMed

Laurent, Pierre; Veyre, Laurent; Thieuleux, Chloé; Donet, Sébastien; Copéret, Christophe

2013-01-07

Silica-supported Pt nanoparticles were prepared from well-defined surface platinum(II) surface species, obtained by grafting of well-defined Pt(II) molecular precursors with specific ligands (Cl, Me, N(SiMe(3))(2), OSi(OtBu)(3)) onto silica partially dehydroxylated at 200 and 700 °C yielding well-defined platinum(II) surface species. This approach allowed for testing the effect of Pt density and ligands on nanoparticle size. Higher grafting densities are achieved on silica partially dehydroxylated at 200 °C due to its initially higher surface silanol density. Surface species have been synthesized from symmetrical and dissymmetrical complexes, namely (COD)Pt(Me)(2), (COD)Pt(OSi(OtBu)(3))(2), (COD)Pt(Me)(OSi(OtBu)(3)), (COD)Pt(Me)(N(SiMe(3))(2)), (COD)Pt(Cl)(N(SiMe(3))(2)) and (COD)Pt(N(SiMe(3))(2))(OSi(OtBu)(3)) yielding mono-grafted complexes of general formula (COD)Pt(R)(OSi≡) according to elemental analyses, diffuse reflectance infrared fourier transform (DRIFT) and carbon-13 solid-state nuclear magnetic resonance (NMR) spectroscopies. While the dimethyl-complex shows low reactivity towards grafting, bis-siloxy and dissymmetric complexes demonstrate better reactivity yielding platinum loadings up to 7.4 wt%. Upon grafting amido complexes, the surface passivation yielding Me(3)SiOSi≡ surface species is demonstrated. Nanoparticles have been synthesized from these well-defined surface species by reduction under H(2) at 300 °C, under static or flow conditions. This process yields nanoparticles with sizes ranging from 2 to 3.3 nm and narrow size dispersion from 0.5 to 1.2 nm. Interestingly, the chloride complex yields large nanoparticles from 5 to 40 nm demonstrating the strong influence of chloride over the nanoparticles growth.

Cell-targeted platinum nanoparticles and nanoparticle clusters.

PubMed

Papst, Stefanie; Brimble, Margaret A; Evans, Clive W; Verdon, Daniel J; Feisst, Vaughan; Dunbar, P Rod; Tilley, Richard D; Williams, David E

2015-06-21

Herein, we report the facile preparation of cell-targeted platinum nanoparticles (PtNPs), through the design of peptides that, as a single molecule added in small concentration during the synthesis, control the size of PtNP clusters during their growth, stabilise the PtNPs in aqueous suspension and enable the functionalisation of the PtNPs with a versatile range of cell-targeting ligands. Water-soluble PtNPs targeted respectively at blood group antigens and at integrin receptors are demonstrated.

Oxygen reduction reaction activity and structural stability of Pt-Au nanoparticles prepared by arc-plasma deposition.

PubMed

Takahashi, Shuntaro; Chiba, Hiroshi; Kato, Takashi; Endo, Shota; Hayashi, Takehiro; Todoroki, Naoto; Wadayama, Toshimasa

2015-07-28

The oxygen reduction reaction (ORR) activity and durability of various Au(x)/Pt100 nanoparticles (where x is the atomic ratio of Au against Pt) are evaluated herein. The samples were fabricated on a highly-oriented pyrolytic graphite substrate at 773 K through sequential arc-plasma depositions of Pt and Au. The electrochemical hydrogen adsorption charges (electrochemical surface area), particularly the characteristic currents caused by the corner and edge sites of the Pt nanoparticles, decrease with increasing Au atomic ratio (x). In contrast, the specific ORR activities of the Au(x)/Pt100 samples were dependent on the atomic ratios of Pt and Au: the Au28/Pt100 sample showed the highest specific activity among all the investigated samples (x = 0-42). As for ORR durability evaluated by applying potential cycles between 0.6 and 1.0 V in oxygen-saturated 0.1 M HClO4, Au28/Pt100 was the most durable sample against the electrochemical potential cycles. The results clearly showed that the Au atoms located at coordinatively-unsaturated sites, e.g. at the corners or edges of the Pt nanoparticles, can improve the ORR durability by suppressing unsaturated-site-induced degradation of the Pt nanoparticles.

Platinum-coated non-noble metal-noble metal core-shell electrocatalysts

DOEpatents

Adzic, Radoslav; Zhang, Junliang; Mo, Yibo; Vukmirovic, Miomir

2015-04-14

Core-shell particles encapsulated by a thin film of a catalytically active metal are described. The particles are preferably nanoparticles comprising a non-noble core with a noble metal shell which preferably do not include Pt. The non-noble metal-noble metal core-shell nanoparticles are encapsulated by a catalytically active metal which is preferably Pt. The core-shell nanoparticles are preferably formed by prolonged elevated-temperature annealing of nanoparticle alloys in an inert environment. This causes the noble metal component to surface segregate and form an atomically thin shell. The Pt overlayer is formed by a process involving the underpotential deposition of a monolayer of a non-noble metal followed by immersion in a solution comprising a Pt salt. A thin Pt layer forms via the galvanic displacement of non-noble surface atoms by more noble Pt atoms in the salt. The overall process is a robust and cost-efficient method for forming Pt-coated non-noble metal-noble metal core-shell nanoparticles.

Poly (vinyl alcohol)/gum karaya electrospun plasma treated membrane for the removal of nanoparticles (Au, Ag, Pt, CuO and Fe3O4) from aqueous solutions.

PubMed

Padil, Vinod Vellora Thekkae; Černík, Miroslav

2015-04-28

In the present work, nanofibre membranes composed of polyvinyl alcohol (PVA) and a natural gum karaya (GK) hydrocolloid were prepared using electrospinning. The electrospun membranes of PVA/GK were cross-linked with heat treatment and later methane plasma was used to obtain a hydrophobic membrane. The morphology, characterization and adsorption ability of P-NFM was assessed using scanning electron microscopy, UV-vis spectroscopy, ATR-FTIR techniques, water contact angle and ICP-MS analytical methods. The membrane was employed for the extraction of nanoparticles (Ag, Au, Pt, CuO and Fe3O4) from water. The nanoparticle extraction kinetic and adsorption isotherm perform the pseudo-second-order model and Langmuir isotherm model, respectively. The adsorption capacities of the membrane for the removal of NPs from water diverge in the order Pt>Au>Ag>CuO>Fe3O4. The high adsorption efficiency for the removal of NPs from water was compared with an untreated membrane. Physisorption, functional group interactions, complexation reactions between metal/metal oxide nanoparticles with various functional groups present in NFM and modified surface properties such as the balance of hydrophilicity/hydrophobicity, surface free energy, and the high surface area of the plasma treated membrane were possible mechanisms of NPs adsorption onto NFM. The regeneration and reusability were tested in five consecutive adsorption/desorption cycles. Copyright © 2015 Elsevier B.V. All rights reserved.

Decorating CoP and Pt Nanoparticles on Graphitic Carbon Nitride Nanosheets to Promote Overall Water Splitting by Conjugated Polymers.

PubMed

Pan, Zhiming; Zheng, Yun; Guo, Fangsong; Niu, Pingping; Wang, Xinchen

2017-01-10

The splitting of water into H 2 and O 2 using solar energy is one of the key steps in artificial photosynthesis for the future production of renewable energy. Here, we show the first use of CoP and Pt nanoparticles as dual co-catalysts to modify graphitic carbon nitride (g-C 3 N 4 ) polymer to achieve overall water splitting under visible light irradiation. Our findings demonstrate that loading dual co-catalysts on delaminated g-C 3 N 4 imparts surface redox sites on the g-C 3 N 4 nanosheets that can not only promote catalytic kinetics but also promote charge separation and migration in the soft interface, thus improving the photocatalytic efficiency for overall water splitting. This robust, abundant, and stable photocatalyst based on covalent organic frameworks is demonstrated to hold great promise by forming heterojunctions with CoP and Pt for catalyzing the direct splitting of water into stoichiometric H 2 and O 2 using energy from photons. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrasensitive electrochemical immunosensors for multiplexed determination using mesoporous platinum nanoparticles as nonenzymatic labels.

PubMed

Cui, Zhentao; Wu, Dan; Zhang, Yong; Ma, Hongmin; Li, He; Du, Bin; Wei, Qin; Ju, Huangxian

2014-01-07

An ultrasensitive multiplexed immunoassay method was developed at a disposable immunosensor array using mesoporous platinum nanoparticles (M-Pt NPs) as nonenzymatic labels. M-Pt NPs were prepared by ultrasonic method and employed to label the secondary antibody (Ab2) for signal amplification. The immunosensor array was constructed by covalently immobilizing capture antibody (Ab1) on graphene modified screen printed carbon electrodes (SPECs). After the sandwich-type immunoreactions, the M-Pt-Ab2 was bound to immunosensor surface to catalyze the electro-reduction of H2O2 reaction, which produced detectable signals for readout of analytes. Using breast cancer related panel of tumor markers (CA125, CA153 and CEA) as model analytes, this method showed wide linear ranges of over 4 orders of magnitude with the detection limits of 0.002 U mL(-1), 0.001 U mL(-1) and 7.0 pg mL(-1) for CA125, CA153 and CEA, respectively. The disposable immunosensor array possessed excellent clinical value in cancer screening as well as convenient point of care diagnostics. Copyright © 2013 Elsevier B.V. All rights reserved.

Mass-produced multi-walled carbon nanotubes as catalyst supports for direct methanol fuel cells.

PubMed

Jang, In Young; Park, Ki Chul; Jung, Yong Chae; Lee, Sun Hyung; Song, Sung Moo; Muramatsu, Hiroyuki; Kim, Yong Jung; Endo, Morinobu

2011-01-01

Commercially mass-produced multi-walled carbon nanotubes, i.e., VGNF (Showa Denko Co.), were applied to support materials for platinum-ruthenium (PtRu) nanoparticles as anode catalysts for direct methanol fuel cells. The original VGNFs are composed of high-crystalline graphitic shells, which hinder the favorable surface deposition of the PtRu nanoparticles that are formed via borohydride reduction. The chemical treatment of VGNFs with potassium hydroxide (KOH), however, enables highly dispersed and dense deposition of PtRu nanoparticles on the VGNF surface. This capability becomes more remarkable depending on the KOH amount. The electrochemical evaluation of the PtRu-deposited VGNF catalysts showed enhanced active surface areas and methanol oxidation, due to the high dispersion and dense deposition of the PtRu nanoparticles. The improvement of the surface deposition states of the PtRu nanoparticles was significantly due to the high surface area and mesorporous surface structure of the KOH-activated VGNFs.

Repetitively Coupled Chemical Reduction and Galvanic Exchange as a Synthesis Strategy for Expanding Applicable Number of Pt Atoms in Dendrimer-Encapsulated Pt Nanoparticles.

PubMed

Cho, Taehoon; Yoon, Chang Won; Kim, Joohoon

2018-06-13

In this study, we report the controllable synthesis of dendrimer-encapsulated Pt nanoparticles (Pt DENs) utilizing repetitively coupled chemical reduction and galvanic exchange reactions. The synthesis strategy allows the expansion of the applicable number of Pt atoms encapsulated inside dendrimers to more than 1000 without being limited by the fixed number of complexation sites for Pt 2+ precursor ions in the dendrimers. The synthesis of Pt DENs is achieved in a short period of time (i.e., ∼10 min) simply by the coaddition of appropriate amounts of Cu 2+ and Pt 2+ precursors into aqueous dendrimer solution and subsequent addition of reducing agents such as BH 4 - , resulting in fast and selective complexation of Cu 2+ with the dendrimers and subsequent chemical reduction of the complexed Cu 2+ while uncomplexed Pt 2+ precursors remain oxidized. Interestingly, the chemical reduction of Cu 2+ , leading to the formation of Cu nanoparticles encapsulated inside the dendrimers, is coupled with the galvanic exchange of the Cu nanoparticles with the nearby Pt 2+ . This coupling repetitively proceeds until all of the added Pt 2+ ions form into Pt nanoparticles encapsulated inside the dendrimers. In contrast to the conventional method utilizing direct chemical reduction, this repetitively coupled chemical reduction and galvanic exchange enables a substantial increase in the applicable number of Pt atoms up to 1320 in Pt DENs while maintaining the unique features of DENs.

Identification of the formation of metal-vinylidene interfacial bonds of alkyne-capped platinum nanoparticles by isotopic labeling.

PubMed

Hu, Peiguang; Chen, Limei; Deming, Christopher P; Bonny, Lewis W; Lee, Hsiau-Wei; Chen, Shaowei

2016-10-07

Stable platinum nanoparticles were prepared by the self-assembly of 1-dodecyne and dodec-1-deuteroyne onto bare platinum colloid surfaces. The nanoparticles exhibited consistent core size and optical properties. FTIR and NMR measurements confirmed the formation of Pt-vinylidene (Pt[double bond, length as m-dash]C[double bond, length as m-dash]CH-) interfacial linkages rather than Pt-acetylide (Pt-C[triple bond, length as m-dash]C-) and platinum-hydride (Pt-H) bonds.

Photoactivation of Diiodido-Pt(IV) Complexes Coupled to Upconverting Nanoparticles.

PubMed

Perfahl, Stefanie; Natile, Marta M; Mohamad, Heba S; Helm, Christiane A; Schulzke, Carola; Natile, Giovanni; Bednarski, Patrick J

2016-07-05

The preparation, characterization, and surface modification of upconverting lanthanide-doped hexagonal NaGdF4 nanocrystals attached to light sensitive diiodido-Pt(IV) complexes is presented. The evaluation for photoactivation and cytotoxicity of the novel carboxylated diiodido-Pt(IV) cytotoxic prodrugs by near-infrared (NIR) light (λ = 980 nm) is also reported. We attempted two different strategies for attachment of light-sensitive diiodido-Pt(IV) complexes to Yb,Er- and Yb,Tm-doped β-NaGdF4 upconverting nanoparticles (UCNPs) in order to provide nanohybrids, which offer unique opportunities for selective drug activation within the tumor cells and subsequent spatiotemporal controlled drug release by NIR-to-visible light-upconversion: (A) covalent attachment of the Pt(IV) complex via amide bond formation and (B) carboxylate exchange of oleate on the surface of the UCNPs with diiodido-Pt(IV) carboxylato complexes. Initial feasibility studies showed that NIR applied by a 980 nm laser had only a slight effect on the stability of the various diiodido-Pt(IV) complexes, but when UCNPs were present more rapid loss of the ligand-metal-charge transfer (LMCT) bands of the diiodido-Pt(IV) complexes was observed. Furthermore, Pt released from the Pt(IV) complexes platinated calf-thymus DNA (ct-DNA) more rapidly when NIR was applied compared to dark controls. Of the two attachment strategies, method A with the covalently attached diiodido-Pt(IV) carboxylates via amide bond formation proved to be the most effective method for generating UCNPs that release Pt when irradiated with NIR; the released Pt was also able to bind irreversibly to calf thymus DNA. Nonetheless, only ca. 20% of the Pt on the surface of the UCNPs was in the Pt(IV) oxidation state, the rest was Pt(II), indicating chemical reduction of the diiodido-Pt(IV) prodrug by the UCNPs. Cytotoxicity studies with the various UCNP-Pt conjugates and constructs, tested on human leukemia HL60 cells in culture, indicated a substantial increase in cytotoxicity when modified UCNPs were combined with five rounds of 30 min irradiation with NIR compared to dark controls, but NIR alone also had a significant cytotoxic effect at this duration.

Glucose oxidase-initiated cascade catalysis for sensitive impedimetric aptasensor based on metal-organic frameworks functionalized with Pt nanoparticles and hemin/G-quadruplex as mimicking peroxidases.

PubMed

Zhou, Xingxing; Guo, Shijing; Gao, Jiaxi; Zhao, Jianmin; Xue, Shuyan; Xu, Wenju

2017-12-15

Based on cascade catalysis amplification driven by glucose oxidase (GOx), a sensitive electrochemical impedimetric aptasensor for protein (carcinoembryonic antigen, CEA as tested model) was proposed by using Cu-based metal-organic frameworks functionalized with Pt nanoparticles, aptamer, hemin and GOx (Pt@CuMOFs-hGq-GOx). CEA aptamer loaded onto Pt@CuMOFs was bound with hemin to form hemin@G-quadruplex (hGq) with mimicking peroxidase activity. Through sandwich-type reaction of target CEA and CEA aptamers (Apt1 and Apt2), the obtained Pt@CuMOFs-hGq-GOx as signal transduction probes (STPs) was captured to the modified electrode interface. When 3,3-diaminobenzidine (DAB) and glucose were introduced, the cascade reaction was initiated by GOx to catalyze the oxidation of glucose, in situ generating H 2 O 2 . Simultaneously, the decomposition of the generated H 2 O 2 was greatly promoted by Pt@CuMOFs and hGq as synergistic peroxide catalysts, accompanying with the significant oxidation process of DAB and the formation of nonconductive insoluble precipitates (IPs). As a result, the electron transfer in the resultant sensing interface was effectively hindered and the electrochemical impedimetric signal (EIS) was efficiently amplified. Thus, the high sensitivity of the proposed CEA aptasensor was successfully improved with 0.023pgmL -1 , which may be promising and potential in assaying certain clinical disease related to CEA. Copyright © 2017 Elsevier B.V. All rights reserved.

Graphitized carbon nanofiber-Pt nanoparticle hybrids as sensitive tool for preparation of screen printing biosensors. Detection of lactate in wines and ciders.

PubMed

Loaiza, Oscar A; Lamas-Ardisana, Pedro J; Añorga, Larraitz; Jubete, Elena; Ruiz, Virginia; Borghei, Maryam; Cabañero, Germán; Grande, Hans J

2015-02-01

This work describes the fabrication of a new lactate biosensor. The strategy is based on the use of a novel hybrid nanomaterial for amperometric biosensors i.e. platinum nanoparticles (PtNps) supported on graphitized carbon nanofibers (PtNps/GCNF) prepared by chemical reduction of the Pt precursor at GCNF surfaces. The biosensors were constructed by covalent immobilization of lactate oxidase (LOx) onto screen printed carbon electrodes (SPCEs) modified with PtNps (PtNps/GCNF-SPCEs) using polyethyleneimine (PEI) and glutaraldehyde (GA). Experimental variables concerning both the biosensor design and the detection process were investigated for an optimal analytical performance. Lactate biosensors show good reproducibility (RSD 4.9%, n=10) and sensitivity (41,302±546) μA/Mcm(2), with a good limit of detection (6.9μM). Covalent immobilization of the enzyme allows the reuse of the biosensor for several measurements, converting them in a cheap alternative to the solid electrodes. The long-term stability of the biosensors was also evaluated. 90% of the signal was kept after 3months of storage at room temperature (RT), while 95% was retained after 18months at -20°C. These results demonstrate that the method provides sensitive electrochemical lactate biosensors where the stability of the enzymatic activity can be preserved for a long period of time in adequate storage conditions. Copyright © 2014 Elsevier B.V. All rights reserved.

Metal nanostructures with complex surface morphology: The case of supported lumpy Pd and Pt nanoparticles produced by laser processing of metal films

NASA Astrophysics Data System (ADS)

Ruffino, F.; Maugeri, P.; Cacciato, G.; Zimbone, M.; Grimaldi, M. G.

2016-09-01

In this work we report on the formation of lumpy Pd and Pt nanoparticles on fluorine-doped tin oxide/glass (FTO/glass) substrate by a laser-based approach. In general, complex-surface morphology metal nanoparticles can be used in several technological applications exploiting the peculiarities of their physical properties as modulated by nanoscale morphology. For example plasmonic metal nanoparticles presenting a lumpy morphology (i.e. larger particles coated on the surface by smaller particles) can be used in plasmonic solar cell devices providing broadband scattering enhancement over the smooth nanoparticles leading, so, to the increase of the device efficiency. However, the use of plasmonic lumpy nanoparticles remains largely unexplored due to the lack of simply, versatile, low-cost and high-throughput methods for the controllable production of such nanostructures. Starting from these considerations, we report on the observation that nanoscale-thick Pd and Pt films (17.6 and 27.9 nm, 12.1 and 19.5 nm, respectively) deposited on FTO/glass surface irradiated by nanosecond pulsed laser at fluences E in the 0.5-1.5 J/cm2 range, produce Pd and Pt lumpy nanoparticles on the FTO surface. In addition, using scanning electron microscopy analyses, we report on the observation that starting from each metal film of fixed thickness h, the fraction F of lumpy nanoparticles increases with the laser fluence E and saturates at the higher fluences. For each fixed fluence, F was found higher starting from the Pt films (at each starting film thickness h) with respect to the Pd films. For each fixed metal and fluence, F was found to be higher decreasing the starting thickness of the deposited film. To explain the formation of the lumpy Pd and Pt nanoparticles and the behavior of F as a function of E and h both for Pd and Pt, the thermodynamic behavior of the Pd and Pt films and nanoparticles due to the interaction with the nanosecond laser is discussed. In particular, the photothermal vaporization and Coulomb explosion processes of the Pd and Pt nanoparticles are invoked as possible mechanisms for the lumpy nanoparticles formation.

Optical characterization of broad plasmon resonances of Pd/Pt nanoparticles

NASA Astrophysics Data System (ADS)

Valizade-Shahmirzadi, N.; Pakizeh, T.

2018-04-01

In this paper, optical properties of nanoparticles (nanodisks and nanospheres) composed of photofunctional metals like palladium (Pd) and platinum (Pt) over a large dimension range are investigated using the electromagnetic simulation and quasi-static theory. These characteristics are compared with their counterparts in plasmonic gold (Au) nanoparticles. Pd/Pt-nanodisks with larger dimension have higher absorption and lower scattering efficiencies than Au-nanodisks that accompany with lower extinction efficiencies and broader resonances. Although an increment in the dimension (diameter and height) of Au/Pd/Pt-nanoparticles decreases the absorption-to-scattering ratios, these ratios are less sensitive to the height size in Au-nanodisks, which causes their LSPR spectra become much broader. It is noteworthy that the LSPR quality factor of Pd nanoparticles is improved by considering the radiative damping and depolarization in quasi-static method unlike the Au nanoparticles. The importance of the highly absorptive Pd/Pt nanoparticles can be traced in the photo-functionalized and energy applications.

High magnetic coercivity of FePt-Ag/MgO granular nanolayers

NASA Astrophysics Data System (ADS)

Roghani, R.; Sebt, S. A.; Khajehnezhad, A.

2018-06-01

L10-FePt ferromagnetic nanoparticles have a hight coercivity of Tesla order. Thus, these nanoparticles, with size of 10 to 15 nm and uniform surface distribution, are suitable in magnetic data storage technology with density of more than 1GB. In order to improve structural and magnetic properties of FePt nanoparticles, some elements and combinations have been added to compound. In this research, we show that due to the presence of the Ag, the phase transition temperature of FePt from fcc to L10-fct phase decreases. The presence of Ag as an additive in FePt-Ag nanocomposite, increases the magnetic coercivity. This nanocomposite, with 10% Ag, was deposited by magnetron sputtering on the MgO heat layer. VSM results of 10 nm nanoparticles show that coercivity has increased up to 1.4 T. XRD and FESEM results confirm that the size of the L10-FePt nanoparticles are 10 nm and their surface distribution are uniform. Ag gradually form nano scale clusters with separate lattice and FePt-Ag nanocomposite appears. The result of this process is emptiness of Ag position in FePt-fcc lattice. So, the mobility of Fe and Pt atoms in this lattice increases and it can be possible for them to move in lower temperature. This mechanism explain the effect of Ag on decreasing the transition temperature to fct-L10 phase, and hight coercivity of FePt nanoparticles.

Palladium and Platinum Nanoparticles Attenuate Aging-Like Skin Atrophy via Antioxidant Activity in Mice

PubMed Central

Shibuya, Shuichi; Ozawa, Yusuke; Watanabe, Kenji; Izuo, Naotaka; Toda, Toshihiko; Yokote, Koutaro; Shimizu, Takahiko

2014-01-01

Cu-Zn superoxide dismutase (Sod1) loss causes a redox imbalance as it leads to excess superoxide generation, which results in the appearance of various aging-related phenotypes, including skin atrophy. Noble metal nanoparticles, such as palladium (Pd) and platinum (Pt) nanoparticles, are considered to function as antioxidants due to their strong catalytic activity. In Japan, a mixture of Pd and Pt nanoparticles called PAPLAL has been used to treat chronic diseases over the past 60 years. In the present study, we investigated the protective effects of PAPLAL against aging-related skin pathologies in mice. Transdermal PAPLAL treatment reversed skin thinning associated with increased lipid peroxidation in Sod1 −/− mice. Furthermore, PAPLAL normalized the gene expression levels of Col1a1, Mmp2, Has2, Tnf-α, Il-6, and p53 in the skin of the Sod1 −/− mice. Pt nanoparticles exhibited marked SOD and catalase activity, while Pd nanoparticles only displayed weak SOD and catalase activity in vitro. Although the SOD and catalase activity of the Pt nanoparticles significantly declined after they had been oxidized in air, a mixture of Pd and Pt nanoparticles continued to exhibit SOD and catalase activity after oxidation. Importantly, a mixture of Pd and Pt nanoparticles with a molar ratio of 3 or 4 to 1 continued to exhibit SOD and catalase activity after oxidation, indicating that Pd nanoparticles prevent the oxidative deterioration of Pt nanoparticles. These findings indicate that PAPLAL stably suppresses intrinsic superoxide generation both in vivo and in vitro via SOD and catalase activity. PAPLAL is a potentially powerful tool for the treatment of aging-related skin diseases caused by oxidative damage. PMID:25333617

Palladium and platinum nanoparticles attenuate aging-like skin atrophy via antioxidant activity in mice.

PubMed

Shibuya, Shuichi; Ozawa, Yusuke; Watanabe, Kenji; Izuo, Naotaka; Toda, Toshihiko; Yokote, Koutaro; Shimizu, Takahiko

2014-01-01

Cu-Zn superoxide dismutase (Sod1) loss causes a redox imbalance as it leads to excess superoxide generation, which results in the appearance of various aging-related phenotypes, including skin atrophy. Noble metal nanoparticles, such as palladium (Pd) and platinum (Pt) nanoparticles, are considered to function as antioxidants due to their strong catalytic activity. In Japan, a mixture of Pd and Pt nanoparticles called PAPLAL has been used to treat chronic diseases over the past 60 years. In the present study, we investigated the protective effects of PAPLAL against aging-related skin pathologies in mice. Transdermal PAPLAL treatment reversed skin thinning associated with increased lipid peroxidation in Sod1-/- mice. Furthermore, PAPLAL normalized the gene expression levels of Col1a1, Mmp2, Has2, Tnf-α, Il-6, and p53 in the skin of the Sod1-/- mice. Pt nanoparticles exhibited marked SOD and catalase activity, while Pd nanoparticles only displayed weak SOD and catalase activity in vitro. Although the SOD and catalase activity of the Pt nanoparticles significantly declined after they had been oxidized in air, a mixture of Pd and Pt nanoparticles continued to exhibit SOD and catalase activity after oxidation. Importantly, a mixture of Pd and Pt nanoparticles with a molar ratio of 3 or 4 to 1 continued to exhibit SOD and catalase activity after oxidation, indicating that Pd nanoparticles prevent the oxidative deterioration of Pt nanoparticles. These findings indicate that PAPLAL stably suppresses intrinsic superoxide generation both in vivo and in vitro via SOD and catalase activity. PAPLAL is a potentially powerful tool for the treatment of aging-related skin diseases caused by oxidative damage.

Ga-Doped Pt-Ni Octahedral Nanoparticles as a Highly Active and Durable Electrocatalyst for Oxygen Reduction Reaction.

PubMed

Lim, JeongHoon; Shin, Hyeyoung; Kim, MinJoong; Lee, Hoin; Lee, Kug-Seung; Kwon, YongKeun; Song, DongHoon; Oh, SeKwon; Kim, Hyungjun; Cho, EunAe

2018-04-11

Bimetallic PtNi nanoparticles have been considered as a promising electrocatalyst for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs) owing to their high catalytic activity. However, under typical fuel cell operating conditions, Ni atoms easily dissolve into the electrolyte, resulting in degradation of the catalyst and the membrane-electrode assembly (MEA). Here, we report gallium-doped PtNi octahedral nanoparticles on a carbon support (Ga-PtNi/C). The Ga-PtNi/C shows high ORR activity, marking an 11.7-fold improvement in the mass activity (1.24 A mg Pt -1 ) and a 17.3-fold improvement in the specific activity (2.53 mA cm -2 ) compared to the commercial Pt/C (0.106 A mg Pt -1 and 0.146 mA cm -2 ). Density functional theory calculations demonstrate that addition of Ga to octahedral PtNi can cause an increase in the oxygen intermediate binding energy, leading to the enhanced catalytic activity toward ORR. In a voltage-cycling test, the Ga-PtNi/C exhibits superior stability to PtNi/C and the commercial Pt/C, maintaining the initial Ni concentration and octahedral shape of the nanoparticles. Single cell using the Ga-PtNi/C exhibits higher initial performance and durability than those using the PtNi/C and the commercial Pt/C. The majority of the Ga-PtNi nanoparticles well maintain the octahedral shape without agglomeration after the single cell durability test (30,000 cycles). This work demonstrates that the octahedral Ga-PtNi/C can be utilized as a highly active and durable ORR catalyst in practical fuel cell applications.

RNA mediated assembly of nanostructures

NASA Astrophysics Data System (ADS)

Rouge, Jessica Lynn

The first chapter of this work presents a comprehensive look at RNA mediated nanoparticle formation. The overall goal of this research is to gain a deeper understanding of the RNA-particle formation mechanism and the basic properties of the materials selected by modified RNA molecules. Understanding such RNA-substrate interactions and how they translate into the physical and chemical characteristics of the nanoparticles they create are important fundamental concepts when considering these biotemplated materials as potential chemical catalysts. The RNA sequences discussed in the first chapter (referred to as Pdases) were discovered using RNA in vitro selection techniques. These Pdases were found to be capable of forming inorganic palladium (Pd) containing nanoparticles with impressive control over an individual particle's size and shape, despite incubation with the same organometallic precursor. This discovery held exciting implications for inorganic nanoparticle design while also generating numerous questions regarding the mechanism of RNA mediated particle growth. The central question that arose after this initial discovery was how could a biomolecule be used to tailor the physical size and shape of inorganic materials? Starting with a chemical proof designed to uncover the composition of the nanoparticles formed by RNA mediation, this chapter investigates the basic material properties of the nanoparticles while also introducing surprising results regarding the effect of multiple sequences on nanoparticle growth outcomes. In the second chapter, the experiments shift to developing methods to investigate nanoparticle growth mechanisms by fluorescence spectroscopy. A fluorescence polarization anisotropy (FPA) assay is presented in which the strengths of the technique are adapted for studying the formation of RNA mediated Pd nanoparticles in real time. This is a unique application of FPA, as it has been adapted to encompass both the biochemical and materials analysis of a single dynamic system. Although the initial studies described in chapter two focus on the growth kinetics of selected Pdases and their organometallic substrate (Pd2DBA3), it is envisioned that this technique can be used to study a variety of biotemplated systems in a similar fashion. For the experiments described, a key interest was to understand if the RNA governed the rates associated with nanoparticle formation and to gain deeper insight in to the potential growth mechanisms of RNA-nanoparticle constructs. Understanding such interactions could help identify the role RNA play in forming materials while also helping to shape the experimental design of future in vitro selections between RNA and materials. The strengths of these FPA experiments are described as well the associated kinetics observed for RNA mediated particle growth. In chapter three, the fundamental concepts surrounding RNA-nanoparticle interactions shifts to the first application-oriented study of RNA mediated nanoparticle formation for chemical catalysis. The product of a second materials selection is presented in which platinum (Pt) rich nanoparticles are formed using pyridyl modified RNA sequences. These RNA-Pt nanoparticle constructs are interfaced with cadmium sulfide (CdS) quantum dots in an effort to assess the ability of the RNA-Pt nanoparticles to serve as functional catalyst for the photocatalytic production of metal hydrides from aqueous solutions at neutral pH. Metal hydride formation is a crucial step in the challenging chemical reaction of water splitting. The results of this hybrid RNA-Pt/CdS water splitting catalyst are described and compared to more traditional catalyst designs. In the final chapter, the combination of concepts and insights gained as presented in chapters 1-3 are systematically combined into the first RNA in vitro selection for photochemically active materials. This novel selection utilizes an RNA library that is chemically modified such that it can both find and assess the ability of a material to perform photon-driven oxidation chemistry in a complex mixture. In order to conduct such a selection, a new DNA phosphoramidite was synthesized and attached to the RNA library prior to beginning the selection. The details of this synthesis are described. Later in this chapter, the results of this complex yet powerful in vitro selection are outlined. In closing, the prospect of using in vitro selection techniques for discovering other chemically active materials is discussed.

Platinum nanoparticles for the photothermal treatment of Neuro 2A cancer cells.

PubMed

Manikandan, M; Hasan, Nazim; Wu, Hui-Fen

2013-07-01

This study demonstrates the effective synthesis of five different sized/shaped Pt NPs, within a narrow size regime of 1-21 nm using a modified methodology and the toxicity/biocompatibility of Pt NPs on Neuro 2A cancer cells was investigated elaborately by using light microscopic observations, tryphan blue exclusion assay, MTT assay and ICP-MS. The Pt NPs-C with sizes 5-6 nm showed superior non-cytotoxic property compared to the other four Pt NPs. These non-cytotoxic Pt NPs were employed for successful photothermal treatment of Neuro 2A cell lines using near-IR 1064 nm of laser irradiation. The Pt NPs-C could generate a 9 °C increase in temperature leading to effective photothermal killing of cancer cells. The MALDI-MS was used to prove the possibility of apoptosis related triggering of cell death in the presence of the Pt NPs. The results confirm that the current approach is an effective platform for in vivo treatment of neuro cancer cells. Copyright © 2013 Elsevier Ltd. All rights reserved.

Fabrication of Highly Stable and Efficient PtCu Alloy Nanoparticles on Highly Porous Carbon for Direct Methanol Fuel Cells.

PubMed

Khan, Inayat Ali; Qian, Yuhong; Badshah, Amin; Zhao, Dan; Nadeem, Muhammad Arif

2016-08-17

Boosting the durability of Pt nanoparticles by controlling the composition and morphology is extremely important for fuel cells commercialization. We deposit the Pt-Cu alloy nanoparticles over high surface area carbon in different metallic molar ratios and optimize the conditions to achieve desired material. The novel bimetallic electro-catalyst {Pt-Cu/PC-950 (15:15%)} offers exceptional electrocatalytic activity when tested for both oxygen reduction reaction and methanol oxidation reactions. A high mass activity of 0.043 mA/μgPt (based on Pt mass) is recorded for ORR. An outstanding longevity of this electro-catalyst is noticed when compared to 20 wt % Pt loaded either on PC-950 or commercial carbon. The high surface area carbon support offers enhanced activity and prevents the nanoparticles from agglomeration, migration, and dissolution as evident by TEM analysis.

Microgravity Effects on Chronoamperometric Ammonia Oxidation Reaction at Platinum Nanoparticles on Modified Mesoporous Carbon Supports

NASA Astrophysics Data System (ADS)

Poventud-Estrada, Carlos M.; Acevedo, Raúl; Morales, Camila; Betancourt, Luis; Diaz, Diana C.; Rodriguez, Manuel A.; Larios, Eduardo; José-Yacaman, Miguel; Nicolau, Eduardo; Flynn, Michael; Cabrera, Carlos R.

2017-10-01

The effect of microgravity on the electrochemical oxidation of ammonia at platinum nanoparticles supported on modified mesoporous carbons (MPC) with three different pore diameters (64, 100, and 137 Å) was studied via the chronoamperometric technique in a half-cell. The catalysts were prepared by a H2 reductive process of PtCl6^{4-} in presence of the mesoporous carbon support materials. A microgravity environment was obtained with an average gravity of less than 0.02 g created aboard an airplane performing parabolic maneuvers. Results show the chronoamperommetry of the ammonia oxidation reaction in 1.0 M NH4OH at 0.60 V vs. RHE under microgravity conditions. The current density, in all three catalysts, decreased while in microgravity conditions when compared to ground based experiments. Under microgravity, all three catalysts yielded a decrease in ammonia oxidation reaction current density between 25 to 63% versus terrestrial experimental results, in time scales between 1 and 15 s. The Pt catalyst prepared with mesoporous carbon of 137 Å porous showed the smallest changes, between 25 to 48%. Nanostructuring catalyst materials have an effect on the level of current density decrease under microgravity conditions.

Block copolymer directed one-pot simple synthesis of L10-phase FePt nanoparticles inside ordered mesoporous aluminosilicate/carbon composites.

PubMed

Kang, Eunae; Jung, Hyunok; Park, Je-Geun; Kwon, Seungchul; Shim, Jongmin; Sai, Hiroaki; Wiesner, Ulich; Kim, Jin Kon; Lee, Jinwoo

2011-02-22

A "one-pot" synthetic method was developed to produce L1(0)-phase FePt nanoparticles in ordered mesostructured aluminosilicate/carbon composites using polyisoprene-block-poly(ethylene oxide) (PI-b-PEO) as a structure-directing agent. PI-b-PEO block copolymers with aluminosilicate sols are self-assembled with a hydrophobic iron precursor (dimethylaminomethyl-ferrocene) and a hydrophobic platinum precursor (dimethyl(1,5-cyclooctadiene)platinum(II)) to obtain mesostructured composites. The as-synthesized material was heat-treated to 800 °C under an Ar/H(2) mixture (5% v/v), resulting in the formation of fct FePt nanocrystals encapsulated in ordered mesopores. By changing the quantities of the Fe and Pt precursors in the composite materials, the average particle size of the resulting fct FePt, estimated using the Debye-Scherer equation with X-ray diffraction patterns, can be easily controlled to be 2.6-10.4 nm. Using this simple synthetic method, we can extend the size of directly synthesized fct FePt up to ∼10 nm, which cannot be achieved directly in the colloidal synthetic method. All fct FePt nanoparticles show hysteresis behavior at room temperature, which indicates that ferromagnetic particles are obtained inside mesostructued channels. Well-isolated, ∼10 nm fct FePt have a coercivity of 1100 Oe at 300 K. This coercivity value is higher than values of fct FePt nanoparticles synthesized through the tedious hard template method by employing SBA-15 as a host material. The coercivity value for FePt-1 (2.6 nm) at 5 K is as high as 11 900 Oe, which is one of the largest values reported for FePt nanoparticles, or any other magnetic nanoparticles. The fct FePt nanoparticles also showed exchange-bias behavior.

Synthesis and hydrogenation application of Pt–Pd bimetallic nanocatalysts stabilized by macrocycle-modified dendrimer

PubMed Central

Xiao, Haiyan; Zhou, Wei; Zhang, Dongqiao; Peng, Xiaohong

2017-01-01

Different generations of poly(propylene imine) (Gn-PPI) terminated with N-containing 15-membered triolefinic macrocycle (GnM) (n = 2, 3, 4, 5) were prepared. The bimetallic nanoparticle catalysts GnM-(Ptx/Pd10−x) (x = 0, 3, 5, 7, 10) were prepared by the synchronous ligand-exchange reaction between GnM and the complexes of Pt(PPh3)4 and Pd(PPh3)4. The structure and catalytic properties of GnM-(Ptx/Pd10−x) were characterized via Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, energy-dispersive spectroscopy and inductively coupled plasma atomic emission spectroscopy. The novel bimetallic Pd–Pt nanoparticle catalysts stabilized by dendrimers (DSNs) present higher catalytic activities for the hydrogenation of dimeric acid (DA) than that of nitrile butadiene rubber (NBR). It can be concluded that bimetallic Pd–Pt DSNs possess alloying and synergistic electronic effects on account of the hydrogenation degree (HD) of DA and NBR. Furthermore, the HD of DA and NBR shows a remarkable decrease with the incremental generations (n) of GnM-(Pt3/Pd7) (n = 2, 3, 4, 5). PMID:29308263

Nano-engineered intrapores in nanoparticles of PtNi networks for increased oxygen reduction reaction activity

NASA Astrophysics Data System (ADS)

Ding, Jieting; Ji, Shan; Wang, Hui; Key, Julian; Brett, Dan J. L.; Wang, Rongfang

2018-01-01

Network-like metallic alloys of solid nanoparticles have been frequently reported as promising electrocatalysts for fuel cells. The three-dimensional structure of such networks is rich in pores in the form of voids between nanoparticles, which collectively expose a large surface area for catalytic activity. Herein, we present a novel solution to this problem using a precursor comprising a flocculent core-shell PtNi@Ni to produce PtNi network catalysts with nanoparticle intraporosity after carefully controlled electrochemical dealloying. Physical characterization shows a hierarchical level of nanoporosity (intrapores within nanoparticles and pores between them) evolves during the controlled electrochemical dealloying, and that a Pt-rich surface also forms after 22 cycles of Ni leaching. In ORR cycling, the PtNi networks gain 4-fold activity in both jECSA and jmass over a state of the art Pt/C electrocatalyst, and also significantly exceed previously reported PtNi networks. In ORR degradation tests, the PtNi networks also proved stable, dropping by 30.4% and 62.6% in jECSA and jmass respectively. The enhanced performance of the catalyst is evident, and we also propose that the presented synthesis procedure can be generally applied to developing other metallic networks.

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 platinum nanoparticle has excellent receptor targeting specificity and enhanced radiation sensitization compared to nanoparticle alone, suggesting potential for clinical applications in breast cancer radiotherapy.« less

Green Synthesis, Characterization and Uses of Palladium/Platinum Nanoparticles

NASA Astrophysics Data System (ADS)

Siddiqi, Khwaja Salahuddin; Husen, Azamal

2016-11-01

Biogenic synthesis of palladium (Pd) and platinum (Pt) nanoparticles from plants and microbes has captured the attention of many researchers because it is economical, sustainable and eco-friendly. Plant and their parts are known to have various kinds of primary and secondary metabolites which reduce the metal salts to metal nanoparticles. Shape, size and stability of Pd and Pt nanoparticles are influenced by pH, temperature, incubation time and concentrations of plant extract and that of the metal salt. Pd and Pt nanoparticles are broadly used as catalyst, as drug, drug carrier and in cancer treatment. They have shown size- and shape-dependent specific and selective therapeutic properties. In this review, we have discussed the biogenic fabrication of Pd/Pt nanoparticles, their potential application as catalyst, medicine, biosensor, medical diagnostic and pharmaceuticals.

Pt-Richcore/Sn-Richsubsurface/Ptskin Nanocubes As Highly Active and Stable Electrocatalysts for the Ethanol Oxidation Reaction.

PubMed

Rizo, Rubén; Arán-Ais, Rosa M; Padgett, Elliot; Muller, David A; Lázaro, Ma Jesús; Solla-Gullón, José; Feliu, Juan M; Pastor, Elena; Abruña, Héctor D

2018-03-14

Direct ethanol fuel cells are one of the most promising electrochemical energy conversion devices for portable, mobile and stationary power applications. However, more efficient and stable and less expensive electrocatalysts are still required. Interestingly, the electrochemical performance of the electrocatalysts toward the ethanol oxidation reaction can be remarkably enhanced by exploiting the benefits of structural and compositional sensitivity and control. Here, we describe the synthesis, characterization, and electrochemical behavior of cubic Pt-Sn nanoparticles. The electrochemical activity of the cubic Pt-Sn nanoparticles was found to be about three times higher than that obtained with unshaped Pt-Sn nanoparticles and six times higher than that of Pt nanocubes. In addition, stability tests indicated the electrocatalyst preserves its morphology and remains well-dispersed on the carbon support after 5000 potential cycles, while a cubic (pure) Pt catalyst exhibited severe agglomeration of the nanoparticles after a similar stability testing protocol. A detailed analysis of the elemental distribution in the nanoparticles by STEM-EELS indicated that Sn dissolves from the outer part of the shell after potential cycling, forming a ∼0.5 nm Pt skin. This particular atomic composition profile having a Pt-rich core, a Sn-rich subsurface layer, and a Pt-skin surface structure is responsible for the high activity and stability.

Size effect on L10 ordering and magnetic properties of chemically synthesized FePt and FePtAu nanoparticles

NASA Astrophysics Data System (ADS)

Jia, Zhiyong; Kang, Shishou; Shi, Shifan; Nikles, David E.; Harrell, J. W.

2005-05-01

There is growing evidence that FePt nanoparticles become increasingly difficult to chemically order as the size approaches a few nanometers. We have studied the chemical ordering of FePt and FePtAu nanoparticle arrays as a function of particle size. Monodisperse Fe49Pt51 and Fe48Pt44Au8 nanoparticles with a size about 6nm were synthesized by the simultaneous decomposition of iron pentacarbonyl and reduction of platinum acetylacetonate and gold (III) acetate in a mixture of phenyl ether and hexadecylamine (HDA), with 1-adamantanecarboxylic acid and HDA as stabilizers. The nanoparticles were dispersed in toluene, films of the particles were cast onto silicon wafers from the dispersion, and the films were annealed in a tube furnace with flowing Ar +5%H2. The magnetic anisotropy and switching volumes were determined from time- and temperature-dependent coercivity measurements. By comparing with 3-nm FePt and FePtAu nanoparticles of comparable composition, the phase transformation is easier for the larger particles. Under the same annealing conditions, the larger particles have higher anisotropy and order parameter. Additive Au is very effective in enhancing the chemical ordering in both small and large particles, with x-ray diffraction superlattice peaks appearing after annealing at 350°C. Dynamic remnant coercivity measurements and magnetic switching volumes suggest particle aggregation at the higher annealing temperatures in both small and large particles.

Atomic layer deposited highly dispersed platinum nanoparticles supported on non-functionalized multiwalled carbon nanotubes for the hydrogenation of xylose to xylitol

NASA Astrophysics Data System (ADS)

Liang, Xinhua; Jiang, Chengjun

2013-09-01

Highly dispersed platinum nanoparticles were deposited on gram quantities of non-functionalized multiwalled carbon nanotubes (MWCNTs) by atomic layer deposition (ALD) in a fluidized bed reactor at 300 °C. (Methylcyclopentadienyl) trimethylplatinum and oxygen were used as precursors. The results of TEM analysis showed that 1.3 nm Pt nanoparticles were highly dispersed on non-functionalized MWCNTs. The porous structures of MWCNTs did not change with the deposition of Pt nanoparticles. For comparison, the commercial 3 wt% Pt/C catalyst was also characterized. The ALD-prepared Pt/MWCNT was used for the hydrogenation of xylose to xylitol. The ALD-prepared Pt/MWCNT showed the best catalytic performance with 100 % conversion of xylose and 99.3 % selectivity to xylitol, compared to commercially available Pt/C, Ru/C, and Raney Ni catalysts. The stability of ALD produced Pt/MWCNT catalyst was higher than that of the commercial Pt/C, due to the presence of surface defects on the MWCNTs and the strong metal-support interaction for the ALD-prepared Pt/MWCNT catalyst.

Preparation of Pt Nanocatalyst on Carbon Materials via a Reduction Reaction of a Pt Precursor in a Drying Process.

PubMed

Lee, Jae-Young; Lee, Woo-Kum; Rim, Hyung-Ryul; Joung, Gyu-Bum; Weidner, John W; Lee, Hong-Ki

2016-06-01

Platinum (Pt) nanocatalyst for a proton-exchange membrane fuel cell (PEMFC) was prepared on a carbon black particle or a graphite particle coated with a nafion polymer via a reduction of platinum(II) bis(acetylacetonate) denoted as Pt(acac)2 as a Pt precursor in a drying process. Sublimed Pt(acac)2 adsorbed on the nafion-coated carbon materials was reduced to Pt nanoparticles in a glass reactor at 180 degrees C of N2 atmosphere. The morphology of Pt nanoparticles on carbon materials was observed by scanning electron microscopy (SEM) and the distribution of Pt nanoparticles was done by transmission electron microscopy (TEM). The particle size was estimated by analyzing the TEM image using an image analyzer. It was found that nano-sized Pt particles were deposited on the surface of carbon materials, and the number density and the average particle size increased with increasing reduction time.

Size-Controlled Synthesis of Sub-10 nm PtNi3 Alloy Nanoparticles and their Unusual Volcano-Shaped Size Effect on ORR Electrocatalysis.

PubMed

Gan, Lin; Rudi, Stefan; Cui, Chunhua; Heggen, Marc; Strasser, Peter

2016-06-01

Dealloyed Pt bimetallic core-shell catalysts derived from low-Pt bimetallic alloy nanoparticles (e.g, PtNi3 ) have recently shown unprecedented activity and stability on the cathodic oxygen reduction reaction (ORR) under realistic fuel cell conditions and become today's catalyst of choice for commercialization of automobile fuel cells. A critical step toward this breakthrough is to control their particle size below a critical value (≈10 nm) to suppress nanoporosity formation and hence reduce significant base metal (e.g., Ni) leaching under the corrosive ORR condition. Fine size control of the sub-10 nm PtNi3 nanoparticles and understanding their size dependent ORR electrocatalysis are crucial to further improve their ORR activity and stability yet still remain unexplored. A robust synthetic approach is presented here for size-controlled PtNi3 nanoparticles between 3 and 10 nm while keeping a constant particle composition and their size-selected growth mechanism is studied comprehensively. This enables us to address their size-dependent ORR activities and stabilities for the first time. Contrary to the previously established monotonic increase of ORR specific activity and stability with increasing particle size on Pt and Pt-rich bimetallic nanoparticles, the Pt-poor PtNi3 nanoparticles exhibit an unusual "volcano-shaped" size dependence, showing the highest ORR activity and stability at the particle sizes between 6 and 8 nm due to their highest Ni retention during long-term catalyst aging. The results of this study provide important practical guidelines for the size selection of the low Pt bimetallic ORR electrocatalysts with further improved durably high activity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of three-dimensional buckypaper catalyst layer with Pt nanoparticles supported on polyelectrolyte functionalized carbon nanotubes for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zhu, Shiyao; Zheng, Junsheng; Huang, Jun; Dai, Ningning; Li, Ping; Zheng, Jim P.

2018-07-01

Polyelectrolyte poly(diallyldimethylammonium chloride) (PDDA) functionalized carbon nanotubes (CNTs) supported Pt electrocatalyst was synthesized as a substitute for commonly used Pt/C and Pt/CNTs (modified by harsh acid-oxidation treatment) catalysts. In addition, this catalyst was fabricated as the cathode catalyst layer (CL) with a unique double-layered structure for proton exchange membrane fuel cells (PEMFCs). Thermogravimetric analysis shows an enhanced thermal stability of Pt/PDDA-CNTs. The Pt/PDDA-CNTs catalyst with an average Pt particle size of ∼3.1 nm exhibits the best electrocatalytic activity and a significantly enhanced electrochemical stability. Scanning electron microscope, energy dispersive spectrometer and mercury intrusion porosimetry results demonstrate the gradient distribution of Pt content and pore size along the thickness of buckypaper catalyst layer (BPCL). The accelerated degradation test results of BPCLs indicate that this gradient structure can ensure a high Pt utilization in the BPCLs (up to 90%) and further improve the catalyst durability. In addition, the membrane electrode assembly (MEA) fabricated with cathode BPCL-PDDA shows the best single cell performance and long-term stability, and a reduction of Pt loading can be achieved. The feasibility of BPCL for improving the Pt utilization is also demonstrated by the cathode cyclic voltammetry in MEA.

Tuning the synthesis of platinum-copper nanoparticles with a hollow core and porous shell for the selective hydrogenation of furfural to furfuryl alcohol.

PubMed

Huang, Shuangshuang; Yang, Nating; Wang, Shibin; Sun, Yuhan; Zhu, Yan

2016-08-07

Pt-Cu nanoparticles constructed with a hollow core and porous shell have been synthesized in which Pt-Cu cages with multiporous outermost shells are formed at the initial stage and then the Pt and Cu atoms in solution continuously fed these hollow-core of cages by passing through the porous tunnels of the outermost shells, finally leading to the formation of hollow structures with different sizes. Furthermore, these hollow-core Pt-Cu nanoparticles are more effective than the solid-core Pt-Cu nanoparticles for the catalytic hydrogenation of furfural toward furfuryl alcohol. The former can achieve almost 100% conversion of furfural with 100% selectivity toward the alcohol.

A method for the formation of Pt metal nanoparticle arrays using nanosecond pulsed laser dewetting

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

Owusu-Ansah, Ebenezer; Horwood, Corie A.; Birss, Viola I.

2015-05-18

Nanosecond pulsed laser dewetting of Pt thin films, deposited on a dimpled Ta (DT) surface, has been studied here in order to form ordered Pt nanoparticle (NP) arrays. The DT substrate was fabricated via a simple electrochemical anodization process in a highly concentrated H{sub 2}SO{sub 4} and HF solution. Pt thin films (3–5 nm) were sputter coated on DT and then dewetted under vacuum to generate NPs using a 355 nm laser radiation (6–9 ns, 10 Hz). The threshold laser fluence to fully dewet a 3.5 nm thick Pt film was determined to be 300 mJ/cm{sup 2}. Our experiments have shown that shorter irradiation timesmore » (≤60 s) produce smaller nanoparticles with more uniform sizes, while longer times (>60 s) give large nanoparticles with wider size distributions. The optimum laser irradiation time of 1 s (10 pulses) has led to the formation of highly ordered Pt nanoparticle arrays with an average nanoparticle size of 26 ± 3 nm with no substrate deformation. At the optimum condition of 1 s and 500 mJ/cm{sup 2}, as many as 85% of the dewetted NPs were found neatly in the well-defined dimples. This work has demonstrated that pulsed laser dewetting of Pt thin films on a pre-patterned dimpled substrate is an efficient and powerful technique to produce highly ordered Pt nanoparticle arrays. This method can thus be used to produce arrays of other high-melting-point metal nanoparticles for a range of applications, including electrocatalysis, functionalized nanomaterials, and analytical purposes.« less

Core-level binding energy shifts in Pt Ru nanoparticles: A puzzle resolved

NASA Astrophysics Data System (ADS)

Lewera, Adam; Zhou, Wei Ping; Hunger, Ralf; Jaegermann, Wolfram; Wieckowski, Andrzej; Yockel, Scott; Bagus, Paul S.

2007-10-01

Synchrotron measurements of Pt and Ru core-level binding energies, BE's, in Pt-Ru nanoparticles, as a function of Pt content, quantify earlier indications that the Pt 4f BE shift is much larger than the Ru 3d BE shift. A complementary theoretical analysis relates the BE shifts to changes in the metal-metal distances as the composition of the nanoparticle changes. We establish that the large Pt and small Ru BE shifts arise from the different response of these metals to changes in the bond distances, an unexpected result. Our results give evidence that the magnitudes of the BE shifts depend on whether the d band is open, as for Ru, or essentially filled, as for Pt.

Templated assembly of Co-Pt nanoparticles via thermal and laser-induced dewetting of bilayer metal films.

PubMed

Oh, Yong-Jun; Kim, Jung-Hwan; Thompson, Carl V; Ross, Caroline A

2013-01-07

Templated dewetting of a Co/Pt metal bilayer film on a topographic substrate was used to assemble arrays of Co-Pt alloy nanoparticles, with highly uniform particle size, shape and notably composition compared to nanoparticles formed on an untemplated substrate. Solid-state and liquid-state dewetting processes, using furnace annealing and laser irradiation respectively, were compared. Liquid state dewetting produced more uniform, conformal nanoparticles but they had a polycrystalline disordered fcc structure and relatively low magnetic coercivity. In contrast, solid state dewetting enabled formation of magnetically hard, ordered L1(0) Co-Pt single-crystal particles with coercivity >12 kOe. Furnace annealing converted the nanoparticles formed by liquid state dewetting into the L1(0) phase.

In Situ Generation of Two-Dimensional Au–Pt Core–Shell Nanoparticle Assemblies

PubMed Central

2010-01-01

Two-dimensional assemblies of Au–Pt bimetallic nanoparticles are generated in situ on polyethyleneimmine (PEI) silane functionalized silicon and indium tin oxide (ITO) coated glass surfaces. Atomic force microscopy (AFM), UV–Visible spectroscopy, and electrochemical measurements reveal the formation of core–shell structure with Au as core and Pt as shell. The core–shell structure is further supported by comparing with the corresponding data of Au nanoparticle assemblies. Static contact angle measurements with water show an increase in hydrophilic character due to bimetallic nanoparticle generation on different surfaces. It is further observed that these Au–Pt core–shell bimetallic nanoparticle assemblies are catalytically active towards methanol electro-oxidation, which is the key reaction for direct methanol fuel cells (DMFCs). PMID:20651923

Multimetallic nanoparticle catalysts with enhanced electrooxidation

DOEpatents

Sun, Shouheng; Zhang, Sen; Zhu, Huiyuan; Guo, Shaojun

2015-07-28

A new structure-control strategy to optimize nanoparticle catalysis is provided. The presence of Au in FePtAu facilitates FePt structure transformation from chemically disordered face centered cubic (fcc) structure to chemically ordered face centered tetragonal (fct) structure, and further promotes formic acid oxidation reaction (FAOR). The fct-FePtAu nanoparticles show high CO poisoning resistance, achieve mass activity as high as about 2810 mA/mg Pt, and retain greater than 90% activity after a 13 hour stability test.

Pd-Pt and Fe-Ni nanoparticles formed by covalent molecular assembly in supercritical carbon dioxide.

PubMed

Puniredd, Sreenivasa Reddy; Weiyi, Seah; Srinivasan, M P

2008-04-01

We report the formation of Pd-Pt nanoparticles within a dendrimer-laden ultrathin film matrix immobilized on a solid support and constructed by covalent layer-by-layer (LbL) assembly using supercritical carbon dioxide (SCCO2) as the processing medium. Particle size distribution and composition were controlled by precursor composition. The precursor compositions are optimized for Pd-Pt nanoparticles and later extended to the formation of Fe-Ni nanoparticles. As an example of the application of nanoparticles in tribology, Fe-Ni nanoparticle-laden films were observed to exhibit better tribological properties than those containing the monometallic species, thereby suggesting that combination of nanoparticles can be used to derive greater benefits.

The microwave-assisted ionic liquid nanocomposite synthesis: platinum nanoparticles on graphene and the application on hydrogenation of styrene

PubMed Central

2013-01-01

The microwave-assisted nanocomposite synthesis of metal nanoparticles on graphene or graphite oxide was introduced in this research. With microwave assistance, the Pt nanoparticles on graphene/graphite oxide were successfully produced in the ionic liquid of 2-hydroxyethanaminium formate [HOCH2CH2NH3][HCO2]. On graphene/graphite oxide, the sizes of Pt nanoparticles were about 5 to 30 nm from transmitted electron microscopy (TEM) results. The crystalline Pt structures were examined by X-ray diffraction (XRD). Since hydrogenation of styrene is one of the important well-known chemical reactions, herein, we demonstrated then the catalytic hydrogenation capability of the Pt nanoparticles on graphene/graphite oxide for the nanocomposite to compare with that of the commercial catalysts (Pt/C and Pd/C, 10 wt.% metal catalysts on activated carbon from Strem chemicals, Inc.). The conversions with the Pt nanoparticles on graphene are >99% from styrene to ethyl benzene at 100°C and under 140 psi H2 atmosphere. However, ethyl cyclohexane could be found as a side product at 100°C and under 1,520 psi H2 atmosphere utilizing the same nanocomposite catalyst. PMID:24103100

Immobilizing Highly Catalytically Active Pt Nanoparticles inside the Pores of Metal-Organic Framework: A Double Solvents Approach

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

Aijaz, Arshad; Karkamkar, Abhijeet J.; Choi, Young Joon

2012-08-29

Ultrafine Pt nanoparticles were successfully immobilized inside the pores of a metal-organic framework MIL-101 without deposition of Pt nanoparticles on the external surfaces of framework by using a 'double solvents' method. The resulting Pt@MIL-101 composites with different Pt loadings represent the first highly active MOF-immobilized metal nanocatalysts for catalytic reactions in all three phases: liquid-phase ammonia borane hydrolysis; solid-phase ammonia borane thermal dehy-drogenation and gas-phase CO oxidation. The observed excellent catalytic performances are at-tributed to the small Pt nanoparticles within the pores of MIL-101. 'We are thankful to AIST and METI for financial support. TA & AK are thankful formore » support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is operated by Battelle.'« less

Carbon nanotubes decorated with Pt nanoparticles via electrostatic self-assembly: a highly active oxygen reduction electrocatalyst

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

Zhang, Sheng; Shao, Yuyan; Yin, Geping

2010-03-20

Carbon nanotubes (CNTs) are noncovalently functionalized with poly(allylamine hydrochloride) (PAH) and then employed as the support of Pt nanoparticles. X-Ray photoelectron spectroscopy confirms the successful functionalization of CNTs with PAH. The negatively charged Pt precursors are adsorbed on positively charged PAH-wrapping CNTs surface via electrostatic self-assembly and then in situ reduced in ethylene glycol. X-Ray diffraction and transmission electron microscope images reveal that Pt nanoparticles with an average size of 2.6 nm are uniformly dispersed on CNT surface. Pt/PAH-CNTs exhibit unexpectedly high activity towards oxygen reduction reaction, which can be attributed to the large electrochemical surface area of Pt nanoparticles.more » It also shows enhanced electrochemical stability due to the structural integrity of PAH-CNTs. This provides a facile approach to synthesize CNTs-based nanoelectrocatalysts.« less

Preparation and characterization of supported magnetic nanoparticles prepared by reverse micelles

PubMed Central

Han, Luyang; Biskupek, Johannes; Kaiser, Ute; Ziemann, Paul

2010-01-01

Summary Monatomic (Fe, Co) and bimetallic (FePt and CoPt) nanoparticles were prepared by exploiting the self-organization of precursor loaded reverse micelles. Achievements and limitations of the preparation approach are critically discussed. We show that self-assembled metallic nanoparticles can be prepared with diameters d = 2–12 nm and interparticle distances D = 20–140 nm on various substrates. Structural, electronic and magnetic properties of the particle arrays were characterized by several techniques to give a comprehensive view of the high quality of the method. For Co nanoparticles, it is demonstrated that magnetostatic interactions can be neglected for distances which are at least 6 times larger than the particle diameter. Focus is placed on FePt alloy nanoparticles which show a huge magnetic anisotropy in the L10 phase, however, this is still less by a factor of 3–4 when compared to the anisotropy of the bulk counterpart. A similar observation was also found for CoPt nanoparticles (NPs). These results are related to imperfect crystal structures as revealed by HRTEM as well as to compositional distributions of the prepared particles. Interestingly, the results demonstrate that the averaged effective magnetic anisotropy of FePt nanoparticles does not strongly depend on size. Consequently, magnetization stability should scale linearly with the volume of the NPs and give rise to a critical value for stability at ambient temperature. Indeed, for diameters above 6 nm such stability is observed for the current FePt and CoPt NPs. Finally, the long-term conservation of nanoparticles by Au photoseeding is presented. PMID:21977392

Platinum porous nanoparticles hybrid with metal ions as probes for simultaneous detection of multiplex cancer biomarkers.

PubMed

Wang, Zifeng; Liu, Na; Ma, Zhanfang

2014-03-15

In this work, platinum porous nanoparticles (PtPNPs) absorbed metal ions as electrochemical signals were fabricated. Clean-surface PtPNPs were prepared by a surfactant-free method and decorated with amino groups via 2-aminoethanethiol. Amino capped PtPNPs complexation with Cd(2+) and Cu(2+) to form PtPNPs-Cd(2+) and PtPNPs-Cu(2+) hybrids, respectively. Anti-CEA and Anti-AFP separately labeled with PtPNPs-Cd(2+) and PtPNPs-Cu(2+) were used as distinguishable signal tags for capturing antigens. The metal ions were detected in a single run through differential pulse voltammetry (DPV) without acid dissolution, electric potentials and peak heights of which reflected the identity and concentrations of the corresponding antigen. Ionic liquid reduced graphene oxide (IL-rGO) modified glassy carbon electrode (GCE) was used as a substrate, which was rich in amino groups to immobilize antibodies by glutaraldehyde through cross-link between aldehyde groups and amino groups. Using the proposed probes and platform, a novel sandwich-type electrochemical immunosensor for simultaneous detecting carcinoembryonic antigen (CEA) and alpha-fetoprotein (AFP) was successfully developed. This immunoassay possessed good linearity from 0.05 ng mL(-1) to 200 ng mL(-1) for both CEA and AFP. The detection limit of CEA was 0.002 ng mL(-1) and that of AFP was 0.05 ng mL(-1) (S/N=3). Furthermore, analysis of clinical serum samples using this immunosensor was well consistent with the data determined by the enzyme-linked immunosorbent assay (ELISA). It suggested that the proposed electrochemical immunoassay provided a potential application of clinical screening for early-stage cancers. © 2013 Published by Elsevier B.V.

Prevention of nanoparticle coalescence under high-temperature annealing.

PubMed

Mizuno, Mikihisa; Sasaki, Yuichi; Yu, Andrew C C; Inoue, Makoto

2004-12-21

An effective method of employing 3-aminopropyldimethylethoxysilane linker molecules to stabilize 4.4 nm FePt nanoparticle monolayer films on a SiO2 substrate as well as to prevent coalescence of the particles under 800 degrees C annealing is reported. As-deposited FePt nanoparticle films in chemically disordered face-centered-cubic phase transform to mostly chemically ordered L1 0 structure after annealing, while the nanoparticles are free from serious coalescence. The method may fulfill the pressing need to prevent nanoparticle coalescence under high-temperature annealing for the development of FePt nanoparticle based products, such as ultrahigh-density magnetic recording media and novel memory devices.

Taming interfacial electronic properties of platinum nanoparticles on vacancy-abundant boron nitride nanosheets for enhanced catalysis

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

Zhu, Wenshuai; Wu, Zili; Foo, Guo Shiou

Taming interfacial electronic effects on Pt nanoparticles modulated by their concomitants has emerged as an intriguing approach to optimize Pt catalytic performance. Here, we report Pt nanoparticles assembled on vacancy-abundant hexagonal boron nitride nanosheets and their use as a model catalyst to embrace an interfacial electronic effect on Pt induced by the nanosheets with N-vacancies and B-vacancies for superior CO oxidation catalysis. Experimental results indicate that strong interaction exists between Pt and the vacancies. Bader charge analysis shows that with Pt on B-vacancies, the nanosheets serve as a Lewis acid to accept electrons from Pt, and on the contrary, whenmore » Pt sits on N-vacancies, the nanosheets act as a Lewis base for donating electrons to Pt. The overall-electronic effect demonstrates an electron-rich feature of Pt after assembling on hexagonal boron nitride nanosheets. Such an interfacial electronic effect makes Pt favour the adsorption of O 2, alleviating CO poisoning and promoting the catalysis.« less

Taming interfacial electronic properties of platinum nanoparticles on vacancy-abundant boron nitride nanosheets for enhanced catalysis

DOE PAGES

Zhu, Wenshuai; Wu, Zili; Foo, Guo Shiou; ...

2017-06-09

Taming interfacial electronic effects on Pt nanoparticles modulated by their concomitants has emerged as an intriguing approach to optimize Pt catalytic performance. Here, we report Pt nanoparticles assembled on vacancy-abundant hexagonal boron nitride nanosheets and their use as a model catalyst to embrace an interfacial electronic effect on Pt induced by the nanosheets with N-vacancies and B-vacancies for superior CO oxidation catalysis. Experimental results indicate that strong interaction exists between Pt and the vacancies. Bader charge analysis shows that with Pt on B-vacancies, the nanosheets serve as a Lewis acid to accept electrons from Pt, and on the contrary, whenmore » Pt sits on N-vacancies, the nanosheets act as a Lewis base for donating electrons to Pt. The overall-electronic effect demonstrates an electron-rich feature of Pt after assembling on hexagonal boron nitride nanosheets. Such an interfacial electronic effect makes Pt favour the adsorption of O 2, alleviating CO poisoning and promoting the catalysis.« less

Enhanced electrocatalytic activity and stability of Pd 3V/C nanoparticles with a trace amount of Pt decoration for the oxygen reduction reaction

DOE PAGES

Liu, Sufen; Han, Lili; Zhu, Jing; ...

2015-09-14

In this study, carbon supported Pd 3V bimetallic alloy nanoparticles (Pd 3V/C) have been successfully synthesized via a simple impregnation–reduction method, followed by high temperature treatment under a H 2 atmosphere. Electrochemical tests reveal that the half-wave potential of Pd 3V/C-500 shifts positively 40 mV compared with Pd/C. However, the catalytic activity of Pd 3V/C-500 suffers from serious degradation after 1k cycles. By a spontaneous displacement reaction or co-reduction method, a trace amount of Pt was decorated on the surface or inside of the Pd 3V/C nanoparticles. The catalytic activity and stability of the Pd 3V@Pt/C and Pt-Pd 3V/C catalystsmore » for the oxygen reduction reaction (ORR) are enhanced significantly, and are comparable to commercial Pt/C. In addition, the Pt mass activity of Pd 3V@Pt/C and Pt-Pd 3V/C improves by factors of 10.9 and 6.5 at 0.80 V relative to Pt/C. Moreover, Pt-decorated Pd 3V/C nanoparticles show almost no obvious morphology change after durability tests, because the Pt-rich shell plays an important role in preventing degradation.« less

Controllable fabrication of Pt nanocatalyst supported on N-doped carbon containing nickel nanoparticles for ethanol oxidation.

PubMed

Yu, Jianguo; Dai, Tangming; Cao, Yuechao; Qu, Yuning; Li, Yao; Li, Juan; Zhao, Yongnan; Gao, Haiyan

2018-08-15

In this paper, platinum nanoparticles were deposited on a carbon carrier with the partly graphitized carbon and the highly dispersive carbon-coated nickel particles. An efficient electron transfer structure can be fabricated by controlling the contents of the deposited platinum. The high resolution transmission electron microscopy images of Pt 2 /Ni@C N-doped sample prove the electron transfer channel from Pt (1 1 1) crystal planes to graphite (1 0 0) or Ni (1 1 1) crystal planes due to these linked together crystal planes. The Pt 3 /Ni@C N-doped with low Pt contents cannot form the electron transfer structure and the Pt 1 /Ni@C N-doped with high Pt contents show an obvious aggregation of Pt nanoparticles. The electrochemical tests of all the catalysts show that the Pt 2 /Ni@C N-doped sample presents the highest catalytic activity, the strongest CO tolerance and the best catalytic stability. The high performance is attributed to the efficient electronic transport structure of the Pt 2 /Ni@C N-doped sample and the synergistic effect between Pt and Ni nanoparticles. This paper provides a promising method for enhancing the conductivity of electrode material. Copyright © 2018 Elsevier Inc. All rights reserved.

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.

A facile approach to the synthesis of highly electroactive Pt nanoparticles on graphene as an anode catalyst for direct methanol fuel cells.

PubMed

Zhou, Yi-Ge; Chen, Jing-Jing; Wang, Feng-bin; Sheng, Zhen-Huan; Xia, Xing-Hua

2010-08-28

A one-step electrochemical approach to the synthesis of highly dispersed Pt nanoparticles on graphene has been proposed. The resultant Pt NPs@G nanocomposite shows higher electrocatalytic activity and long-term stability towards methanol electrooxidation than the Pt NPs@Vulcan.

Oxygen reduction kinetics on Pt monolayer shell highly affected by the structure of bimetallic AuNi cores

DOE PAGES

Chen, Guangyu; Kuttiyiel, Kurian A.; Su, Dong; ...

2016-07-12

Here, we describe pronounced effects of structural changes of the AuNi cores on the oxygen reduction reaction (ORR) activity of a Pt monolayer shell. The study of alloyed AuNi nanoparticles compared with AuNi core–shell structured nanoparticles revealed configurations having different electronic and electrochemical properties. Controlled alloying of Au with Ni was essential to tune the electronic properties of Au interacting with the Pt monolayer shell to achieve suitable adsorption of O 2 on Pt for expediting the ORR. The alloyed AuNi nanoparticles made the Pt shell more catalytically active for the ORR than the core–shell structured AuNi nanoparticles. The Ptmore » monolayer supported on the alloyed AuNi nanoparticles showed the Pt mass and specific activities as high as 1.52 A mg –1 and 1.18 mA cm –2, respectively, with almost no loss over 5 000 cycles of stability test. This high ORR activity is ascribed to the role of nonspecific steric configuration of Ni atoms changing the electronic properties of the alloy that affect the oxygen and water interaction with the Pt shell and facilitate increased ORR kinetics.« less

Synthesis and characterization of magnetically hard Fe-Pt alloy nanoparticles and nano-islands

NASA Astrophysics Data System (ADS)

Hu, Xiaocao

In this dissertation, we explored the fabrication of FePt nanoparticles and nano-islands with the face-centered tetragonal (fct, L10) phase prepared by both chemical synthesis routes and physical vapor deposition. Microstructure and magnetic properties characterizations were used to gain a fundamental understanding of the nano-structure formation and atomic ordering behavior and determine the possible applications in the next generation ultra-high density magnetic storage media. FePt nanoparticles prepared by thermal decomposition of iron pentacarbonyl [Fe(CO)5] have been widely investigated and by tuning the processing procedure monodispersed FePt nanoparticles with good assembly can be obtained. The as-made FePt nanoparticles are usually in the magnetically soft face-centered cubic (fcc) phase. To transformation to the fct phase, post-annealing at above 600°C is needed which, however, introduces undesirable agglomeration and sintering. To address this problem, we used three different fabrication processes which are discussed below. In the first fabrication experiment, the FePt nanoparticles were fabricated by a novel environmental friendly method involving crystalline saline complex hexaaquairon (II) hexachloroplatinate ([Fe(H2O)6]PtCl 6) with a special layered structure. Then the precursor was ball milled with NaCl and annealed at temperatures above 400°C under a reducing atmosphere of forming gas (95% Ar and 5% H2) FePt nanoparticles were obtained after washing away NaCl with deionized water. This method avoids the use of the very poisonous Fe(CO)5 and other organic solvents such as oleylamine and oleic acid. Instead, environmentally friendly NaCl and water were used. The size of FePt nanoparticles was controlled by varying the proportion of precursor and NaCl (from 10mg/20g to 50mg/20g). Particles with size in the range of 6.2--13.2 nm were obtained. All the nanoparticles annealed above 400°C are in the highly ordered fct phase with a coercivity range of 4.7 kOe to 10.7 kOe. Compared with reported high annealing temperatures above 600°C, this fabrication process led to a significantly decreased temperature to achieve the L10 phase FePt by 200°C. A qualitative model was set up to explain the surprising low L10 phase achievement temperature and the influence of annealing temperature on the microstructure and magnetic properties was investigated. Although FePt nanoparticles with high coercivity and small size were successfully obtained by the first fabrication method, agglomeration happened during the washing procedure due to the large inter-particle magnetostatic force caused by their high magnetization. To avoid this agglomeration, exfoliated graphene was introduced in the second preparation method to keep the nanoparticles separated. Different from the traditional solvent-phase reaction to disperse FePt nanoparticles onto the exfoliated graphene, a novel solid-phase reaction was used in this dissertation involving the layered precursor [Fe(H2 O)6]PtCl6 molecule. The [Fe(H2O) 6]PtCl6 water solution was mixed with exfoliated graphene oxide (GO) and then the top solution was removed. Fe2+ and Pt2+ ions were absorbed onto the surface of GO. The remaining product was annealed under a reducing atmosphere of forming gas at different temperatures (500°C to 950°C). During the reduction process, GO was reduced to "graphene" and FePt nanoparticles were formed on the surface of exfoliated graphene. The separation effect by the exfoliated graphene increased the phase transformation temperature to 600°C compared to the first method. However, even at an annealing temperature as high as 750°C, we could still obtained separated, small size FePt nanoparticles with coercivity of 8.3 kOe. The third preparation method used in this dissertation is the traditional magnetron sputtering with very short deposition time (10 s to 25 s) on heated MgO (001) substrate to form separate nano-islands instead of continuous thin films. The ordering of FePt nano-islands were studied by high resolution transmission electron microscopy. Because of the low degree of atomic ordering of the as-prepared nano-islands, post annealing at 700°C under an atmosphere of forming gas was introduced. Ordering of nano-islands of as small as 3 nm was revealed. We discovered that in the ordered FePt nano-islands, there are defects present. Particularly, we observed an onion like structure in a FePt nano-island composed of c-domains perpendicular to each other. These defects explained the low coercivity of the L10 ordered FePt nano-islands, which was envisioned theoretically. In summary, in this dissertation, novel solid-phase, environmentally friendly synthesis methods to fabricate FePt nanoparticles and FePt nanoparticles on "graphene" with high coercivity are first reported. Also, a special onion-like structure was first discovered by high-resolution microscopy and theoretical simulation was done with good agreement with the experimental results.

Making ultrafine and highly-dispersive multimetallic nanoparticles in three-dimensional graphene with supercritical fluid as excellent electrocatalyst for oxygen reduction reaction

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

Zhou, Yazhou; Yen, Clive H.; Hu, Yun Hang

2016-01-01

Three-dimensional (3D) graphene showed an advanced support for designing porous electrode materials due to its high specific surface area, large pore volume, and excellent electronic property. However, the electrochemical properties of reported porous electrode materials still need to be improved further. The current challenge is how to deposit desirable nanoparticles (NPs) with controllable structure, loading and composition in 3D graphene while maintaining the high dispersion. Herein, we demonstrate a modified supercritical fluid (SCF) technique to address this issue by controlling the SCF system. Using this superior method, a series of Pt-based/3D graphene materials with the ultrafine-sized, highly dispersive and controllablemore » composition multimetallic NPs were successfully synthesized. Specifically, the resultant Pt40Fe60/3D graphene showed a significant enhancement in electrocatalytic performance for the oxygen reduction reaction (ORR), including a factor of 14.2 enhancement in mass activity (1.70 A mgPt 1), a factor of 11.9 enhancement in specific activity (1.55 mA cm 2), and higher durability compared with that of Pt/C catalyst. After careful comparison, the Pt40Fe60/3D graphene catalyst shows the higher ORR activity than most of the reported similar 3D graphene-based catalysts. The successful synthesis of such attractive materials by this method also paves the way to develop 3D graphene in widespread applications.« less

Electrochemical investigations of Co3Fe-RGO as a bifunctional catalyst for oxygen reduction and evolution reactions in alkaline media

NASA Astrophysics Data System (ADS)

Kumar, Surender; Kumar, Divyaratan; Kishore, Brij; Ranganatha, Sudhakar; Munichandraiah, Nookala; Venkataramanan, Natarajan S.

2017-10-01

Nanoparticles of Co3Fe alloy is prepared on reduced graphene oxide (RGO) sheets by modified polyol method. Synthesized alloy particles are characterized by various physicochemical techniques. TEM and SEM pictures showed homogeneously dispersed alloy nanoparticles on the RGO sheets. Electrochemistry of alloy nanoparticles is investigated in alkaline medium. The result shows that oxygen evaluation reaction (OER) activity of Co3Fe-RGO is higher than Pt-black particles. RDE studies in alkaline medium shows that oxygen reduction reaction (ORR) follow four electron pathway. It is suggest that Co3Fe-RGO is an efficient non-precious catalyst for oxygen (ORR/OER) reactions in alkaline electrolyte for PEMFC applications.

Synthesis of Pd 9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

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

Sun, Yu; Hsieh, Yu -Chi; Chang, Li -Chung

2014-11-22

Nanoparticles of PdRu, Pd₃Ru, and Pd₉Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, Pd xRu/C (x=1/3/9), suggest succesful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of Pd xRu/C. Among these samples, the Pd₉Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in anmore » oxygen-saturated 0.1 M aqueous HClO₄ solution. Subsequently, the Pd₉Ru/C undegoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd₉Ru surface (Pd₉Ru@Pt). The Pd₉Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg⁻¹ Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg⁻¹ Pt). Thus, the mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd₉Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.« less

Synthesis of Pd9Ru@Pt nanoparticles for oxygen reduction reaction in acidic electrolytes

NASA Astrophysics Data System (ADS)

Sun, Yu; Hsieh, Yu-Chi; Chang, Li-Chung; Wu, Pu-Wei; Lee, Jyh-Fu

2015-03-01

Nanoparticles of PdRu, Pd3Ru, and Pd9Ru are synthesized and impregnated on carbon black via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples, PdxRu/C (x = 1/3/9), suggest successful formation of alloy without presence of individual Pd and Ru nanoparticles. Images from transmission electron microscope confirm irregularly-shaped nanoparticles with average size below 3 nm. Analysis from extended X-ray absorption fine structure on both Pd and Ru K-edge absorption profiles indicate the Ru atoms are enriched on the surface of PdxRu/C. Among these samples, the Pd9Ru/C exhibits the strongest electrocatalytic activity for oxygen reduction reaction (ORR) in an oxygen-saturated 0.1 M aqueous HClO4 solution. Subsequently, the Pd9Ru/C undergoes Cu under potential deposition, followed by a galvanic displacement reaction to deposit a Pt monolayer on the Pd9Ru surface (Pd9Ru@Pt). The Pd9Ru@Pt reveals better ORR performance than that of Pt, reaching a mass activity of 0.38 mA μg-1Pt, as compared to that of commercially available Pt nanoparticles (0.107 mA μg-1Pt). The mechanisms responsible for the ORR enhancement are attributed to the combined effects of lattice strain and ligand interaction. In addition, this core-shell Pd9Ru@Pt electrocatalyst represents a substantial reduction in the amount of Pt consumption and raw material cost.

One-pot solvothermal synthesis of ordered intermetallic Pt{sub 2}In{sub 3} as stable and efficient electrocatalyst towards direct alcohol fuel cell application

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

Jana, Rajkumar; Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in

Ordered intermetallic Pt{sub 2}In{sub 3} nanoparticles have been synthesized by superhydride reduction of K{sub 2}PtCl{sub 4} and InCl{sub 3}.xH{sub 2}O precursors using facile, one-pot solvothermal method. We report surfactant free solvothermal synthesis of a novel ordered Pt{sub 2}In{sub 3} intermetallic nanoparticles for the first time. The structure and morphology of the catalyst has been confirmed by powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, energy-dispersive spectrometry and X-ray photoelectron spectroscopy. The electrocatalytic properties of the catalysts have been investigated by cyclic voltammetry and chronoamperometry. The as prepared Pt{sub 2}In{sub 3} catalyst exhibit far superior electrocatalytic activity andmore » stability towards alcohol oxidation over commercial Pt/C. The specific activity of as synthesized catalyst was found to be ~3.2 and ~2.3 times higher than commercial Pt/C for methanol and ethanol oxidation, respectively. This improved activity and durability of the Pt{sub 2}In{sub 3} nanoparticles can make the catalyst an ideal catalyst candidate for direct alcohol fuel cell. - Graphical abstract: The ordered structure of Pt{sub 2}In{sub 3} nanoparticles synthesized by solvothermal method has confirmed through XRD and TEM. Cyclic voltametry and chronoamperometry showed improved catalytic activity and stability compared to commercial Pt/C. - Highlights: • Ordered Pt{sub 2}In{sub 3} nanoparticles were synthesized by solvothermal method. • Electrooxidation of alcohols on Pt{sub 2}In{sub 3} catalyst was investigated in acidic medium. • Pt{sub 2}In{sub 3} catalyst has superior catalytic activity compared to commercial Pt/C. • Pt{sub 2}In{sub 3} catalyst exhibited much higher stability than commercial Pt/C.« less

Local Chemical Ordering and Negative Thermal Expansion in PtNi Alloy Nanoparticles.

PubMed

Li, Qiang; Zhu, He; Zheng, Lirong; Fan, Longlong; Wang, Na; Rong, Yangchun; Ren, Yang; Chen, Jun; Deng, Jinxia; Xing, Xianran

2017-12-13

An atomic insight into the local chemical ordering and lattice strain is particular interesting to recent emerging bimetallic nanocatalysts such as PtNi alloys. Here, we reported the atomic distribution, chemical environment, and lattice thermal evolution in full-scale structural description of PtNi alloy nanoparticles (NPs). The different segregation of elements in the well-faceted PtNi nanoparticles is convinced by extended X-ray absorption fine structure (EXAFS). Atomic pair distribution function (PDF) study evidences the coexistence of the face-centered cubic and tetragonal ordering parts in the local environment of PtNi nanoparticles. Further reverse Monte Carlo (RMC) simulation with PDF data obviously exposed the segregation as Ni and Pt in the centers of {111} and {001} facets, respectively. Layer-by-layer statistical analysis up to 6 nm for the local atomic pairs revealed the distribution of local tetragonal ordering on the surface. This local coordination environment facilitates the distribution of heteroatomic Pt-Ni pairs, which plays an important role in the negative thermal expansion of Pt 41 Ni 59 NPs. The present study on PtNi alloy NPs from local short-range coordination to long-range average lattice provides a new perspective on tailoring physical properties in nanomaterials.

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

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanningmore » transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

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

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy

The surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. Moreover, the evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annularmore » dark-field scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. The catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

Electrodeposition of platinum nanoparticles in a room-temperature ionic liquid.

PubMed

Zhang, Da; Chang, Wan Cheng; Okajima, Takeyoshi; Ohsaka, Takeo

2011-12-06

The electrochemistry of the [PtCl(6)](2-)-[PtCl(4)](2-)-Pt redox system on a glassy carbon (GC) electrode in a room-temperature ionic liquid (RTIL) [i.e., N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMEBF(4))] has been examined. The two-step four-electron reduction of [PtCl(6)](2-) to Pt, i.e., reduction of [PtCl(6)](2-) to [PtCl(4)](2-) and further reduction of [PtCl(4)](2-) to Pt, occurs separately in this RTIL in contrast to the one-step four-electron reduction of [PtCl(6)](2-) to Pt in aqueous media. The cathodic and anodic peaks corresponding to the [PtCl(6)](2-)/[PtCl(4)](2-) redox couple were observed at ca. -1.1 and 0.6 V vs a Pt wire quasi-reference electrode, respectively, while those observed at -2.8 and -0.5 V were found to correspond to the [PtCl(4)](2-)/Pt redox couple. The disproportionation reaction of the two-electron reduction product of [PtCl(6)](2-) (i.e., [PtCl(4)](2-)) to [PtCl(6)](2-) and Pt metal was also found to occur significantly. The electrodeposition of Pt nanoparticles could be carried out on a GC electrode in DEMEBF(4) containing [PtCl(6)](2-) by holding the potential at -3.5 or -2.0 V. At -3.5 V, the four-electron reduction of [PtCl(6)](2-) to Pt can take place, while at -2.0 V the two-electron reduction of [PtCl(6)](2-) to [PtCl(4)](2-) occurs. The results obtained demonstrate that the electrodeposition of Pt at -3.5 V may occur via a series of reductions of [PtCl(6)](2-) to [PtCl(4)](2-) and further [PtCl(4)](2-) to Pt and at -2.0 V via a disproportionation reaction of [PtCl(4)](2-) to [PtCl(6)](2-) and Pt. Furthermore, the deposition potential of Pt nanoparticles was found to largely influence their size and morphology as well as the relative ratio of Pt(110) and Pt(100) crystalline orientation domains. The sizes of the Pt nanoparticles prepared by holding the electrode potential at -2.0 and -3.5 V are almost the same, in the range of ca. 1-2 nm. These small nanoparticles are "grown" to form bigger particles with different morphologies: In the case of the deposition at -2.0 V, the GC electrode surface is totally, relatively compactly covered with Pt particles of relatively uniform size of ca. 10-50 nm. On the other hand, in the case of the electrodeposition at -3.5 V, small particles of ca. 50-100 nm and the grown-up particles of ca. 100-200 nm cover the GC surface irregularly and coarsely. Interestingly, the Pt nanoparticles prepared by holding the potential at -2.0 and -3.5 V are relatively enriched in Pt(100) and Pt(110) facets, respectively. © 2011 American Chemical Society

Chemical synthesis of L10 Fe-Pt-Ni alloy nanoparticles

NASA Astrophysics Data System (ADS)

Deepchand, Vimal; Abel, Frank M.; Tzitzios, Vasileios; Hadjipanayis, George C.

2018-05-01

This work focuses on the study of the magnetic and structural properties of chemically synthesized FePt1-xNix nanoparticles, with Ni content x in the range 0.2-0.4. We report the effect of Ni substitution on the L10 structure, on both the as-synthesized and annealed nanoparticles. A decrease in nanoparticle size as well as in chemical order is observed with an increase in Ni content, for both the as-made and annealed nanoparticles. The results also show that the post annealing procedure at 700oC significantly enhanced the L10 ordering of the nanoparticles. Substitution of nickel leads to a decrease in coercivity from 14.9 kOe in FePt to 0.8 kOe for FePt0.6Ni0.4 alloy, while the magnetization at 3 T is increased from 48 emu/g to 88 emu/g.

Various types of semiconductor photocatalysts modified by CdTe QDs and Pt NPs for toluene photooxidation in the gas phase under visible light

NASA Astrophysics Data System (ADS)

Marchelek, M.; Grabowska, E.; Klimczuk, T.; Lisowski, W.; Zaleska-Medynska, A.

2017-01-01

A novel synthesis process was used to prepare TiO2 microspheres, TiO2 P-25, SrTiO3 and KTaO3 decorated by CdTe QDs and/or Pt NPs. The effect of semiconductor matrix, presence of CdTe QDs and/or Pt NPs on the semiconductor surface as well as deposition technique of Pt NPs (photodeposition or radiolysis) on the photocatalytic activity were investigated. The as-prepared samples were characterized by X-ray powder diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) with energy-dispersive X-ray (EDX) spectroscopy, scanning electron microscopy (SEM), photoluminescence spectrometry (PL), Fourier transform infrared (FT-IR) and Raman spectra, diffuse reflectance spectroscopy (DRS) and BET surface area analysis. The photocatalytic decomposition of toluene in gas phase, activated by light-emitting diodes (LEDs), with the CdTe/Pt nanoparticles-modified TiO2 microspheres, P25, SrTiO3 and KTaO3 semiconductors was investigated under UV-vis and visible irradiation.The results showed that the photoactivity depends on semiconductor matrix. The highest photoactivity under Vis light was observed for KTaO3/CdTe-Pt(R) sample (56% of toluene was decompose after 30 min of irradiation). The efficiency of the most active sample was 3 times higher than result for P25 and two times higher than for unmodified KTaO3.

Low platinum loading cathode modified with Cs3H2PMo10V2O40 for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Renzi, M.; D'Angelo, G.; Marassi, R.; Nobili, F.

2016-09-01

The catalytic activity of commercial Pt nanoparticles mixed with mesoporous polyoxometalate Cs3H2PMo10V2O40 towards oxygen reduction reaction is evaluated. The polyoxometalate co-catalyst is prepared by titration of an aqueous solution of phosphovanadomolibdic acid. SEM micrography shows reduction particle size to less than 300 nm, while XRD confirms that the resulting salt maintains the Kegging structure. The composite catalyst is prepared by mixing the POM salt with Pt/C by sonication. RRDE studies show better kinetics for ORR with low Pt loading at the electrode surface. A MEA is assembled by using a Pt/POM-based cathode, in order to assess performance in a working fuel cell. Current vs. potential curves reveals comparable or better performances at 100%, 62% and 17% relative humidity for the POM-modified MEA with respect to a commercial MEA with higher Pt loading at the cathode. Electrochemical impedance spectroscopy (EIS) confirms better kinetics at low relative humidity. Finally, an accelerated stress test (AST) with square wave (SW) between 0.4 V and 0.8 V is performed to evaluate MEA stability for at least 100 h and make predictions about lifetime, showing that after initial losses the catalytic system can retain stable performance and good morphological stability.

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-8 and Au/ZIF-8 shows that the nanoparticles of Au ZIF-8 remain within experimental uncertainty and unchanged, whereas Au nanoparticles of Au/ZIF suffered from server sintering. We performed solvent assisted linker exchange, a single-crystal to single-crystal transformation, on Pt ZIF-8 to exchange the 2-methylimidazole linkers with imidazole to form Pt SALEM-2. Since Pt SALEM-2 should have larger apertures than Pt ZIF-8, we investigated Pt ZIF-8 and Pt SALEM-2 as catalysts for the hydrogenation of substrates with increasingly larger kinetic diameter: 1-octene, cis-cyclohexene, and beta-pinene. Both catalysts were active for the hydrogenation of 1-octene, while only Pt SALEM-2 was active for cis-cyclohexene hydrogenation. Neither catalyst was active for the hydrogenation of beta-pinene, indicating that the Pt nanoparticles remained well encapsulated throughout the SALE process.

Pt nanoparticle-reduced graphene oxide nanohybrid for proton exchange membrane fuel cells.

PubMed

Park, Dae-Hwan; Jeon, Yukwon; Ok, Jinhee; Park, Jooil; Yoon, Seong-Ho; Choy, Jin-Ho; Shul, Yong-Gun

2012-07-01

A platinum nanoparticle-reduced graphene oxide (Pt-RGO) nanohybrid for proton exchange membrane fuel cell (PEMFC) application was successfully prepared. The Pt nanoparticles (Pt NPs) were deposited onto chemically converted graphene nanosheets via ethylene glycol (EG) reduction. According to the powder X-ray diffraction (XRD) pattern and transmission electron microscopy (TEM) analysis, the face-centered cubic Pt NPs (3-5 nm in diameter) were homogeneously dispersed on the RGO nanosheets. The electrochemically active surface area and PEMFC power density of the Pt-RGO nanohybrid were determined to be 33.26 m2/g and 480 mW/cm2 (maximum values), respectively, at 75 degrees C and at a relative humidity (RH) of 100% in a single-cell test experiment.

Pt 3Re alloy nanoparticles as electrocatalysts for the oxygen reduction reaction

DOE PAGES

Raciti, David; Kubal, Joseph; Ma, Cheng; ...

2015-12-25

Development of renewable energy technologies requires advanced catalysts for efficient electrical-chemical energy conversion reactions. Here in this paper, we report the study of Pt-Re alloy nanoparticles as an electrocatalyst for the oxygen reduction reaction (ORR). An organic solution approach is developed to synthesize monodisperse and homogeneous Pt 3Re alloy nanoparticles. Electrochemical studies show that these nanoparticles exhibit an improvement factor of 4 in catalytic activity for the ORR compared to commercial Pt catalysts of similar particle sizes. Fundamental understanding of the structure-property relationship is established by combining material characterization using X-ray spectroscopy and atomically resolved electron microscopy, as well asmore » Density Functional Theory (DFT) calculations. Lastly, our work revealed that an electronic modification of the surface properties of Pt by subsurface Re (ligand effect) accounts for the catalytic enhancement.« less

Pt L3,2-edge whiteline anomaly and its implications for the chemical behaviour of Pt 5d5/2 and 5d3/2 electronic states - a study of Pt-Au nanowires and nanoparticles

NASA Astrophysics Data System (ADS)

Sham, T. K.; Ward, M. J.; Murphy, M. W.; Liu, L. J.; Han, W. Q.

2013-04-01

We report the L3,2-edge whiteline anomaly observed in PtAu nanowire, PtAu and Pt nanoparticles deposited on Si nanowire, and their comparison with that of Pt metal. It is found that charge redistribution upon the formation of these materials can indeed be tracked with the L3,2 whiteline intensity. The implications of these findings are discussed.

Ultrasensitive electroanalytical tool for detecting, sizing, and evaluating the catalytic activity of platinum nanoparticles.

PubMed

Dasari, Radhika; Robinson, Donald A; Stevenson, Keith J

2013-01-16

Here we describe a very simple, reliable, low-cost electrochemical approach to detect single nanoparticles (NPs) and evaluate NP size distributions and catalytic activity in a fast and reproducible manner. Single NPs are detected through an increase in current caused by electrocatalytic oxidation of N(2)H(4) at the surface of the NP when it contacts a Hg-modified Pt ultramicroelectrode (Hg/Pt UME). Once the NP contacts the Hg/Pt UME, Hg poisons the Pt NP, deactivating the N(2)H(4) oxidation reaction. Hence, the current response is a "spike" that decays to the background current level rather than a stepwise "staircase" response as previously described for a Au UME. The use of Hg as an electrode material has several quantitative advantages including suppression of the background current by 2 orders of magnitude over a Au UME, increased signal-to-noise ratio for detection of individual collisions, precise integration of current transients to determine charge passed and NP size, reduction of surface-induced NP aggregation and electrode fouling processes, and reproducible and renewable electrodes for routine detection of catalytic NPs. The NP collision frequency was found to scale linearly with the NP concentration (0.016 to 0.024 pM(-1)s(-1)). NP size distributions of 4-24 nm as determined from the current-time transients correlated well with theory and TEM-derived size distributions.

An ultrasensitive luminol cathodic electrochemiluminescence immunosensor based on glucose oxidase and nanocomposites: graphene-carbon nanotubes and gold-platinum alloy.

PubMed

Jiang, Xinya; Chai, Yaqin; Yuan, Ruo; Cao, Yaling; Chen, Yingfeng; Wang, Haijun; Gan, Xianxue

2013-06-14

In the present study, a novel and ultrasensitive electrochemiluminescence (ECL) immunosensor based on luminol cathodic ECL was fabricated by using Au nanoparticles and Pt nanoparticles (nano-AuPt) electrodeposited on graphene-carbon nanotubes nanocomposite as platform for the detection of carcinoembryonic antigen (CEA). For this introduced immunosensor, graphene (GR) and single wall carbon nanotubes (CNTs) dispersed in chitosan (Chi-GR-CNTs) were firstly decorated on the bare gold electrode (GE) surface. Then nano-AuPt were electrodeposited (DpAu-Pt) on the Chi-GR-CNTs modified electrode. Subsequently, glucose oxidase (GOD) was employed to block the non-specific sites of electrode surface. When glucose was present in the working buffer solution, GOD immediately catalyzed the oxidation of glucose to in situ generate hydrogen peroxide (H2O2), which could subsequently promote the oxidation of luminol with an amplified cathodic ECL signal. The proposed immunosensor was performed at low potential (-0.1 to 0.4V) and low concentration of luminol. The CEA was determined in the range of 0.1 pg mL(-1) to 40 ng mL(-1) with a limit of detection down to 0.03 pg mL(-1) (SN(-1)=3). Moreover, with excellent sensitivity, selectivity, stability and simplicity, the as-proposed luminol-based ECL immunosensor provided great potential in clinical applications. Copyright © 2013 Elsevier B.V. All rights reserved.

WO3/Pt nanoparticles promote light-induced lipid peroxidation and lysosomal instability within tumor cells

NASA Astrophysics Data System (ADS)

Clark, Andrea J.; Petty, Howard R.

2016-02-01

Although metal-metal oxide nanoparticles have attracted considerable interest as catalysts, they have attracted little interest in nanomedicine. This is likely due to the fact that metal oxide semiconductors generally require biologically harmful ultraviolet excitation. In contrast, this study focuses upon WO3/Pt nanoparticles, which can be excited by visible light. To optimize the nanoparticles’ catalytic performance, platinization was performed at alkaline pH. These nanoparticles destroyed organic dyes, consumed dissolved oxygen and produced hydroxyl radicals. 4T1 breast cancer cells internalized WO3/Pt nanoparticles within the membrane-bound endo-lysosomal compartment as shown by electron and fluorescence microscopy. During visible light exposure, but not in darkness, WO3/Pt nanoparticles manufacture reactive oxygen species, promote lipid peroxidation, and trigger lysosomal membrane disruption. As cells of the immune system degrade organic molecules, produce reactive oxygen species, and activate the lipid peroxidation pathway within target cells, these nanoparticles mimic the chemical attributes of immune effector cells. These biomimetic nanoparticles should become useful in managing certain cancers, especially ocular cancer.

A Sinter-Resistant Catalytic System Based on Platinum Nanoparticles Supported on TiO2 Nanofibers and Covered by Porous Silica

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

Dai, Yunqian; Lim, Byungkwon; Yang, Yong

2010-10-25

Platinum is a key catalyst that is invaluable in many important industrial processes such as CO oxidation in catalytic converters, oxidation and reduction reactions in fuel cells, nitric acid production, and petroleum cracking.[1] Many of these applications utilize Pt nanoparticles supported on oxides or porous carbon.[2] However, in practical applications that involve high temperatures (typically higher than 3008C), the Pt nanoparticles tend to lose their specific surface area and thus catalytic activity during operation because of sintering. Recent studies have shown that a porous oxide shell can act as a physical barrier to prevent sintering of unsupported metal nanoparticles and,more » at the same time, provide channels for chemical species to reach the surface of the nanoparticles, thus allowing the catalytic reaction to occur. This concept has been demonstrated in several systems, including Pt@SiO2,[3] Pt@CoO,[4] Pt/CeO2@SiO2,[5] Pd@SiO2,[6] Au@SiO2,[7] Au@SnO2 [8] and Au@ZrO2 [9] core– shell nanostructures. Despite these results, a sinter-resistant system has not been realized in supported Pt nanoparticle catalysts.« less

Rationalization of Au concentration and distribution in AuNi@Pt core-shell nanoparticles for oxygen reduction reaction

DOE PAGES

An, Wei; Liu, Ping

2015-09-18

Improving the activity and stability of Pt-based core–shell nanocatalysts for proton exchange membrane fuel cells while lowering Pt loading has been one of the big challenges in electrocatalysis. Here, using density functional theory, we report the effect of adding Au as the third element to enhance the durability and activity of Ni@Pt core–shell nanoparticles (NPs) during the oxygen reduction reaction (ORR). Our results show that the durability and activity of a Ni@Pt NP can be finely tuned by controlling Au concentration and distribution. For a NiAu@Pt NP, the durability can be greatly promoted by thermodynamically favorable segregation of Au tomore » replace the Pt atoms at vertex, edge, and (100) facets on the shell, while still keeping the ORR activity on the active Pt(111) shell as high as that of Ni@Pt nanoparticles. Such behavior strongly depends on a direct interaction with the Ni interlayer. The results not only highlight the importance of interplay between surface strain on the shell and the interlayer–shell interaction in determining the durability and activity but also provide guidance on how to maximize the usage of Au to optimize the performance of core–shell (Pt) nanoparticles. As a result, such understanding has allowed us to discover a novel NiAu@Pt nanocatalyst for the ORR.« less

A New Green Chemical Synthesis Strategy for Synthesis of L10 FePt Nanoparticles from Layered Precursor Fe(H2O)6PtCl6

NASA Astrophysics Data System (ADS)

Hadjipanayis, George; Hu, Xiaocao; Capobianchi, Aldo; Gallagher, Ryan

2014-03-01

In this work, a new green chemical strategy for the synthesis of L10 FePt nanoparticles is reported. The starting material is a polycrystalline molecular complex (Fe(H2O)6PtCl6) , in which Fe and Pt atoms are arranged on alternating planes. The starting compound was milled with crystalline NaCl and then annealed under forming gas (5 % H2 and 95 % Ar) at 450 °C for 2h. Finally, the mixture was washed with water to remove the NaCl and L10 FePt nanoparticles were obtained. Transmission electron microscopy (TEM) images revealed that this method is able to produce L10 nanoparticles with different average size varying from 13.9 nm to 5.4 nm depending on the (Fe(H2O)6PtCl6) /NaCl ratio. With smaller (Fe(H2O)6PtCl6) /NaCl ratio(10mg/20g) and longer milling time(15h), FePt nanoparticles had a smaller size and narrower size distribution. The X-Ray Diffraction (XRD) pattern showed the presence of the characteristic peaks of the fct phase. The hysteresis loop, measured both at room temperature and 50 K, shows a high coercivity of 7.6 kOe and 11.2 kOe, respectively as expected for the high anisotropy L10 phase. Larger precursor/NaCl ratio and shorter ball milling time led to larger coercivity.

Ultrasensitive hydrogen sensor based on Pt-decorated WO₃ nanorods prepared by glancing-angle dc magnetron sputtering.

PubMed

Horprathum, M; Srichaiyaperk, T; Samransuksamer, B; Wisitsoraat, A; Eiamchai, P; Limwichean, S; Chananonnawathorn, C; Aiempanakit, K; Nuntawong, N; Patthanasettakul, V; Oros, C; Porntheeraphat, S; Songsiriritthigul, P; Nakajima, H; Tuantranont, A; Chindaudom, P

2014-12-24

In this work, we report an ultrasensitive hydrogen (H2) sensor based on tungsten trioxide (WO3) nanorods decorated with platinum (Pt) nanoparticles. WO3 nanorods were fabricated by dc magnetron sputtering with a glancing angle deposition (GLAD) technique, and decorations of Pt nanoparticles were performed by normal dc sputtering on WO3 nanorods with varying deposition time from 2.5 to 15 s. Crystal structures, morphologies, and chemical information on Pt-decorated WO3 nanorods were characterized by grazing-incident X-ray diffraction, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and photoelectron spectroscopy, respectively. The effect of the Pt nanoparticles on the H2-sensing performance of WO3 nanorods was investigated over a low concentration range of 150-3000 ppm of H2 at 150-350 °C working temperatures. The results showed that the H2 response greatly increased with increasing Pt-deposition time up to 10 s but then substantially deteriorated as the deposition time increased further. The optimally decorated Pt-WO3 nanorod sensor exhibited an ultrahigh H2 response from 1530 and 214,000 to 150 and 3000 ppm of H2, respectively, at 200 °C. The outstanding gas-sensing properties may be attributed to the excellent dispersion of fine Pt nanoparticles on WO3 nanorods having a very large effective surface area, leading to highly effective spillover of molecular hydrogen through Pt nanoparticles onto the WO3 nanorod surface.

Synthesis and characterization of CoPt nanoparticles prepared by room temperature chemical reduction with PAMAM dendrimer as template.

PubMed

Wan, Haiying; Shi, Shifan; Bai, Litao; Shamsuzzoha, Mohammad; Harrell, J W; Street, Shane C

2010-08-01

We describe an approach to synthesize monodisperse CoPt nanoparticles with dendrimer as template by a simple chemical reduction method in aqueous solution using NaBH4 as reducing agent at room temperature. The as-made CoPt nanoparticles buried in the dendrimer matrix have the chemically disordered fcc structure and can be transformed to the fct phase after annealing at 700 degrees C. This is the first report of dendrimer-mediated room temperature synthesis of monodisperse magnetic nanoparticles in aqueous solution.

Probing Interaction Between Platinum Group Metal (PGM) and Non-PGM Support Through Surface Characterization and Device Performance

NASA Astrophysics Data System (ADS)

Saha, Shibely

High cost and limited abundance of Platinum (Pt) have hindered effective commercialization of Proton Exchange Membrane Fuel Cell and Electrolyzer. Efforts have been undertaken to reduce precious group metal (PGM) requirement for these devices without compromising the activity of the catalyst by using transition metal carbides (TMC) as non-PGM support thanks to their similar electronic and geometric structures as Pt. In this work Mo2C was selected as non-PGM support and Pt was used as the PGM of interest. We hypothesize that the hollow nanotube morphology of Mo2C support combined with Pt nano particles deposited on it via atomic layer deposition (ALD) technique would allow increased interaction between them which may increase the activity of Pt and Mo2C as well as maximize the Pt active surface area. Specifically, a rotary ALD equipment was used to grow Pt particles from atomic level to 2--3 nanometers by simply adjusting number of ALD cycles in order to probe the interaction between the deposited Pt nanoparticles and Mo2C nanotube support. Interaction between the Pt and Mo2 C was analyzed via surface characterization and electrochemical characterization. Interaction between Pt and Mo2C arises due to the lattice mismatch between Pt and Mo2C as well as electron migration between them. Lattice spacing analysis using high resolution transmission electron microscopy (HRTEM) images, combined with Pt binding energy shift in XPS results, clearly showed strong bonding between Pt nanoparticles and the Mo2C nanotube support in all the resultant Pt/Mo2C samples. We postulate that this strong interaction is responsible for the significantly enhanced durability observed in our constant potential electrolysis (CPE) and accelerated degradation testing (ADT). Of the three samples from different ALD cycles (15, 50 and 100), Mo2C nanotubes modified by 50 (1.07 wt% Pt loading) and 100 cycles (4.4 wt% Pt) of Pt deposition, showed higher HER and HOR activity per Pt mass than commercial 20% Pt supported on carbon black. Finally, we report the systematic investigation of the feasibility of this nanoscale Pt/Mo 2C catalyst in a practical device setting. The ORR activity of 100 Pt/Mo 2C was determined using the catalyst in the cathode of the MEA. Performance of this catalyst led the Pt utilization to be 10.35kWgPt-1 outperforming the target set by DOE for 2017--2020 by 30%.

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.

Electrochemical sensor based on molecularly imprinted membranes at platinum nanoparticles-modified electrode for determination of 17β-estradiol.

PubMed

Yuan, Lihua; Zhang, Jun; Zhou, Ping; Chen, Jiaxing; Wang, Ruoyu; Wen, Tingting; Li, Yun; Zhou, Xuemin; Jiang, Huijun

2011-11-15

In this paper, an electrochemical sensor for 17β-estradiol (E2) based on the molecular imprinting polymer (MIP) membranes had been constructed. 6-mercaptonicotinic acid (MNA) and E2 were first assembled on the surface of platinum nanoparticles-modified glassy carbon electrode (PtNPs/GCE) by the formation of Pt-S bonds and hydrogen-bonding interactions, and subsequently the polymer membranes were formed by electropolymerization. Finally, a novel molecularly imprinted sensor (MIS) was obtained after removal of E2. Experimental parameters such as deposition time, scan cycles, pH value and accumulation condition were optimized. Under optimal conditions, the MIS exhibited a large adsorption capacity and high selectivity. A good linearity was obtained in the range of 3.0×10(-8)-5.0×10(-5)molL(-1) (r=0.996) with an estimated detection limit of 1.6×10(-8)molL(-1). MIS had been successfully used to analyze E2 in water samples without complex pretreatment. Meanwhile, the average recoveries were higher than 93.9% with RSD<3.7%. All results above reveal that MIS is an effective electrochemical technique to determine E2 real-time in complicated matrix. Copyright © 2011 Elsevier B.V. All rights reserved.

Photocatalytic events of CdSe quantum dots in confined media. Electrodic behavior of coupled platinum nanoparticles.

PubMed

Harris, Clifton; Kamat, Prashant V

2010-12-28

The electrodic behavior of platinum nanoparticles (2.8 nm diameter) and their role in influencing the photocatalytic behavior of CdSe quantum dots (3.4 nm diameter) has been evaluated by confining both nanoparticles together in heptane/dioctyl sulphosuccinate/water reverse micelles. The particles spontaneously couple together within the micelles via micellar exchange processes and thus facilitate experimental observation of electron transfer reactions inside the water pools. Electron transfer from CdSe to Pt is found to occur with a rate constant of 1.22 × 10(9) s(-1). With the use of methyl viologen (MV(2+)) as a probe molecule, the role of Pt in the photocatalytic process is established. Ultrafast oxidation of the photogenerated MV(+•) radicals indicates that Pt acts as an electron sink, scavenging electrons from MV(+•) with a rate constant of 3.1 × 10(9) s(-1). The electron transfer between MV(+•) and Pt, and a drastically lower yield of MV(+•) under steady state irradiation, confirms the ability of Pt nanoparticles to discharge electrons quickly. The kinetic details of photoinduced processes in CdSe-Pt assemblies and the electrodic behavior of Pt nanoparticles provide important information for the development of light energy conversion devices.

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

High-density platinum nanoparticle-decorated titanium dioxide nanofiber networks for efficient capillary photocatalytic hydrogen generation

Treesearch

Zhaodong Li; Chunhua Yao; Yi-Cheng Wang; Solomon Mikael; Sundaram Gunasekaran; Zhenqiang Ma; Zhiyong Cai; Xudong Wang

2016-01-01

Aldehyde-functionalized cellulose nanofibers (CNFs) were applied to synthesize Pt nanoparticles (NPs) on CNF surfaces via on-site Pt ion reduction and achieve high concentration and uniform Pt NP loading. ALD could then selectively deposit TiO2 on CNFs and keep the Pt NPs uncovered due to their drastically different hydro-affinity properties. The...

Ag–Pt compositional intermetallics made from alloy nanoparticles

DOE PAGES

Pan, Yung -Tin; Yan, Yuqi; Shao, Yu -Tsun; ...

2016-09-07

Intermetallics are compounds with long-range structural order that often lies in a state of thermodynamic minimum. They are usually considered as favorable structures for catalysis due to their high activity and robust stability. However, formation of intermetallic compounds is often regarded as element specific. For instance, Ag and Pt do not form alloy in bulk phase through the conventional metallurgy approach in almost the entire range of composition. Herein, we demonstrate a bottom-up approach to create a new Ag–Pt compositional intermetallic phase from nanoparticles. By thermally treating the corresponding alloy nanoparticles in inert atmosphere, we obtained an intermetallic material thatmore » has an exceptionally narrow Ag/Pt ratio around 52/48 to 53/47, and a structure of interchangeable closely packed Ag and Pt layers with 85% on tetrahedral and 15% on octahedral sites. This rather unique stacking results in wavy patterns of Ag and Pt planes revealed by scanning transmission electron microscope (STEM). Finally, this Ag–Pt compositional intermetallic phase is highly active for electrochemical oxidation of formic acid at low anodic potentials, 5 times higher than its alloy nanoparticles, and 29 times higher than the reference Pt/C at 0.4 V (vs RHE) in current density.« less

Ag–Pt compositional intermetallics made from alloy nanoparticles

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

Pan, Yung -Tin; Yan, Yuqi; Shao, Yu -Tsun

Intermetallics are compounds with long-range structural order that often lies in a state of thermodynamic minimum. They are usually considered as favorable structures for catalysis due to their high activity and robust stability. However, formation of intermetallic compounds is often regarded as element specific. For instance, Ag and Pt do not form alloy in bulk phase through the conventional metallurgy approach in almost the entire range of composition. Herein, we demonstrate a bottom-up approach to create a new Ag–Pt compositional intermetallic phase from nanoparticles. By thermally treating the corresponding alloy nanoparticles in inert atmosphere, we obtained an intermetallic material thatmore » has an exceptionally narrow Ag/Pt ratio around 52/48 to 53/47, and a structure of interchangeable closely packed Ag and Pt layers with 85% on tetrahedral and 15% on octahedral sites. This rather unique stacking results in wavy patterns of Ag and Pt planes revealed by scanning transmission electron microscope (STEM). Finally, this Ag–Pt compositional intermetallic phase is highly active for electrochemical oxidation of formic acid at low anodic potentials, 5 times higher than its alloy nanoparticles, and 29 times higher than the reference Pt/C at 0.4 V (vs RHE) in current density.« less

Electrocatalytic activity of spots of electrodeposited noble-metal catalysts on carbon nanotubes modified glassy carbon.

PubMed

Chen, Xingxing; Eckhard, Kathrin; Zhou, Min; Bron, Michael; Schuhmann, Wolfgang

2009-09-15

A strategy for the screening of the electrocatalytic activity of electrocatalysts for possible application in fuel cells and other devices is presented. In this approach, metal nanoclusters (Pt, Au, Ru, and Rh and their codeposits) were prepared using a capillary-based droplet-cell by pulsed electrodeposition in a diffusion-restricted viscous solution. A glassy carbon surface was modified with carbon nanotubes (CNTs) by electrophoretic accumulation and was used as substrate for metal nanoparticle deposition. The formed catalyst spots on the CNT-modified glassy carbon surface were investigated toward their catalytic activity for oxygen reduction as a test reaction employing the redox competition mode of scanning electrochemical microscopy (RC-SECM). Qualitative information on the electrocatalytic activity of the catalysts was obtained by varying the potential applied to the substrate; semiquantitative evaluation was based on the determination of the electrochemically deposited catalyst loading by means of the charge transferred during the metal nanoparticle deposition. Qualitatively, Au showed the highest electrocatalytic activity toward the oxygen reduction reaction (ORR) in phosphate buffer among all investigated single metal catalysts which was attributed to the much higher loading of Au achieved during electrodeposition. Coelectrodeposited Au-Pt catalysts showed a more positive onset potential (-150 mV in RC-SECM experiments) of the ORR in phosphate buffer at pH 6.7. After normalizing the SECM image by the charge during the metal nanocluster deposition which represents the mass loading of the catalyst, Ru showed a higher electrocatalytic activity toward the ORR than Au.

CeO2/rGO/Pt sandwich nanostructure: rGO-enhanced electron transmission between metal oxide and metal nanoparticles for anodic methanol oxidation of direct methanol fuel cells.

PubMed

Yu, Xue; Kuai, Long; Geng, Baoyou

2012-09-21

Pt-based nanocomposites have been of great research interest. In this paper, we design an efficient MO/rGO/Pt sandwich nanostructure as an anodic electrocatalyst for DMFCs with combination of the merits of rigid structure of metallic oxides (MOs) and excellent electronic conductivity of reduced oxidized graphene (rGO) as well as overcoming their shortcomings. In this case, the CeO(2)/rGO/Pt sandwich nanostructure is successfully fabricated through a facile hydrothermal approach in the presence of graphene oxide and CeO(2) nanoparticles. This structure has a unique building architecture where rGO wraps up the CeO(2) nanoparticles and Pt nanoparticles are homogeneously dispersed on the surface of rGO. This novel structure endows this material with great electrocatalytic performance in methanol oxidation: it reduces the overpotential of methanol oxidation significantly and its electrocatalytic activity and stability are much enhanced compared with Pt/rGO, CeO(2)/Pt and Pt/C catalysts. This work supplies a unique MO/rGO/Pt sandwich nanostructure as an efficient way to improve the electrocatalytic performance, which will surely shed some light on the exploration of some novel structures of electrocatalyst for DMFCs.

Synthesis and structural, magnetic and electrochemical characterization of PtCo nanoparticles prepared by water-in-oil microemulsion

NASA Astrophysics Data System (ADS)

Solla-Gullón, J.; Gómez, Elvira; Vallés, Elisa; Aldaz, Antonio; Feliu, Juan M.

2010-05-01

PtCo nanoparticles with homogeneous size (around 3-4 nm) have been synthesized in a water-in-oil microemulsion of water/polyethylenglycol-dodecylether (BRIJ®30)/n-heptane. X-ray diffraction study revealed the formation of a cubic phase with a gradual decrease of the cell parameter with increasing cobalt incorporation in the crystalline lattice of platinum. In relation to their magnetic properties, the PtCo nanoparticles present a superparamagnetic behaviour even after annealing, although higher permeability was induced by the thermal treatment. Finally, the electrocatalytic activity of the particles towards oxalic acid oxidation in H2SO4 was evaluated. The Pt74Co26 nanoparticles showed the highest reactivity for this reaction.

A novel non-invasive detection method for the FGFR3 gene mutation in maternal plasma for a fetal achondroplasia diagnosis based on signal amplification by hemin-MOFs/PtNPs.

PubMed

Chen, Jun; Yu, Chao; Zhao, Yilin; Niu, Yazhen; Zhang, Lei; Yu, Yujie; Wu, Jing; He, Junlin

2017-05-15

The small amount of cell-free fetal DNA (cffDNA) can be a useful biomarker for early non-invasive prenatal diagnosis (NIPD) of achondroplasia. In this study, a novel non-invasive electrochemical DNA sensor for ultrasensitive detecting FGFR3 mutation gene, a pathogenic gene of achondroplasia, based on biocatalytic signal materials and the biotin-streptavidin system are presented. Notably encapsulation of hemin in metal-organic frameworks-based materials (hemin-MOFs) and platinum nanoparticles (PtNPs) were used to prepare hemin-MOFs/PtNPs composites via a one-beaker-one-step reduction. We utilized hemin-MOFs/PtNPs for signal amplification because the promising hemin-MOFs/PtNPs nanomaterial has remarkable ability of catalyze H 2 O 2 as well as excellent conductivity. To further amplify the electrochemical signal, reduced graphene oxide-tetraethylene pentamine (rGO-TEPA), gold nanoparticles and streptavidin were selected for modification of the electrode to enhance the conductivity and immobilize more biotin-modified capture probe (Bio-CP) through the high specificity and superior affinity between streptavidin and biotin. The electrochemical signal was primarily derived from the synergistic catalysis of H 2 O 2 by hemin and PtNPs and recorded by Chronoamperometry. Under the optimal conditions, this newly designed biosensor exhibited sensitive detection of FGFR3 from 0.1fM to 1nM with a low detection limit of 0.033fM (S/N=3). We proposed that this ultrasensitive biosensor is useful for the early non-invasive prenatal diagnosis of achondroplasia. Copyright © 2016 Elsevier B.V. All rights reserved.

Ru-decorated Pt surfaces as model fuel cell electrocatalysts for CO electrooxidation.

PubMed

Maillard, F; Lu, G-Q; Wieckowski, A; Stimming, U

2005-09-01

This feature article concerns Pt surfaces modified (decorated) by ruthenium as model fuel cell electrocatalysts for electrooxidation processes. This work reveals the role of ruthenium promoters in enhancing electrocatalytic activity toward organic fuels for fuel cells, and it particularly concerns the methanol decomposition product, surface CO. A special focus is on surface mobility of the CO as it is catalytically oxidized to CO(2). Different methods used to prepare Ru-decorated Pt single crystal surfaces as well as Ru-decorated Pt nanoparticles are reviewed, and the methods of characterization and testing of their activity are discussed. The focus is on the origin of peak splitting involved in the voltammetric electrooxidation of CO on Ru-decorated Pt surfaces, and on the interpretative consequences of the splitting for single crystal and nanoparticle Pt/Ru bimetallic surfaces. Apparently, screening through the literature allows formulating several models of the CO stripping reaction, and the validity of these models is discussed. Major efforts are made in this article to compare the results reported by the Urbana-Champaign group and the Munich group, but also by other groups. As electrocatalysis is progressively more and more driven by theory, our review of the experimental findings may serve to summarize the state of the art and clarify the roads ahead. Future studies will deal with highly dispersed and reactive nanoscale surfaces and other more advanced catalytic materials for fuel cell catalysis and related energy applications. It is expected that the metal/metal and metal/substrate interactions will be increasingly investigated on atomic and electronic levels, with likewise increasing participation of theory, and the structure and reactivity of various monolayer catalytic systems involving more than two metals (that is ternary and quaternary systems) will be interrogated.

Highly dispersed Pt-Ni nanoparticles on nitrogen-doped carbon nanotubes for application in direct methanol fuel cells.

PubMed

Jiang, Shujuan; Ma, Yanwen; Tao, Haisheng; Jian, Guoqiang; Wang, Xizhang; Fan, Yining; Zhu, Jianmin; Hu, Zheng

2010-06-01

Binary Pt-Ni alloyed nanoparticles supported on nitrogen-doped carbon nanotubes (NCNTs) have been facilely constructed without pre-modification by making use of the active sites in NCNTs due to the N-participation. So-obtained binary Pt-Ni alloyed nanoparticles have been highly dispersed on the outer surface of the support with the size of about 3-4 nm. The electrochemical properties of the catalysts for methanol oxidation have been systematically evaluated. Binary Pt-Ni alloyed composites with molar ratio (Pt:Ni) of 3:2 and 3:1 present enhanced electrocatalytic activities and improved tolerance to CO poisoning as well as the similar stability, in comparison with the commercial Pt/C catalyst and the monometallic Pt/NCNTs catalysts. These results imply that so-constructed nanocomposite catalysts have the potential for applications in direct methanol fuel cells.

Thermal stability of Pt nanoclusters interacting to carbon sublattice

NASA Astrophysics Data System (ADS)

Baidyshev, V. S.; Gafner, Yu. Ya.; Gafner, S. L.; Redel, L. V.

2017-12-01

The catalytic activity of Pt clusters is dependent not only on the nanoparticle size and its composition, but also on its internal structure. To determine the real structure of the nanoparticles used in catalysis, the boundaries of the thermal structure stability of Pt clusters to 8.0 nm in diameter interacting with carbon substrates of two types: a fixed α-graphite plane and a mobile substrate with the diamond structure. The effect of a substrate on the processes melting of Pt nanoclusters is estimated. The role of the cooling rate in the formation of the internal structure of Pt clusters during crystallization is studied. The regularities obtained in the case of "free" Pt clusters and Pt clusters on a substrate are compared. It is concluded that platinum nanoparticles with diameter D ≤ 4.0 nm disposed on a carbon substrate conserve the initial fcc structure during cooling.

Determination of Magneto-crystalline Anisotropy Energy (MAE) Of ordered L10 CoPt and FePt nanoparticles

NASA Astrophysics Data System (ADS)

Alsaad, A.; Ahmad, A. A.; Shukri, A. A.; Bani-Younes, O. A.

2018-02-01

The structural and magnetic properties of both L10 ordered FePt and CoPt nanoparticles make them potential candidates for optical-electronic and magneto-optical devices. First, we carried out an ab initio total energy minimization study to find the geometrical optimization of both L10 phases of FePt and CoPt nanoparticles. Then, we investigated the magnetocrystalline anisotropy energy (MAE) of both systems along special line joining the points of high symmetry (A,B and C points) using super-cell slap approach with alternating layers Fe/Co and Pt along the (001) direction. We found that the point (A) has the highest MAE value for both systems, where the value of MAE in FePt is 8.89 × 107 erg/cm3 and in CoPt is 6.40 × 107 erg/cm3. Our spin density based calculations indicate that large spin-orbit interaction and the hybridization between Pt 5d states and Fe/Co 3d states are the dominant factors in determining the MAE in both systems.

WO3/Pt nanoparticles are NADPH oxidase biomimetics that mimic effector cells in vitro and in vivo.

PubMed

Clark, Andrea J; Coury, Emma L; Meilhac, Alexandra M; Petty, Howard R

2016-02-12

To provide a means of delivering an artificial immune effector cell-like attack on tumor cells, we report the tumoricidal ability of inorganic WO3/Pt nanoparticles that mimic a leukocyte's functional abilities. These nanoparticles route electrons from organic structures and electron carriers to form hydroxyl radicals within tumor cells. During visible light exposure, WO3/Pt nanoparticles manufacture hydroxyl radicals, degrade organic compounds, use NADPH, trigger lipid peroxidation, promote lysosomal membrane disruption, promote the loss of reduced glutathione, and activate apoptosis. In a model of advanced breast cancer metastasis to the eye's anterior chamber, we show that WO3/Pt nanoparticles prolong the survival of 4T1 tumor-bearing Balb/c mice. This new generation of inorganic photosensitizers do not photobleach, and therefore should provide an important therapeutic advance in photodynamic therapy. As biomimetic nanoparticles destroy targeted cells, they may be useful in treating ocular and other forms of cancer.

WO3/Pt nanoparticles are NADPH oxidase biomimetics that mimic effector cells in vitro and in vivo

NASA Astrophysics Data System (ADS)

Clark, Andrea J.; Coury, Emma L.; Meilhac, Alexandra M.; Petty, Howard R.

2016-02-01

To provide a means of delivering an artificial immune effector cell-like attack on tumor cells, we report the tumoricidal ability of inorganic WO3/Pt nanoparticles that mimic a leukocyte’s functional abilities. These nanoparticles route electrons from organic structures and electron carriers to form hydroxyl radicals within tumor cells. During visible light exposure, WO3/Pt nanoparticles manufacture hydroxyl radicals, degrade organic compounds, use NADPH, trigger lipid peroxidation, promote lysosomal membrane disruption, promote the loss of reduced glutathione, and activate apoptosis. In a model of advanced breast cancer metastasis to the eye’s anterior chamber, we show that WO3/Pt nanoparticles prolong the survival of 4T1 tumor-bearing Balb/c mice. This new generation of inorganic photosensitizers do not photobleach, and therefore should provide an important therapeutic advance in photodynamic therapy. As biomimetic nanoparticles destroy targeted cells, they may be useful in treating ocular and other forms of cancer.

Simple synthesized Pt/GNs/TiO2 with good mass activity and stability for methanol oxidation

NASA Astrophysics Data System (ADS)

Zhang, Jianbo; Hu, Xiulan; Zhu, Faquan; Su, Nan; Huang, Huihong; Cheng, Jiexu; Yang, Hui

2017-12-01

Pt/GNs/TiO2 (GNs, graphene nanosheets) catalyst was synthesized by a simple two-step method, including a rapid solution plasma technique to obtained Pt nanoparticles with a size of 2-5 nm and followed by an ultrasonic mixing of the Pt, GNs and TiO2 nanoparticles. After coupling with TiO2 nanoparticles, the Pt/GNs/TiO2 catalyst exhibited a promoting catalytic activity towards methanol oxidation, which was superior to the Pt/GNs catalyst. The mass activity of the Pt/GNs/TiO2 catalyst was 3464 mA mgPt -1, which was 3.5 and 3.4 times higher than those of the Pt/GNs and the commercial Pt/C, respectively. And the Pt/GNs/TiO2 showed a strongly negative shift onset potential of methanol oxidation. The results of long-term cyclic voltammetry and CO-stripping tests showed an improved CO tolerance of the Pt/GNs/TiO2. Moreover, the mass activity of the Pt/GNs/TiO2 was further enhanced under light irradiation, with the mass activity of 4715 mA mgPt -1, which was 1.4 times higher than that of in dark. This work provides new opportunities for exploiting efficient visible photo-assisted electro-catalytic methanol oxidation.

Multifunctional nanocomposites of carbon nanotubes and nanoparticles formed via vacuum filtration

DOEpatents

Hersam, Mark C; Ostojic, Gordana; Liang, Yu Teng

2013-10-22

In one aspect, the present invention provides a method of forming a film of nanocomposites of carbon nanotubes (CNTs) and platinum (Pt) nanoparticles. In one embodiment, the method includes the steps of (a) providing a first solution that contains a plurality of CNTs, (b) providing a second solution that contains a plurality of Pt nanoparticles, (c) combining the first solution and the second solution to form a third solution, and (d) filtering the third solution through a nanoporous membrane using vacuum filtration to obtain a film of nanocomposites of CNTs and Pt nanoparticles.

Novel platinum-palladium bimetallic nanoparticles synthesized by Dioscorea bulbifera: anticancer and antioxidant activities.

PubMed

Ghosh, Sougata; Nitnavare, Rahul; Dewle, Ankush; Tomar, Geetanjali B; Chippalkatti, Rohan; More, Piyush; Kitture, Rohini; Kale, Sangeeta; Bellare, Jayesh; Chopade, Balu A

2015-01-01

Medicinal plants serve as rich sources of diverse bioactive phytochemicals that might even take part in bioreduction and stabilization of phytogenic nanoparticles with immense therapeutic properties. Herein, we report for the first time the rapid efficient synthesis of novel platinum-palladium bimetallic nanoparticles (Pt-PdNPs) along with individual platinum (PtNPs) and palladium (PdNPs) nanoparticles using a medicinal plant, Dioscorea bulbifera tuber extract (DBTE). High-resolution transmission electron microscopy revealed monodispersed PtNPs of size 2-5 nm, while PdNPs and Pt-PdNPs between 10 and 25 nm. Energy dispersive spectroscopy analysis confirmed 30.88% ± 1.73% elemental Pt and 68.96% ± 1.48% elemental Pd in the bimetallic nanoparticles. Fourier transform infrared spectra indicated strong peaks at 3,373 cm(-1), attributed to hydroxyl group of polyphenolic compounds in DBTE that might play a key role in bioreduction in addition to the sharp peaks at 2,937, 1,647, 1,518, and 1,024 cm(-1), associated with C-H stretching, N-H bending in primary amines, N-O stretching in nitro group, and C-C stretch, respectively. Anticancer activity against HeLa cells showed that Pt-PdNPs exhibited more pronounced cell death of 74.25% compared to individual PtNPs (12.6%) or PdNPs (33.15%). Further, Pt-PdNPs showed an enhanced scavenging activity against 2,2-diphenyl-1-picrylhydrazyl, superoxide, nitric oxide, and hydroxyl radicals.

Performance evaluation of platinum-molybdenum carbide nanocatalysts with ultralow platinum loading on anode and cathode catalyst layers of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Saha, Shibely; Cabrera Rodas, José Andrés; Tan, Shuai; Li, Dongmei

2018-02-01

An alternative catalyst platform, consisting of a phase-pure transition carbide (TMC) support and Pt nanoparticles (NPs) in the range of subnanometer to < 2.7 nm, is established that can be used in both anode and cathode catalyst layers. While some TMCs with low Pt loadings have demonstrated similar activity as commercial Pt catalyst in idealized disk electrode screening tests, few to none have been applied in a realistic fuel cell membrane electrode assembly (MEA). We recently reported that β-Mo2C hollow nanotubes modified with Pt NPs via atomic layer deposition (ALD) possess better activity and durability than 20% Pt/C. This paper presents systematic evaluation of the Pt/Mo2C catalysts in a MEA, investigating effects of different MEA preparation techniques, gas diffusion layers (GDL) and various Pt loadings in the ultralow range (<0.04 mg/cm2) on MEA performance. Most importantly, we demonstrate, for the first time, that Pt/Mo2C catalyst on both anode and cathode, with a loading of 0.02 mg (Pt) cm-2, generated peak power density of 414 mW cm-2 that corresponds to 10.35 kWgPt-1 using hydrogen (H2) and oxygen (O2). Accelerated degradation tests (ADT) on Pt/Mo2C catalysts show 111% higher power density than commercial 20% Pt/C after the vigorous ADT.

Critical switching fluence of L10-FePt nanoparticles with practical size to ultrafast all-optical polarization switching

NASA Astrophysics Data System (ADS)

Huang, Tao; Wang, Haiwei; Cheng, Weiming; Zou, Yuhao; Xie, Changsheng

2017-06-01

The magnetic storage industry will be pushed into a new era by emerging magnetic materials and ingenious read/write techniques. Recently, L10-FePt nanoparticles with exceptionally high uniaxial anisotropy, combined with the technique of all-optical magnetic switching, have increasingly drawn the attention of researchers. Focusing on L10-FePt nanoparticles, we report the superparamagnetic size limits and three elaborate stages of magnetic orientation switching, which demonstrate that in terms of the opto-magnetic responses of L10-FePt nanoparticles with the size of 6 nm, the fluence of an ultrashort laser pulse should not be larger than the level of 40 mJ/cm2 in order to achieve the helicity-dependent all-optical switching.

Noncovalently functionalized graphitic mesoporous carbon as a stable support of Pt nanoparticles for oxygen reduction

NASA Astrophysics Data System (ADS)

Shao, Yuyan; Zhang, Sheng; Kou, Rong; Wang, Xiqing; Wang, Chongmin; Dai, Sheng; Viswanathan, Vilayanur; Liu, Jun; Wang, Yong; Lin, Yuehe

We report a durable electrocatalyst support, highly graphitized mesoporous carbon (GMPC), for oxygen reduction in polymer electrolyte membrane (PEM) fuel cells. GMPC is prepared through graphitizing the self-assembled soft-template mesoporous carbon (MPC) under high temperature. Heat-treatment at 2800 °C greatly improves the degree of graphitization while most of the mesoporous structures and the specific surface area of MPC are retained. GMPC is then noncovalently functionalized with poly(diallyldimethylammonium chloride) (PDDA) and loaded with Pt nanoparticles by reducing Pt precursor (H 2PtCl 6) in ethylene glycol. Pt nanoparticles of ∼3.0 nm in diameter are uniformly dispersed on GMPC. Compared to Pt supported on Vulcan XC-72 carbon black (Pt/XC-72), Pt/GMPC exhibits a higher mass activity towards oxygen reduction reaction (ORR) and the mass activity retention (in percentage) is improved by a factor of ∼2 after 44 h accelerated degradation test under the potential step (1.4-0.85 V) electrochemical stressing condition which focuses on support corrosion. The enhanced activity and durability of Pt/GMPC are attributed to the graphitic structure of GMPC which is more resistant to corrosion. These findings demonstrate that GMPC is a promising oxygen reduction electrocatalyst support for PEM fuel cells. The approach reported in this work provides a facile, eco-friendly promising strategy for synthesizing stable metal nanoparticles on hydrophobic support materials.

Electrocatalytic effect of polyvinyl pyrrolidone capped platinum nanoparticles electrodeposited on platinum electrode for ammonia oxidation

NASA Astrophysics Data System (ADS)

Mayedwa, Noluthando; Matinise, Nolubabalo; Mongwaketsi, Nametso; Maaza, Malik

2018-05-01

The aim of this work was to study structural and kinetic parameters as well as the mechanism of platinum nanoparticles (PtNP) reduced with sodium borohydride (NaBH4) and capped with polyvinyl pyrrolidone (PVP). The nanoparticles were supported on Pt electrode for ammonia oxidation in fuel cell application. X-ray diffraction (XRD) was used to study structural composition and high resolution transmission electron microscopy (HRTEM) was used for morphological study of the nanoalloy. The electrocatalysts were studied in alkaline solution of potassium hydroxide (KOH) by cyclic voltammetry (CV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS). CV showed that the ammonia oxidation over potential for PtNP was -431 mV and with exchange current density of 1.726 × 10-4 A. EIS showed that the charge transfer resistance (Rct) of PtNP was the lowest (Rct = 1.943 × 106 Ω) compared to that of bare Pt working electrode (2.0604 × 106 Ω), indicating that the Pt nanoparticles have good conductivity and played an important role in accelerating the transfer of electrons.

Sintering-Resistant Nanoparticles in Wide-Mouthed Compartments for Sustained Catalytic Performance

NASA Astrophysics Data System (ADS)

Liu, Jia; Ji, Qingmin; Imai, Tsubasa; Ariga, Katsuhiko; Abe, Hideki

2017-02-01

Particle sintering is one of the most significant impediments to functional nanoparticles in many valuable applications especially catalysis. Herein, we report that sintering-resistant nanoparticle systems can be realized through a simple materials-design which maximizes the particle-to-particle traveling distance of neighbouring nanoparticles. As a demonstration, Pt nanoparticles were placed apart from each other in wide-mouthed compartments tailored on the surface of self-assembled silica nanosheets. These Pt nanoparticles retained their particle size after calcination at elevated temperatures because the compartment wall elongates the particle-to-particle traveling distance to preclude the possibility of sintering. Moreover, these Pt nanoparticles in wide-mouthed compartments were fully accessible to the environment and exhibited much higher catalytic activity for CO oxidation than the nanoparticles confined in the nanochannels of mesoporous silica. The proposed materials-design strategy is applicable not only to industrial catalysts operating in harsh conditions, but also opens up possibilities in developing advanced nanoparticle-based materials with sustained performance.

Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts

DOE PAGES

Sasaki, Kotaro; Marinkovic, Nebojsa; Isaacs, Hugh S.; ...

2015-11-17

Understanding oxidation/dissolution mechanisms of Pt is critical in designing durable catalysts for the oxygen reduction reaction (ORR), but exact mechanisms remain unclear. Our present work explores the oxidation/dissolution of Pt and Pt monolayer (ML) electrocatalysts over a wide range of applied potentials using cells that facilitate in situ measurements by combining X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements. Furthermore, the X-ray absorption near edge structure (XANES) measurement demonstrated that Pt nanoparticle surfaces were oxidized from metallic Pt to α-PtO 2-type oxide during the potential sweep from 0.41 to 1.5 V, and the transition state of O or OHmore » adsorption on Pt and the onset of the place exchange process were revealed by the delta mu (Δμ) method. Only the top layers of Pt nanoparticles were oxidized, while the inner Pt atoms remained intact. At a higher potential over 1.9 V, α-PtO 2-type surface oxides dissolve due to local acidification caused by the oxygen evolution reaction and carbon corrosion. Pt oxidation of Pt ML on the Pd nanoparticle electrocatalyst is considerably hampered compared with the Pt/C catalyst, presumably because preferential Pd oxidation proceeds at the defects in Pt MLs up to 0.91 V and through O penetrated through the Pt MLs by the place exchange process above 1.11 V.« less

Platinum nanoparticles on carbon-nanotube support prepared by room-temperature reduction with H2 in ethylene glycol/water mixed solvent as catalysts for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Zheng, Yuying; Dou, Zhengjie; Fang, Yanxiong; Li, Muwu; Wu, Xin; Zeng, Jianhuang; Hou, Zhaohui; Liao, Shijun

2016-02-01

Polyol approach is commonly used in synthesizing Pt nanoparticles in polymer electrolyte membrane fuel cells. However, the application of this process consumes a great deal of time and energy, as the reduction of precursors requires elevated temperatures and several hours. Moreover, the ethylene glycol and its oxidizing products bound to Pt are difficult to remove. In this work, we utilize the advantages of ethylene glycol and prepare Pt nanoparticles through a room-temperature hydrogen gas reduction in an ethylene glycol/water mixed solvent, which is followed by subsequent harvesting by carbon nanotubes as electrocatalysts. This method is simple, facile, and time-efficient, as the entire room-temperature reduction process is completed in a few minutes. As the solvent changes from water to an ethylene glycol/water mix, the size of Pt nanoparticles varies from 10 to 3 nm and their shape transitions from polyhedral to spherical. Pt nanoparticles prepared in a 1:1 volume ratio mixture of ethylene glycol/water are uniformly dispersed with an average size of ∼3 nm. The optimized carbon nanotube-supported Pt electrocatalyst exhibits excellent methanol oxidation and oxygen reduction activities. This work demonstrates the potential use of mixed solvents as an approach in materials synthesis.

Temperature-dependent local structural properties of redox Pt nanoparticles on TiO 2 and ZrO 2 supports

DOE PAGES

Jeong, Eun -Suk; Park, Chang -In; Jin, Zhenlan; ...

2015-01-21

This paper examined the local structural properties of Pt nanoparticles on SiO 2, TiO 2–SiO 2, and ZrO 2–SiO 2 supports to better understand the impact of oxide-support type on the performance of Pt-based catalysts. In situ X-ray absorption fine structure (XAFS) measurements were taken for the Pt L3-edge in a temperature range from 300 to 700 K in He, H 2, and O 2 gas environments. The XAFS measurements demonstrated that Pt atoms were highly dispersed on TiO 2–SiO 2 and ZrO 2–SiO 2 forming pancake-shaped nanoparticles, whereas Pt atoms formed larger particles of hemispherical shapes on SiO 2more » supports. Contrary to the SiO 2 case, the coordination numbers for Pt, Ti, and Zr around Pt atoms on the TiO 2–SiO 2 and ZrO 2–SiO 2 supports were nearly constant from 300 to 700 K under the different gas environments. These results are consistent with the improvements in thermal stability of Pt nanoparticles achieved by incorporating TiO 2 or ZrO 2 on the surface of SiO 2 supports. XAFS analysis further indicated that the enhanced dispersion and stability of Pt were a consequence of the strong metal support interaction via Pt–Ti and Pt–Zr bonds.« less

Controlled surface segregation leads to efficient coke-resistant nickel/platinum bimetallic catalysts for the dry reforming of methane

DOE PAGES

Li, Lidong; Zhou, Lu; Ould-Chikh, Samy; ...

2015-02-03

Surface composition and structure are of vital importance for heterogeneous catalysts, especially for bimetallic catalysts, which often vary as a function of reaction conditions (known as surface segregation). The preparation of bimetallic catalysts with controlled metal surface composition and structure is very challenging. In this study, we synthesize a series of Ni/Pt bimetallic catalysts with controlled metal surface composition and structure using a method derived from surface organometallic chemistry. The evolution of the surface composition and structure of the obtained bimetallic catalysts under simulated reaction conditions is investigated by various techniques, which include CO-probe IR spectroscopy, high-angle annular dark-field scanningmore » transmission electron microscopy, energy-dispersive X-ray spectroscopy, extended X-ray absorption fine structure analysis, X-ray absorption near-edge structure analysis, XRD, and X-ray photoelectron spectroscopy. It is demonstrated that the structure of the bimetallic catalyst is evolved from Pt monolayer island-modified Ni nanoparticles to core–shell bimetallic nanoparticles composed of a Ni-rich core and a Ni/Pt alloy shell upon thermal treatment. As a result, these catalysts are active for the dry reforming of methane, and their catalytic activities, stabilities, and carbon formation vary with their surface composition and structure.« less

High loading of uniformly dispersed Pt nanoparticles on polydopamine coated carbon nanotubes and its application in simultaneous determination of dopamine and uric acid

NASA Astrophysics Data System (ADS)

Lin, Mouhong; Huang, Haoliang; Liu, Yingju; Liang, Canjian; Fei, Shidong; Chen, Xiaofen; Ni, Chunlin

2013-02-01

Multiwalled carbon nanotubes (MWCNT) were homogeneously covered with a bio-functional polydopamine (PDOP) by a simple dip-coating approach in mild basic solution. Then, uniformly dispersed and highly loaded platinum nanoparticles (PtNPs) were deposited on MWCNT@PDOP by a mild reductant, and were characterized by transmission electron microscopy and x-ray photoelectron spectroscopy. Afterwards, this nanocomposite was modified on the glass carbon electrode and applied to simultaneously determine dopamine (DA) and uric acid (UA) by differential pulse voltammetry (DPV). Results showed that a linear electro-oxidation response was found for DA and UA in the range of 0.25-20 μM and 0.3-13 μM with the detection limit (S/N = 3) of 0.08 μM and 0.12 μM, respectively. In addition, the detection sensitivities for DA and UA by DPV were 1.03 μA μM-1 and 2.09 μA μM-1, respectively, which were much higher than those from a cyclic voltammogram. Finally, the reproducibility and stability of the nanocomposite were also evaluated, demonstrating that such MWCNT@PDOP@PtNPs can be a promising candidate for advanced electrode material in electrochemical sensing and other electrocatalytic applications.

Targeted delivery of cisplatin to prostate cancer cells by aptamer functionalized Pt(IV) prodrug-PLGA-PEG nanoparticles.

PubMed

Dhar, Shanta; Gu, Frank X; Langer, Robert; Farokhzad, Omid C; Lippard, Stephen J

2008-11-11

Cisplatin is used to treat a variety of tumors, but dose limiting toxicities or intrinsic and acquired resistance limit its application in many types of cancer including prostate. We report a unique strategy to deliver cisplatin to prostate cancer cells by constructing Pt(IV)-encapsulated prostate-specific membrane antigen (PSMA) targeted nanoparticles (NPs) of poly(D,L-lactic-co-glycolic acid) (PLGA)-poly(ethylene glycol) (PEG)-functionalized controlled release polymers. By using PLGA-b-PEG nanoparticles with PSMA targeting aptamers (Apt) on the surface as a vehicle for the platinum(IV) compound c,t,c-[Pt(NH(3))(2)(O(2)CCH(2)CH(2)CH(2)CH(2)CH(3))(2)Cl(2)] (1), a lethal dose of cisplatin was delivered specifically to prostate cancer cells. PSMA aptamer targeted delivery of Pt(IV) cargos to PSMA(+) LNCaP prostate cancer cells by endocytosis of the nanoparticle vehicles was demonstrated using fluorescence microscopy by colocalization of green fluorescent labeled cholesterol-encapsulated NPs and early endosome marker EEA-1. The choice of linear hexyl chains in 1 was the result of a systematic study to optimize encapsulation and controlled release from the polymer without compromising either feature. Release of cisplatin from the polymeric nanoparticles after reduction of 1 and formation of cisplatin 1,2-intrastrand d(GpG) cross-links on nuclear DNA was confirmed by using a monoclonal antibody for the adduct. A comparison between the cytotoxic activities of Pt(IV)-encapsulated PLGA-b-PEG NPs with the PSMA aptamer on the surface (Pt-NP-Apt), cisplatin, and the nontargeted Pt(IV)-encapsulated NPs (Pt-NP) against human prostate PSMA-overexpressing LNCaP and PSMA(-) PC3 cancer cells revealed significant differences. The effectiveness of PSMA targeted Pt-NP-Apt nanoparticles against the PSMA(+) LNCaP cells is approximately an order of magnitude greater than that of free cisplatin.

Enhanced Catalytic Activities of NiPt Truncated Octahedral Nanoparticles toward Ethylene Glycol Oxidation and Oxygen Reduction in Alkaline Electrolyte.

PubMed

Xia, Tianyu; Liu, Jialong; Wang, Shouguo; Wang, Chao; Sun, Young; Gu, Lin; Wang, Rongming

2016-05-04

The high cost and poor durability of Pt nanoparticles (NPs) are great limits for the proton exchange membrane fuel cells (PEMFCs) from being scaled-up for commercial applications. Pt-based bimetallic NPs together with a uniform distribution can effectively reduce the usage of expensive Pt while increasing poison resistance of intermediates. In this work, a simple one-pot method was used to successfully synthesize ultrafine (about 7.5 nm) uniform NiPt truncated octahedral nanoparticles (TONPs) in dimethylformamid (DMF) without any seeds or templates. The as-prepared NiPt TONPs with Pt-rich surfaces exhibit greatly improved catalytic activities together with good tolerance and better stability for ethylene glycol oxidation reaction (EGOR) and oxygen reduction reaction (ORR) in comparison with NiPt NPs and commercial Pt/C catalysts in alkaline electrolyte. For example, the value of mass and specific activities for EGOR are 23.2 and 17.6 times higher comparing with those of commercial Pt/C, respectively. Our results demonstrate that the dramatic enhancement is mainly attributed to Pt-rich surface, larger specific surface area, together with coupling between Ni and Pt atoms. This developed method provides a promising pathway for simple preparation of highly efficient electrocatalysts for PEMFCs in the near future.

Synthesis and In Vitro Performance of Polypyrrole-Coated Iron-Platinum Nanoparticles for Photothermal Therapy and Photoacoustic Imaging

NASA Astrophysics Data System (ADS)

Phan, Thi Tuong Vy; Bui, Nhat Quang; Moorthy, Madhappan Santha; Lee, Kang Dae; Oh, Junghwan

2017-10-01

Multifunctional nano-platform for the combination of photo-based therapy and photoacoustic imaging (PAI) for cancer treatment has recently attracted much attention to nanotechnology development. In this study, we developed iron-platinum nanoparticles (FePt NPs) with the polypyrrole (PPy) coating as novel agents for combined photothermal therapy (PTT) and PAI. The obtained PPy-coated FePt NPs (FePt@PPy NPs) showed excellent biocompatibility, photothermal stability, and high near-infrared (NIR) absorbance for the combination of PTT and PAI. In vitro investigation experimentally demonstrated the effectiveness of FePt@PPy NPs in killing cancer cells with NIR laser irradiation. Moreover, the phantom test of PAI used in conjunction with FePt@PPy NPs showed a strong photoacoustic signal. Thus, the novel FePt@PPy NPs could be considered as promising multifunctional nanoparticles for further applications of photo-based diagnosis and treatment.

Rapid synthesis of dendritic Pt/Pb nanoparticles and their electrocatalytic performance toward ethanol oxidation

NASA Astrophysics Data System (ADS)

Zhang, Ke; Xu, Hui; Yan, Bo; Wang, Jin; Gu, Zhulan; Du, Yukou

2017-12-01

This article reports a rapid synthetic method for the preparation of dendritic platinum-lead bimetallic catalysts by using an oil bath for 5 min in the presence of hexadecyltrimethylammonium chloride (CTAC) and ascorbic acid (AA). CTAC acts as a shape-direction agent, and AA acts as a reducing agent during the reaction process. A series of physical techniques are used to characterize the morphology, structure and electronic properties of the dendritic Pt/Pb nanoparticles, indicating the Pt/Pb dendrites are porous, highly alloying, and self-supported nanostructures. Various electrochemical techniques were also investigated the catalytic performance of the Pt/Pb catalysts toward the ethanol electrooxidation reaction. Cyclic voltammetry and chronoamperometry indicated that the synthesized dendritic Pt/Pb nanoparticles possessed much higher electrocatalytic performance than bulk Pt catalyst. This study may inspire the engineering of dendritic bimetallic catalysts, which are expected to have great potential applications in fuel cells.

DNA-mediated inhibition of peroxidase-like activities on platinum nanoparticles for simple and rapid colorimetric detection of nucleic acids.

PubMed

Chen, Weiwei; Fang, Xueen; Li, Hua; Cao, Hongmei; Kong, Jilie

2017-08-15

In this research, we found that the peroxidase-like activities of noncovalent DNA-Pt hybrid nanoparticles could be obviously blocked, when Pt nanoparticles (PtNPs) were synthesized in situ using DNA as a template. Moreover, this self-assembled synthetic process was very convenient and rapid (within few mintues), and the inhibition mediated by DNA was also very effective. First, by the paper-based analytical device (PAD) we found the catalytic activities of DNA-Pt hybrid nanoparticles exhibited a linear response to the concentration of DNA in the range from 0.0075 to 0.25µM. Then, with the magnetic bead isolated system and target DNA-induced hybridization chain reaction (HCR), we realized the specific target DNA analysis with a low detection of 0.228nM, and demonstrated its effectivity in distinguishing the target DNA from other interferences. To our knowledge, this is the first report that used the nanoassembly between DNA and PtNPs for colorimetric detection of nucleic acids, which was based on DNA-mediated inhibition of catalytic activities of platinum nanoparticles. The results may be useful for understanding the interactions between DNA and metal nanoparticles, and for development of other convenient and effective analytical strategies. Copyright © 2017. Published by Elsevier B.V.

In-Situ Anomalous Small-Angle X-ray Scattering Studies of Polymer Electrolyte Membrane Fuel Cell Catalyst Degradation

NASA Astrophysics Data System (ADS)

Gilbert, James Andrew

Polymer electrolyte membrane fuel cells (PEMFCs) are a promising high efficiency energy conversion technology, but their cost effective implementation, especially for automotive power, has been hindered by degradation of the electrochemically-active surface area (ECA) of the Pt nanoparticle electrocatalysts. While numerous studies using ex-situ post-mortem techniques have provided insight into the effect of operating conditions on ECA loss, the governing mechanisms and underlying processes are not fully understood. Toward the goal of elucidating the electrocatalyst degradation mechanisms, we have followed particle size distribution (PSD) growth evolutions of Pt and Pt-alloy nanoparticle catalysts during potential cycling in an aqueous acidic environment (with and without flow of electrolyte) and in a fuel cell environment using in-situ anomalous small-angle X-ray scattering (ASAXS). The results of this thesis show a surface area loss mechanism of Pt nanoparticles supported on carbon to be predominantly controlled by Pt dissolution, the particle size dependence of Pt dissolution, the loss of dissolved Pt into the membrane and electrolyte, and, to a lesser extent, the re-deposition of dissolved Pt onto larger particles. The relative extent of these loss mechanisms are shown to be dependent on the environment, the temperature, and the potential cycling conditions. Correlation of ASAXS-determined particle growth with both calculated and voltammetrically-determined oxide coverages demonstrates that the oxide coverage is playing a key role in the dissolution process and in the corresponding growth of the mean Pt nanoparticle size and loss of ECA. This understanding potentially reduces the complex changes in PSDs and ECA resulting from various voltage profiles to the response to a single variable, oxide coverage. A better understanding of the degradation mechanisms of Pt and Pt-alloy nanoparticle distributions could lead to more stable electrocatalysts while simultaneously reducing the cost of the materials, thereby supporting more durable and lower cost PEMFCs.

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.

Beet juice utilization: Expeditious green synthesis of nobel metal nanoparticles (Ag, Au, Pt, and Pd) using microwaves

EPA Science Inventory

Metal nanoparticles of Ag, Au, Pt, and Pd were prepared in aqueous solutions via a rapid microwave-assisted green method using beet juice, an abundant sugar-rich agricultural produce, served as both a reducing and a capping reagent. The Ag nanoparticles with capping prepared by b...

Synthesis and Cs-Corrected Scanning Transmission Electron Microscopy Characterization of Multimetallic Nanoparticles

NASA Astrophysics Data System (ADS)

Khanal, Subarna; Bhattarai, Nabraj; Velázquez-Salazar, Jesus; Jose-Yacaman, Miguel; Subarna Khanal Team

2014-03-01

Multimetallic nanoparticles have been attracted greater attention both in materials science and nanotechnology due to its unique electronic, optical, biological, and catalytic properties lead by physiochemical interactions among different atoms and phases. The distinct features of multimetallic nanoparticles enhanced synergetic properties, large surface to volume ratio and quantum size effects ultimately lead to novel and wide range of possibilities for different applications than monometallic counterparts. For instance, PtPd, Pt/Cu, Au-Au3Cu, AgPd/Pt, AuCu/Pt and many other multimetallic nanoparticles have raised interest for their various applications in fuel cells, ethanol and methanol oxidation reactions, hydrogen storage, and so on. The nanostructures were analyzed by transmission electron microscopy (TEM) and by aberration-corrected scanning transmission electron microscopy (Cs-corrected STEM), in combination with high angle annular dark field (HAADF), bright field (BF), energy dispersive X-ray spectroscopy (EDS), and electron energy loss spectroscopy (EELS) detectors. These techniques allowed us to probe the structure at the atomic level of the nanoparticles revealing new structural information and elemental composition of the nanoparticles. The authors would like to acknowledge NSF grants DMR-1103730, ``Alloys at the Nanoscale: The Case of Nanoparticles Second Phase'' and NSF PREM Grant # DMR 0934218.

Ordered Pt 3Co Intermetallic Nanoparticles Derived from Metal–Organic Frameworks for Oxygen Reduction

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

Wang, Xiao Xia; Hwang, Sooyeon; Pan, Yung-Tin

Highly ordered Pt alloy structures are proved effective to improve their catalytic activity and stability for the oxygen reduction reaction (ORR) for proton exchange membrane fuel cells. Here, we report a new approach to preparing ordered Pt 3Co intermetallic nanoparticles through a facile thermal treatment of Pt nanoparticles supported on Co-doped metal-organic framework (MOF)-derived carbon. In particular, the atomically dispersed Co sites, which are originally embedded into MOF-derived carbon, diffuse into Pt nanocrystals and form ordered Pt 3Co structures. It is very crucial for the formation of the ordered Pt 3Co to carefully control the doping content of Co intomore » the MOFs and the heating temperatures for Co diffusion. The optimal Pt 3Co nanoparticle catalyst has achieved significantly enhanced activity and stability, exhibiting a half-wave potential up to 0.92 V vs. RHE and only losing 12 mV after 30,000 potential cycling between 0.6 and 1.0 V. The highly ordered intermetallic structure was retained after the accelerated stress tests evidenced by atomic-scale elemental mapping. Fuel cell tests further verified the high intrinsic activity of the ordered Pt 3Co catalysts. Unlike the direct use of MOF-derived carbon supports for depositing Pt, we utilized MOF-derived carbon containing atomically dispersed Co sites as Co sources to prepare ordered Pt 3Co intermetallic catalysts. Finally, the new synthesis approach provides an effective strategy to develop active and stable Pt alloy catalysts by leveraging the unique properties of MOFs such as 3D structures, high surface areas, and controlled nitrogen doping.« less

Ordered Pt 3Co Intermetallic Nanoparticles Derived from Metal–Organic Frameworks for Oxygen Reduction

DOE PAGES

Wang, Xiao Xia; Hwang, Sooyeon; Pan, Yung-Tin; ...

2018-06-06

Highly ordered Pt alloy structures are proved effective to improve their catalytic activity and stability for the oxygen reduction reaction (ORR) for proton exchange membrane fuel cells. Here, we report a new approach to preparing ordered Pt 3Co intermetallic nanoparticles through a facile thermal treatment of Pt nanoparticles supported on Co-doped metal-organic framework (MOF)-derived carbon. In particular, the atomically dispersed Co sites, which are originally embedded into MOF-derived carbon, diffuse into Pt nanocrystals and form ordered Pt 3Co structures. It is very crucial for the formation of the ordered Pt 3Co to carefully control the doping content of Co intomore » the MOFs and the heating temperatures for Co diffusion. The optimal Pt 3Co nanoparticle catalyst has achieved significantly enhanced activity and stability, exhibiting a half-wave potential up to 0.92 V vs. RHE and only losing 12 mV after 30,000 potential cycling between 0.6 and 1.0 V. The highly ordered intermetallic structure was retained after the accelerated stress tests evidenced by atomic-scale elemental mapping. Fuel cell tests further verified the high intrinsic activity of the ordered Pt 3Co catalysts. Unlike the direct use of MOF-derived carbon supports for depositing Pt, we utilized MOF-derived carbon containing atomically dispersed Co sites as Co sources to prepare ordered Pt 3Co intermetallic catalysts. Finally, the new synthesis approach provides an effective strategy to develop active and stable Pt alloy catalysts by leveraging the unique properties of MOFs such as 3D structures, high surface areas, and controlled nitrogen doping.« less

Anode catalysts for direct ethanol fuel cells utilizing directly solar light illumination.

PubMed

Chu, Daobao; Wang, Shuxi; Zheng, Peng; Wang, Jian; Zha, Longwu; Hou, Yuanyuan; He, Jianguo; Xiao, Ying; Lin, Huashui; Tian, Zhaowu

2009-01-01

Shine a light: A PtNiRu/TiO(2) anode catalyst for direct ethanol fuel cells shows photocatalytic activity. The peak current density for ethanol oxidation under solar light illumination is 2-3 times greater than that in the absence of solar light. Ethanol is oxidized by light-generated holes, and the electrons are collected by the TiO(2) support to generate the oxidation current.Novel PtNiRu/TiO(2) anode catalysts for direct ethanol fuel cells (DEFCs) were prepared from PtNiRu nanoparticles (1:1:1 atomic ratios) and a nanoporous TiO(2) film by a sol-gel and electrodeposition method. The performances of the catalysts for ethanol oxidation were investigated by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. The results indicate a remarkable enhancement of activity for ethanol oxidation under solar light illumination. Under solar light illumination, the generated oxidation peak current density is 24.6 mA cm(-2), which is about 2.5 times higher than that observed without solar light (9.9 mA cm(-2)). The high catalytic activity of the PtNiRu/TiO(2) complex catalyst for the electrooxidation of ethanol may be attributed to the modified metal/nanoporous TiO(2) film, and the enhanced electrooxidation of ethanol under solar light may be due to the photogeneration of holes in the modified nanoporous TiO(2) film.

One-pot solvothermal synthesis of ordered intermetallic Pt2In3 as stable and efficient electrocatalyst towards direct alcohol fuel cell application

NASA Astrophysics Data System (ADS)

Jana, Rajkumar; Peter, Sebastian C.

2016-10-01

Ordered intermetallic Pt2In3 nanoparticles have been synthesized by superhydride reduction of K2PtCl4 and InCl3.xH2O precursors using facile, one-pot solvothermal method. We report surfactant free solvothermal synthesis of a novel ordered Pt2In3 intermetallic nanoparticles for the first time. The structure and morphology of the catalyst has been confirmed by powder X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, energy-dispersive spectrometry and X-ray photoelectron spectroscopy. The electrocatalytic properties of the catalysts have been investigated by cyclic voltammetry and chronoamperometry. The as prepared Pt2In3 catalyst exhibit far superior electrocatalytic activity and stability towards alcohol oxidation over commercial Pt/C. The specific activity of as synthesized catalyst was found to be 3.2 and 2.3 times higher than commercial Pt/C for methanol and ethanol oxidation, respectively. This improved activity and durability of the Pt2In3 nanoparticles can make the catalyst an ideal catalyst candidate for direct alcohol fuel cell.

Impact of metal cations on the electrocatalytic properties of Pt/C nanoparticles at multiple phase interfaces.

PubMed

Durst, Julien; Chatenet, Marian; Maillard, Frédéric

2012-10-05

Proton-exchange membrane fuel cells (PEMFCs) use carbon-supported nanoparticles based on platinum and its alloys to accelerate the rate of the sluggish oxygen-reduction reaction (ORR). The most common metals alloyed to Pt include Co, Ni and Cu, and are thermodynamically unstable in the PEMFC environment. Their dissolution yields the formation and redistribution of metal cations (M(y+)) within the membrane electrode assembly (MEA). Metal cations can also contaminate the MEA when metallic bipolar plates are used as current collectors. In each case, the electrical performance of the PEMFC severely decreases, an effect that is commonly attributed to the poisoning of the sulfonic acid groups of the perfluorosulfonated membrane (PEM) and the resulting decrease of the proton transport properties. However, the impact of metal cations on the kinetics of electrochemical reactions involving adsorption/desorption and bond-breaking processes remains poorly understood. In this paper, we use model electrodes to highlight the effect of metal cations on Pt/C nanoparticles coated or not with a perfluorosulfonated ionomer for the CO electrooxidation reaction and the oxygen reduction reaction. We show that metal cations negatively impact the ORR kinetics and the mass-transport resistance of molecular oxygen. However, the specific adsorption of sulfonate groups of the Nafion® ionomer locally modifies the double layer structure and increases the tolerance to metal cations, even in the presence of sulphate ions in the electrolyte. The survey is extended by using an ultramicroelectrode with cavity and a solid state cell (SSC) specifically developed for this study.

Restructuring and Hydrogen Evolution on Pt Nanoparticle† †Electronic supplementary information (ESI) available: Discussions on the structures of Pt clusters and the stability of the subsurface H atoms in Pt cluster, TS structure of H–H coupling on {111} facets of Pt44H80, XYZ coordinate of Pt44 and Pt44H80. Movie of structure evolution at Pt44H50 See DOI: 10.1039/c4sc02806f Click here for additional data file. Click here for additional data file.

PubMed Central

Wei, Guang-Feng

2015-01-01

The restructuring of nanoparticles at the in situ condition is a common but complex phenomenon in nanoscience. Here, we present the first systematic survey on the structure dynamics and its catalytic consequence for hydrogen evolution reaction (HER) on Pt nanoparticles, as represented by a magic number Pt44 octahedron (∼1 nm size). Using a first principles calculation based global structure search method, we stepwise follow the significant nanoparticle restructuring under HER conditions as driven by thermodynamics to expose {100} facets, and reveal the consequent large activity enhancement due to the marked increase of the concentration of the active site, being identified to be apex atoms. The enhanced kinetics is thus a “byproduct” of the thermodynamical restructuring. Based on the results, the best Pt catalyst for HER is predicted to be ultrasmall Pt particles without core atoms, a size below ∼20 atoms. PMID:29560237

Lattice parameter evolution in Pt nanoparticles during photo-thermally induced sintering and grain growth

DOE PAGES

Kelly, B.G.; Loether, A.; DiChiara, A. D.; ...

2017-04-20

An in-situ optical pump/x-ray probe technique has been used to study the size dependent lattice parameter of Pt nanoparticles subjected to picosecond duration optical laser pulses. The as-prepared Pt nanoparticles exhibited a contracted lattice parameter consistent with the response of an isolated elastic sphere to a compressive surface stress. During photo-thermally induced sintering and grain growth, however, the Pt lattice parameter did not evolve with the inverse particle size dependence predicted by simple surface stress models. Lastly, the observed behavior could be attributed to the combined effects of a compressive surface/interface stress and a tensile stress arising from intergranular material.

Lattice parameter evolution in Pt nanoparticles during photo-thermally induced sintering and grain growth

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

Kelly, B.G.; Loether, A.; DiChiara, A. D.

An in-situ optical pump/x-ray probe technique has been used to study the size dependent lattice parameter of Pt nanoparticles subjected to picosecond duration optical laser pulses. The as-prepared Pt nanoparticles exhibited a contracted lattice parameter consistent with the response of an isolated elastic sphere to a compressive surface stress. During photo-thermally induced sintering and grain growth, however, the Pt lattice parameter did not evolve with the inverse particle size dependence predicted by simple surface stress models. Lastly, the observed behavior could be attributed to the combined effects of a compressive surface/interface stress and a tensile stress arising from intergranular material.

High-durability catalytic electrode composed of Pt nanoparticle-supported carbon nanowalls synthesized by radical-injection plasma-enhanced chemical vapor deposition

NASA Astrophysics Data System (ADS)

Imai, Shun; Kondo, Hiroki; Cho, Hyungjun; Kano, Hiroyuki; Ishikawa, Kenji; Sekine, Makoto; Hiramatsu, Mineo; Ito, Masafumi; Hori, Masaru

2017-10-01

For polymer electrolyte fuel cell applications, carbon nanowalls (CNWs) were synthesized by radical-injection plasma-enhanced chemical vapor deposition, and a high density of Pt nanoparticles (>1012 cm-2) was supported on the CNWs using a supercritical fluid deposition system. The high potential cycle tests were applied and the electrochemical surface area of the Pt nanoparticle-supported CNWs did not change significantly, even after 20 000 high potential cycles. According to transmission electron microscopy observations, the mean diameter of Pt changed slightly after the cycle tests, while the crystallinity of the CNWs evaluated using Raman spectroscopy showed almost no change.

Synthesis of platinum nanoparticles using dried Anacardium occidentale leaf and its catalytic and thermal applications.

PubMed

Sheny, D S; Philip, Daizy; Mathew, Joseph

2013-10-01

An environment friendly approach for the synthesis of Pt nanoparticles (NPs) using dried leaf powder of Anacardium occidentale is reported. The formation of Pt NPs is monitored using UV-Vis spectrophotometer. FTIR spectra reveal that proteins are bound to Pt nanoparticles. TEM images show irregular rod shaped particles which are crystalline. The quantity of leaf powder plays a vital role in determining the size of particles. Synthesized NPs exhibit good catalytic activity in the reduction of aromatic nitrocompound. The effective thermal conductivity of synthesized Pt/water nanofluid has been measured and found to be enhanced to a good extent. Copyright © 2013 Elsevier B.V. All rights reserved.

Ultralow content of Pt on Pd–Co–Cu/C ternary nanoparticles with excellent electrocatalytic activity and durability for the oxygen reduction reaction

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

Liu, Sufen; Xiao, Weiping; Wang, Jie

Optimizing the utilization of Pt to catalyze the sluggish kinetics of the oxygen reduction reaction (ORR) is of vital importance in proton exchange membrane fuel cells. One of the strategies is to spread Pt atoms over the surface of a substrate to increase the surface area. We report a facile method to synthesize Pd6CoCu@Pt/C core-shell nanoparticles with an ultralow amount of Pt. It was found that Pt-coated layer on Pd6CoCu cores plays a vital role in enhancing the ORR activity and the cycling stability. The half-wave potential of Pd6CoCu@Pt/C positively shifts about 50 mV and 17 mV relative to Pd6CoCu/Cmore » and Pt/C, respectively. The Pt mass activity on Pd6CoCu@Pt/C was calculated to be about 27 times higher than that on Pt/C catalysts at 0.9 V. Furthermore, the Pd6CoCu@Pt/C nanoparticles exhibit superior stability with almost no decay for the ORR polarization curves during 10,000 potential cycles and the core-shell structure remains with only a slight increase in the thickness of the Pt overlayer. Our findings provide a methodology for synthesizing highly efficient catalytic materials for the cathodic application in fuel cells.« less

Ultralow content of Pt on Pd–Co–Cu/C ternary nanoparticles with excellent electrocatalytic activity and durability for the oxygen reduction reaction

DOE PAGES

Liu, Sufen; Xiao, Weiping; Wang, Jie; ...

2016-08-01

Optimizing the utilization of Pt to catalyze the sluggish kinetics of the oxygen reduction reaction (ORR) is of vital importance in proton exchange membrane fuel cells. One of the strategies is to spread Pt atoms over the surface of a substrate to increase the surface area. We report a facile method to synthesize Pd6CoCu@Pt/C core-shell nanoparticles with an ultralow amount of Pt. It was found that Pt-coated layer on Pd6CoCu cores plays a vital role in enhancing the ORR activity and the cycling stability. The half-wave potential of Pd6CoCu@Pt/C positively shifts about 50 mV and 17 mV relative to Pd6CoCu/Cmore » and Pt/C, respectively. The Pt mass activity on Pd6CoCu@Pt/C was calculated to be about 27 times higher than that on Pt/C catalysts at 0.9 V. Furthermore, the Pd6CoCu@Pt/C nanoparticles exhibit superior stability with almost no decay for the ORR polarization curves during 10,000 potential cycles and the core-shell structure remains with only a slight increase in the thickness of the Pt overlayer. Our findings provide a methodology for synthesizing highly efficient catalytic materials for the cathodic application in fuel cells.« less

A highly active PtCu3 intermetallic core-shell, multilayered Pt-skin, carbon embedded electrocatalyst produced by a scale-up sol-gel synthesis.

PubMed

Bele, M; Jovanovič, P; Pavlišič, A; Jozinović, B; Zorko, M; Rečnik, A; Chernyshova, E; Hočevar, S; Hodnik, N; Gaberšček, M

2014-11-07

We present a novel, scaled-up sol-gel synthesis which enables one to produce 20 g batches of highly active and stable carbon supported PtCu3 nanoparticles as cathode materials for low temperature fuel cell application. We confirm the presence of an ordered intermetallic phase underneath a multilayered Pt-skin together with firm embedment of nanoparticles in the carbon matrix.

Heterogeneous enantioselective hydrogenation of beta-keto esters using chirally modified supported Ni nanoparticles

NASA Astrophysics Data System (ADS)

Acharya, Sushma

Enantioselective heterogeneous catalysis is an important and rapidly expanding research area. The two most heavily researched examples of this type of catalysis are the enantioselective hydrogenation of α-keto-esters over Pt-based catalysts and the enantioselective hydrogenation of β-keto-esters over Ni-based catalysts. These enantioselective surface reactions are controlled by the presence of adsorbed chiral molecules i.e. tartaric acid on the surface of the metal component of the catalyst. The work presented in this thesis focuses on two parts, the synthesis of pure nickel nanoparticles and enantioselective behavior of the modified nickel nanoparticles. The works on the synthesis of pure nickel nanoparticles were carried out using two methods, the reverse microemulsion and the reduction method. It was discovered that the reverse microemulsion method produced nickel oxide nanoparticles, whereas the reduction method produced pure nickel nanoparticles. Chiral modifications of Raney nickel (RNi) and C-supported catalysts were studied. The catalysts were employed in enantioselective hydrogenation of methyl acetoacetate (MAA) to (R) - and (S)-enantiomers of methyl 3-hydroxybutyrate (MHB). The effects of modification and hydrogenation parameters such as concentration of modifier temperature, pressure and solvent on the enantioselectivity of MAA hydrogenation were discussed. For RNi methanol was found to be the best solvent, with tartaric acid concentration 0.2 mol/L for achieving the highest enantiomeric excess under 8 bar at 70 oC. Characteristic features of the in-situ modification of Raney nickel and C-supported Ni were also evaluated and the results obtained were compared with the conventional (pre-modification) approach. Parameters for the conventional and in-situ methods were optimised in a series of experiments for both types of catalysts. The in-situ modified catalyst was found more active for both RNi and C-supported catalysts with 98 % and 42% enantiomeric excess, respectively.

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.

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.

Synthesis of ZnO-Pt nanoflowers and their photocatalytic applications.

PubMed

Yuan, Jiaquan; Choo, Eugene Shi Guang; Tang, Xiaosheng; Sheng, Yang; Ding, Jun; Xue, Junmin

2010-05-07

The photocatalytic behaviors of ZnO nanoparticles have been intensively studied recently. However, the photocatalytic efficiency of pure ZnO nanoparticles always suffers from the quick recombination of photoexcited electrons and holes. In order to suppress the electron-hole recombination and then raise the photocatalytic efficiency of ZnO, metal nanoparticles have been combined with ZnO to form ZnO-metal heterostructures. In this work, the feasibility of synthesizing ZnO-Pt composite nanoflowers for optimized catalytic properties was studied. Three different Pt nanocrystals, i.e. cubic Pt nanocrystals enclosed by {100} facets, octahedral Pt nanocrystals enclosed by {111} facets, and truncated octahedral Pt nanocrystals enclosed by both {111} and {100} facets, were selected as seeds for epitaxial growth of ZnO. A ZnO-Pt flowerlike nanostructure was formed by selective growth of ZnO nanolobes at {111} facets of the truncated octahedral Pt nanocrystals. The resultant nanoflowers had well defined ZnO-Pt interfaces and exposed Pt {100} facets, as confirmed by transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) measurements. The photocatalytic behaviors of the resultant ZnO-Pt nanoflowers were demonstrated in the photodegradation of ethyl violet. In comparison with the commercial TiO(2) photocatalyst P25, the ZnO-Pt flowerlike nanostructures showed improved catalytic efficiency. Notable ferromagnetism of the obtained ZnO-Pt flowerlike nanostructures was also observed. It is believed that the ZnO-Pt interface played an important role in the enlarged magnetic coercivity of the ZnO-Pt nanoflowers.

Platinum nanoparticles decorated dendrite-like gold nanostructure on glassy carbon electrodes for enhancing electrocatalysis performance to glucose oxidation

NASA Astrophysics Data System (ADS)

Jia, Hongmei; Chang, Gang; Lei, Ming; He, Hanping; Liu, Xiong; Shu, Honghui; Xia, Tiantian; Su, Jie; He, Yunbin

2016-10-01

Platinum nanoparticles decorated dendrite-like gold nanostructure, bimetal composite materials on glassy carbon electrode (Pt/DGNs/GC) for enhancing electrocatalysis to glucose oxidation was designed and successfully fabricated by a facile two-step deposition method without any templates, surfactants, or stabilizers. Dendrite-like gold nanostructure was firstly deposited on the GC electrode via the potentiostatic method, and then platinum nanoparticles were decorated on the surface of gold substrate through chemical reduction deposition. X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), energy-dispersive X-ray spectroscopy (EDS) were applied to characterize the evolution of morphology and structure of the as-prepared Pt/DGNs/GC. Based on electrochemical measurements such as cyclic voltammetry, linear voltammetry and chronoamperometry, Pt/DGNs/GC exhibited significantly enhanced electrocatalytic performance to glucose oxidation compared those of pure dendrite-like Au nanoparticles in our previous report. Controlling chemical reduction deposition time, the amount of platinum nanoparticles on Au surface could be regulated, which further tuned electrocatalytic properties toward glucose oxidation. The dendrite-like gold surface partially covered by platinum nanoparticles dramatically enhanced the electrocatalytic performance for the oxidation of glucose because of excellent synergetic effects between gold and platinum species and the increased electrochemical active area from Pt nanoparticles loading. The non-enzymatic glucose biosensor based on Pt/DGNs/GC showed a rapid respond time (within 2 s), wide linear range (from 0.1 mM to 14 mM), low detection limit (0.01 mM), supernal sensitivity (275.44 μA cm-2 mM-1, R = 0.993), satisfactory reproducibility and good stability for glucose sensing. It was demonstrated that Pt/DGNs/GC could work as promising candidate for factual non-enzymatic glucose detection.

Pd@Pt Core–Shell Nanoparticles with Branched Dandelion-like Morphology as Highly Efficient Catalysts for Olefin Reduction

EPA Science Inventory

A facile synthesis based on the addition of ascorbic acid to a mixture of Na2PdCl4, K2PtCl6, and Pluronic P123 results in highly branched core–shell nanoparticles (NPs) with a micro–mesoporous dandelion-like morphology comprising Pd core and Pt shell. The slow reduction kinetics ...

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.

Preparation and electrocatalytic properties of Pt-SiO2 nanocatalysts for ethanol electrooxidation.

PubMed

Liu, B; Chen, J H; Zhong, X X; Cui, K Z; Zhou, H H; Kuang, Y F

2007-03-01

Due to their high stability in general acidic solutions, SiO(2) nanoparticles were selected as the second catalyst for ethanol oxidation in sulfuric acid aqueous solution. Pt-SiO(2) nanocatalysts were prepared in this paper. The micrography and elemental composition of Pt-SiO(2) nanoparticles were characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy, respectively. The electrocatalytic properties of Pt-SiO(2) nanocatalysts for ethanol oxidation were investigated by cyclic voltammetry. Under the same Pt loading mass and experimental conditions for ethanol oxidation, Pt-SiO(2) nanocatalysts show higher activity than PtRu/C (E-Tek), Pt/C (E-Tek), and Pt catalysts. Additionally, Pt-SiO(2) nanocatalysts possess good anti-poisoning ability. The results indicate that Pt-SiO(2) nanocatalysts may have good potential applications in direct ethanol fuel cells.

Punica granatum fabricated platinum nanoparticles: A therapeutic pill for breast cancer

NASA Astrophysics Data System (ADS)

Jha, Babita; Rao, Mugdha; Chattopadhyay, A.; Bandyopadhyay, A.; Prasad, K.; Jha, Anal K.

2018-05-01

The current research highlights the fabrication of biocompatible platinum nanoparticles (Pt NPs) in first hand from arils of Punica granatum by using green chemistry approach. Formation of Pt NPs was determined by UV-visible, X-ray diffraction, and FTIR techniques. The anti-cancer potential of fabricated Pt NPs was evaluated by MTT assay on MCF7 and MDA-MB-231 breast cancer cell lines. This work is foreshadowing the prospect of Pt NPs application as a therapeutic drug for cancer treatment.

Plasma-induced synthesis of Pt nanoparticles supported on TiO2 nanotubes for enhanced methanol electro-oxidation

NASA Astrophysics Data System (ADS)

Su, Nan; Hu, Xiulan; Zhang, Jianbo; Huang, Huihong; Cheng, Jiexu; Yu, Jinchen; Ge, Chao

2017-03-01

A Pt/C/TiO2 nanotube composite catalyst was successfully prepared for enhanced methanol electro-oxidation. Pt nanoparticles with a particle size of 2 nm were synthesized by plasma sputtering in water, and anatase TiO2 nanotubes with an inner diameter of approximately 100 nm were prepared by a simple two-step anodization method and annealing process. Field-emission scanning electron microscopy images indicated that the different morphologies of TiO2 synthesized on the surface of Ti foils were dependent on the different anodization parameters. The electrochemical performance of Pt/C/TiO2 catalysts for methanol oxidation showed that TiO2 nanotubes were more suitable for use as Pt nanoparticle support materials than irregular TiO2 short nanorods due to their tubular morphology and better electronic conductivity. X-ray photoelectron spectroscopy characterization showed that the binding energies of the Pt 4f of the Pt/C/TiO2 nanotubes exhibited a slightly positive shift caused by the relatively strong interaction between Pt and the TiO2 nanotubes, which could mitigate the poisoning of the Pt catalyst by COads, and further enhance the electrocatalytic performance. Thus, the as-obtained Pt/C/TiO2 nanotubes composites may become a promising catalyst for methanol electro-oxidation.

Boron-doped graphene as promising support for platinum catalyst with superior activity towards the methanol electrooxidation reaction

NASA Astrophysics Data System (ADS)

Sun, Yongrong; Du, Chunyu; An, Meichen; Du, Lei; Tan, Qiang; Liu, Chuntao; Gao, Yunzhi; Yin, Geping

2015-12-01

We report the synthesis of boron-doped graphene by thermally annealing the mixture of graphene oxide and boric acid, and its usage as the support of Pt catalyst towards the methanol oxidation reaction. The composition, structure and morphology of boron-doped graphene and its supported Pt nanoparticles (Pt/BG) are characterized by transmission electron microscopy, inductively coupled plasma mass spectrometry, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. It is revealed that boron atoms are doped into graphene network in the form of BC2O and BCO2 bonds, which lead to the increase in defect sites and facilitate the subsequent deposition of Pt nanoparticles. Therefore, the Pt/BG catalyst presents smaller particle size and narrower size distribution than the graphene supported Pt (Pt/G) catalyst. When evaluated as the electrocatalyst for the methanol oxidation reaction, the Pt/BG catalyst exhibits excellent electrochemical activity and stability demonstrated by cyclic voltammetry and chronoamperometry tests. The enhanced activity is mainly ascribed to the electronic interaction between boron-doped graphene and Pt nanoparticles, which lowers the d-band center of Pt and thus weakens the absorption of the poisoning intermediate CO. Our work provides an alternative approach of improving the reaction kinetics for the oxidation of small organic molecules.

Combining Electronic and Geometric Effects of ZnO-Promoted Pt Nanocatalysts for Aqueous Phase Reforming of 1-Propanol

DOE PAGES

Lei, Yu; Lee, Sungsik; Low, Ke -Bin; ...

2016-04-26

Compared with Pt/Al 2O 3, sintering-resistant Pt nanoparticle catalysts promoted by ZnO significantly improved the reactivity and selectivity toward hydrogen formation in the aqueous phase reforming (APR) of 1-propanol. The improved performance was found to benefit from both the electronic and geometric effects of ZnO thin films. In situ small-angle X-ray scattering and scanning transmission electron microscopy showed that ZnO-promoted Pt possessed promising thermal stability under APR reaction conditions. In situ X-ray absorption spectroscopy showed clear charge transfer between ZnO and Pt nanoparticles. The improved reactivity and selectivity seemed to benefit from having both Pt-ZnO and Pt-Al 2O 3 interfaces.

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

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.

Spectroscopic Study of the Thermal Degradation of PVP-capped Rh and Pt Nanoparticles in H2 and O2 Environments

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

Borodko, Yuri; Lee, Hyun Sook; Joo, Sang Hoon

2009-09-15

Poly(N-vinylpyrrolidone) (PVP) capped platinum and rhodium nanoparticles (7-12 nm) have been studied with UV-VIS, FTIR and Raman spectroscopy. The absorption bands in the region 190-900 nm are shown to be sensitive to the electronic structure of surface Rh and Pt atoms as well as to the aggregation of the nanoparticles. In-situ FTIR-DRIFT spectroscopy of the thermal decay of PVP stabilized Rh and Pt nanoparticles in H{sub 2} and O{sub 2} atmospheres in temperatures ranging from 30 C-350 C reveal that decomposition of PVP above 200 C, PVP transforms into a 'polyamidpolyene' - like material that is in turn converted intomore » a thin layer of amorphous carbon above 300 C. Adsorbed carbon monoxide was used as a probing molecule to monitor changes of electronic structure of surface Rh and Pt atoms and accessible surface area. The behavior of surface Rh and Pt atoms with ligated CO and amide groups of pyrrolidones resemble that of surface coordination compounds.« less

Construction of Au@Pt core—satellite nanoparticles based on in-situ reduction of polymeric ionic liquid protected gold nanoparticles

NASA Astrophysics Data System (ADS)

Wu, Wenlan; Li, Junbo; Zou, Sheng; Guo, Jinwu; Zhou, Huiyun

2017-03-01

A method of in-situ reduction to prepare Au@Pt core-satellite nanoparticles (NPs) is described by using Au NPs coating poly[1-methyl 3-(2-methacryloyloxy propylimidazolium bromine)] (PMMPImB-@-Au NPs) as the template. After electrostatic complex chloroplatinic acid with PMMPImB shell, the composite NP was directly reduced with N2H4 to produce Au@Pt core-satellite NPs. The characterization of composite and core-satellite NPs under different amounts of chloroplatinic acid were studied by DLS, UV-vis absorption spectrum and TEM. The satellite Pt NPs with a small size ( 2 nm) dotted around Au core, and the resulting Au@Pt core-satellite NPs showed a red-shift surface plasmon resonance (SPR) and a good dispersion due to effectively electrostatic repulsion providing by the polymeric ionic liquid (PIL) shell. Finally, Au@Pt core-satellite NPs exhibit an enhanced catalytic activity and cycled catalytic capability for the reduction of p-nitrophenol with NaBH4.

Solid solutions of platinum(II) and palladium(II) oxalato-complex salt as precursors of nanoalloys

NASA Astrophysics Data System (ADS)

Zadesenets, A. V.; Asanova, T. I.; Vikulova, E. S.; Filatov, E. Yu.; Plyusnin, P. E.; Baidina, I. A.; Asanov, I. P.; Korenev, S. V.

2013-03-01

A solid solution of platinum (II) and palladium (II) oxalato-complex salt, (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O, has been synthesized and studied as a precursor for preparing bimetallic PtPd nanoparticles through its thermal decomposition. The smallest homogenous bimetallic PtPd nanoparticles were found to form in hydrogen and helium atmospheres. The annealing temperature and time have low effect on the bimetallic particles size. Comparative analysis of structural and thermal properties of the solid solution and individual Pt, Pd oxalato-complex salts was performed to investigate a mechanism of thermal decomposition of (NH4)2[Pt0.5Pd0.5(C2O4)2]·2H2O. Based on in situ X-ray photoemission spectroscopy investigation it was proposed a mechanism of formation of bimetallic PtPd nanoparticles from the solid-solution oxalato-complex salt during thermal decomposition.

First direct visualization of spillover species emitted from pt nanoparticles.

PubMed

Takakusagi, Satoru; Fukui, Ken-ichi; Tero, Ryugo; Asakura, Kiyotaka; Iwasawa, Yasuhiro

2010-11-02

We studied the methanol adsorption behavior of Pt nanoparticles that were vacuum-deposited on a TiO(2)(110) surface at room temperature by using an ultrahigh vacuum (UHV) scanning tunneling microscope (STM). A large number of bright spots were observed on fivefold-coordinated Ti (Ti(5c)) rows of the TiO(2)(110) surface after exposure of the Pt/TiO(2)(110) to methanol vapor. We assigned the bright spots to methoxy species. These were mobile and were found to hop along the Ti(5c) rows. In situ time-resolved STM observations of the formation and migration of the bright spots on the Pt/TiO(2)(110) were carried out in the presence of methanol. The bright spots were produced at the periphery of the Pt nanoparticles and migrated to the substrate Ti(5c) rows. We discuss the spillover process and behavior of the methoxy species on the Pt/TiO(2)(110).

Colloidal strategies for controlling the morphology, composition, and crystal structure of inorganic nanoparticles

NASA Astrophysics Data System (ADS)

Hodges, James M.

Emerging applications and fundamental studies require nanomaterials with increasingly sophisticated architectures that have precise composition, morphology, and crystal structure. Colloidal nanochemistry has emerged as one of the most effective methods for generating high quality, monodisperse nanoparticles with diverse structural features and highly complex geometries. These wet-chemical approaches offer an array of synthetic levers that can be used to tailor nanoparticles for targeted applications, and deliver solution-dispersible solids that are easily integrated onto device architectures. Additionally, colloidal nanoparticles can be used as building blocks for constructing periodic superlattices and multicomponent hybrid nanoparticles, which offer unique properties that can support next-generation technologies. As the applications for colloidal nanoparticles continue to expand, the architectural and compositional requirements for these materials are becoming increasingly rigid. Conventional colloidal methods are effective for generating diverse nanoparticle systems, but rely on complex nucleation and growth processes, which are often poorly understood and difficult to control in dynamic reaction environments. For these reasons, there are a number of high profile nanoparticle targets that remain out of reach. Accordingly, new approaches are needed that can circumvent these synthetic bottlenecks and narrow the growing disconnect between nano-design and synthetic capability. In this dissertation, I present several colloidal strategies for engineering synthetically challenging nanomaterials using multistep reaction sequences that, in many ways, parallel the total-synthesis framework that organic chemists use to access complex molecules. A variety of approaches are discussed, including nanoscale ion exchange transformations and seeded-growth protocol for constructing multicomponent hybrid nanoparticles. First, I demonstrate that solution-mediated anion and cation exchange can be integrated into one multistep reaction sequence, which leads to a complete material transformation of a pre-synthesized nanotemplate. Importantly, although the final product does not contain any of the original elements, the morphology is retained, effectively decoupling morphology and composition control. Next, I demonstrate that both anion and cation sublattice features of preformed Cu2-xS nanocrystals can be retained during cation exchange with Co2+ and Mn2+, yielding wurtzite-type CoS and MnS polymorphs that are metastable in bulk systems. This study was enabled by new cation exchange chemistry with previously unexplored 3d transition metal systems, and offers new guidelines for predictably targeting sublattice features in colloidal nanomaterials. To conclude the dissertation, I offer two studies investigating the seeded-growth synthesis of three-component Ag-Pt-Fe3O4 heterotrimer nanoparticles, which are generated by adding a Ag domain to preformed Pt-Fe 3O4 heterodimers. First, to gain access to the alternate Pt-Fe3O4-Ag configuration, I demonstrate that a thin iron oxide shell can be applied to the Pt surface of the Pt-Fe3O 4 seeds, which acts as a solid-state protecting group that can direct Ag growth onto the Fe3O4 domain, producing the otherwise inaccessible Pt-Fe3O4-Ag architecture. This strategy is inspired by similar techniques used in organic synthesis, and represents an important addition to the 'total synthesis toolbox' used to construct colloidal hybrid nanoparticles. Finally, I offer an in-depth microscopic investigation that probes the chemoselective addition of Ag to Pt-Fe 3O4 to form the Ag-Pt-Fe3O4 heterotrimer product. This study reveals that Ag indiscriminately nucleates on both the Pt and Fe3O4 domains of the Pt-Fe3O 4 seeds during the early stages of the reaction, followed by a surface-mediated coalescence of Ag onto the Pt domain to yield the Ag-Pt-Fe3O 4 configuration. The mechanistic insights gained in this work provide new design criteria for synthesizing multicomponent hybrid nanoparticle systems with targeted configurations.

Platinum adlayered ruthenium nanoparticles, method for preparing, and uses thereof

DOEpatents

Tong, YuYe; Du, Bingchen

2015-08-11

A superior, industrially scalable one-pot ethylene glycol-based wet chemistry method to prepare platinum-adlayered ruthenium nanoparticles has been developed that offers an exquisite control of the platinum packing density of the adlayers and effectively prevents sintering of the nanoparticles during the deposition process. The wet chemistry based method for the controlled deposition of submonolayer platinum is advantageous in terms of processing and maximizing the use of platinum and can, in principle, be scaled up straightforwardly to an industrial level. The reactivity of the Pt(31)-Ru sample was about 150% higher than that of the industrial benchmark PtRu (1:1) alloy sample but with 3.5 times less platinum loading. Using the Pt(31)-Ru nanoparticles would lower the electrode material cost compared to using the industrial benchmark alloy nanoparticles for direct methanol fuel cell applications.

Palladium and platinum-based nanoparticle functional sensor layers for selective H2 sensing

DOEpatents

Ohodnicki, Jr., Paul R.; Baltrus, John P.; Brown, Thomas D.

2017-07-04

The disclosure relates to a plasmon resonance-based method for H.sub.2 sensing in a gas stream utilizing a hydrogen sensing material. The hydrogen sensing material is comprises Pd-based or Pt-based nanoparticles having an average nanoparticle diameter of less than about 100 nanometers dispersed in an inert matrix having a bandgap greater than or equal to 5 eV, and an oxygen ion conductivity less than approximately 10.sup.-7 S/cm at a temperature of 700.degree. C. Exemplary inert matrix materials include SiO.sub.2, Al.sub.2O.sub.3, and Si.sub.3N.sub.4 as well as modifications to modify the effective refractive indices through combinations and/or doping of such materials. The hydrogen sensing material utilized in the method of this disclosure may be prepared using means known in the art for the production of nanoparticles dispersed within a supporting matrix including sol-gel based wet chemistry techniques, impregnation techniques, implantation techniques, sputtering techniques, and others.

Pt skin on Pd–Co–Zn/C ternary nanoparticles with enhanced Pt efficiency toward ORR

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

Xiao, Weiping; Zhu, Jing; Han, Lili

Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). A highly active, durable, carbon supported, and monolayer Pt coated Pd–Co–Zn nanoparticle is synthesized via a simple impregnation–reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition–activity volcano curve for the Pd–Co–Zn nanoparticles and determined that Pd : Co : Zn = 8 : 1 : 1 is the optimal composition. Compared with pure Pd/C, the Pd 8CoZn/C nanoparticles show a substantial enhancement in bothmore » the catalytic activity and the durability toward the ORR. Moreover, the durability and activity are further enhanced by forming a Pt skin on Pd 8CoZn/C nanocatalysts. Interestingly, after 10 000 potential cycles in N 2-saturated 0.1 M HClO 4 solution, Pd 8CoZn@Pt/C shows improved mass activity (2.62 A mg -1Pt) and specific activity (4.76 A m -2total), which are about 1.4 and 4.4 times higher than the initial values, and 37.4 and 5.5 times higher than those of Pt/C catalysts, respectively. After accelerated stability testing in O 2-saturated 0.1 M HClO 4 solution for 30 000 potential cycles, the half-wave potential negatively shifts about 6 mV. Our results show that the Pt skin plays an important role in enhancing the activity as well as preventing degradation.« less

Pt skin on Pd–Co–Zn/C ternary nanoparticles with enhanced Pt efficiency toward ORR

DOE PAGES

Xiao, Weiping; Zhu, Jing; Han, Lili; ...

2016-07-15

Exploring highly active, stable and relatively low-cost nanomaterials for the oxygen reduction reaction (ORR) is of vital importance for the commercialization of proton exchange membrane fuel cells (PEMFCs). A highly active, durable, carbon supported, and monolayer Pt coated Pd–Co–Zn nanoparticle is synthesized via a simple impregnation–reduction method, followed by spontaneous displacement of Pt. By tuning the atomic ratios, we obtain the composition–activity volcano curve for the Pd–Co–Zn nanoparticles and determined that Pd : Co : Zn = 8 : 1 : 1 is the optimal composition. Compared with pure Pd/C, the Pd 8CoZn/C nanoparticles show a substantial enhancement in bothmore » the catalytic activity and the durability toward the ORR. Moreover, the durability and activity are further enhanced by forming a Pt skin on Pd 8CoZn/C nanocatalysts. Interestingly, after 10 000 potential cycles in N 2-saturated 0.1 M HClO 4 solution, Pd 8CoZn@Pt/C shows improved mass activity (2.62 A mg -1Pt) and specific activity (4.76 A m -2total), which are about 1.4 and 4.4 times higher than the initial values, and 37.4 and 5.5 times higher than those of Pt/C catalysts, respectively. After accelerated stability testing in O 2-saturated 0.1 M HClO 4 solution for 30 000 potential cycles, the half-wave potential negatively shifts about 6 mV. Our results show that the Pt skin plays an important role in enhancing the activity as well as preventing degradation.« less

Synthesis of an excellent electrocatalyst for oxygen reduction reaction with supercritical fluid: Graphene cellular monolith with ultrafine and highly dispersive multimetallic nanoparticles

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

Zhou, Yazhou; Cheng, Xiaonong; Yen, Clive H.

Graphene cellular monolith (GCM) can be used as an excellent support for nanoparticles in widespread applications. However, it's still a great challenge to deposit the desirable nanoparticles in GCM that have small size, controllable structure, composition, and high dispersion using the current methods. Here we demonstrate a green, efficient and large-scale method to address this challenge using supercritical fluid (SCF). By this superior method, graphene hydrogel can be transferred into GCM while being deposited with ultrafine and highly dispersive nanoparticles. Specifically, the bimetallic PtFe/GCM and the trimetallic PtFeCo/GCM catalysts are successfully synthesized, and their electrocatalytic performances toward oxygen reduction reactionmore » (ORR) are also studied. The resultant PtFe/GCM shows the significant enhancement in ORR activity, including a factor of 8.47 enhancement in mass activity (0.72 A mgPt-1), and a factor of 7.67 enhancement in specific activity (0.92 mA cm-2), comparing with those of the commercial Pt/C catalyst (0.085 A mgPt-1, 0.12 mA cm-2). Importantly, by introducing the Co, the trimetallic PtFeCo/GCM exhibits the further improved ORR activities (1.28 A mgPt-1, 1.80 mA cm-2). The high ORR activity is probably attributed to the alloying structure, ultrafine size, highly dispersive, well-defined, and a better interface with 3D porous graphene support.« less

Synthesis of an excellent electrocatalyst for oxygen reduction reaction with supercritical fluid: Graphene cellular monolith with ultrafine and highly dispersive multimetallic nanoparticles

NASA Astrophysics Data System (ADS)

Zhou, Yazhou; Cheng, Xiaonong; Yen, Clive H.; Wai, Chien M.; Wang, Chongmin; Yang, Juan; Lin, Yuehe

2017-04-01

Graphene cellular monolith (GCM) can be used as an excellent support for nanoparticles in widespread applications. However, it's still a great challenge to deposit the desirable nanoparticles in GCM that have small size, controllable structure, composition, and high dispersion using the current methods. Here we demonstrate a green, efficient and large-scale method to address this challenge using supercritical fluid (SCF). By this superior method, graphene hydrogel can be transferred into GCM while being deposited with ultrafine and highly dispersive nanoparticles. Specifically, the bimetallic PtFe/GCM and the trimetallic PtFeCo/GCM catalysts are successfully synthesized, and their electrocatalytic performances toward oxygen reduction reaction (ORR) are also studied. The resultant PtFe/GCM shows the significant enhancement in ORR activity, including a factor of 8.47 enhancement in mass activity (0.72 A mgPt-1), and a factor of 7.67 enhancement in specific activity (0.92 mA cm-2), comparing with those of the commercial Pt/C catalyst (0.085 A mgPt-1, 0.12 mA cm-2). Importantly, by introducing the Co, the trimetallic PtFeCo/GCM exhibits the further improved ORR activities (1.28 A mgPt-1, 1.80 mA cm-2). The high ORR activity is probably attributed to the alloying structure, ultrafine size, highly dispersive, well-defined, and a better interface with 3D porous graphene support.

Tungsten trioxide nanoplate array supported platinum as a highly efficient counter electrode for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Song, Dandan; Cui, Peng; Zhao, Xing; Li, Meicheng; Chu, Lihua; Wang, Tianyue; Jiang, Bing

2015-03-01

A tungsten trioxide (WO3) nanoplate array is fabricated directly on the FTO/glass substrate and used as a platinum (Pt) nanoscale supporter for a highly efficient and low Pt-consumption counter electrode (CE) in dye-sensitized solar cells (DSCs). A Pt/WO3 composite structure, with Pt nanoparticles having a diameter of 2-3 nm, increases the electrochemical catalytic activity in catalyzing the reduction of triiodide. Accordingly, the power conversion efficiency is increased from less than 1% for WO3 CE and 8.1% for Pt CE, respectively, to 8.9% for Pt/WO3 CE. Moreover, the use of Pt/WO3 CE can dramatically reduce the consumption of scarce Pt material, with a relatively low Pt-loading of ~2 μg cm-2, while maintaining a much better performance. The excellent performance of Pt/WO3 CE is attributed to the efficient electron injection and transport via WO3 supporters, as well as the nanostructure array morphology of WO3 for deposition of fine Pt nanoparticles. This work provides an approach for developing highly catalytic and low-cost Pt based CEs, which also has implications for the development of Pt/WO3 nanoplate arrays for other applications.A tungsten trioxide (WO3) nanoplate array is fabricated directly on the FTO/glass substrate and used as a platinum (Pt) nanoscale supporter for a highly efficient and low Pt-consumption counter electrode (CE) in dye-sensitized solar cells (DSCs). A Pt/WO3 composite structure, with Pt nanoparticles having a diameter of 2-3 nm, increases the electrochemical catalytic activity in catalyzing the reduction of triiodide. Accordingly, the power conversion efficiency is increased from less than 1% for WO3 CE and 8.1% for Pt CE, respectively, to 8.9% for Pt/WO3 CE. Moreover, the use of Pt/WO3 CE can dramatically reduce the consumption of scarce Pt material, with a relatively low Pt-loading of ~2 μg cm-2, while maintaining a much better performance. The excellent performance of Pt/WO3 CE is attributed to the efficient electron injection and transport via WO3 supporters, as well as the nanostructure array morphology of WO3 for deposition of fine Pt nanoparticles. This work provides an approach for developing highly catalytic and low-cost Pt based CEs, which also has implications for the development of Pt/WO3 nanoplate arrays for other applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr06787h

Reverse Micelle Synthesis and Characterization of Supported Pt/Ni Bimetallic Catalysts on gamma-Al2O3

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

B Cheney; J Lauterbach; J Chen

2011-12-31

Reverse micelle synthesis was used to improve the nanoparticle size uniformity of bimetallic Pt/Ni nanoparticles supported on {gamma}-Al{sub 2}O{sub 3}. Two impregnation methods were investigated to optimize the use of the micelle method: (1) step-impregnation, where Ni nanoparticles were chemically reduced in microemulsion and then supported, followed by Pt deposition using incipient wetness impregnation, and (2) co-impregnation, where Ni and Pt were chemically reduced simultaneously in microemulsion and then supported. Transmission electron microscopy (TEM) was used to characterize the particle size distribution. Atomic absorption spectroscopy (AAS) was used to perform elemental analysis of bimetallic catalysts. Extended X-ray absorption fine structuremore » (EXAFS) measurements were utilized to confirm the formation of the Pt-Ni bimetallic bond in the step-impregnated catalyst. CO pulse chemisorption and Fourier transform infrared spectroscopy (FTIR) studies of 1,3-butadiene hydrogenation in a batch reactor were performed to determine the catalytic activity. Step-impregnated Pt/Ni catalyst demonstrated enhanced hydrogenation activity over the parent monometallic Pt and Ni catalysts due to bimetallic bond formation. The catalyst synthesized using co-impregnation showed no enhanced activity, behaving similarly to monometallic Ni. Overall, our results indicate that reverse micelle synthesis combined with incipient wetness impregnation produced small, uniform nanoparticles with bimetallic bonds that enhanced hydrogenation activity.« less

Carbon supported Pt-NiO nanoparticles for ethanol electro-oxidation in acid media

NASA Astrophysics Data System (ADS)

Comignani, Vanina; Sieben, Juan Manuel; Brigante, Maximiliano E.; Duarte, Marta M. E.

2015-03-01

In the present work, the influence of nickel oxide as a co-catalyst of Pt nanoparticles for the electro-oxidation of ethanol in the temperature range of 23-60 °C was investigated. The carbon supported nickel oxide and platinum nanoparticles were prepared by hydrothermal synthesis and microwave-assisted polyol process respectively, and characterized by XRD, EDX, TEM and ICP analysis. The electrocatalytic activity of the as-prepared materials was studied by cyclic voltammetry and chronoamperometry. Small metal nanoparticles with sizes in the range of 3.5-4.5 nm were obtained. The nickel content in the as-prepared Pt-NiO/C catalysts was between 19 and 35 at.%. The electrochemical experiments showed that the electrocatalytic activity of the Pt-NiO/C materials increase with NiO content in the entire temperature range. The apparent activation energy (Ea,app) for the overall ethanol oxidation reaction was found to decrease with NiO content (24-32 kJ mol-1 at 0.3 V), while for Pt/C the activation energy exceeds 48 kJ mol-1. The better performance of the Pt-NiO/C catalysts compared to Pt/C sample is ascribed to the activation of both the C-H and O-H bonds via oxygen-containing species adsorbed on NiO molecules and the modification of the surface electronic structure (changes in the density of states near the Fermi level).

Thermal dewetting with a chemically heterogeneous nano-template for self-assembled L1(0) FePt nanoparticle arrays.

PubMed

Wang, Liang-Wei; Cheng, Chung-Fu; Liao, Jung-Wei; Wang, Chiu-Yen; Wang, Ding-Shuo; Huang, Kuo-Feng; Lin, Tzu-Ying; Ho, Rong-Ming; Chen, Lih-Juann; Lai, Chih-Huang

2016-02-21

A design for the fabrication of metallic nanoparticles is presented by thermal dewetting with a chemically heterogeneous nano-template. For the template, we fabricate a nanostructured polystyrene-b-polydimethylsiloxane (PS-b-PDMS) film on a Si|SiO2 substrate, followed by a thermal annealing and reactive ion etching (RIE) process. This gives a template composed of an ordered hexagonal array of SiOC hemispheres emerging in the polystyrene matrix. After the deposition of a FePt film on this template, we utilize the rapid thermal annealing (RTA) process, which provides in-plane stress, to achieve thermal dewetting and structural ordering of FePt simultaneously. Since the template is composed of different composition surfaces with periodically varied morphologies, it offers more tuning knobs to manipulate the nanostructures. We show that both the decrease in the area of the PS matrix and the increase in the strain energy relaxation transfer the dewetted pattern from the randomly distributed nanoparticles into a hexagonal periodic array of L10 FePt nanoparticles. Transmission electron microscopy with the in situ heating stage reveals the evolution of the dewetting process, and confirms that the positions of nanoparticles are aligned with those of the SiOC hemispheres. The nanoparticles formed by this template-dewetting show an average diameter and center-to-center distance of 19.30 ± 2.09 nm and 39.85 ± 4.80 nm, respectively. The hexagonal array of FePt nanoparticles reveals a large coercivity of 1.5 T, much larger than the nanoparticles fabricated by top-down approaches. This approach offers an efficient pathway toward self-assembled nanostructures in a wide range of material systems.

High-Pressure Catalytic Reactions of C6 Hydrocarbons on PlatinumSingle-Crystals and nanoparticles: A Sum Frequency Generation VibrationalSpectroscopic and Kinetic Study

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

Bratlie, Kaitlin

Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10 -6 Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C 6H 11) and π-allyl Cmore » 6H 9, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, π-allyl C 6H 9, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, π-allyl c-C 6H 9 was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found to exhibit a compensation effect and was analyzed using the selective energy transfer (SET) model. The SET model suggests that the Pt-H system donates energy to the E 2u mode of free benzene, which leads to catalysis. Linear C 6 (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) hydrocarbons were also investigated in the presence and absence of excess hydrogen on Pt(100). Based on spectroscopic signatures, mechanisms for catalytic isomerization and dehydrocyclization of n-hexane were identified. The structure sensitivity of benzene hydrogenation on shape controlled platinum nanoparticles was also studied. The nanoparticles showed similar selectivities to those found for Pt(111) and Pt(100) single-crystals. Additionally, the nanoparticles have lower activation energies than their single-crystal counterparts.« less

Enhanced vapour sensing using silicon nanowire devices coated with Pt nanoparticle functionalized porous organic frameworks.

PubMed

Cao, Anping; Shan, Meixia; Paltrinieri, Laura; Evers, Wiel H; Chu, Liangyong; Poltorak, Lukasz; Klootwijk, Johan H; Seoane, Beatriz; Gascon, Jorge; Sudhölter, Ernst J R; de Smet, Louis C P M

2018-04-19

Recently various porous organic frameworks (POFs, crystalline or amorphous materials) have been discovered, and used for a wide range of applications, including molecular separations and catalysis. Silicon nanowires (SiNWs) have been extensively studied for diverse applications, including as transistors, solar cells, lithium ion batteries and sensors. Here we demonstrate the functionalization of SiNW surfaces with POFs and explore its effect on the electrical sensing properties of SiNW-based devices. The surface modification by POFs was easily achieved by polycondensation on amine-modified SiNWs. Platinum nanoparticles were formed in these POFs by impregnation with chloroplatinic acid followed by chemical reduction. The final hybrid system showed highly enhanced sensitivity for methanol vapour detection. We envisage that the integration of SiNWs with POF selector layers, loaded with different metal nanoparticles will open up new avenues, not only in chemical and biosensing, but also in separations and catalysis.

Atomistic nucleation sites of Pt nanoparticles on N-doped carbon nanotubes.

PubMed

Sun, Chia-Liang; Pao, Chih-Wen; Tsai, Huang-Ming; Chiou, Jau-Wern; Ray, Sekhar C; Wang, Houng-Wei; Hayashi, Michitoshi; Chen, Li-Chyong; Lin, Hong-Ji; Lee, Jyh-Fu; Chang, Li; Tsai, Min-Hsiung; Chen, Kuei-Hsien; Pong, Way-Faung

2013-08-07

The atomistic nucleation sites of Pt nanoparticles (Pt NPs) on N-doped carbon nanotubes (N-CNTs) were investigated using C and N K-edge and Pt L3-edge X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy. Transmission electron microscopy and XANES/EXAFS results revealed that the self-organized Pt NPs on N-CNTs are uniformly distributed because of the relatively high binding energies of the adsorbed Pt atoms at the imperfect sites. During the atomistic nucleation process of Pt NPs on N-CNTs, stable Pt-C and Pt-N bonds are presumably formed, and charge transfer occurs at the surface/interface of the N-CNTs. The findings in this study were consistent with density functional theory calculations performed using cluster models for the undoped, substitutional-N-doped and pyridine-like-N-doped CNTs.

Editors' Choice—Electrochemically Active Surface Area Measurement of Aged Pt Alloy Catalysts in PEM Fuel Cells by CO Stripping

DOE PAGES

Garrick, Taylor R.; Moylan, Thomas E.; Carpenter, Michael K.; ...

2016-12-13

The use of hydrogen adsorption/desorption (HAD) is a convenient method to measure the Pt surface area of a catalyst. However, it was shown that electrochemical charges measured by this technique can underestimate the Pt surface area by up to a factor of two for small Pt nanoparticles or Pt alloy nanoparticles. Electrooxidation of CO, so-called CO stripping, has been shown to be more accurate. Yet measurements of CO stripping in MEAs are scarce, especially on high activity alloy catalysts. In this study we investigated CO stripping and the ratio between Pt surface areas measured by CO and by HAD onmore » several Pt and Pt alloy catalysts. The effects on these measurements of temperature and catalyst aging by voltage cycling are discussed.« less

Editors' Choice—Electrochemically Active Surface Area Measurement of Aged Pt Alloy Catalysts in PEM Fuel Cells by CO Stripping

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

Garrick, Taylor R.; Moylan, Thomas E.; Carpenter, Michael K.

The use of hydrogen adsorption/desorption (HAD) is a convenient method to measure the Pt surface area of a catalyst. However, it was shown that electrochemical charges measured by this technique can underestimate the Pt surface area by up to a factor of two for small Pt nanoparticles or Pt alloy nanoparticles. Electrooxidation of CO, so-called CO stripping, has been shown to be more accurate. Yet measurements of CO stripping in MEAs are scarce, especially on high activity alloy catalysts. In this study we investigated CO stripping and the ratio between Pt surface areas measured by CO and by HAD onmore » several Pt and Pt alloy catalysts. The effects on these measurements of temperature and catalyst aging by voltage cycling are discussed.« less

Microwave-assisted synthesis of Pt/CNT nanocomposite electrocatalysts for PEM fuel cells.

PubMed

Zhang, Weimin; Chen, Jun; Swiegers, Gerhard F; Ma, Zi-Feng; Wallace, Gordon G

2010-02-01

Microwave-assisted heating of functionalized, single-wall carbon nanotubes (FCNTs) in ethylene glycol solution containing H(2)PtCl(6), led to the reductive deposition of Pt nanoparticles (2.5-4 nm) over the FCNTs, yielding an active catalyst for proton-exchange membrane fuel cells (PEMFCs). In single-cell testing, the Pt/FCNT composites displayed a catalytic performance that was superior to Pt nanoparticles supported by raw (unfunctionalized) CNTs (RCNTs) or by carbon black (C), prepared under identical conditions. The supporting single-wall carbon nanotubes (SWNTs), functionalized with carboxyl groups, were studied by thermogravimetric analysis (TGA), cyclic voltammetry (CV), and Raman spectroscopy. The loading level, morphology, and crystallinity of the Pt/SWNT catalysts were determined using TGA, SEM, and XRD. The electrochemically active catalytic surface area of the Pt/FCNT catalysts was 72.9 m(2)/g-Pt.

Wet-chemical synthesis and properties of CoPt and CoPt3 alloy nanoparticles.

PubMed

Frommen, Christoph; Rösner, Harald; Fenske, Dieter

2002-10-01

Surface-protected, air-stable nanoparticles of CoPt and CoPt3 were prepared by thermal decomposition/reduction of organometallic precursors with a long-chain aliphatic diol, also known as the polyol process. Particles 3 nm in diameter showed ferromagnetic behavior up to 350 K (Hc = 65 Oe at T = 300 K; Hc = 410 Oe at T = 5K) and underwent a disordering-ordering phase transformation after annealing that resulted in an increase in coercivity (Hc = 170 Oe at T = 300 K; Hc = 2000 Oe at T = 5 K).

Investigation of the stability of Platinum nanoparticles incorporated in mesoporous silica with different pore sizes.

PubMed

Yano, Kazuhisa; Zhang, Shuyi; Pan, Xiaoqing; Tatsuda, Narihito

2014-05-01

The effect of the pore size of mesoporous silica on the stability of Pt nanoparticles (NPs) has been investigated. TEM observation and XRD measurement were conducted in situ for Pt loaded mesoporous silica with different mesopore sizes. It turns out that smaller pores are more effective to stabilize Pt NPs below 600 °C. However, aggregation of Pt NPs on the surface of particles is not fully suppressed more than 1000 °C in ambient atmosphere even though smaller mesopore size is applied. The type of precursor does not affect the stability of Pt NPs. Copyright © 2014. Published by Elsevier Inc.

Direct synthesis of few-layer graphene supported platinum nanocatalyst for methanol oxidation

NASA Astrophysics Data System (ADS)

Tan, Hong; Ma, Xiaohui; Sheng, Leimei; An, Kang; Yu, Liming; Zhao, Hongbin; Xu, Jiaqiang; Ren, Wei; Zhao, Xinluo

2014-11-01

High-crystalline few-layer graphene supported Pt nanoparticles have been synthesized by arc discharge evaporation of carbon electrodes containing Pt element. A high-temperature treatment under hydrogen atmosphere has been carried out to obtain a new type of Pt/graphene catalyst for methanol oxidation in direct methanol fuel cell. The morphology and structure characterizations of as-grown few-layer graphene supported Pt nanoparticles and Pt/graphene catalysts have been studied by Raman spectroscopy, scanning electron microscopy with energy-dispersive spectroscopy, and high-resolution transmission electron microscopy. Cyclic voltammograms and chronoamperometric curves show that our present Pt/graphene catalysts have larger current density for methanol oxidation, higher tolerance to carbon monoxide poisoning, and better stability during the operating procedure, compared to commercial Pt/C catalysts.

Platinum-nanoparticle-supported core-shell polymer nanospheres with unexpected water stability and facile further modification

NASA Astrophysics Data System (ADS)

Yuan, Conghui; Xu, Yiting; Luo, Weiang; Zeng, Birong; Qiu, Wuhui; Liu, Jie; Huang, Huiling; Dai, Lizong

2012-05-01

Core-shell nanospheres (CSNSs) with hydrophobic cores and hydrophilic shells were fabricated via a simple mini-emulsion polymerization for the stabilization of platinum nanoparticles (Pt-NPs). The CSNSs showed extremely high loading capacity of Pt-NPs (the largest loading amount of the Pt-NPs was about 49.2 wt%). Importantly, the Pt-NPs/CSNSs nanocomposites had unexpected stability in aqueous solution. DLS results revealed that the CSNSs loaded with Pt-NPs exhibited almost no aggregation after standing for a long time . However, the Pt-NPs immobilized on the CSNSs were not straitlaced: they could transport and redistribute between CSNSs freely when the environmental temperature was higher than the melting point of the CSNS shell. Owing to their excellent stability in aqueous solution, the surface of the Pt-NPs/CSNSs nanocomposites could be further decorated easily. For example, polyaniline (PANI)-coated Pt-NPs/CSNSs, nickel (Ni)-coated Pt-NPs/CSNSs and PANI/Pt-NPs dual-layer hollow nanospheres were facilely fabricated from the Pt-NPs/CSNS nanocomposites.

Biosynthesis of silver and platinum nanoparticles using orange peel extract: characterisation and applications.

PubMed

Castro, Laura; Blázquez, María Luisa; González, Felisa; Muñoz, Jesús Ángel; Ballester, Antonio

2015-10-01

This study focuses on the green synthesis of noble metal nanoparticles (silver (Ag) and platinum (Pt)) and how the size and shape of the nanoparticles produced can be controlled through changes in the initial pH value of the precursor solution. The nanoparticles were characterised by ultra-violet-visible spectroscopy, transmission electron microscopy and X-ray diffraction. This simple and environmentally friendly method allows the synthesis of diverse nanostructures in the absence of a surfactant or polymer to direct nanoparticle growth, and without externally adding seed crystallites. The antibacterial effects of Ag nanoparticles and catalytic properties of Pt nanoparticles were explored for future promising biotechnological approaches in different fields.

Pt-decorated PdCo@Pd/C core-shell nanoparticles with enhanced stability and electrocatalytic activity for the oxygen reduction reaction.

PubMed

Wang, Deli; Xin, Huolin L; Yu, Yingchao; Wang, Hongsen; Rus, Eric; Muller, David A; Abruña, Hector D

2010-12-22

A simple method for the preparation of PdCo@Pd core-shell nanoparticles supported on carbon based on an adsorbate-induced surface segregation effect has been developed. The stability of these PdCo@Pd nanoparticles and their electrocatalytic activity for the oxygen reduction reaction (ORR) were enhanced by decoration with a small amount of Pt deposited via a spontaneous displacement reaction. The facile method described herein is suitable for large-scale, lower-cost production and significantly lowers the Pt loading and thus the cost. The as-prepared PdCo@Pd and Pd-decorated PdCo@Pd nanocatalysts have a higher methanol tolerance than Pt/C in the ORR and are promising cathode catalysts for fuel cell applications.

Pt-Decorated PdCo@Pd/C Core-Shell Nanoparticles with Enhanced Stability and Electrocatalytic Activity for the Oxygen Reduction Reaction

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

Wang, Deli; Xin, Huolin L.; Yu, Yingchao

2010-11-24

A simple method for the preparation of PdCo@Pd core-shell nanoparticles supported on carbon based on an adsorbate-induced surface segregation effect has been developed. The stability of these PdCo@Pd nanoparticles and their electrocatalytic activity for the oxygen reduction reaction (ORR) were enhanced by decoration with a small amount of Pt deposited via a spontaneous displacement reaction. The facile method described herein is suitable for large-scale, lower-cost production and significantly lowers the Pt loading and thus the cost. The as-prepared PdCo@Pd and Pd-decorated PdCo@Pd nanocatalysts have a higher methanol tolerance than Pt/C in the ORR and are promising cathode catalysts for fuelmore » cell applications.« less

Electronically conducting hybrid material as high performance catalyst support for electrocatalytic application

NASA Astrophysics Data System (ADS)

Rajesh, B.; Ravindranathan Thampi, K.; Bonard, J.-M.; Mathieu, H. J.; Xanthopoulos, N.; Viswanathan, B.

The electronically conducting hybrid material based on transition metal oxide and conducting polymer has been used as the catalyst support for Pt nanoparticles. The Pt nanoparticles loaded hybrid organic (polyaniline)-inorganic (vanadium pentoxide) composite has been used as the electrode material for methanol oxidation, a reaction of importance for the development of direct methanol fuel cells (DMFC). The hybrid material exhibited excellent electrochemical and thermal stability in comparison to the physical mixture of conducting polymer and transition metal oxide. The Pt nanoparticles loaded hybrid material exhibited high electrocatalytic activity and stability for methanol oxidation in comparison to the Pt supported on the Vulcan XC 72R carbon support. The higher activity and stability is attributed to the better CO tolerance of the composite material.

Pt/glassy carbon model catalysts prepared from PS-b-P2VP micellar templates.

PubMed

Gu, Yunlong; St-Pierre, Jean; Ploehn, Harry J

2008-11-04

Poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer was used as a micellar template to fabricate arrays of Pt nanoparticles on mica and glassy carbon (GC) supports. Polymer micellar deposition yields Pt nanoparticles with tunable particle size and surface number density on both mica and GC. After deposition of precursor-loaded micelles onto GC, oxygen plasma etching removes the polymer shell, followed by thermal treatment with H2 gas to reduce the Pt. Etching conditions were optimized to maximize removal of the polymer while minimizing damage to the GC. Arrays of Pt nanoparticles with controlled size and surface number density can be prepared on mica (for particle size characterization) and GC to make Pt/GC model catalysts. These model catalysts were characterized by tapping mode atomic force microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry to measure activity for oxidation of carbon monoxide or methanol. Cyclic voltammetry results demonstrate the existence of a correlation between Pt particle size and electrocatalytic properties including onset potential, tolerance of carbonaceous adsorbates, and intrinsic activity (based on active Pt area from CO stripping voltammetry). Results obtained with Pt/GC model catalysts duplicate prior results obtained with Pt/porous carbon catalysts therefore validating the synthesis approach and offering a new, tunable platform to study catalyst structure and other effects such as aging on proton exchange membrane fuel cell (PEMFC) reactions.

PtCo Cathode Catalyst Morphological and Compositional Changes after PEM Fuel Cell Accelerated Stress Testing

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

Sneed, Brian T.; Cullen, David A.; Mukundan, R.

Development of Pt catalysts alloyed with transition metals has led to a new class of state-of-the-art electrocatalysts for oxygen reduction at the cathode of proton exchange membrane fuel cells; however, the durability of Pt-based alloy catalysts is challenged by poor structural and chemical stability. There is a need for better understanding of the morphological and compositional changes that occur to the catalyst under fuel cell operation. In this work, we report in-depth characterization results of a Pt-Co electrocatalyst incorporated in the cathode of membrane electrode assemblies, which were evaluated before and after accelerated stress tests designed specifically to enhance catalystmore » degradation. Electron microscopy, spectroscopy, and 3D electron tomography analyses of the Pt-Co nanoparticle structures suggest that the small- and intermediate-sized Pt-Co particles, which are typically Pt-rich in the fresh condition, undergo minimal morphological changes, whereas intermediate- and larger-sized Pt-Co nanoparticles that exhibit a porous “spongy” morphology and initially have a higher Co content, transform into hollowed-out shells, which is driven by continuous leaching of Co from the Pt-Co catalysts. We further show how these primary Pt-Co nanoparticle morphologies group toward a lower Co, larger size portion of the size vs. composition distribution, and provide details of their nanoscale morphological features.« less

PtCo Cathode Catalyst Morphological and Compositional Changes after PEM Fuel Cell Accelerated Stress Testing

DOE PAGES

Sneed, Brian T.; Cullen, David A.; Mukundan, R.; ...

2018-03-01

Development of Pt catalysts alloyed with transition metals has led to a new class of state-of-the-art electrocatalysts for oxygen reduction at the cathode of proton exchange membrane fuel cells; however, the durability of Pt-based alloy catalysts is challenged by poor structural and chemical stability. There is a need for better understanding of the morphological and compositional changes that occur to the catalyst under fuel cell operation. In this work, we report in-depth characterization results of a Pt-Co electrocatalyst incorporated in the cathode of membrane electrode assemblies, which were evaluated before and after accelerated stress tests designed specifically to enhance catalystmore » degradation. Electron microscopy, spectroscopy, and 3D electron tomography analyses of the Pt-Co nanoparticle structures suggest that the small- and intermediate-sized Pt-Co particles, which are typically Pt-rich in the fresh condition, undergo minimal morphological changes, whereas intermediate- and larger-sized Pt-Co nanoparticles that exhibit a porous “spongy” morphology and initially have a higher Co content, transform into hollowed-out shells, which is driven by continuous leaching of Co from the Pt-Co catalysts. We further show how these primary Pt-Co nanoparticle morphologies group toward a lower Co, larger size portion of the size vs. composition distribution, and provide details of their nanoscale morphological features.« less

The effect of metal cluster deposition route on structure and photocatalytic activity of mono- and bimetallic nanoparticles supported on TiO2 by radiolytic method

NASA Astrophysics Data System (ADS)

Klein, Marek; Nadolna, Joanna; Gołąbiewska, Anna; Mazierski, Paweł; Klimczuk, Tomasz; Remita, Hynd; Zaleska-Medynska, Adriana

2016-08-01

TiO2 (P25) was modified with small and relatively monodisperse mono- and bimetallic clusters (Ag, Pd, Pt, Ag/Pd, Ag/Pt and Pd/Pt) induced by radiolysis to improve its photocatalytic activity. The as-prepared samples were characterized by X-ray fluorescence spectrometry (XRF), photoluminescence spectrometry (PL), diffuse reflectance spectroscopy (DRS), X-ray powder diffractometry (XRD), scanning transition electron microscopy (STEM) and BET surface area analysis. The effect of metal type (mono- and bimetallic modification) as well as deposition method (simultaneous or subsequent deposition of two metals) on the photocatalytic activity in toluene removal in gas phase under UV-vis irradiation (light-emitting diodes- LEDs) and phenol degradation in liquid phase under visible light irradiation (λ > 420 nm) were investigated. The highest photoactivity under Vis light was observed for TiO2 co-loaded with platinum (0.1%) and palladium (0.1%) clusters. Simultaneous addition of metal precursors results in formation of larger metal nanoparticles (15-30 nm) on TiO2 surface and enhances the Vis-induced activity of Ag/Pd-TiO2 up to four times, while the subsequent metal ions addition results in formation of metal particle size ranging from 4 to 20 nm. Subsequent addition of metal precursors results in formation of BNPs (bimetallic nanoparticle) composites showing higher stability in four cycles of toluene degradation under UV-vis. Obtained results indicated that direct electron transfer from the BNPs to the conduction band of the semiconductor is responsible for visible light photoactivity, whereas superoxide radicals (such as O2rad- and rad OOH) are responsible for pollutants degradation over metal-TiO2 composites.

Dissolution of Pt during Oxygen Reduction Reaction Produces Pt Nanoparticles

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

Bae, Je Hyun; Brocenschi, Ricardo F.; Kisslinger, Kim

The loss of Pt during the oxygen reduction reaction (ORR) affects the performance and economic viability of fuel cells and sensors. Our group previously observed the dissolution of Pt nanoelectrodes at moderately negative potentials during the ORR. Here we report a more detailed study of this process and identify its product. The nanoporous Pt surface formed during the ORR was visualized by AFM and high-resolution SEM, which also showed ~5 nm sized Pt particles on the glass surface surrounding the electrode. Furthermore, the release of these nanoparticles into the solution was confirmed by monitoring their catalytically amplified collisions with amore » Hg-coated microelectrode used as the tip in the scanning electrochemical microscope (SECM).« less

Dissolution of Pt during Oxygen Reduction Reaction Produces Pt Nanoparticles

DOE PAGES

Bae, Je Hyun; Brocenschi, Ricardo F.; Kisslinger, Kim; ...

2017-11-15

The loss of Pt during the oxygen reduction reaction (ORR) affects the performance and economic viability of fuel cells and sensors. Our group previously observed the dissolution of Pt nanoelectrodes at moderately negative potentials during the ORR. Here we report a more detailed study of this process and identify its product. The nanoporous Pt surface formed during the ORR was visualized by AFM and high-resolution SEM, which also showed ~5 nm sized Pt particles on the glass surface surrounding the electrode. Furthermore, the release of these nanoparticles into the solution was confirmed by monitoring their catalytically amplified collisions with amore » Hg-coated microelectrode used as the tip in the scanning electrochemical microscope (SECM).« less

Propitious Dendritic Cu2O-Pt Nanostructured Anodes for Direct Formic Acid Fuel Cells.

PubMed

El-Nagar, Gumaa A; Mohammad, Ahmad M; El-Deab, Mohamed S; El-Anadouli, Bahgat E

2017-06-14

This study introduces a novel competent dendritic copper oxide-platinum nanocatalyst (nano-Cu 2 O-Pt) immobilized onto a glassy carbon (GC) substrate for formic acid (FA) electro-oxidation (FAO); the prime reaction in the anodic compartment of direct formic acid fuel cells (DFAFCs). Interestingly, the proposed catalyst exhibited an outstanding improvement for FAO compared to the traditional platinum nanoparticles (nano-Pt) modified GC (nano-Pt/GC) catalyst. This was evaluated from steering the reaction mechanism toward the desired direct route producing carbon dioxide (CO 2 ); consistently with mitigating the other undesired indirect pathway producing carbon monoxide (CO); the potential poison deteriorating the catalytic activity of typical Pt-based catalysts. Moreover, the developed catalyst showed a reasonable long-term catalytic stability along with a significant lowering in onset potential of direct FAO that ultimately reduces the polarization and amplifies the fuel cell's voltage. The observed catalytic enhancement was believed to originate bifunctionally; while nano-Pt represented the base for the FA adsorption, nanostructured copper oxide (nano-Cu 2 O) behaved as a catalytic mediator facilitating the charge transfer during FAO and providing the oxygen atmosphere inspiring the poison's (CO) oxidation at relatively lower potential. Surprisingly, moreover, nano-Cu 2 O induced a surface retrieval of nano-Pt active sites by capturing the poisoning CO via "a spillover mechanism" to renovate the Pt surface for the direct FAO. Finally, the catalytic tolerance of the developed catalyst toward halides' poisoning was discussed.

Pt Catalyst Degradation in Aqueous and Fuel Cell Environments studied via In-Operando Anomalous Small-Angle X-ray Scattering

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

Gilbert, James A.; Kariuki, Nancy N.; Wang, Xiaoping

2015-08-01

The evolution of Pt nanoparticle cathode electrocatalyst size distribution in a polymer electrolyte membrane fuel cell (PEMFC) was followed during accelerated stress tests using in-operando anomalous small-angle X-ray scattering (ASAXS). This evolution was compared to that observed in an aqueous electrolyte environment using stagnant electrolyte, flowing electrolyte, and flowing electrolyte at elevated temperature to reveal the different degradation trends in the PEMFC and aqueous environments and to determine the relevance of aqueous measurements to the stability of Pt nanoparticle catalyst in the fuel cell environment. The observed changes in the particle size distributions (PSDs) were analyzed to elucidate the extentmore » and mechanisms of particle growth and corresponding mass and active surface area losses in the different environments. These losses indicate a Pt nanoparticle surface area loss mechanism controlled by Pt dissolution, the particle size dependence of Pt dissolution, the loss of dissolved Pt into the membrane and electrolyte, and, to a lesser extent, the re-deposition of dissolved Pt onto larger particles. Based on the geometric surface area loss, mass loss, and mean particle size increase trends, the aqueous environment best reflecting the fuel cell environment was found to be one in which the electrolyte is flowing rather than stagnant. Pt nanoparticle surface area loss resulting from potential cycling can be inhibited by reducing the number of particles smaller than a critical particle diameter (CPD), which was found to be similar to 3.5 to similar to 4 nm, with the CPD dependent on both the cycling protocol (square wave vs triangle wave) and the catalyst environment (fuel cell, aqueous stagnant, aqueous flowing electrolyte, or elevated temperature flowing electrolyte)« less

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.

Magnetic switching in granular FePt layers promoted by near-field laser enhancement

DOE PAGES

Granitzka, Patrick W.; Jal, Emmanuelle; Le Guyader, Loic; ...

2017-03-08

Light-matter interaction at the nanoscale in magnetic materials is a topic of intense research in view of potential applications in next-generation high-density magnetic recording. Laser-assisted switching provides a pathway for overcoming the material constraints of high-anisotropy and high-packing density media, though much about the dynamics of the switching process remains unexplored. We use ultrafast small-angle X-ray scattering at an X-ray free-electron laser to probe the magnetic switching dynamics of FePt nanoparticles embedded in a carbon matrix following excitation by an optical femtosecond laser pulse. We observe that the combination of laser excitation and applied static magnetic field, 1 order ofmore » magnitude smaller than the coercive field, can overcome the magnetic anisotropy barrier between “up” and “down” magnetization, enabling magnetization switching. This magnetic switching is found to be inhomogeneous throughout the material with some individual FePt nanoparticles neither switching nor demagnetizing. The origin of this behavior is identified as the near-field modification of the incident laser radiation around FePt nanoparticles. Furthermore, the fraction of not-switching nanoparticles is influenced by the heat flow between FePt and a heat-sink layer.« less

Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study.

PubMed

Sheng, Tian; Lin, Xiao; Chen, Zhao-Yang; Hu, P; Sun, Shi-Gang; Chu, You-Qun; Ma, Chun-An; Lin, Wen-Feng

2015-10-14

In exploration of low-cost electrocatalysts for direct methanol fuel cells (DMFCs), Pt modified tungsten carbide (WC) materials are found to be great potential candidates for decreasing Pt usage whilst exhibiting satisfactory reactivity. In this work, the mechanisms, onset potentials and activity for electrooxidation of methanol were studied on a series of Pt-modified WC catalysts where the bare W-terminated WC(0001) substrate was employed. In the surface energy calculations of a series of Pt-modified WC models, we found that the feasible structures are mono- and bi-layer Pt-modified WCs. The tri-layer Pt-modified WC model is not thermodynamically stable where the top layer Pt atoms tend to accumulate and form particles or clusters rather than being dispersed as a layer. We further calculated the mechanisms of methanol oxidation on the feasible models via methanol dehydrogenation to CO involving C-H and O-H bonds dissociating subsequently, and further CO oxidation with the C-O bond association. The onset potentials for the oxidation reactions over the Pt-modified WC catalysts were determined thermodynamically by water dissociation to surface OH* species. The activities of these Pt-modified WC catalysts were estimated from the calculated kinetic data. It has been found that the bi-layer Pt-modified WC catalysts may provide a good reactivity and an onset oxidation potential comparable to pure Pt and serve as promising electrocatalysts for DMFCs with a significant decrease in Pt usage.

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

Low-temperature CO oxidation over Cu/Pt co-doped ZrO2 nanoparticles synthesized by solution combustion.

PubMed

Singhania, Amit; Gupta, Shipra Mital

2017-01-01

Zirconia (ZrO 2 ) nanoparticles co-doped with Cu and Pt were applied as catalysts for carbon monoxide (CO) oxidation. These materials were prepared through solution combustion in order to obtain highly active and stable catalytic nanomaterials. This method allows Pt 2+ and Cu 2+ ions to dissolve into the ZrO 2 lattice and thus creates oxygen vacancies due to lattice distortion and charge imbalance. High-resolution transmission electron microscopy (HRTEM) results showed Cu/Pt co-doped ZrO 2 nanoparticles with a size of ca. 10 nm. X-ray diffraction (XRD) and Raman spectra confirmed cubic structure and larger oxygen vacancies. The nanoparticles showed excellent activity for CO oxidation. The temperature T 50 (the temperature at which 50% of CO are converted) was lowered by 175 °C in comparison to bare ZrO 2 . Further, they exhibited very high stability for CO reaction (time-on-stream ≈ 70 h). This is due to combined effect of smaller particle size, large oxygen vacancies, high specific surface area and better thermal stability of the Cu/Pt co-doped ZrO 2 nanoparticles. The apparent activation energy for CO oxidation is found to be 45.6 kJ·mol -1 . The CO conversion decreases with increase in gas hourly space velocity (GHSV) and initial CO concentration.

A comparative investigation of metal-support interactions on the catalytic activity of Pt nanoparticles for ethanol oxidation in alkaline medium

NASA Astrophysics Data System (ADS)

Godoi, Denis R. M.; Villullas, Hebe M.; Zhu, Fu-Chun; Jiang, Yan-Xia; Sun, Shi-Gang; Guo, Junsong; Sun, Lili; Chen, Rongrong

2016-04-01

The effects of interactions of Pt nanoparticles with hybrid supports on reactivity towards ethanol oxidation in alkaline solution are investigated. Studies involve catalysts with identical Pt nanoparticles on six hybrid supports containing carbon powder and transition metal oxides (TiO2, ZrO2, SnO2, CeO2, MoO3 and WO3). In situ X-ray absorption spectroscopy (XAS) results evidence that metal-support interactions produce changes in the Pt 5d band vacancy, which appears to determine the catalytic activity. The highest and lowest activities are observed for Pt nanoparticles on hybrid supports containing TiO2 and CeO2, respectively. Further studies are presented for these two catalysts. In situ FTIR reflection spectroscopy measurements, taken using both multi-stepped FTIR spectroscopy (MS-FTIR) and single potential alteration FTIR spectroscopy (SPA-FTIR), evidence that the main product of ethanol oxidation is acetate, although signals attributed to carbonate and CO2 indicate some differences in CO2 production. Fuel cell performances of these catalysts, tested in a 4.5 cm2 single cell at different temperatures (40-90 °C) show good agreement with data obtained by electrochemical techniques. Results of this comprehensive study point out the possibility of compensating a reduction of noble metal load with an increase in activity promoted by interactions between metallic nanoparticles and a support.

Localized-Surface-Plasmon Enhanced the 357 nm Forward Emission from ZnMgO Films Capped by Pt Nanoparticles

PubMed Central

2009-01-01

The Pt nanoparticles (NPs), which posses the wider tunable localized-surface-plasmon (LSP) energy varying from deep ultraviolet to visible region depending on their morphology, were prepared by annealing Pt thin films with different initial mass-thicknesses. A sixfold enhancement of the 357 nm forward emission of ZnMgO was observed after capping with Pt NPs, which is due to the resonance coupling between the LSP of Pt NPs and the band-gap emission of ZnMgO. The other factors affecting the ultraviolet emission of ZnMgO, such as emission from Pt itself and light multi-scattering at the interface, were also discussed. These results indicate that Pt NPs can be used to enhance the ultraviolet emission through the LSP coupling for various wide band-gap semiconductors. PMID:20596433

Hollow ZSM-5 encapsulated Pt nanoparticles for selective catalytic reduction of NO by hydrogen

NASA Astrophysics Data System (ADS)

Hong, Zhe; Wang, Zhong; Chen, Dan; Sun, Qiang; Li, Xuebing

2018-05-01

Pt nanoparticles were successfully encapsulated in hollow ZSM-5 single crystals by tetrapropylammonium hydroxide (TPAOH) hydrothermal treatment with an "dissolution-recrystallization" process. The prepared Pt/hollow ZSM-5 (Pt/h-ZSM-5re) sample exhibited the best activity and a maximum NO conversion of 84% can be achieved at 90 °C with N2 selectivity of 92% (GHSV = 50,000 h-1). Meanwhile, Pt/h-ZSM-5re catalyst exhibited excellent SO2, H2O resistance and durability, which was related to the stabilization of Pt active sites by hollow structure during H2-SCR. It was found that the increase of NO2 concentration in the feed gas mixture led to an activity decline. In addition, the H2-SCR reaction routes over Pt/hollow ZSM-5 catalyst at different temperature were investigated.

MnO2/CNT supported Pt and PtRu nanocatalysts for direct methanol fuel cells.

PubMed

Zhou, Chunmei; Wang, Hongjuan; Peng, Feng; Liang, Jiahua; Yu, Hao; Yang, Jian

2009-07-07

Pt/MnO2/carbon nanotube (CNT) and PtRu/MnO2/CNT nanocomposites were synthesized by successively loading hydrous MnO2 and Pt (or PtRu alloy) nanoparticles on CNTs and were used as anodic catalysts for direct methanol fuel cells (DMFCs). The existence of MnO2 on the surface of CNTs effectively increases the proton conductivity of the catalyst, which then could remarkably improve the performance of the catalyst in methanol electro-oxidation. As a result, Pt/MnO2/CNTs show higher electrochemical active surface area and better methanol electro-oxidation activity, compared with Pt/CNTs. As PtRu alloy nanoparticles were deposited on the surface of MnO2/CNTs instead of Pt, the PtRu/MnO2/CNT catalyst shows not only excellent electro-oxidation activity to methanol with forward anodic peak current density of 901 A/gPt but also good CO oxidation ability with lower preadsorbed CO oxidation onset potential (0.33 V vs Ag/AgCl) and peak potential (0.49 V vs Ag/AgCl) at room temperature.

Real-time electrochemical detection of hydrogen peroxide secretion in live cells by Pt nanoparticles decorated graphene-carbon nanotube hybrid paper electrode.

PubMed

Sun, Yimin; He, Kui; Zhang, Zefen; Zhou, Aijun; Duan, Hongwei

2015-06-15

In this work, we develop a new type of flexible and lightweight electrode based on highly dense Pt nanoparticles decorated free-standing graphene-carbon nanotube (CNT) hybrid paper (Pt/graphene-CNT paper), and explore its practical application as flexible electrochemical biosensor for the real-time tracking hydrogen peroxide (H2O2) secretion by live cells. For the fabrication of flexible nanohybrid electrode, the incorporation of CNT in graphene paper not only improves the electrical conductivity and the mechanical strength of graphene paper, but also increases its surface roughness and provides more nucleation sites for metal nanoparticles. Ultrafine Pt nanoparticles are further decorated on graphene-CNT paper by well controlled sputter deposition method, which offers several advantages such as defined particle size and dispersion, high loading density and strong adhesion between the nanoparticles and the substrate. Consequently, the resultant flexible Pt/graphene-CNT paper electrode demonstrates a variety of desirable electrochemical properties including large electrochemical active surface area, excellent electrocatalytic activity, high stability and exceptional flexibility. When used for nonenzymatic detection of H2O2, Pt/graphene-CNT paper exhibits outstanding sensing performance such as high sensitivity, selectivity, stability and reproducibility. The sensitivity is 1.41 µA µM(-1) cm(-2) with a linear range up to 25 µM and a low detection limit of 10 nM (S/N=3), which enables the resultant biosensor for the real-time tracking H2O2 secretion by live cells macrophages. Copyright © 2015. Published by Elsevier B.V.

Synthesis of Pt nanoparticles as catalysts of oxygen reduction with microbubble-assisted low-voltage and low-frequency solution plasma processing

NASA Astrophysics Data System (ADS)

Horiguchi, Genki; Chikaoka, Yu; Shiroishi, Hidenobu; Kosaka, Shinpei; Saito, Morihiro; Kameta, Naohiro; Matsuda, Naoki

2018-04-01

In the preparation of metallic nanoparticles by conventional solution plasma (SP) techniques, unstable plasma emission becomes an issue when the voltage and frequency of the waves applied between two electrodes placed in solution are lowered to avoid the boiling of the solution. In this study, we confirm that, in the presence of microbubbles, plasma is generated stably at low voltage (440 V) and low frequency (50-100 Hz) and small-size (≤10 nm) Pt nanoparticles (PtNPs) are synthesized in succession using a flow cell. The smallest PtNPs, ∼3.3 nm in diameter, are obtained using half-wave rectification, a tungsten wire anode, and a platinum wire cathode. The PtNPs are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and thermogravimeter-differential thermal analysis. The oxygen reduction reaction (ORR) is investigated in 0.1 M HClO4 solution on carbon-supported PtNPs using a rotating ring-disk electrode. The catalytic activities per initial electrochemical active surface area of the carbon-supported PtNPs synthesized employing the low-voltage, low-frequency (LVLF)-SP technique is higher than that of the commercially available 20 wt% Pt on Vulcan XC-72R. These results indicate that the LVLF-SP technique is a promising approach to producing carbon-supported PtNPs that catalyze ORR with low energy consumption.

Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction

NASA Astrophysics Data System (ADS)

Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

2015-12-01

Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.

Visualization of gold and platinum nanoparticles interacting with Salmonella Enteritidis and Listeria monocytogenes

PubMed Central

Sawosz, Ewa; Chwalibog, André; Szeliga, Jacek; Sawosz, Filip; Grodzik, Marta; Rupiewicz, Marlena; Niemiec, Tomasz; Kacprzyk, Katarzyna

2010-01-01

Purpose Rapid development of nanotechnology has recently brought significant attention to the extraordinary biological features of nanomaterials. The objective of the present investigation was to evaluate morphological characteristics of the assembles of gold and platinum nanoparticles (nano-Au and nano-Pt respectively), with Salmonella Enteritidis (Gram-negative) and Listeria monocytogenes (Gram-positive), to reveal possibilities of constructing bacteria-nanoparticle vehicles. Methods Hydrocolloids of nano-Au or nano-Pt were added to two bacteria suspensions in the following order: nano-Au + Salmonella Enteritidis; nano-Au + Listeria monocytogenes; nano-Pt + Salmonella Enteritidis; nano-Pt + Listeria monocytogenes. Samples were inspected by transmission electron microscope. Results Visualization of morphological interaction between nano-Au and Salmonella Enteritidis and Listeria monocytogenes, showed that nano-Au were aggregated within flagella or biofilm network and did not penetrate the bacterial cell. The analysis of morphological effects of interaction of nano-Pt with bacteria revealed that nano-Pt entered cells of Listeria monocytogenes and were removed from the cells. In the case of Salmonella Enteritidis, nano-Pt were seen inside bacteria cells, probably bound to DNA and partly left bacterial cells. After washing and centrifugation, some of the nano-Pt-DNA complexes were observed within Salmonella Enteritidis. Conclusion The results indicate that the bacteria could be used as a vehicle to deliver nano-Pt to specific points in the body. PMID:20856838

Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction.

PubMed

Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

2015-12-18

Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.

Comparative study of different carbon-supported Fe2O3-Pt catalysts for oxygen reduction reaction.

PubMed

Tellez-Cruz, M M; Padilla-Islas, M A; Pérez-González, M; Solorza-Feria, O

2017-11-01

One of the challenges in electrocatalysis is the adequate dispersion of the catalyst on an appropriate porous support matrix, being up to now the most commonly used the carbon-based supports. To overcome this challenge, carbon supports must first be functionalized to guide the catalyst's nucleation, thereby, improving the dispersion and allowing the use of smaller amount of the catalyst material to achieve a higher electrochemically active surface area. This study present the effect of functionalized Vulcan carbon XC72 (FVC) and functionalized Black Pearl carbon (FBPC) as supports on the catalytic activity of decorated Fe 2 O 3 with Pt. Both carbons were functionalized with HNO 3 and subsequently treated with ethanolamine. Fe 2 O 3 nanoparticles were synthesized by chemical reduction and decorated with platinum by epitaxial growth. Pt and Fe 2 O 3 structural phases were identified by XRD and XPS; the Pt content was measured by XPS, and results showed to a high Pt content in Fe 2 O 3 -Pt/FBPC. TEM micrographs reveal nanoparticles with an average size of 2 nm in both supported catalysts. The Fe 2 O 3 -Pt/FVC catalyst presents the highest specific activity and mass activity, 0.21 mA cm -2 Pt and 140 mA mg Pt -1 , respectively, associated to the appropriate distribution of platinum on the Fe 2 O 3 nanoparticles.

Effective anodic oxidation of naproxen by platinum nanoparticles coated FTO glass.

PubMed

Chin, Ching-Ju Monica; Chen, Tsan-Yao; Lee, Menshan; Chang, Chiung-Fen; Liu, Yu-Ting; Kuo, Yu-Tsun

2014-07-30

This study investigated applications of the electrochemical anodic oxidation process with Pt-FTO and Pt/MWCNTs-FTO glasses as anodes on the treatment of one of the most important emerging contaminants, naproxen. The anodes used in this study have been synthesized using commercial FTO, MWCNTs and Pt nanoparticles (PtNP). XRD patterns of Pt nanoparticles coated on FTO and MWCNTs revealed that MWCNTs can prevent the surface of PtNPs from sintering and thus provide a greater reaction sites density to interact with naproxen, which have also been confirmed by higher degradation and mineralization efficiencies in the Pt/MWCNTs-FTO system. Results from the CV analysis showed that the Pt-FTO and Pt/MWCNTs-FTO electrodes possessed dual functions of decreasing activation energy and interactions between hydroxyl radicals to effectively degrade naproxen. The lower the solution pH value, the better the degradation efficiency. The existence of humic acid indeed inhibited the degradation ability of naproxen due to the competitions in the multiple-component system. The electrochemical degradation processes were controlled by diffusion mechanism and two major intermediates of 2-acetyl-6-methoxynaphthalene and 2-(6-Hydroxy-2-naphthyl)propanoic acid were identified. This study has successfully demonstrated new, easy, flexible and effective anodic materials which can be feasibly applied to the electrochemical oxidation of naproxen. Copyright © 2014 Elsevier B.V. All rights reserved.

Bacopa monnieri Phytochemicals Mediated Synthesis of Platinum Nanoparticles and Its Neurorescue Effect on 1-Methyl 4-Phenyl 1,2,3,6 Tetrahydropyridine-Induced Experimental Parkinsonism in Zebrafish

PubMed Central

Nellore, Jayshree; Pauline, Cynthia; Amarnath, Kanchana

2013-01-01

Current discovery demonstrates the rapid formation of platinum nanoparticles using leaf extract of a neurobeneficial plant, Bacopa monnieri (BmE). The nanoparticles (BmE-PtNPs) were stabilized and then coated with varied phytochemicals present within the leaf extract. These nanoparticles demonstrated the same activity of Complex I, as that of oxidizing NADH to NAD+ using a spectrophotometric method. This suggests that BmE-PtNPs are a potential medicinal substance for oxidative stress mediated disease with suppressed mitochondrial complex I, namely, Parkinson's disease (PD). Hence, the neuroprotective potentials of the phytochemical coated nanoparticle were explored in 1-methyl 4-phenyl 1,2,3,6 tetrahydropyridine- (MPTP-)induced experimental Parkinsonism in zebrafish model. BmE-PtNPs pretreatment significantly reversed toxic effects of MPTP by increasing the levels of dopamine, its metabolites, GSH and activities of GPx, catalase, SOD and complex I, and reducing levels of MDA along with enhanced locomotor activity. Taken together, these findings suggest that BmE-PtNPs have protective effect in MPTP-induced neurotoxicity in this model of Parkinson's disease via their dual functions as mitochondrial complex I and antioxidant activity. PMID:26317003

A sinter-resistant catalytic system fabricated by maneuvering the selectivity of SiO2 deposition onto the TiO2 surface versus the Pt nanoparticle surface.

PubMed

Lu, Ping; Campbell, Charles T; Xia, Younan

2013-10-09

A triphasic catalytic system (Pt/TiO2-SiO2) with an "islands in the sea" configuration was fabricated by controlling the selectivity of SiO2 deposition onto the surface of TiO2 versus the surface of Pt nanoparticles. The Pt surface was exposed, while the nanoparticles were supported on TiO2 and isolated from each other by SiO2 to achieve both significantly improved sinter resistance up to 700 °C and outstanding activity after high-temperature calcination. This work not only demonstrates the feasibility of using a new triphasic system with uncovered catalyst to maximize the thermal stability and catalytic activity but also offers a general approach to the synthesis of high-performance catalytic systems with tunable compositions.

Preparation and characterization of Fe3O4-Pt nanoparticles

NASA Astrophysics Data System (ADS)

Andrade, Ângela Leão; Cavalcante, Luis Carlos Duarte; Fabris, José Domingos; Pereira, Márcio César; Ardisson, José Domingos; Domingues, Rosana Zacarias

2017-11-01

Pt and Pt-based nanomaterials are active anticancer drugs for their ability to inhibit the division of living cells. Nanoparticles of magnetite containing variable proportions of platinum were prepared in the laboratory. The magnetite nanoparticles with platinum (Pt-Fe3O4) were obtained by reducing the Fe3+ of the maghemite ( γ Fe2O3) mixed with platinum (II) acetylacetonate and sucrose in two inversely coupled ceramic crucibles and heated in a furnace at 400 °C for 20 min. The formed carbon during this preparation acts to chemically reduce the ferric iron in maghemite. Moreover, its residual layer on the particle surface prevents the forming magnetite from oxidizing in air and helps retain the platinum in the solid mixture. The produced Pt-magnetite samples were characterized by 57Fe-Mössbauer spectroscopy, powder X-ray diffraction, scanning electron microscopy, and magnetization measurements. Measurements of AC magnetic-field-induced heating properties of the obtained nanocomposites, in aqueous solution, showed that they are suitable as a hyperthermia agent for biological applications.

Protective effects of platinum nanoparticles against UV-light-induced epidermal inflammation.

PubMed

Yoshihisa, Yoko; Honda, Ayumi; Zhao, Qing-Li; Makino, Teruhiko; Abe, Riichiro; Matsui, Kotaro; Shimizu, Hiroshi; Miyamoto, Yusei; Kondo, Takashi; Shimizu, Tadamichi

2010-11-01

Intracellular reactive oxygen species (ROS) and apoptosis play important roles in the ultraviolet (UV)-induced inflammatory responses in the skin. Metal nanoparticles have been developed to increase the catalytic activity of metals, which is because of the large surface area of smaller particles. Platinum nanoparticles (nano-Pt) protected by poly acrylic acid were manufactured by reduction with ethanol. A marked increase in ROS production was observed in UV-treated HaCaT keratinocytes cell lines, while a decrease in ROS production was observed in nano-Pt-treated cells. Pretreatment of the cells with nano-Pt also caused a significant inhibition of UVB- and UVC-induced apoptosis. Furthermore, we found that mice treated with nano-Pt gel prior to UV irradiation showed significant inhibition of UVB-induced inflammation and UVA-induced photoallergy compared to UV-irradiated control mice. These results suggest that nano-Pt effectively protects against UV-induced inflammation by decreasing ROS production and inhibiting apoptosis in keratinocytes. © 2010 John Wiley & Sons A/S.

An efficient polymeric micromotor doped with Pt nanoparticle@carbon nanotubes for complex bio-media.

PubMed

Li, Yana; Wu, Jie; Xie, Yuzhe; Ju, Huangxian

2015-04-14

A highly efficient polymeric tubular micromotor doped with Pt nanoparticle@carbon nanotubes is fabricated by template-assisted electrochemical growth. The micromotors preserve good navigation in multi-media and surface modification, along with simple synthesis, easy functionalization and good biocompatibility, displaying great promise in biological applications.

Influence of ball milling and annealing conditions on the properties of L10 FePt nanoparticles fabricated by a new green chemical synthesis method

NASA Astrophysics Data System (ADS)

Hu, X. C.; Capobianchi, A.; Gallagher, R.; Hadjipanayis, G. C.

2014-05-01

In this work, a new green chemical strategy for the synthesis of L10 FePt alloy nanoparticles is reported. The precursor is a polycrystalline molecular complex (Fe(H2O)6PtCl6), in which Fe and Pt atoms are arranged on alternating planes and milled with NaCl to form nanocrystals. Then the mixture was annealed under reducing atmosphere (5% H2 and 95% Ar) at temperatures varying from 350 °C to 500 °C for 2 h with a heating rate of 5 °C/min. After the reduction, the mixture was washed with water to remove the NaCl and L10 FePt nanoparticles were obtained. The X-Ray Diffraction pattern showed the presence of the characteristic peaks of the fct phase of FePt nanoparticles. Influence of precursor/NaCl ratio and ball milling time on particle size was investigated. Transmission electron microscopy images revealed that smaller precursor/NaCl ratio (10 mg/20 g) and longer milling time (15 h) lead to smaller particle size and narrower size distribution. Milling time does not influence the coercivity much but the decrease of the amount of precursor leads to a decrease of coercivity from 10.8 kOe to 4.8 kOe.

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.

A novel hierarchical Pt- and FTO-free counter electrode for dye-sensitized solar cell

PubMed Central

2014-01-01

A novel hierarchical Pt- and FTO-free counter electrode (CE) for the dye-sensitized solar cell (DSSC) was prepared by spin coating the mixture of TiO2 nanoparticles and poly(3,4-ethylenedioxy-thiophene):poly(styrenesulfonate) (PEDOT:PSS) solution onto the glass substrate. Compared with traditional Pt/FTO CE, the cost of the new CE is dramatically reduced by the application of bilayer TiO2-PEDOT:PSS/PEDOT:PSS film and the glass substrate. The sheet resistance of this composite film is 35 Ω sq−1 and is low enough to be used as an electrode. The surface morphologies of TiO2-PEDOT:PSS layer and modified PEDOT:PSS layer were characterized by scanning electron microscope, which shows that the former had larger surface areas than the latter. Electrochemical impedance spectra and Tafel polarization curves prove that the catalytic activity of TiO2-PEDOT:PSS/PEDOT:PSS/glass CE is higher than that of PEDOT:PSS/FTO CE and is similar to Pt/FTO CE's. This new fabricated device with TiO2-PEDOT:PSS/PEDOT:PSS/glass CE achieves a high power conversion efficiency (PCE) of 4.67%, reaching 91.39% of DSSC with Pt/FTO CE (5.11%). PMID:24808802

Same-View Nano-XAFS/STEM-EDS Imagings of Pt Chemical Species in Pt/C Cathode Catalyst Layers of a Polymer Electrolyte Fuel Cell.

PubMed

Takao, Shinobu; Sekizawa, Oki; Samjeské, Gabor; Nagamatsu, Shin-ichi; Kaneko, Takuma; Yamamoto, Takashi; Higashi, Kotaro; Nagasawa, Kensaku; Uruga, Tomoya; Iwasawa, Yasuhiro

2015-06-04

We have made the first success in the same-view imagings of 2D nano-XAFS and TEM/STEM-EDS under a humid N2 atmosphere for Pt/C cathode catalyst layers in membrane electrode assemblies (MEAs) of polymer electrolyte fuel cells (PEFCs) with Nafion membrane to examine the degradation of Pt/C cathodes by anode gas exchange cycles (start-up/shut-down simulations of PEFC vehicles). The same-view imaging under the humid N2 atmosphere provided unprecedented spatial information on the distribution of Pt nanoparticles and oxidation states in the Pt/C cathode catalyst layer as well as Nafion ionomer-filled nanoholes of carbon support in the wet MEA, which evidence the origin of the formation of Pt oxidation species and isolated Pt nanoparticles in the nanohole areas of the cathode layer with different Pt/ionomer ratios, relevant to the degradation of PEFC catalysts.

Dynamic wet-ETEM observation of Pt/C electrode catalysts in a moisturized cathode atmosphere.

PubMed

Yoshida, Kenta; Bright, Alexander N; Ward, Michael R; Lari, Leonardo; Zhang, Xudong; Hiroyama, Tomoki; Boyes, Edward D; Gai, Pratibha L

2014-10-24

The gas injection line of the latest spherical aberration-corrected environmental transmission electron microscope has been modified for achieving real-time/atomic-scale observations in moisturised gas atmospheres for the first time. The newly developed Wet-TEM system is applied to platinum carbon electrode catalysts to investigate the effect of water molecules on the platinum/carbon interface during deactivation processes such as sintering and corrosion. Dynamic in situ movies obtained in dry and 24% moisturised nitrogen environments visualize the rapid rotation, migration and agglomeration of platinum nanoparticles due to the physical adsorption of water and the hydroxylation of the carbon surface. The origin of the long-interconnected aggregation of platinum nanoparticles was discovered to be a major deactivation process in addition to conventional carbon corrosion.

Tungsten trioxide nanoplate array supported platinum as a highly efficient counter electrode for dye-sensitized solar cells.

PubMed

Song, Dandan; Cui, Peng; Zhao, Xing; Li, Meicheng; Chu, Lihua; Wang, Tianyue; Jiang, Bing

2015-03-19

A tungsten trioxide (WO₃) nanoplate array is fabricated directly on the FTO/glass substrate and used as a platinum (Pt) nanoscale supporter for a highly efficient and low Pt-consumption counter electrode (CE) in dye-sensitized solar cells (DSCs). A Pt/WO₃ composite structure, with Pt nanoparticles having a diameter of 2-3 nm, increases the electrochemical catalytic activity in catalyzing the reduction of triiodide. Accordingly, the power conversion efficiency is increased from less than 1% for WO₃ CE and 8.1% for Pt CE, respectively, to 8.9% for Pt/WO₃ CE. Moreover, the use of Pt/WO₃ CE can dramatically reduce the consumption of scarce Pt material, with a relatively low Pt-loading of ∼2 μg cm(-2), while maintaining a much better performance. The excellent performance of Pt/WO₃ CE is attributed to the efficient electron injection and transport via WO₃ supporters, as well as the nanostructure array morphology of WO₃ for deposition of fine Pt nanoparticles. This work provides an approach for developing highly catalytic and low-cost Pt based CEs, which also has implications for the development of Pt/WO₃ nanoplate arrays for other applications.

Multi-photon excited luminescence of magnetic FePt core-shell nanoparticles.

PubMed

Seemann, K M; Kuhn, B

2014-07-01

We present magnetic FePt nanoparticles with a hydrophilic, inert, and biocompatible silico-tungsten oxide shell. The particles can be functionalized, optically detected, and optically manipulated. To show the functionalization the fluorescent dye NOPS was bound to the FePt core-shell nanoparticles with propyl-triethoxy-silane linkers and fluorescence of the labeled particles were observed in ethanol (EtOH). In aqueous dispersion the NOPS fluorescence is quenched making them invisible using 1-photon excitation. However, we observe bright luminescence of labeled and even unlabeled magnetic core-shell nanoparticles with multi-photon excitation. Luminescence can be detected in the near ultraviolet and the full visible spectral range by near infrared multi-photon excitation. For optical manipulation, we were able to drag clusters of particles, and maybe also single particles, by a focused laser beam that acts as optical tweezers by inducing an electric dipole in the insulated metal nanoparticles. In a first application, we show that the luminescence of the core-shell nanoparticles is bright enough for in vivo multi-photon imaging in the mouse neocortex down to cortical layer 5.

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

Evidence for the Formation of Nitrogen-Rich Platinum and Palladium Nitride Nanoparticles

DOE PAGES

Veith, Gabriel M.; Lupini, Andrew R.; Baggetto, Loïc; ...

2013-12-03

Here, we report evidence for the formation of nitrogen-rich precious metal nanoparticles (Pt, Pd) prepared by reactive sputtering of the pure metal in a N 2 plasma. The composition of the nanoparticles varies as a function of particle size and growth conditions. For the smallest particles the nitrogen content appears to be as high as 6.7 N atoms for each Pd atom or 5.9 N atoms for each Pt atom whereas bulk films have nominal compositions of Pt 7.3N and Pd 2.5N. The nanoparticles are metastable in air and moisture, slowly decomposing over several years. This paper describes the synthesismore » of these materials along with experimental evidence of the composition, oxidation state, and growth modes. Moreover, the catalytic properties of these N-rich nanoparticles were accessed by rotating disk electrode electrochemical studies, the liquid phase oxidation of benzyl alcohol and gas phase CO oxidation and support the experimental evidence for the materials composition.« less

Growth of block copolymer stabilized metal nanoparticles probed simultaneously by in situ XAS and UV-Vis spectroscopy.

PubMed

Nayak, C; Bhattacharyya, D; Jha, S N; Sahoo, N K

2016-01-01

The growth of Au and Pt nanoparticles from their respective chloride precursors using block copolymer-based reducers has been studied by simultaneous in situ measurement of XAS and UV-Vis spectroscopy at the energy-dispersive EXAFS beamline (BL-08) at INDUS-2 SRS at RRCAT, Indore, India. While the XANES spectra of the precursor give real-time information on the reduction process, the EXAFS spectra reveal the structure of the clusters formed at the intermediate stages of growth. The growth kinetics of both types of nanoparticles are found to be almost similar and are found to follow three stages, though the first stage of nucleation takes place earlier in the case of Au than in the case of Pt nanoparticles due to the difference in the reduction potential of the respective precursors. The first two stages of the growth of Au and Pt nanoparticles as obtained by in situ XAS measurements could be corroborated by simultaneous in situ measurement of UV-Vis spectroscopy also.

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

NASA Astrophysics Data System (ADS)

Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

2013-05-01

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

PubMed Central

Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

2013-01-01

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

Pt nanoparticles residing in the pores of porous LaNiO₃ nanocubes as high-efficiency electrocatalyst for direct methanol fuel cells.

PubMed

Yu, Nan; Kuai, Long; Wang, Qing; Geng, Baoyou

2012-09-07

Pt-filled porous LaNiO₃ cubes are prepared through a facile route. The characterizations reveal that large numbers of pores (9-10 nm) are distributed homogeneously in porous LaNiO₃ cubes. The Pt nanoparticles residing in the pores of porous LaNiO₃ cubes are about 5 nm in size. The investigation on the electrocatalytic activity reveals that electrocatalytic activity of the obtained Pt loaded porous LaNiO₃ nanocubes exhibit a significantly improved electrochemical active surface area (EASA) and a remarkably enhanced electrocatalytic performance toward methanol oxidation. The results are significant for improving the efficiency of Pt-based catalysts for DMFCs as well as the applications of perovskite compounds.

Resistive switching characteristics of manganese oxide thin film and nanoparticle assembly hybrid devices

NASA Astrophysics Data System (ADS)

Abbas, Haider; Park, Mi Ra; Abbas, Yawar; Hu, Quanli; Kang, Tae Su; Yoon, Tae-Sik; Kang, Chi Jung

2018-06-01

Improved resistive switching characteristics are demonstrated in a hybrid device with Pt/Ti/MnO (thin film)/MnO (nanoparticle)/Pt structure. The hybrid devices of MnO thin film and nanoparticle assembly were fabricated. MnO nanoparticles with an average diameter of ∼30 nm were chemically synthesized and assembled as a monolayer on a Pt bottom electrode. A MnO thin film of ∼40 nm thickness was deposited on the nanoparticle assembly to form the hybrid structure. Resistive switching could be induced by the formation and rupture of conducting filaments in the hybrid oxide layers. The hybrid device exhibited very stable unipolar switching with good endurance and retention characteristics. It showed a larger and stable memory window with a uniform distribution of SET and RESET voltages. Moreover, the conduction mechanisms of ohmic conduction, space-charge-limited conduction, Schottky emission, and Poole–Frenkel emission have been investigated as possible conduction mechanisms for the switching of the devices. Using MnO nanoparticles in the thin film and nanoparticle heterostructures enabled the appropriate control of resistive random access memory (RRAM) devices and markedly improved their memory characteristics.

Quantitative analysis of the protein corona on FePt nanoparticles formed by transferrin binding

PubMed Central

Jiang, Xiue; Weise, Stefan; Hafner, Margit; Röcker, Carlheinz; Zhang, Feng; Parak, Wolfgang J.; Nienhaus, G. Ulrich

2010-01-01

Nanoparticles are finding a rapidly expanding range of applications in research and technology, finally entering our daily life in medical, cosmetic or food products. Their ability to invade all regions of an organism including cells and cellular organelles offers new strategies for medical diagnosis and therapy (nanomedicine), but their safe use requires a deep knowledge about their interactions with biological systems at the molecular level. Upon incorporation, nanoparticles are exposed to biological fluids from which they adsorb proteins and other biomolecules to form a ‘protein corona’. These nanoparticle–protein interactions are still poorly understood and quantitative studies to characterize them remain scarce. Here we have quantitatively analysed the adsorption of human transferrin onto small (radius approx. 5 nm) polymer-coated FePt nanoparticles by using fluorescence correlation spectroscopy. Transferrin binds to the negatively charged nanoparticles with an affinity of approximately 26 µM in a cooperative fashion and forms a monolayer with a thickness of 7 nm. By using confocal fluorescence microscopy, we have observed that the uptake of FePt nanoparticles by HeLa cells is suppressed by the protein corona compared with the bare nanoparticles. PMID:19776149

Synthesis and characteristics of Ag/Pt bimetallic nanocomposites by arc-discharge solution plasma processing.

PubMed

Pootawang, Panuphong; Saito, Nagahiro; Takai, Osamu; Lee, Sang-Yul

2012-10-05

Arc discharge in solution, generated by applying a high voltage of unipolar pulsed dc to electrodes of Ag and Pt, was used as a method to form Ag/Pt bimetallic nanocomposites via electrode erosion by the effects of the electric arc at the cathode (Ag rod) and the sputtering at the anode (Pt rod). Ag/Pt bimetallic nanocomposites were formed as colloidal particles dispersed in solution via the reduction of hydrogen radicals generated during discharge without the addition of chemical precursor or reducing agent. At a discharge time of 30 s, the fine bimetallic nanoparticles with a mean particle size of approximately 5 nm were observed by transmission electron microscopy (TEM). With increasing discharge time, the bimetallic nanoparticle size tended to increase by forming an agglomeration. The presence of the relatively small amount of Pt dispersed in the Ag matrix could be observed by the analytical mapping mode of energy-dispersive x-ray spectroscopy and high-resolution TEM. This demonstrated that the synthesized particle was in the form of a nanocomposite. No contamination of other chemical substances was detected by x-ray photoelectron spectroscopy. Hence, solution plasma could be a clean and simple process to effectively synthesize Ag/Pt bimetallic nanocomposites and it is expected to be widely applicable in the preparation of several types of nanoparticle.

Identification of platinum nanoparticles in road dust leachate by single particle inductively coupled plasma-mass spectrometry.

PubMed

Folens, Karel; Van Acker, Thibaut; Bolea-Fernandez, Eduardo; Cornelis, Geert; Vanhaecke, Frank; Du Laing, Gijs; Rauch, Sebastien

2018-02-15

Elevated platinum (Pt) concentrations are found in road dust as a result of emissions from catalytic converters in vehicles. This study investigates the occurrence of Pt in road dust collected in Ghent (Belgium) and Gothenburg (Sweden). Total Pt contents, determined by tandem ICP-mass spectrometry (ICP-MS/MS), were in the range of 5 to 79ngg -1 , comparable to the Pt content in road dust of other medium-sized cities. Further sample characterization was performed by single particle (sp) ICP-MS following an ultrasonic extraction procedure using stormwater runoff for leaching. The method was found to be suitable for the characterization of Pt nanoparticles in road dust leachates. The extraction was optimized using road dust reference material BCR-723, for which an extraction efficiency of 2.7% was obtained by applying 144kJ of ultrasonic energy. Using this method, between 0.2% and 18% of the Pt present was extracted from road dust samples. spICP-MS analysis revealed that Pt in the leachate is entirely present as nanoparticles of sizes between 9 and 21nm. Although representing only a minor fraction of the total content in road dust, the nanoparticulate Pt leachate is most susceptible to biological uptake and hence most relevant in terms of bioavailability. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis and characterization of diverse Pt nanostructures in Nafion.

PubMed

Ingle, N J C; Sode, A; Martens, I; Gyenge, E; Wilkinson, D P; Bizzotto, D

2014-02-25

With the aid of TEM characterization, we describe two distinct Pt nanostructures generated via the electroless reduction of Pt(NH3)4(NO2)2 within Nafion. Under one set of conditions, we produce bundles of Pt nanorods that are 2 nm in diameter and 10-20 nm long. These bundled Pt nanorods, uniformly distributed within 5 μm of the Nafion surface, are strikingly similar to the proposed hydrated nanomorphology of Nafion, and therefore strongly suggestive of Nafion templating. By altering the reaction environment (pH, reductant strength, and Nafion hydration), we can also generate nonregular polyhedron Pt nanoparticles that range in size from a few nanometers in diameter up to 20 nm. These Pt nanoparticles form a dense Pt layer within 100-200 nm from the Nafion surface and show a power-law dependence of particle size and distribution on the distance from the Nafion membrane surface. Control over the distribution and the type of Pt nanostructures in the surface region may provide a cost-effective, simple, and scaleable pathway for enhancing manufacturability, activity, stability, and utilization efficiency of Pt catalysts for electrochemical devices.

Short peptide-directed synthesis of one-dimensional platinum nanostructures with controllable morphologies

PubMed Central

Tao, Kai; Wang, Jiqian; Li, Yanpeng; Xia, Daohong; Shan, Honghong; Xu, Hai; Lu, Jian R.

2013-01-01

Although one dimensional (1D) Pt nanostructures with well-defined sizes and shapes have fascinating physiochemical properties, their preparation remains a great challenge. Here we report an easy and novel synthesis of 1D Pt nanostructures with controllable morphologies, through the combination of designer self-assembling I3K and phage-displayed P7A peptides. The nanofibrils formed via I3K self-assembly acted as template. Pt precursors ((PtCl4)2− and (PtCl6)2−) were immobilized by electrostatic interaction on the positively charged template surface and subsequent reduction led to the formation of 1D Pt nanostructures. P7A was applied to tune the continuity of the Pt nanostructures. Here, the electrostatic repulsion between the deprotonated C-terminal carboxyl groups of P7A molecules was demonstrated to play a key role. We finally showed that continuous and ordered 1D Pt morphology had a significantly improved electrochemical performance for the hydrogen and methanol electro-oxidation in comparison with either 1D discrete Pt nanoparticle assemblies or isolated Pt nanoparticles. PMID:23995118

Radiolytic Synthesis of Pt-Particle/ABS Catalysts for H₂O₂ Decomposition in Contact Lens Cleaning.

PubMed

Ohkubo, Yuji; Aoki, Tomonori; Seino, Satoshi; Mori, Osamu; Ito, Issaku; Endo, Katsuyoshi; Yamamura, Kazuya

2017-08-23

A container used in contact lens cleaning requires a Pt plating weight of 1.5 mg for H₂O₂ decomposition although Pt is an expensive material. Techniques that decrease the amount of Pt are therefore needed. In this study, Pt nanoparticles instead of Pt plating film were supported on a substrate of acrylonitrile-butadiene-styrene copolymer (ABS). This was achieved by the reduction of Pt ions in an aqueous solution containing the ABS substrate using high-energy electron-beam irradiation. Pt nanoparticles supported on the ABS substrate (Pt-particle/ABS) had a size of 4-10 nm. The amount of Pt required for Pt-particle/ABS was 250 times less than that required for an ABS substrate covered with Pt plating film (Pt-film/ABS). The catalytic activity for H₂O₂ decomposition was estimated by measuring the residual H₂O₂ concentration after immersing the catalyst for 360 min. The Pt-particle/ABS catalyst had a considerably higher specific catalytic activity for H₂O₂ decomposition than the Pt-film/ABS catalyst. In addition, sterilization performance was estimated from the initial rate of H₂O₂ decomposition over 60 min. The Pt-particle/ABS catalyst demonstrated a better sterilization performance than the Pt-film/ABS catalyst. The difference between Pt-particle/ABS and Pt-film/ABS was shown to reflect the size of the O₂ bubbles formed during H₂O₂ decomposition.

Highly Sensitive Electrochemical Biosensor for Evaluation of Oxidative Stress Based on the Nanointerface of Graphene Nanocomposites Blended with Gold, Fe3O4, and Platinum Nanoparticles.

PubMed

Wang, Le; Zhang, Yuanyuan; Cheng, Chuansheng; Liu, Xiaoli; Jiang, Hui; Wang, Xuemei

2015-08-26

High levels of H2O2 pertain to high oxidative stress and are associated with cancer, autoimmune, and neurodegenerative disease, and other related diseases. In this study, a sensitive H2O2 biosensor for evaluation of oxidative stress was fabricated on the basis of the reduced graphene oxide (RGO) nanocomposites decorated with Au, Fe3O4, and Pt nanoparticles (RGO/AuFe3O4/Pt) modified glassy carbon electrode (GCE) and used to detect the released H2O2 from cancer cells and assess the oxidative stress elicited from H2O2 in living cells. Electrochemical behavior of RGO/AuFe3O4/Pt nanocomposites exhibits excellent catalytic activity toward the relevant reduction with high selection and sensitivity, low overpotential of 0 V, low detection limit of ∼0.1 μM, large linear range from 0.5 μM to 11.5 mM, and outstanding reproducibility. The as-prepared biosensor was applied in the measurement of efflux of H2O2 from living cells including healthy normal cells and tumor cells under the external stimulation. The results display that this new nanocomposites-based biosensor is a promising candidate of nonenzymatic H2O2 sensor which has the possibility of application in clinical diagnostics to assess oxidative stress of different kinds of living cells.

Au@Pt nanoparticles as catalase mimics to attenuate tumor hypoxia and enhance immune cell-mediated cytotoxicity

NASA Astrophysics Data System (ADS)

Liang, Hong; Wu, Ying; Ou, Xiang-Yu; Li, Jing-Ying; Li, Juan

2017-11-01

Hypoxic tumor microenvironment (TME) is closely linked to tumor progression, heterogeneity and immune suppression. Therefore, the development of effective methods to overcome hypoxia and substantially enhance the immunotherapy efficacy remains a desirable goal. Herein, we engineered a biocompatible Au core/Pt shell nanoparticles (Au@Pt NPs) to reoxygenate the TME by reacting with endogenous H2O2. Treatment with Au@Pt NPs appeared to improve oxygen in intracellular environments and decrease hypoxia-inducible factor-1α expression. Furthermore, the integration of high catalytic efficiency of Au@Pt NPs with cytokine-induced killer (CIK) cell immunotherapy, could lead to significantly improve the effect of CIK cell-mediated cytotoxicity. These results suggest great potential of Au@Pt NPs for regulation of the hypoxic TME and enhance immune cell mediated anti-tumor immunity.

Preparation of the vulcan XC-72R-supported Pt nanoparticles for the hydrogen evolution reaction in PEM water electrolysers

NASA Astrophysics Data System (ADS)

Du Nguyen, Huy; Thuy Luyen Nguyen, T.; Nguyen, Khac Manh; Ha, Thuc Huy; Hien Nguyen, Quoc

2015-01-01

Pt nanoparticles on vulcan XC-72R support (Pt/vulcan XC-72R) were prepared by the impregnation-reduction method. The Pt content, the morphological properties and the electrochemical catalysis of the Pt/vulcan XC 72R materials have been investigated by ICP-OES analysis, FESEM, TEM, and cyclic voltammetry. These materials were then used as catalyst for hydrogen evolution reaction at the cathode of proton exchange membrane (PEM) water electrolysers. The best catalyst was Pt/vulcan XC-72R prepared by the impregnation-reduction method which is conducted in two reducing steps with the reductants of sodium borohydride and ethylene glycol, respectively. The current density of PEM water electrolysers reached 1.0 A cm-2 when applying a voltage of 2.0 V at 25 °C.

Preparation of platinum-decorated porous graphite nanofibers, and their hydrogen storage behaviors.

PubMed

Kim, Byung-Joo; Lee, Young-Seak; Park, Soo-Jin

2008-02-15

In this work, the hydrogen storage behaviors of porous graphite nanofibers (GNFs) decorated by Pt nanoparticles were investigated. The Pt nanoparticles were introduced onto the GNF surfaces using a well-known chemical reduction method. We investigated the hydrogen storage capacity of the Pt-doped GNFs for the platinum content range of 1.3-7.5 mass%. The microstructure of the Pt/porous GNFs was characterized by X-ray diffraction and transmission electron microscopy. The hydrogen storage behaviors of the Pt/GNFs were studied using a PCT apparatus at 298 K and 10 MPa. It was found that amount of hydrogen stored increased with increasing Pt content to 3.4 mass%, and then decreased. This result indicates that the hydrogen storage capacity of porous carbons is based on both their metal content and dispersion rate.

New Electrochemical Methods for Studying Nanoparticle Electrocatalysis and Neuronal Exocytosis

NASA Astrophysics Data System (ADS)

Cox, Jonathan T.

This dissertation presents the construction and application of micro and nanoscale electrodes for electroanalytical analysis. The studies presented herein encompass two main areas: electrochemical catalysis, and studies of the dynamics of single cell exocytosis. The first portion of this dissertation engages the use of Pt nanoelectrodes to study the stability and electrocatalytic properties of materials. A single nanoparticle electrode (SNPE) was fabricated by immobilizing a single Au nanoparticle on a Pt disk nanoelectrode via an amine-terminated silane cross linker. In this manner we were able to effectively study the electrochemistry and electrocatalytic activity of single Au nanoparticles and found that the electrocatalytic activity is dependent on nanoparticle size. This study can further the understanding of the structure-function relationship in nanoparticle based electrocatalysis. Further work was conducted to probe the stability of Pt nanoelectrodes under conditions of potential cycling. Pt based catalysts are known to deteriorate under such conditions due to losses in electrochemical surface area and Pt dissolution. By using Pt disk nanoelectrodes we were able to study Pt dissolution via steady-state voltammetry. We observed an enhanced dissolution rate and higher charge density on nanoelectrodes than that previously found on macro scale electrodes. The goal of the second portion of this dissertation is to develop new analytical methods to study the dynamics of exocytosis from single cells. The secretion of neurotransmitters plays a key role in neuronal communication, and our studies highlight how bipolar electrochemistry can be employed to enhance detection of neurotransmitters from single cells. First, we developed a theory to quantitatively characterize the voltammetric behavior of bipolar carbon fiber microelectrodes and secondly applied those principles to single cell detection. We showed that by simply adding an additional redox mediator to the back-fill solution of a carbon fiber microelectrode, there is a significant enhancement in detection. Additionally we used solid state nanopores to detect individual phospholipid vesicles in solution. Vesicles are key cellular components that play essential biological roles especially in neurotransmission. This work represents preliminary studies in detection and size determination from vesicles isolated from individual cells.

Platinum nanoparticles and their cellular uptake and DNA platination at non-cytotoxic concentrations.

PubMed

Gehrke, Helge; Pelka, Joanna; Hartinger, Christian G; Blank, Holger; Bleimund, Felix; Schneider, Reinhard; Gerthsen, Dagmar; Bräse, Stefan; Crone, Marlene; Türk, Michael; Marko, Doris

2011-07-01

Three differently sized, highly dispersed platinum nanoparticle (Pt-NP) preparations were generated by supercritical fluid reactive deposition (SFRD) and deposited on a β-cyclodextrin matrix. The average particle size and size distribution were steered by the precursor reduction conditions, resulting in particle preparations of <20, <100 and >100 nm as characterised by TEM and SEM. As reported previously, these Pt-NPs were found to cause DNA strand breaks in human colon carcinoma cells (HT29) in a concentration- and time-dependent manner and a distinct size dependency. Here, we addressed the question whether Pt-NPs might affect directly DNA integrity in these cells and thus behave analogous to platinum-based chemotherapeutics such as cisplatin. Therefore, DNA-associated Pt as well as the translocation of Pt-NPs through a Caco-2 monolayer was quantified by ICP-MS. STEM imaging demonstrated that Pt-NPs were taken up into HT29 cells in their particulate and aggregated form, but appear not to translocate into the nucleus or interact with mitochondria. The platinum content of the DNA of HT29 cells was found to increase in a time- and concentration-dependent manner with a maximal effect at 1,000 ng/cm(2). ICP-MS analysis of the cell culture medium indicated the formation of soluble Pt species, although to a limited extent. The observations suggest that DNA strand breaks mediated by metallic Pt-NPs are caused by Pt ions forming during the incubation of cells with these nanoparticles.

The control of Pt and Ru nanoparticle size on high surface area supports.

PubMed

Liu, Qiuli; Joshi, Upendra A; Über, Kevin; Regalbuto, John R

2014-12-28

Supported Ru and Pt nanoparticles are synthesized by the method of strong electrostatic adsorption and subsequently treated under different steaming-reduction conditions to achieve a series of catalysts with controlled particle sizes, ranging from 1 to 8 nm. While in the case of oxidation-reduction conditions, only Pt yielded particles ranging from 2.5 to 8 nm in size and a loss of Ru was observed. Both Ru and Pt sinter faster in air than in hydrogen. This methodology allows the control of particle size using a "production-scalable" catalyst synthesis method which can be applied to high surface area supports with common metal precursors.

Systematic study on the discharge product of Pt-based lithium oxygen batteries

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

Wu, Feng; Xing, Yi; Bi, Xuanxuan

Lithium oxygen batteries have attracted much attention due to the high theoretical energy density. However, they suffer a large overpotential during oxygen evolution process and thus catalysts play a vital role in the reaction. Here, we systematically explored the influence of Pt-based nanoparticle catalysts on the discharge product Li 2O 2. Because of the superior electrical conductivity and the strong binding with oxygen, Pt-based nanoparticles serve as active sites which are favorable for the growth of toroidal Li 2O 2. We also found that the content and composition of Pt-based nanoparticle catalysts exert a significant influence on the electrochemical performancemore » of lithium oxygen batteries. The discharge products are composed of crystalline Li 2O 2 and oxygen-rich LiO 2 characterized by high-energy X-ray diffraction and Raman. Atomic force microscopy further provides detailed information of the particle size and surface roughness. The loading of Pt catalysts determines the phase and size of Li 2O 2 on the discharged electrode surface. This study will be beneficial for the optimization of Pt-based catalysts used in non-aqueous lithium oxygen batteries.« less

Systematic study on the discharge product of Pt-based lithium oxygen batteries

NASA Astrophysics Data System (ADS)

Wu, Feng; Xing, Yi; Bi, Xuanxuan; Yuan, Yifei; Wang, Hsien-Hau; Shahbazian-Yassar, Reza; Li, Li; Chen, Renjie; Lu, Jun; Amine, Khalil

2016-11-01

Lithium oxygen batteries have attracted much attention due to the high theoretical energy density. However, they suffer a large overpotential during oxygen evolution process and thus catalysts play a vital role in the reaction. Here, we systematically explored the influence of Pt-based nanoparticle catalysts on the discharge product Li2O2. Because of the superior electrical conductivity and the strong binding with oxygen, Pt-based nanoparticles serve as active sites which are favorable for the growth of toroidal Li2O2. We also found that the content and composition of Pt-based nanoparticle catalysts exert a significant influence on the electrochemical performance of lithium oxygen batteries. The discharge products are composed of crystalline Li2O2 and oxygen-rich LiO2 characterized by high-energy X-ray diffraction and Raman. Atomic force microscopy further provides detailed information of the particle size and surface roughness. The loading of Pt catalysts determines the phase and size of Li2O2 on the discharged electrode surface. This study will be beneficial for the optimization of Pt-based catalysts used in non-aqueous lithium oxygen batteries.

Facile Fabrication of Platinum-Cobalt Alloy Nanoparticles with Enhanced Electrocatalytic Activity for a Methanol Oxidation Reaction

NASA Astrophysics Data System (ADS)

Huang, Huihong; Hu, Xiulan; Zhang, Jianbo; Su, Nan; Cheng, Jiexu

2017-03-01

Decreasing the cost associated with platinum-based catalysts along with improving their catalytic properties is a major challenge for commercial direct methanol fuel cells. In this work, a simple and facile strategy was developed for the more efficient preparation of multi-walled carbon nanotube (MWCNT) -supported Pt/CoPt composite nanoparticles (NPs) via solution plasma sputtering with subsequent thermal annealing. Quite different from general wet synthesis methods, Pt/CoPt composite NPs were directly derived from metal wire electrodes without any additions. The obtained Pt/CoPt/MWCNTs composite catalysts exhibited tremendous improvement in the electro-oxidation of methanol in acidic media with mass activities of 1719 mA mg-1Pt. This value is much higher than that of previous reports of Pt-Co alloy and commercial Pt/C (3.16 times) because of the many active sites and clean surface of the catalysts. The catalysts showed good stability due to the special synergistic effects of the CoPt alloy. Pt/CoPt/MWCNTs can be used as a promising catalyst for direct methanol fuel cells. In addition, this solution plasma sputtering-assisted synthesis method introduces a general and feasible route for the synthesis of binary alloys.

Facile Fabrication of Platinum-Cobalt Alloy Nanoparticles with Enhanced Electrocatalytic Activity for a Methanol Oxidation Reaction.

PubMed

Huang, Huihong; Hu, Xiulan; Zhang, Jianbo; Su, Nan; Cheng, JieXu

2017-03-30

Decreasing the cost associated with platinum-based catalysts along with improving their catalytic properties is a major challenge for commercial direct methanol fuel cells. In this work, a simple and facile strategy was developed for the more efficient preparation of multi-walled carbon nanotube (MWCNT) -supported Pt/CoPt composite nanoparticles (NPs) via solution plasma sputtering with subsequent thermal annealing. Quite different from general wet synthesis methods, Pt/CoPt composite NPs were directly derived from metal wire electrodes without any additions. The obtained Pt/CoPt/MWCNTs composite catalysts exhibited tremendous improvement in the electro-oxidation of methanol in acidic media with mass activities of 1719 mA mg -1 Pt . This value is much higher than that of previous reports of Pt-Co alloy and commercial Pt/C (3.16 times) because of the many active sites and clean surface of the catalysts. The catalysts showed good stability due to the special synergistic effects of the CoPt alloy. Pt/CoPt/MWCNTs can be used as a promising catalyst for direct methanol fuel cells. In addition, this solution plasma sputtering-assisted synthesis method introduces a general and feasible route for the synthesis of binary alloys.

A novel binary Pt 3Te x/C nanocatalyst for ethanol electro-oxidation

NASA Astrophysics Data System (ADS)

Huang, Meihua; Wang, Fei; Li, Lirong; Guo, Yonglang

The Pt 3Te x/C nanocatalyst was prepared and its catalytic performance for ethanol oxidation was investigated for the first time. The Pt 3Te/C nanoparticles were characterized by an X-ray diffractometer (XRD), transmission electron microscope (TEM) and energy dispersive X-ray spectroscopy equipped with TEM (TEM-EDX). The Pt 3Te/C catalyst has a typical fcc structure of platinum alloys with the presence of Te. Its particle size is about 2.8 nm. Among the synthesized catalysts with different atomic ratios, the Pt 3Te/C catalyst has the highest anodic peak current density. The cyclic voltammograms (CV) show that the anodic peak current density for the Pt 3Te/C, commercial PtRu/C and Pt/C catalysts reaches 1002, 832 and 533 A g -1, respectively. On the current-time curve, the anodic current on the Pt 3Te/C catalyst was higher than those for the catalysts reported. So, these findings show that the Pt 3Te/C catalyst has uniform nanoparticles and the best activity among the synthesized catalysts, and it is better than commercial PtRu/C and Pt/C catalysts for ethanol oxidation at room temperature.

Detecting decompositions of sulfur hexafluoride using reduced graphene oxide decorated with Pt nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Dachang; Tang, Ju; Zhang, Xiaoxing; Fang, Jiani; Li, Yi; Zhuo, Ran

2018-05-01

The resistance-typed gas sensing material of Pt nanoparticles (PtNPs) decorated reduced graphene oxide (RGO) synthesized by one-step chemical reduction for the detection of four types of SF6 decompositions was explored. The PtNPs disperse uniformly on RGO with particle size near 2–4 nm and a small number of particles are larger than 10 nm. Gas sensing tests suggest that the introduction of PtNPs increases the response to SO2, SOF2 and H2S compared to pure RGO and PtNPs-RGO experiences resistance reducing in SO2 and SOF2 while presenting the opposite case in H2S. Elevating the temperature enhances the recovery properties to SO2 and H2S but lowers the sensitivity. The sensing mechanism for Pt-RGO in low oxygen and water environment depends mainly on the charge transfer between gas and adsorbent and the solvent on material surface. The work provides experimental investigation of Pt-RGO to detect SF6 decompositions.

Facile one-pot synthesis of platinum nanoparticles decorated nitrogen-graphene with high electrocatalytic performance for oxygen reduction and anodic fuels oxidation

NASA Astrophysics Data System (ADS)

Navaee, Aso; Salimi, Abdollah; Soltanian, Saeid; Servati, Peyman

2015-03-01

Due to exceptional electronic properties of graphene (Gr) and nitrogen doped graphene (N-Gr), they are considered as superior supporting platforms for novel metal nanoparticle decorations. Here, we report, a novel one-step electrochemical method for synthesis of Nitrogen-doped graphene sheets uniformly decorated with platinum nanoparticles (Pt/N-Gr). A graphite rod and platinum wire are respectively used for graphene and platinum nanoparticles production. The potential is cycled from -3V to +3V in acetonitrile solution as a nitrogen dopant source. By increasing the number of cycles the nitrogen-doped graphene/platinum nanoparticles composite is generated. After heat-treating the composite is characterized with various techniques such as FTIR, Raman, XPS, SEM and TEM. The electrocatalytic activity of the prepared composite toward the reduction of O2 and the oxidation of usual anodic fuels such as methanol, ethanol, hydrazine and formic acid is investigated using cyclic voltammetry technique. In comparison to commercial platinum/carbon, the onset potentials and the current densities for both O2 reduction and fuels oxidation are remarkably improved. Furthermore, the modified electrode by this composite shows good long-term stability and poisoning tolerance.

Platinum nanoparticles: the crucial role of crystal face and colloid stabilizer in the diastereoselective hydrogenation of cinchonidine.

PubMed

Schmidt, Erik; Kleist, Wolfgang; Krumeich, Frank; Mallat, Tamas; Baiker, Alfons

2010-02-15

The preparation of stable metal nanoparticles requires a strong interaction between the (organic) stabilizer and the metal surface that might alter the catalytic properties. This behavior has been described as "poisoning" since the stabilizer normally decreases the catalytic activity due to site blocking. Here we show a striking influence of the stabilizer on the selectivity in the hydrogenation of cinchonidine (CD) over poly(acrylic acid) (PAA)-stabilized Pt nanoparticles with well-defined shape distributions. In the hydrogenation of the heteroaromatic ring of cinchonidine in toluene, the diastereomeric excess of the (S)-hexahydrocinchonidine increased upon increasing Pt{111}/Pt{100} ratio, but this distinct shape selectivity was observed only after the oxidative removal of PAA at 473 K. The use of the as-prepared nanoparticles inverted the major diastereomer to R, and this isomer was formed also in acetic acid. This striking change in the diastereoselectivity indicates that poly(acrylic acid), which remains on the Pt surface after preparation, interacts with CD during hydrogenation almost as strongly as the solvent acetic acid. The PAA stabilizer plays a dual role: it allows one to control the size and shape of the nanoparticles during their synthesis, and it affects the rate and diastereoselectivity of the hydrogenation of CD probably through a "surface-localized acidification".

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 Pt 3Y and Other Early–Late Intermetallic Nanoparticles by Way of a Molten Reducing Agent

DOE PAGES

Kanady, Jacob S.; Leidinger, Peter; Haas, Andreas; ...

2017-03-29

Early–late intermetallic phases have garnered increased attention recently for their catalytic properties. To achieve the high surface areas needed for industrially relevant applications, these phases must be synthesized as nanoparticles in a scalable fashion. Herein, Pt 3Y—targeted as a prototypical example of an early–late intermetallic—has been synthesized as nanoparticles approximately 5–20 nm in diameter via a solution process and characterized by XRD, TEM, EDS, and XPS. The key development is the use of a molten borohydride (MEt 3BH, M = Na, K) as both the reducing agent and reaction medium. Readily available halide precursors of the two metals are used.more » Accordingly, no organic ligands are necessary, as the resulting halide salt byproduct prevents sintering, which further permits dispersion of the nanoscale intermetallic onto a support. The versatility of this approach was validated by the synthesis of other intermetallic phases such as Pt 3Sc, Pt 3Lu, Pt 2Na, and Au 2Y.« less

Synthesis of Pt 3Y and Other Early–Late Intermetallic Nanoparticles by Way of a Molten Reducing Agent

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

Kanady, Jacob S.; Leidinger, Peter; Haas, Andreas

Early–late intermetallic phases have garnered increased attention recently for their catalytic properties. To achieve the high surface areas needed for industrially relevant applications, these phases must be synthesized as nanoparticles in a scalable fashion. Herein, Pt 3Y—targeted as a prototypical example of an early–late intermetallic—has been synthesized as nanoparticles approximately 5–20 nm in diameter via a solution process and characterized by XRD, TEM, EDS, and XPS. The key development is the use of a molten borohydride (MEt 3BH, M = Na, K) as both the reducing agent and reaction medium. Readily available halide precursors of the two metals are used.more » Accordingly, no organic ligands are necessary, as the resulting halide salt byproduct prevents sintering, which further permits dispersion of the nanoscale intermetallic onto a support. The versatility of this approach was validated by the synthesis of other intermetallic phases such as Pt 3Sc, Pt 3Lu, Pt 2Na, and Au 2Y.« less

Effects of Au content on the structure and magnetic properties of L1{sub 0}-FePt nanoparticles synthesized by the sol–gel method

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

Liu, Yang; Institute of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013; Jiang, Yuhong

2014-07-01

(FePt){sub 100−x}Au{sub x} (x=0, 5, 10, and 20) nanoparticles were synthesized by the sol–gel method, and effects of Au content on the structural and magnetic properties of samples were investigated. Au doping reduced the phase transition temperature from face-centered cubic (FCC) to face-centered tetragonal (FCT) structure. In addition, additive Au promotes the chemical ordering of L1{sub 0} FePt NPs and increases the grain size of L1{sub 0} FePt NPs. When Au content increased from 0 to 10 at%, the coercivity (H{sub c}) increased due to the increase in degree of ordering S and grain size of L1{sub 0} FePt NPs.more » By increasing the Au content to 20 at%, H{sub c} decreased. - Graphical abstract: (FePt){sub 100}Au{sub 0} NPs are the coexistence of FCT and FCC phases. However, no hints of FCC phase were found for the (FePt){sub 100−x}Au{sub x} NPs (x=5, 10 and 20), which indicates that addition of gold greatly promotes the FCC to FCT phase transition. - Highlights: • (FePt){sub 100−x}Au{sub x} (x=0, 5, 10 and 20) nanoparticles (NPs) were synthesized. • Au addition promotes the chemical ordering of L1{sub 0} FePt NPs. • Au addition reduces ordering temperature of L1{sub 0} FePt NPs from FCC to FCT phase. • (FePt){sub 90}Au{sub 10} NPs show a high coercivity of 9585 Oe at room temperature.« less

Impact of ultra-low Pt loadings on the performance of anode/cathode in a proton-exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Billy, E.; Maillard, F.; Morin, A.; Guetaz, L.; Emieux, F.; Thurier, C.; Doppelt, P.; Donet, S.; Mailley, S.

This study focuses on the elaboration of PEMFC electrodes containing ultra-low platinum (Pt) loadings by direct liquid injection metal organic chemical vapor deposition (DLI-MOCVD). DLI-MOCVD offers a large number of advantages for the elaboration of model PEMFC electrodes. First, by using different metal precursors or elaboration temperature, the size of the Pt nanoparticles and thus the intrinsic catalytic activity can easily be tailored in the nanometer range. In this work, Pt nanoparticles (1-5 nm) with remarkable low degree of agglomeration and uniform distribution were deposited onto the microporous side of a commercial gas-diffusion layer (GDL). Second, reduction of the Pt loading is made possible by varying the Pt deposition time and its influence of the cell performance can be extracted without variation of the thickness of the catalytic layer (in previous studies, a decrease of the catalyst utilization was observed when increasing the Pt loading, i.e. the thickness of the catalytic layer (CL)). The electrocatalytic activity of home-made Pt nanoparticles elaborated by DLI-MOCVD was measured in liquid electrolyte or in complete fuel cell operating on H 2/O 2 or H 2/air and compared vs. that of a commercially available electrode containing 500 μg Pt cm -2 (Pt Ref500). At the cathode, the performance of the electrodes containing 104-226 μg of Pt per cm 2 of electrode compares favorably with that of the Pt Ref500 in H 2/O 2 conditions. In H 2/air conditions, additional mass-transport losses are detected in the low-current density region but the high effectiveness of our electrodes improves the performance in the high-current density region. At the anode, the Pt loading can be reduced to 35 μg Pt cm -2 without any voltage loss in agreement with previous observations.

Seed-mediated synthesis of cross-linked Pt-NiO nanochains for methanol oxidation

NASA Astrophysics Data System (ADS)

Gu, Zhulan; Bin, Duan; Feng, Yue; Zhang, Ke; Wang, Jin; Yan, Bo; Li, Shumin; Xiong, Zhiping; Wang, Caiqin; Shiraishi, Yukihide; Du, Yukou

2017-07-01

A simple method was reported for employing NiO nanoparticles act as seeds and then different amounts of Pt2+ were reduced on the NiO nanoparticles, forming a cross-linked Pt-NiO nanocatalysts. These as-prepared catalysts were characterized using different physical-chemical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the morphology of the cross-linked Pt-NiO nanochain was successfully produced regardless of the molar ratio of Pt2+ to NiO precursors. The electrochemical characteristics of Pt-NiO nanochain catalysts were evaluated for the oxidation of methanol as a model reaction, which verify that the Pt-NiO catalysts show enhanced activity and high stability in comparison with the commercial Pt/C catalyst. The optimized ratio of Pt to NiO is 1:1, then tuned by simple adjusting the feed ratio of the precursors as well. The synthesized nanocatalysts will be found the great potential applications as electrocatalysts for fuel cells owe to their enhanced catalytic performance and long-term 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

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

Boosting hot electron flux and catalytic activity at metal-oxide interfaces of PtCo bimetallic nanoparticles.

PubMed

Lee, Hyosun; Lim, Juhyung; Lee, Changhwan; Back, Seoin; An, Kwangjin; Shin, Jae Won; Ryoo, Ryong; Jung, Yousung; Park, Jeong Young

2018-06-08

Despite numerous studies, the origin of the enhanced catalytic performance of bimetallic nanoparticles (NPs) remains elusive because of the ever-changing surface structures, compositions, and oxidation states of NPs under reaction conditions. An effective strategy for obtaining critical clues for the phenomenon is real-time quantitative detection of hot electrons induced by a chemical reaction on the catalysts. Here, we investigate hot electrons excited on PtCo bimetallic NPs during H 2 oxidation by measuring the chemicurrent on a catalytic nanodiode while changing the Pt composition of the NPs. We reveal that the presence of a CoO/Pt interface enables efficient transport of electrons and higher catalytic activity for PtCo NPs. These results are consistent with theoretical calculations suggesting that lower activation energy and higher exothermicity are required for the reaction at the CoO/Pt interface.

Platinum nanoparticles reduce ovariectomy-induced bone loss by decreasing osteoclastogenesis

PubMed Central

Kim, Woon-Ki; Kim, Jin-Chun; Park, Hyun-Jung; Sul, Ok-Joo; Lee, Mi-Hyun; Kim, Ji-Soon

2012-01-01

Platinum nanoparticles (PtNP) exhibit remarkable antioxidant activity. There is growing evidence concerning a positive relationship between oxidative stress and bone loss, suggesting that PtNP could protect against bone loss by modulating oxidative stress. Intragastric administration of PtNP reduced ovariectomy (OVX)-induced bone loss with a decreased level of activity and number of osteoclast (OC) in vivo. PtNP inhibited OC formation by impairing the receptor activator of nuclear factor-κB ligand (RANKL) signaling. This impairment was due to a decreased activation of nuclear factor-κB and a reduced level of nuclear factor in activated T-cells, cytoplasmic 1 (NFAT2). PtNP lowered RANKL-induced long lasting reactive oxygen species as well as intracellular concentrations of Ca2+ oscillation. Our data clearly highlight the potential of PtNP for the amelioration of bone loss after estrogen deficiency by attenuated OC formation. PMID:22525805

The effect of platinum precursor concentrations on chlorine sensing characteristics of platinum nanoparticles-loaded single walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Choi, Sun-Woo; Byun, Young Tae

2018-03-01

The correlation between platinum (Pt) functionalization and chlorine (Cl2) sensing capability in single-walled carbon nanotubes (SWCNTs) was investigated. Utilizing a photoreduction technique via ultraviolet (UV) irradiation, the Pt nanoparticles (NPs) with various diameters of 7-80 nm, which were controlled by Pt precursor concentrations, were successfully functionalized on the sidewalls of SWCNTs. The discrete Pt NP-loaded SWCNTs exhibited significantly enhanced response value (-(ΔR/R0) × 100 = 33.8%) for 1 ppm Cl2 at room temperature (25 °C) compared with that (no response) of pure SWCNTs. On the other hand, in case of continuous Pt NP-loaded SWCNTs, Cl2 sensing capabilities were significantly degraded. The Cl2 sensing capabilities of fabricated sensors tended to correlate with geometric configurations of the catalytic Pt NPs on the sidewalls of SWCNTs, due to differences in the electron pathway.

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

Parallel fabrication of sub-50-nm uniformly sized nanoparticles by deposition through a patterned silicon nitride nanostencil.

PubMed

Yan, X-M; Contreras, A M; Koebel, M M; Liddle, J A; Somorjai, G A

2005-06-01

Using low-pressure chemical vapor deposition of silicon dioxide, we have reduced the size of 56-nm features in a silicon nitride membrane, called a stencil, down to 36 nm. Sub-50-nm uniformly sized nanoparticles are fabricated by electron-beam deposition of Pt through the stencil mask. A self-assembled monolayer (SAM) of tridecafluoro-1,1,2,2-tetrahydrooctyl-1-trichlorosilane was used to reduce Pt clogging of the nanosize holes during deposition as well as to protect the stencil during the postdeposition Pt removal. X-ray photoelectron spectroscopy shows that the SAM protects the stencil efficiently during this postdeposition removal of Pt.

Effect of Pt Nanoparticles on the Photocatalytic Activity of ZnO Nanofibers

NASA Astrophysics Data System (ADS)

Di Mauro, Alessandro; Zimbone, Massimo; Scuderi, Mario; Nicotra, Giuseppe; Fragalà, Maria Elena; Impellizzeri, Giuliana

2015-12-01

For this study, we originally realized ZnO nanofibers (˜50 nm in mean radius) mixed with Pt nanoparticles (˜30 nm in mean radius), prepared by pulsed laser ablation in liquid, and investigated their photocatalytic performance. The material was synthesized by the simple electrospinning method coupled with subsequent thermal treatments. Methylene blue was employed as a representative dye pollutant to evaluate the photocatalytic activity of the nanofibers. It was found that the Pt-ZnO fibers exhibit a photodegradation reaction rate that is ˜40 % higher than the one obtained for reference ZnO fibers. These encouraging results demonstrate that Pt-ZnO nanofibers can be fruitfully applied for environmental applications.

Metallic nanoparticle-based strain sensors elaborated by atomic layer deposition

NASA Astrophysics Data System (ADS)

Puyoo, E.; Malhaire, C.; Thomas, D.; Rafaël, R.; R'Mili, M.; Malchère, A.; Roiban, L.; Koneti, S.; Bugnet, M.; Sabac, A.; Le Berre, M.

2017-03-01

Platinum nanoparticle-based strain gauges are elaborated by means of atomic layer deposition on flexible polyimide substrates. Their electro-mechanical response is tested under mechanical bending in both buckling and conformational contact configurations. A maximum gauge factor of 70 is reached at a strain level of 0.5%. Although the exponential dependence of the gauge resistance on strain is attributed to the tunneling effect, it is shown that the majority of the junctions between adjacent Pt nanoparticles are in a short circuit state. Finally, we demonstrate the feasibility of an all-plastic pressure sensor integrating Pt nanoparticle-based strain gauges in a Wheatstone bridge configuration.

In Situ Generation of Pd-Pt Core-Shell Nanoparticles on Reduced Graphene Oxide (Pd@Pt/rGO) Using Microwaves: Applications in Dehalogenation Reactions and Reduction of Olefins.

PubMed

Goswami, Anandarup; Rathi, Anuj K; Aparicio, Claudia; Tomanec, Ondrej; Petr, Martin; Pocklanova, Radka; Gawande, Manoj B; Varma, Rajender S; Zboril, Radek

2017-01-25

Core-shell nanocatalysts are a distinctive class of nanomaterials with varied potential applications in view of their unique structure, composition-dependent physicochemical properties, and promising synergism among the individual components. A one-pot microwave (MW)-assisted approach is described to prepare the reduced graphene oxide (rGO)-supported Pd-Pt core-shell nanoparticles, (Pd@Pt/rGO); spherical core-shell nanomaterials (∼95 nm) with Pd core (∼80 nm) and 15 nm Pt shell were nicely distributed on the rGO matrix in view of the choice of reductant and reaction conditions. The well-characterized composite nanomaterials, endowed with synergism among its components and rGO support, served as catalysts in aromatic dehalogenation reactions and for the reduction of olefins with high yield (>98%), excellent selectivity (>98%) and recyclability (up to 5 times); both Pt/rGO and Pd/rGO and even their physical mixtures showed considerably lower conversions (20 and 57%) in dehalogenation of 3-bromoaniline. Similarly, in the reduction of styrene to ethylbenzene, Pd@Pt core-shell nanoparticles (without rGO support) possess considerably lower conversion (60%) compared to Pd@Pt/rGO. The mechanism of dehalogenation reactions with Pd@Pt/rGO catalyst is discussed with the explicit premise that rGO matrix facilitates the adsorption of the reducing agent, thus enhancing its local concentration and expediting the hydrazine decomposition rate. The versatility of the catalyst has been validated via diverse substrate scope for both reduction and dehalogenation reactions.

An aptamer-based colorimetric Pt(II) assay based on the use of gold nanoparticles and a cationic polymer.

PubMed

Sang, Fuming; Liu, Jia; Zhang, Xue; Pan, Jianxin

2018-04-25

A colorimetric method is described for the determination of Pt(II). It is based on the use of gold nanoparticles (AuNPs) which are known to aggregate in the presence of a cationic polymer such as poly(diallyldimethylammonium chloride) (PDDA). If, however, a mismatched aptamer (AA) electrostatically binds to PDDA, aggregation is prevented. Upon the addition of Pt(II), it will bind to the aptamer and induce the formation of a hairpin structure. Hence, interaction between aptamer and PDDA is suppressed and PDDA will induce the aggregation of the AuNPs. This is accompanied by a color change from red to blue. The effect can be observed with bare eyes and quantified by colorimetry via measurement of the ratio of absorbances at 610 nm and 520 nm. Response is linear in the 0.24-2 μM Pt(II) concentration range, and the detection limit is 58 nM. The assay is completed within 15 min and selective for Pt(II) even in the presence of other metal ions. It was successfully applied to the rapid determination of Pt(II) in spiked soil samples. Graphical abstract Schematic representation of the method for detection of Pt(II) based on the use of a cationic polymer and gold nanoparticles. In the presence of Pt(II), aptamer interacts with the Pt(II) and prevents the interaction between aptamer and cationic polymer. Hence, cationic polymer induce the aggregation of the AuNPs and lead to the color change from red to blue.

In situ glass antifouling using Pt nanoparticle coating for periodic electrolysis of seawater

NASA Astrophysics Data System (ADS)

Xue, Yuxi; Zhao, Jin; Qiu, Ri; Zheng, Jiyong; Lin, Cunguo; Ma, Bojiang; Wang, Peng

2015-12-01

In situ electrochemical chlorination is a promising way to prohibit the biofouling on glass used for optical devices in seawater. To make this approach practical, a conductive glass should have low overpotential to generate Cl2, so that the electrical energy consumption, a critical issue for field application, will be low. Moreover, a long sustainability should also be taken into consideration from the application perspective. Following these criteria, we propose Pt/ITO surface to electrochemically generate Cl2, which immunizes biofouling for glass substrate. In this report, firstly, Pt nanoparticle/ITO is prepared via an electrodeposition approach. Secondly, electrocatalysis capability of Pt/ITO is elucidated, which shows the catalysis for Cl2 generation from NaCl solution and seawater has been sparked with Pt on the surface. Also, Pt/ITO is more sustainable and efficient than the bare ITO in natural seawater. Thirdly, the antifouling property is evaluated taking diatom as the target organism. Electrochemical chlorination on Pt/ITO can efficiently prevent the glass from fouling.

Boosting Photocatalytic Hydrogen Production of a Metal-Organic Framework Decorated with Platinum Nanoparticles: The Platinum Location Matters.

PubMed

Xiao, Juan-Ding; Shang, Qichao; Xiong, Yujie; Zhang, Qun; Luo, Yi; Yu, Shu-Hong; Jiang, Hai-Long

2016-08-01

Improving the efficiency of electron-hole separation and charge-carrier utilization plays a central role in photocatalysis. Herein, Pt nanoparticles of ca. 3 nm are incorporated inside or supported on a representative metal-organic framework (MOF), UiO-66-NH2 , denoted as Pt@UiO-66-NH2 and Pt/UiO-66-NH2 , respectively, for photocatalytic hydrogen production via water splitting. Compared with the pristine MOF, both Pt-decorated MOF nanocomposites exhibit significantly improved yet distinctly different hydrogen-production activities, highlighting that the photocatalytic efficiency strongly correlates with the Pt location relative to the MOF. The Pt@UiO-66-NH2 greatly shortens the electron-transport distance, which favors the electron-hole separation and thereby yields much higher efficiency than Pt/UiO-66-NH2 . The involved mechanism has been further unveiled by means of ultrafast transient absorption and photoluminescence spectroscopy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Growing Platinum-Ruthenium-Tin ternary alloy nanoparticles on reduced graphene oxide for strong ligand effect toward enhanced ethanol oxidation reaction.

PubMed

Xia, Qing Qing; Zhang, Lian Ying; Zhao, Zhi Liang; Li, Chang Ming

2017-11-15

Uniform Pt 1 Ru 0.5 Sn 0.5 ternary alloy nanoparticles are in situ deposited on reduced graphene oxide (Pt 1 Ru 0.5 Sn 0.5 -RGO) through its functional groups and defects as nucleation sites to greatly electrocatalyze ethanol oxidation reaction for much higher mass current densities, larger apparent specific current densities and better stability than commercial Pt-C catalyst (Pt-C(commer)). Mechanistic studies indicate that the excellent electrocatalytic activity and anti-poisoning are resulted from a strong ligand effect of the ternary alloy components, in which the charge transfer is boosted while decreasing the density of states close to the Fermi level of Pt to reduce bond energy between Pt and CO-like adsorbates for greatly improved anti-poisoning ability. This work holds a great promise to fabricate a high performance anode catalyst with a low Pt loading for direct ethanol fuel cells. Copyright © 2017. Published by Elsevier Inc.

Enhanced electrocatalytic activity of the Au-electrodeposited Pt nanoparticles-coated conducting oxide for the quantum dot-sensitized solar cells

NASA Astrophysics Data System (ADS)

Yoon, Yeung-Pil; Kim, Jae-Hong; Kang, Soon-Hyung; Kim, Hyunsoo; Choi, Chel-Jong; Kim, Kyong-Kook; Ahn, Kwang-Soon

2014-08-01

Au was electrodeposited potentiostatically at 0.3 V for 5 min on nanoporous Pt nanoparticle-coated F-doped SnO2 (FTO/Pt) substrates. For comparison, Au-electrodeposited FTO (FTO/Au) and Au-uncoated FTO/Pt were prepared. FTO/Au showed large-sized Au clusters dispersed sparsely over FTO, which resulted in lower electrocatalytic activity than FTO/Pt. In contrast, FTO/Pt exhibited poor stability unlike FTO/Au due to poisoning by the adsorption of sulfur species. The Au-electrodeposited FTO/Pt (FTO/Pt/Au) consisted of small Au clusters deposited over the entire area of Pt due to the effective Au nucleation provided by nanoporous metallic Pt. FTO/Pt/Au exhibited enhanced electrocatalytic activity and excellent stability because the small Au particles well-dispersed over the nanoporous metallic Pt network provided numerous electrochemical reaction sites, and the Pt surface was not exposed to the electrolyte. When FTO/Pt/Au was used as the counter electrode (CE) of a quantum dot-sensitized solar cell, the significantly enhanced electrocatalytic activity of the FTO/Pt/Au CE facilitated the reduction reaction of Sn2- + 2e- (CE) → Sn-12- + S2- at the CE/electrolyte interface, resulting in a significantly hindered recombination reaction, Sn2- + 2e- (TiO2 in the photoanode) → Sn-12- + S2-, and significantly improved overall energy conversion efficiency.

The Effect of deposition rate on FePt/MgO crystal orientation

NASA Astrophysics Data System (ADS)

Sheikhi, M.; Sebt, S. A.; Khajehnezhad, A.

2018-06-01

FePt granular layers which are made in suitable conditions can have three types of ordering that are crystalline, compositional orders and directional configuration of nanoparticles. Formation of fct structure with L10 compositional ordering requires high temperature. At this temperature, a problem is the size control of the nanoparticles and another problem is control of their crystal orientation. Fabrication method and the use of suitable substrates can help solving these problems. In direct synthesis by sputtering method on the warm substrate the size of FePt nanoparticles in L10 compositional ordered phase can be controlled. We show that crystal orientation of L10-FePt nanoparticles on a thin layer of MgO depends on the rate of deposition. This becomes clear from the results of the XRD analyses of samples. Based on these results in synthesis at room temperature with deposition rate of upper than 1.5 Å/s after annealing, (001) peak is dominated and at rate of lower than 1.0 Å/s just (111) peak is appeared. In direct synthesis with intermediate rate (111) and (110) peaks can be seen. Moreover, the difference of the shape of hysteresis loops of samples in parallel and vertical directions are the witnesses for orientation of samples in presence of MgO layer and the effect of FePt deposition rate on it.

Tungsten carbide/porous carbon composite as superior support for platinum catalyst toward methanol electro-oxidation

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

Jiang, Liming; Fu, Honggang, E-mail: fuhg@vip.sina.com; Key Laboratory of Functional Inorganic Material Chemistry, Heilongjiang University, Harbin 150080

2014-01-01

Graphical abstract: The WC nanoparticles are well dispersed in the carbon matrix. The size of WC nanoparticles is about 30 nm. It can be concluded that tungsten carbide and carbon composite was successfully prepared by the present synthesis conditions. - Highlights: • The WC/PC composite with high specific surface area was prepared by a simple way. • The Pt/WC/PC catalyst has superior performance toward methanol electro-oxidation. • The current density for methanol electro-oxidation is as high as 595.93 A g{sup −1} Pt. • The Pt/WC/PC catalyst shows better durability and stronger CO electro-oxidation. • The performance of Pt/WC/PC is superiormore » to the commercial Pt/C (JM) catalyst. - Abstract: Tungsten carbide/porous carbon (WC/PC) composites have been successfully synthesized through a surfactant assisted evaporation-induced-assembly method, followed by a thermal treatment process. In particular, WC/PC-35-1000 composite with tungsten content of 35% synthesized at the carbonized temperature of 1000 °C, exhibited a specific surface area (S{sub BET}) of 457.92 m{sup 2} g{sup −1}. After loading Pt nanoparticles (NPs), the obtained Pt/WC/PC-35-1000 catalyst exhibits the highest unit mass electroactivity (595.93 A g{sup −1} Pt) toward methanol electro-oxidation, which is about 2.6 times as that of the commercial Pt/C (JM) catalyst. Furthermore, the Pt/WC/PC-35-1000 catalyst displays much stronger resistance to CO poisoning and better durability toward methanol electrooxidation compared with the commercial Pt/C (JM) catalyst. The high electrocatalytic activity, strong poison-resistivity and good stability of Pt/WC/PC-35-1000 catalyst are attributed to the porous structures and high specific surface area of WC/PC support could facilitate the rapid mass transportation. Moreover, synergistic effect between WC and Pt NPs is favorable to the higher catalytic performance.« less

Highly monodisperse multiple twinned AuCu-Pt trimetallic nanoparticles with high index surfaces.

PubMed

Khanal, Subarna; Bhattarai, Nabraj; McMaster, David; Bahena, Daniel; Velazquez-Salazar, J Jesus; Jose-Yacaman, Miguel

2014-08-14

Trimetallic nanoparticles possess different properties than their mono- and bi-metallic counterparts, opening a wide range of possibilities for diverse potential applications with the notion to study possible morphology, atomic ordering, reduce precious metal consumption and many others. In this paper, we present a comprehensive experimental study on AuCu-Pt trimetallic nanoparticles with an average diameter of 15 ± 1.0 nm, synthesized in a one-pot synthesis method and characterized by the Cs-corrected scanning transmission electron microscopy technique that allowed us to probe the structure at the atomic level resolution. A new way to control the nanoparticle morphology by the presence of third metal (Pt) is also discussed by the overgrowth of Pt on the as prepared AuCu core by Frank-van der Merwe (FM) layer-by-layer and Stranski-Krastanov (SK) island-on-wetting-layer growth modes. With the application of this research, we are now a step closer to produce optimum catalysts in which the active phase forms only surface monolayers. In addition, the nanoalloy exhibits high index facet surfaces with {211} and {321} families that are highly open-structure surfaces and are interesting for the catalytic applications.

Highly Monodisperse Multiple Twinned AuCu/Pt Trimetallic Nanoparticles with High Index Surfaces

PubMed Central

Khanal, Subarna; Bhattarai, Nabraj; McMaster, David; Bahena, Daniel; Velazquez-Salazar, J. Jesus

2014-01-01

Trimetallic nanoparticles present different properties than their mono- and bi-metallic counterparts, opening a wide range of possibilities for diverse potential applications with the notion to study possible morphology, atomic ordering, reduce precious metal consumption and many others. In this paper, we are presenting a comprehensive experimental study on AuCu/Pt trimetallic nanoparticles with an average diameter 15 ± 1.0 nm, synthesized in one-pot synthesis method and characterized by Cs-corrected scanning transmission electron microscopy technique that allowed us to probe the structure at the atomic level resolution. A new way to control the nanoparticle morphology by the presence of third metal (Pt) is also discussed by the overgrowth of Pt on as prepared AuCu core by Frank–van der Merwe (FM) layer-by-layer and Stranski–Krastanov (SK) island-on-wetting-layer growth modes. With the application of this research, we are now a step closer to produce optimum catalysts in which the active phase forms only surface monolayers. In addition, the nanoalloy presents high index facet surfaces with {211} and {321} families, that are highly open-structure surfaces and are interesting for the catalytic applications. PMID:24975090

Fe-based magnetic nanomaterials: Wet chemical synthesis, magnetic properties and exploration on applications

NASA Astrophysics Data System (ADS)

Xiaoliang, Hong

Even though the start of research based on Fe-based magnetic nanomaterials could be dated back to hundreds years ago, the considerably large amount of emerging fields for their applications, including spintronic structures in information storage, biomedical and environmental applications, magnetic sensors, magnetic energy harvesters, has spurred renewed interest on the application-related properties of Fe-based nanomaterial in both the nanoparticle and film forms. Besides, an exploration of a simple, wide, effective technique that can be used for growth of high-quality Fe-based magnetic nanoparticles and films is of great importance for better materialization of these potential Fe-based devices. This thesis mainly focuses on fabricating different magnetic Fe-based materials (ferrites and ferrous alloys, nanoparticle and film) with wet chemical method, investigating their growth mechanism and magnetic and electrical properties. In addition, the possible applications of as-fabricated Fe-based nanoparticles and films are studied. The contribution of the work is summarized as below: (1) Investigation indicated that the external magnetic field plays an important role in determining the microstructure, magnetic properties of the Fe3O4 nanoparticles. The magnetic field can promote the change of Fe3O4 nanocuboctahedrons to nanocubes. Compared the hyperthermia property of as-fabricated nanocuboctahedrons and nanocubes Fe3O4, the intrinsic loss power (ILP) of the Fe3O4 nanocubes was much higher than that of nanocuboctahedrons due to the surface magnetic effect. (2) A general and facile method for broadly deposition of thick Fe 3O4 film and other ferrites has been demonstrated. It had been found that the epitaxial high-quality Fe3O4 film could be deposited either on MgO substrates directly or Si substrates with Fe3O4 seed layer deposited by PLD. As-deposited Fe 3O4 film could be easily patterned and shows potential applications for microwave and MEMS supercapacitor. Besides Fe3O4, different ferrite compounds have been successfully fabricated, including Co-ferrite with high coercivity and perpendicular anisotropy, and Ni-ferrite with high resistivity and enhanced magnetization. (3) A typical Fe-3d alloy, FeCo, was studied in our work. Monodispersed FeCo nanoparticles were synthesized by a safe and ecofriendly facile chemical process. The FeCo nanoparticles have saturation magnetization up to 187 emu/g and shows excellent chemical stability. In addition, the control Fe/Co ratio could be achieved by change of precursor ratio and tuning of particle size could be realized through change of surfactant amount used. The cytotoxicity of as-synthesized nanoparticles was investigated after transferring the nanoparticle to water phase by the emulsion process and the results demonstrated high biocompatibility. The results showed that this method could also fabricate spherical Fe 3O4 particles and self-assembly Co nanoneedles. With the similar method that was applied to deposit Fe3O4, bcc-FeCo film could be fabricated through thermal decomposition with the saturation magnetization around 1300 emu/cc. (4) Fe-5d alloy, FePt, was investigated in both nanoparticle and film form. fcc-Fe76Pt24 nanoparticles were synthesized by thermal decomposition. TEM image showed the particle size was around 15 nm. From in-plane hysteresis loop, the coercivity of samples was about 150 Oe. The presence of nonzero value for the coercivity suggests that some amount of ordering should be present in fcc- Fe76Pt24 nanoparticles. In addition, fcc and L10-FePt films had been deposited on Pt substrate via a combination of chemical deposition and post-annealing process. Pt-doped Fe films were deposited on Pt substrate using thermal deposition and the as-deposited films were subsequently annealed from 300°C to 800°C, FePt films were achieved through diffusion and rearrangement of Fe and Pt atoms in post-annealing process. The transformation from disordering fcc to ordering L10 phase had been observed from X-ray diffraction results. The L10-FePt film possessed an out-of-plane anisotropy and a coercivity of 9 kOe after annealing at 600°C. A further increase in annealing temperature led to lower value of coercivity, probably due to grain growth. In addition, the thickness of Pt-doped Fe films was tunable by adjusting amount of surfactant used. Our SQUID analysis showed that Pt dopant could significantly improve the chemical stability of Fe films in air.

Three dimensional graphene foam supported platinum-ruthenium bimetallic nanocatalysts for direct methanol and direct ethanol fuel cell applications

NASA Astrophysics Data System (ADS)

Kung, Chih-Chien; Lin, Po-Yuan; Xue, Yuhua; Akolkar, Rohan; Dai, Liming; Yu, Xiong; Liu, Chung-Chiun

2014-06-01

A novel composite material of hierarchically structured platinum-ruthenium (PtRu) nanoparticles grown on large surface area three dimensional graphene foam (3D GF) is reported. 3D GF was incorporated with PtRu bimetallic nanoparticles as an electrochemical nanocatalyst for methanol and ethanol oxidation. PtRu/3D GF nanocatalyst showed a higher tolerance to poisoning by CO and exhibited improved catalytic activity for both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). Cyclic voltammetry (CV) results and long-term cycling stability tests demonstrated that GF provided a promising platform for the development of electrochemical nanocatalysts. Specifically, PtRu/3D GF nanocatalyst showed excellent catalytic activity toward MOR and EOR compared with PtRu/Graphene (Commercial graphene), PtRu/C (Vulcan XC-72R carbon), and PtRu alone. The crystal size of PtRu on 3D GF was reduced to 3.5 nm and its active surface area was enhanced to 186.2 m2 g-1. Consequently, the MOR and EOR rates were nearly doubled on PtRu/3D GF compared to those on PtRu/Graphene.

Photoelectrocatalytic reduction of CO2 into chemicals using Pt-modified reduced graphene oxide combined with Pt-modified TiO2 nanotubes.

PubMed

Cheng, Jun; Zhang, Meng; Wu, Gai; Wang, Xin; Zhou, Junhu; Cen, Kefa

2014-06-17

The photoelectrocatalytic (PEC) reduction of CO2 into high-value chemicals is beneficial in alleviating global warming and advancing a low-carbon economy. In this work, Pt-modified reduced graphene oxide (Pt-RGO) and Pt-modified TiO2 nanotubes (Pt-TNT) were combined as cathode and photoanode catalysts, respectively, to form a PEC reactor for converting CO2 into valuable chemicals. XRD, XPS, TEM, AFM, and SEM were employed to characterize the microstructures of the Pt-RGO and Pt-TNT catalysts. Reduction products, such as C2H5OH and CH3COOH, were obtained from CO2 under band gap illumination and biased voltage. A combined liquid product generation rate (CH3OH, C2H5OH, HCOOH, and CH3COOH) of approximately 600 nmol/(h·cm(2)) was observed. Carbon atom conversion rate reached 1,130 nmol/(h·cm(2)), which were much higher than those achieved using Pt-modified carbon nanotubes and platinum carbon as cathode catalysts.

Dynamics of Transformation from Platinum Icosahedral Nanoparticles to Larger FCC Crystal at Millisecond Time Resolution

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

Gao, Wenpei; Wu, Jianbo; Yoon, Aram

Atomic motion at grain boundaries is essential to microstructure development, growth and stability of catalysts and other nanostructured materials. However, boundary atomic motion is often too fast to observe in a conventional transmission electron microscope (TEM) and too slow for ultrafast electron microscopy. We report on the entire transformation process of strained Pt icosahedral nanoparticles (ICNPs) into larger FCC crystals, captured at 2.5 ms time resolution using a fast electron camera. Results show slow diffusive dislocation motion at nm/s inside ICNPs and fast surface transformation at μm/s. By characterizing nanoparticle strain, we show that the fast transformation is driven bymore » inhomogeneous surface stress. And interaction with pre-existing defects led to the slowdown of the transformation front inside the nanoparticles. Particle coalescence, assisted by oxygen-induced surface migration at T ≥ 300°C, also played a critical role. Thus by studying transformation in the Pt ICNPs at high time and spatial resolution, we obtain critical insights into the transformation mechanisms in strained Pt nanoparticles.« less

Photoacoustically-guided photothermal killing of mosquitoes targeted by nanoparticles.

PubMed

Foster, Stephen R; Galanzha, Ekaterina I; Totten, Daniel C; Beneš, Helen; Shmookler Reis, Robert J; Zharov, Vladimir P

2014-07-01

In biomedical applications, nanoparticles have demonstrated the potential to eradicate abnormal cells in small localized pathological zones associated with cancer or infections. Here, we introduce a method for nanotechnology-based photothermal (PT) killing of whole organisms considered harmful to humans or the environment. We demonstrate that laser-induced thermal, and accompanying nano- and microbubble phenomena, can injure or kill C. elegans and mosquitoes fed carbon nanotubes, gold nanospheres, gold nanoshells, or magnetic nanoparticles at laser energies that are safe for humans. In addition, a photoacoustic (PA) effect was used to control nanoparticle delivery. Through the integration of this technique with molecular targeting, nanoparticle clustering, magnetic capturing and spectral sharpening of PA and PT plasmonic resonances, our laser-based PA-PT nano-theranostic platform can be applied to detection and the physical destruction of small organisms and carriers of pathogens, such as malaria vectors, spiders, bed bugs, fleas, ants, locusts, grasshoppers, phytophagous mites, or other arthropod pests, irrespective of their resistance to conventional treatments. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancement of the electrooxidation of ethanol on Pt-Sn-P/C catalysts prepared by chemical deposition process

NASA Astrophysics Data System (ADS)

Xue, Xinzhong; Ge, Junjie; Tian, Tian; Liu, Changpeng; Xing, Wei; Lu, Tianhong

In this paper, five Pt 3Sn 1/C catalysts have been prepared using three different methods. It was found that phosphorus deposited on the surface of carbon with Pt and Sn when sodium hypophosphite was used as reducing agent by optimization of synthetic conditions such as pH in the synthetic solution and temperature. The deposition of phosphorus should be effective on the size reduction and markedly reduces PtSn nanoparticle size, and raise electrochemical active surface (EAS) area of catalyst and improve the catalytic performance. TEM images show PtSnP nanoparticles are highly dispersed on the carbon surface with average diameters of 2 nm. The optimum composition is Pt 3Sn 1P 2/C (note PtSn/C-3) catalyst in my work. With this composition, it shows very high activity for the electrooxidation of ethanol and exhibit enhanced performance compared with other two Pt 3Sn 1/C catalysts that prepared using ethylene glycol reduction method (note PtSn/C-EG) and borohydride reduction method (note PtSn/-B). The maximum power densities of direct ethanol fuel cell (DEFC) were 61 mW cm -2 that is 150 and 170% higher than that of the PtSn/C-EG and PtSn/C-B catalyst.

Facile Fabrication of Platinum-Cobalt Alloy Nanoparticles with Enhanced Electrocatalytic Activity for a Methanol Oxidation Reaction

PubMed Central

Huang, Huihong; Hu, Xiulan; Zhang, Jianbo; Su, Nan; Cheng, JieXu

2017-01-01

Decreasing the cost associated with platinum-based catalysts along with improving their catalytic properties is a major challenge for commercial direct methanol fuel cells. In this work, a simple and facile strategy was developed for the more efficient preparation of multi-walled carbon nanotube (MWCNT) -supported Pt/CoPt composite nanoparticles (NPs) via solution plasma sputtering with subsequent thermal annealing. Quite different from general wet synthesis methods, Pt/CoPt composite NPs were directly derived from metal wire electrodes without any additions. The obtained Pt/CoPt/MWCNTs composite catalysts exhibited tremendous improvement in the electro-oxidation of methanol in acidic media with mass activities of 1719 mA mg−1Pt. This value is much higher than that of previous reports of Pt-Co alloy and commercial Pt/C (3.16 times) because of the many active sites and clean surface of the catalysts. The catalysts showed good stability due to the special synergistic effects of the CoPt alloy. Pt/CoPt/MWCNTs can be used as a promising catalyst for direct methanol fuel cells. In addition, this solution plasma sputtering-assisted synthesis method introduces a general and feasible route for the synthesis of binary alloys. PMID:28358143

Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen

NASA Astrophysics Data System (ADS)

Shan, Junjun; Lucci, Felicia R.; Liu, Jilei; El-Soda, Mostafa; Marcinkowski, Matthew D.; Allard, Lawrence F.; Sykes, E. Charles H.; Flytzani-Stephanopoulos, Maria

2016-08-01

The non-oxidative dehydrogenation of methanol to formaldehyde is considered a promising method to produce formaldehyde and clean hydrogen gas. Although Cu-based catalysts have an excellent catalytic activity in the oxidative dehydrogenation of methanol, metallic Cu is commonly believed to be unreactive for the dehydrogenation of methanol in the absence of oxygen adatoms or oxidized copper. Herein we show that metallic Cu can catalyze the dehydrogenation of methanol in the absence of oxygen adatoms by using water as a co-catalyst both under realistic reaction conditions using silica-supported PtCu nanoparticles in a flow reactor system at temperatures below 250 °C, and in ultra-high vacuum using model PtCu(111) catalysts. Adding small amounts of isolated Pt atoms into the Cu surface to form PtCu single atom alloys (SAAs) greatly enhances the dehydrogenation activity of Cu. Under the same reaction conditions, the yields of formaldehyde from PtCu SAA nanoparticles are more than one order of magnitude higher than on the Cu nanoparticles, indicating a significant promotional effect of individual, isolated Pt atoms. Moreover, this study also shows the unexpected role of water in the activation of methanol. Water, a catalyst for methanol dehydrogenation at low temperatures, becomes a reactant in the methanol steam reforming reactions only at higher temperatures over the same metal catalyst.

Combining protein-shelled platinum nanoparticles with graphene to build a bionanohybrid capacitor.

PubMed

San, Boi Hoa; Kim, Jang Ah; Kulkarni, Atul; Moh, Sang Hyun; Dugasani, Sreekantha Reddy; Subramani, Vinod Kumar; Thorat, Nanasaheb D; Lee, Hyun Ho; Park, Sung Ha; Kim, Taesung; Kim, Kyeong Kyu

2014-12-23

The electronic properties of biomolecules and their hybrids with inorganic materials can be utilized for the fabrication of nanoelectronic devices. Here, we report the charge transport behavior of protein-shelled inorganic nanoparticles combined with graphene and demonstrate their possible application as a bionanohybrid capacitor. The conductivity of PepA, a bacterial aminopeptidase used as a protein shell (PS), and the platinum nanoparticles (PtNPs) encapsulated by PepA was measured using a field effect transistor (FET) and a graphene-based FET (GFET). Furthermore, we confirmed that the electronic properties of PepA-PtNPs were controlled by varying the size of the PtNPs. The use of two poly(methyl methacrylate) (PMMA)-coated graphene layers separated by PepA-PtNPs enabled us to build a bionanohybrid capacitor with tunable properties. The combination of bioinorganic nanohybrids with graphene is regarded as the cornerstone for developing flexible and biocompatible bionanoelectronic devices that can be integrated into bioelectric circuits for biomedical purposes.

Heterogeneous hydrogenation using stable and reusable calix[4]pyrrole fenced Pt nanoparticles and its mechanistic insight

NASA Astrophysics Data System (ADS)

Kongor, Anita; Panchal, Manthan; Athar, Mohd; Mehta, Viren; Bhatt, Keyur; Jha, P. C.; Jain, Vinod

2018-04-01

Novel calix[4]pyrrole encapsulated platinum nanoparticles (PtNPs) have been prepared in the aqueous medium using meso-tetra(methoxy) meso-tetra (4-phenoxy acetohydrazide) calix[4]pyrrole (MCPTH) as both reducing as well as the capping agent. The developed MCPTH-PtNPs nano-assembly has been characterized by HRTEM, XRD, XPS, TGA and FTIR methods. Grafting capability of MCPTH on PtNPs was envisaged by molecular dynamics simulations that renders towards the complemented role of ligand in capping the surface via metal-acceptor interactions. These nanoparticles have been exploited for chemoselective hydrogenation of nitroarenes using molecular hydrogen at room temperature. Supplemented computational and experimental apprehension clearly corroborates that hydrazide group remains in close contact with the surface and provides adequate coordination sites for the adsorption of nitrenes; required for hydrogenation. This catalytic approach can be conceived as an important tool for determining the electronic and structural influence on the catalytic activity which may open new vistas pertaining to the use of calix functionalized nanocatalyst.

CuPt and CuPtRu Nanostructures for Ammonia Oxidation Reaction

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

Manso, R H.; Song, L.; Liang, Z.

Liquid fuels, such as methanol, ethanol, and ammonia, are attractive alternative to hydrogen for fuel cells due to their lower costs for storage and distribution. However, lack of sufficiently active catalysts for their oxidation reactions is a roadblock. Our previous study found that Pt 3Cu nanodendrites yielded higher activity and durability than Pt nanoparticles for methanol oxidation reaction (MOR) in acid. In this study, we synthesized two types of nanostructures of CuPt and CuPtRu catalysts via seed-mediated growth of Pt and Ru on Cu and tested their performance for ammonia oxidation reaction (AOR) in alkaline solution. Unlike for MOR, themore » nanodendrites do not promote AOR activity - CuPt performs similar to Pt and CuPtRu is less active than Pt. Interestingly, the AOR peak current is increased by 64% on CuPt nanowires and 330% on CuPtRu nanowires as compared to Pt nanoparticles. These results suggest that AOR prefers extended surface on long nanowires, distinctly differing from MOR. This can be contributed to two factors: NH 3 oxidization to N 2 involves dimerization of two N-containing intermediates to form the N-N bond and diffusion batters for adsorbed intermediates are generally lower on terrace than at low-coordination sites. This demonstrated strong effect of surface morphology will be further studied and utilized in developing advanced AOR nanocatalysts.« less

Au-Pt alloy nanoparticles obtained by nanosecond laser irradiation of gold and platinum bulk targets in an ethylene glycol solution

NASA Astrophysics Data System (ADS)

Moniri, Samira; Reza Hantehzadeh, Mohammad; Ghoranneviss, Mahmood; Asadi Asadabad, Mohsen

2017-07-01

Au-Pt alloy nanoparticles (NPs) of different compositions ( Au0Pt100 , Au30Pt70 , Au50Pt50 , Au70Pt30 , and Au100Pt0 were obtained using the nanosecond laser ablation of gold and platinum bulk targets in ethylene glycol, followed by mixing highly monodisperse Au and Pt nanocolloids, for the first time. UV-vis absorption spectra of NPs showed that by increasing the Au content in the Au-Pt NPs, the surface plasmon resonance (SPR) peak red-shifted, from 260 to 573nm in a nonlinear way. In addition, the mean crystalline size, crystal structure, d-spacing, and lattice parameters of NPs were estimated from the XRD spectra. Microscopy studies revealed the most NPs have a spherical or near-spherical shape, and the average sizes of Au0Pt100 , Au30Pt70 , Au50Pt50 , Au70Pt30 , and Au100Pt0 NPs were calculated to be 12.50, 14.15, 18.53, 19.29, and 26.38nm, respectively. Also, the chemical identity of the molecules adhering to the NPs surface was considered by Raman and FT-IR spectroscopy techniques. Among different synthesis methods, the demonstrated technique allows easy synthesis of alloy NPs in aqueous media at room temperature with no formation of by-products.

CuPt and CuPtRu Nanostructures for Ammonia Oxidation Reaction

DOE PAGES

Manso, R H.; Song, L.; Liang, Z.; ...

2018-04-01

Liquid fuels, such as methanol, ethanol, and ammonia, are attractive alternative to hydrogen for fuel cells due to their lower costs for storage and distribution. However, lack of sufficiently active catalysts for their oxidation reactions is a roadblock. Our previous study found that Pt 3Cu nanodendrites yielded higher activity and durability than Pt nanoparticles for methanol oxidation reaction (MOR) in acid. In this study, we synthesized two types of nanostructures of CuPt and CuPtRu catalysts via seed-mediated growth of Pt and Ru on Cu and tested their performance for ammonia oxidation reaction (AOR) in alkaline solution. Unlike for MOR, themore » nanodendrites do not promote AOR activity - CuPt performs similar to Pt and CuPtRu is less active than Pt. Interestingly, the AOR peak current is increased by 64% on CuPt nanowires and 330% on CuPtRu nanowires as compared to Pt nanoparticles. These results suggest that AOR prefers extended surface on long nanowires, distinctly differing from MOR. This can be contributed to two factors: NH 3 oxidization to N 2 involves dimerization of two N-containing intermediates to form the N-N bond and diffusion batters for adsorbed intermediates are generally lower on terrace than at low-coordination sites. This demonstrated strong effect of surface morphology will be further studied and utilized in developing advanced AOR nanocatalysts.« less

Nitrogen-doped hierarchical lamellar porous carbon synthesized from the fish scale as support material for platinum nanoparticle electrocatalyst toward the oxygen reduction reaction.

PubMed

Liu, Haijing; Cao, Yinliang; Wang, Feng; Huang, Yaqin

2014-01-22

Novel hierarchical lamellar porous carbon (HLPC) with high BET specific surface area of 2730 m(2) g(-1) and doped by nitrogen atoms has been synthesized from the fish scale without any post-synthesis treatment, and applied to support the platinum (Pt) nanoparticle (NP) catalysts (Pt/HLPC). The Pt NPs could be highly dispersed on the porous surface of HLPC with a narrow size distribution centered at ca. 2.0 nm. The results of the electrochemical analysis reveal that the electrochemical active surface area (ECSA) of Pt/HLPC is larger than the Pt NP electrocatalyst supported on the carbon black (Pt/Vulcan XC-72). Compared with the Pt/Vulcan XC-72, the Pt/HLPC exhibits larger current density, lower overpotential, and enhanced catalytic activity toward the oxygen reduction reaction (ORR) through the direct four-electron pathway. The improved catalytic activity is mainly attributed to the high BET specific surface area, hierarchical porous structures and the nitrogen-doped surface property of HLPC, indicating the superiority of HLPC as a promising support material for the ORR electrocatalysts.

A label-free colorimetric aptasensor for simple, sensitive and selective detection of Pt (II) based on platinum (II)-oligonucleotide coordination induced gold nanoparticles aggregation.

PubMed

Fan, Daoqing; Zhai, Qingfeng; Zhou, Weijun; Zhu, Xiaoqing; Wang, Erkang; Dong, Shaojun

2016-11-15

Herein, a gold nanoparticles (AuNPs) based label-free colorimetric aptasensor for simple, sensitive and selective detection of Pt (II) was constructed for the first time. Four bases (G-G mismatch) mismatched streptavidin aptamer (MSAA) was used to protect AuNPs from salt-induced aggregation and recognize Pt (II) specifically. Only in the presence of Pt (II), coordination occurs between G-G bases and Pt (II), leading to the activation of streptavidin aptamer. Streptavidin coated magnetic beads (MBs) were used as separation agent to separate Pt (II)-coordinated MSAA. The residual less amount of MSAA could not efficiently protect AuNPs anymore and aggregation of AuNPs will produce a colorimetric product. With the addition of Pt (II), a pale purple-to-blue color variation could be observed by the naked eye. A detection limit of 150nM and a linear range from 0.6μM to 12.5μM for Pt (II) could be achieved without any amplification. Copyright © 2016 Elsevier B.V. All rights reserved.

Screening reactive oxygen species scavenging properties of platinum nanoparticles on a microfluidic chip.

PubMed

Zheng, Wenfu; Jiang, Bo; Hao, Yi; Zhao, Yuyun; Zhang, Wei; Jiang, Xingyu

2014-09-12

Hyperglycemia, hyperlipidemia and inflammation are key risk factors for atherosclerosis and can lead to overproduction of reactive oxygen species (ROS), which plays a critical role in vascular endothelial dysfunction and subsequent progress of atherosclerosis. However, there is currently a lack of effective drugs that deal with ROS. Platinum nanoparticles (Pt-NPs) have proven to be promising antioxidant drugs in vitro and in vivo. To optimize the efficacy of Pt-NP based drugs, we synthesized and characterized the ROS scavenging properties of three kinds of small molecules that capped Pt-NPs (Pt-AMP-NPs, Pt-ATT-NPs, Pt-MI-NPs) on a blood vessel-mimicking microfluidic chip. The Pt-NPs showed superior superoxide dismutase (SOD)-like functions and can scavenge ROS and recover compromised cell-cell junctions under hyperglycemic, hyperlipidemic and proinflammatory conditions. Amongst these NPs, Pt-AMP-NPs showed the most superior antioxidant properties, suggesting its potency to serve as a novel drug to treat vascular diseases such as atherosclerosis. Our microfluidic chip, providing physiological hemodynamic conditions for the experiments, is potentially a promising tool for a wide range of biological research on the vascular system.

Behavior of oxidized platinum nanoparticles on an aligned carbon nanotube forest

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

Matsuda, Keita, E-mail: matsuda.keita@c.mbox.nagoya-u.ac.jp; Norimatsu, Wataru; Arai, Shigeo

2016-10-14

We observed and analyzed the behavior of platinum nanoparticles (PtNPs) supported on aligned-carbon nanotubes (CNTs) at high temperatures by X-ray photoelectron spectroscopy and high-resolution transmission electron microscope observations. We found that the PtNPs moved toward the inner-side along each CNT on which they were deposited. The mechanism of this behavior is related to the redox reaction of Pt with the carbon atoms in the CNT. We also performed in-situ observation of this process at a high temperature using an environmental transmission electron microscope under an oxygen atmosphere. We found that the PtNPs penetrated down into a high-density aligned CNT forestmore » along the tube axis and that the PtNPs changed their shape to fit the structure of the CNTs during their movement.« less

Identification of a Catalytically Highly Active Surface Phase for CO Oxidation over PtRh Nanoparticles under Operando Reaction Conditions

NASA Astrophysics Data System (ADS)

Hejral, U.; Franz, D.; Volkov, S.; Francoual, S.; Strempfer, J.; Stierle, A.

2018-03-01

Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with in situ mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

NASA Astrophysics Data System (ADS)

Kim, Minjoong; Kwon, Chorong; Eom, Kwangsup; Kim, Jihyun; Cho, Eunae

2017-03-01

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2.

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability.

PubMed

Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

2017-03-14

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO 2 (Nb-TiO 2 ) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO 2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb 0.25 Ti 0.75 O 2 ). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO 2 -nanofibers (Pt/Nb-TiO 2 ) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO 2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO 2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO 2 nanofiber catalyst can be attributed to high corrosion resistance of TiO 2 and strong interaction between Pt and TiO 2 .

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

PubMed Central

Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

2017-01-01

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2. PMID:28290503

A Multimethod Approach for Investigating Algal Toxicity of Platinum Nanoparticles.

PubMed

Sørensen, Sara N; Engelbrekt, Christian; Lützhøft, Hans-Christian H; Jiménez-Lamana, Javier; Noori, Jafar S; Alatraktchi, Fatima A; Delgado, Cristina G; Slaveykova, Vera I; Baun, Anders

2016-10-04

The ecotoxicity of platinum nanoparticles (PtNPs) widely used in for example automotive catalytic converters, is largely unknown. This study employs various characterization techniques and toxicity end points to investigate PtNP toxicity toward the green microalgae Pseudokirchneriella subcapitata and Chlamydomonas reinhardtii. Growth rate inhibition occurred in standard ISO tests (EC 50 values of 15-200 mg Pt/L), but also in a double-vial setup, separating cells from PtNPs, thus demonstrating shading as an important artifact for PtNP toxicity. Negligible membrane damage, but substantial oxidative stress was detected at 0.1-80 mg Pt/L in both algal species using flow cytometry. PtNPs caused growth rate inhibition and oxidative stress in P. subcapitata, beyond what was accounted for by dissolved Pt, indicating NP-specific toxicity of PtNPs. Overall, P. subcapitata was found to be more sensitive toward PtNPs and higher body burdens were measured in this species, possibly due to a favored binding of Pt to the polysaccharide-rich cell wall of this algal species. This study highlights the importance of using multimethod approaches in nanoecotoxicological studies to elucidate toxicity mechanisms, influence of NP-interactions with media/organisms, and ultimately to identify artifacts and appropriate end points for NP-ecotoxicity testing.

Photothermal Nanotherapeutics and Nanodiagnostics for Selective Killing of Bacteria Targeted with Gold Nanoparticles

PubMed Central

Zharov, Vladimir P.; Mercer, Kelly E.; Galitovskaya, Elena N.; Smeltzer, Mark S.

2006-01-01

We describe a new method for selective laser killing of bacteria targeted with light-absorbing gold nanoparticles conjugated with specific antibodies. The multifunctional photothermal (PT) microscope/spectrometer provides a real-time assessment of this new therapeutic intervention. In this integrated system, strong laser-induced overheating effects accompanied by the bubble-formation phenomena around clustered gold nanoparticles are the main cause of bacterial damage. PT imaging and time-resolved monitoring of the integrated PT responses assessed these effects. Specifically, we used this technology for selective killing of the Gram-positive bacterium Staphylococcus aureus by targeting the bacterial surface using 10-, 20-, and 40-nm gold particles conjugated with anti-protein A antibodies. Labeled bacteria were irradiated with focused laser pulses (420–570 nm, 12 ns, 0.1–5 J/cm2, 100 pulses), and laser-induced bacterial damage observed at different laser fluences and nanoparticle sizes was verified by optical transmission, electron microscopy, and conventional viability testing. PMID:16239330

Surface science approach to Pt/carbon model catalysts: XPS, STM and microreactor studies

NASA Astrophysics Data System (ADS)

Motin, Abdul Md.; Haunold, Thomas; Bukhtiyarov, Andrey V.; Bera, Abhijit; Rameshan, Christoph; Rupprechter, Günther

2018-05-01

Pt nanoparticles supported on carbon are an important technological catalyst. A corresponding model catalyst was prepared by physical vapor deposition (PVD) of Pt on sputtered HOPG (highly oriented pyrolytic graphite). The carbon substrate before and after sputtering as well as the Pt/HOPG system before and after Pt deposition and annealing were examined by XPS and STM. This yielded information on the surface density of defects, which serve as nucleation centres for Pt, and on the size distribution (mean size/height) of the Pt nanoparticles. Two different model catalysts were prepared with mean sizes of 2.0 and 3.6 nm, both turned out to be stable upon UHV-annealing to 300 °C. After transfer into a UHV-compatible flow microreactor and subsequent cleaning in UHV and under mbar pressure, the catalytic activity of the Pt/HOPG model system for ethylene hydrogenation was examined under atmospheric pressure flow conditions. This enabled to determine temperature-dependent conversion rates, turnover frequencies (TOFs) and activation energies. The catalytic results obtained are in line with the characteristics of technological Pt/C, demonstrating the validity of the current surface science based model catalyst approach.

Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

2016-02-01

In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells.

PubMed

Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

2016-02-15

In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

PtRu nanoparticles embedded in nitrogen doped carbon with highly stable CO tolerance and durability

NASA Astrophysics Data System (ADS)

Ling, Ying; Yang, Zehui; Yang, Jun; Zhang, Yunfeng; Zhang, Quan; Yu, Xinxin; Cai, Weiwei

2018-02-01

As is well known, the lower durability and sluggish methanol oxidation reaction (MOR) of PtRu alloy electrocatalyst blocks the commercialization of direct methanol fuel cells (DMFCs). Here, we design a new PtRu electrocatalyst, with highly stable CO tolerance and durability, in which the PtRu nanoparticles are embedded in nitrogen doped carbon layers derived from carbonization of poly(vinyl pyrrolidone). The newly fabricated electrocatalyst exhibits no loss in electrochemical surface area (ECSA) and MOR activity after potential cycling from 0.6-1.0 V versus reversible hydrogen electrode, while commercial CB/PtRu retains only 50% of its initial ECSA. Meanwhile, due to the same protective layers, the Ru dissolution is decelerated, resulting in stable CO tolerance. Methanol oxidation reaction (MOR) testing indicates that the activity of newly fabricated electrocatalyst is two times higher than that of commercial CB/PtRu, and the fuel cell performance of the embedded PtRu electrocatalyst was comparable to that of commercial CB/PtRu. The embedded PtRu electrocatalyst is applicable in real DMFC operation. This study offers important and useful information for the design and fabrication of durable and CO tolerant electrocatalysts.

Self-deposition of Pt nanoparticles on graphene woven fabrics for enhanced hybrid Schottky junctions and photoelectrochemical solar cells.

PubMed

Kang, Zhe; Tan, Xinyu; Li, Xiao; Xiao, Ting; Zhang, Li; Lao, Junchao; Li, Xinming; Cheng, Shan; Xie, Dan; Zhu, Hongwei

2016-01-21

In this study, we demonstrated a self-deposition method to deposit Pt nanoparticles (NPs) on graphene woven fabrics (GWF) to improve the performance of graphene-on-silicon solar cells. The deposition of Pt NPs increased the work function of GWF and reduced the sheet resistance of GWF, thereby improving the power conversion efficiency (PCE) of graphene-on-silicon solar cells. The PCE (>10%) was further enhanced via solid electrolyte coating of the hybrid Schottky junction in the photoelectrochemical solar cells. These results suggest that the combination of self-deposition of Pt NPs and solid-state electrolyte coating of graphene-on-silicon is a promising way to produce high performance graphene-on-semiconductor solar cells.

Polymersomes from dual responsive block copolymers: drug encapsulation by heating and acid-triggered release.

PubMed

Qiao, Zeng-Ying; Ji, Ran; Huang, Xiao-Nan; Du, Fu-Sheng; Zhang, Rui; Liang, De-Hai; Li, Zi-Chen

2013-05-13

A series of well-defined thermoresponsive diblock copolymers (PEO45-b-PtNEAn, n=22, 44, 63, 91, 172) were prepared by the atom transfer radical polymerization of trans-N-(2-ethoxy-1,3-dioxan-5-yl) acrylamide (tNEA) using a poly(ethylene oxide) (PEO45) macroinitiator. All copolymers are water-soluble at low temperature, but upon quickly heating to 37 °C, laser light scattering (LLS) and transmission electron microscopy (TEM) characterizations indicate that these copolymers self-assemble into aggregates with different morphologies depending on the chain length of PtNEA and the polymer concentration; the morphologies gradually evolved from spherical solid nanoparticles to a polymersome as the degree of polymerization ("n") of PtNEA block increased from 22 to 172, with the formation of clusters with rod-like structure at the intermediate PtNEA length. Both the spherical nanoparticle and the polymersome are stable at physiological pH but susceptible to the mildly acidic medium. Acid-triggered hydrolysis behaviors of the aggregates were investigated by LLS, Nile red fluorescence, TEM, and (1)H NMR spectroscopy. The results revealed that the spherical nanoparticles formed from PEO45-b-PtNEA44 dissociated faster than the polymersomes of PEO45-b-PtNEA172, and both aggregates showed an enhanced hydrolysis under acidic conditions. Both the spherical nanoparticle and polymersome are able to efficiently load the hydrophobic doxorubicin (DOX), and water-soluble fluorescein isothiocyanate-lysozyme (FITC-Lys) can be conveniently encapsulated into the polymersome without using any organic solvent. Moreover, FITC-Lys and DOX could be coloaded in the polymersome. The drugs loaded either in the polymersome or in the spherical nanoparticle could be released by acid triggering. Finally, the DOX-loaded assemblies display concentration-dependent cytotoxicity to HepG2 cells, while the copolymers themselves are nontoxic.

Platinum Nanocatalyst Amplification: Redefining the Gold Standard for Lateral Flow Immunoassays with Ultrabroad Dynamic Range

PubMed Central

2017-01-01

Paper-based lateral flow immunoassays (LFIAs) are one of the most widely used point-of-care (PoC) devices; however, their application in early disease diagnostics is often limited due to insufficient sensitivity for the requisite sample sizes and the short time frames of PoC testing. To address this, we developed a serum-stable, nanoparticle catalyst-labeled LFIA with a sensitivity surpassing that of both current commercial and published sensitivities for paper-based detection of p24, one of the earliest and most conserved biomarkers of HIV. We report the synthesis and characterization of porous platinum core–shell nanocatalysts (PtNCs), which show high catalytic activity when exposed to complex human blood serum samples. We explored the application of antibody-functionalized PtNCs with strategically and orthogonally modified nanobodies with high affinity and specificity toward p24 and established the key larger nanoparticle size regimes needed for efficient amplification and performance in LFIA. Harnessing the catalytic amplification of PtNCs enabled naked-eye detection of p24 spiked into sera in the low femtomolar range (ca. 0.8 pg·mL–1) and the detection of acute-phase HIV in clinical human plasma samples in under 20 min. This provides a versatile absorbance-based and rapid LFIA with sensitivity capable of significantly reducing the HIV acute phase detection window. This diagnostic may be readily adapted for detection of other biomolecules as an ultrasensitive screening tool for infectious and noncommunicable diseases and can be capitalized upon in PoC settings for early disease detection. PMID:29215864

Slowing of Femtosecond Laser-Generated Nanoparticles in a Background Gas

DOE PAGES

Rouleau, Christopher M.; Puretzky, Alexander A.; Geohegan, David B.

2014-11-25

The slowing of Pt nanoparticles in argon background gas was characterized by Rayleigh scattering imaging using a plume of nanoparticles generated by femtosecond laser through thin film ablation (fs-TTFA) of 20 nanometers-thick Pt films. The ablation was performed at threshold laser energy fluences for complete film removal to provide a well-defined plume consisting almost entirely of nanoparticles traveling with a narrow velocity distribution, providing a unique system to unambiguously characterize the slowing of nanoparticles during interaction with background gases. Nanoparticles of ~200 nm diameter were found to decelerate in background Ar gas with pressures less than 50 Torr in goodmore » agreement with a linear drag model in the Epstein regime. Based on this model, the stopping distance of small nanoparticles in the plume was predicted and tested by particle collection in an off-axis geometry, and size distribution analysis by transmission electron microscopy. These results permit a basis to interpret nanoparticle propagation through background gases in laser ablation plumes that contain mixed components.« less

Platinum nanoparticles induce damage to DNA and inhibit DNA replication

PubMed Central

Nejdl, Lukas; Kudr, Jiri; Moulick, Amitava; Hegerova, Dagmar; Ruttkay-Nedecky, Branislav; Gumulec, Jaromir; Cihalova, Kristyna; Smerkova, Kristyna; Dostalova, Simona; Krizkova, Sona; Novotna, Marie; Kopel, Pavel

2017-01-01

Sparsely tested group of platinum nanoparticles (PtNPs) may have a comparable effect as complex platinum compounds. The aim of this study was to observe the effect of PtNPs in in vitro amplification of DNA fragment of phage λ, on the bacterial cultures (Staphylococcus aureus), human foreskin fibroblasts and erythrocytes. In vitro synthesized PtNPs were characterized by dynamic light scattering (PtNPs size range 4.8–11.7 nm), zeta potential measurements (-15 mV at pH 7.4), X-ray fluorescence, UV/vis spectrophotometry and atomic absorption spectrometry. The PtNPs inhibited the DNA replication and affected the secondary structure of DNA at higher concentrations, which was confirmed by polymerase chain reaction, DNA sequencing and DNA denaturation experiments. Further, cisplatin (CisPt), as traditional chemotherapy agent, was used in all parallel experiments. Moreover, the encapsulation of PtNPs in liposomes (LipoPtNPs) caused an approximately 2.4x higher of DNA damage in comparison with CisPt, LipoCisPt and PtNPs. The encapsulation of PtNPs in liposomes also increased their antibacterial, cytostatic and cytotoxic effect, which was determined by the method of growth curves on S. aureus and HFF cells. In addition, both the bare and encapsulated PtNPs caused lower oxidative stress (determined by GSH/GSSG ratio) in the human erythrocytes compared to the bare and encapsulated CisPt. CisPt was used in all parallel experiments as traditional chemotherapy agent. PMID:28704436

Platinum nanoparticles induce damage to DNA and inhibit DNA replication.

PubMed

Nejdl, Lukas; Kudr, Jiri; Moulick, Amitava; Hegerova, Dagmar; Ruttkay-Nedecky, Branislav; Gumulec, Jaromir; Cihalova, Kristyna; Smerkova, Kristyna; Dostalova, Simona; Krizkova, Sona; Novotna, Marie; Kopel, Pavel; Adam, Vojtech

2017-01-01

Sparsely tested group of platinum nanoparticles (PtNPs) may have a comparable effect as complex platinum compounds. The aim of this study was to observe the effect of PtNPs in in vitro amplification of DNA fragment of phage λ, on the bacterial cultures (Staphylococcus aureus), human foreskin fibroblasts and erythrocytes. In vitro synthesized PtNPs were characterized by dynamic light scattering (PtNPs size range 4.8-11.7 nm), zeta potential measurements (-15 mV at pH 7.4), X-ray fluorescence, UV/vis spectrophotometry and atomic absorption spectrometry. The PtNPs inhibited the DNA replication and affected the secondary structure of DNA at higher concentrations, which was confirmed by polymerase chain reaction, DNA sequencing and DNA denaturation experiments. Further, cisplatin (CisPt), as traditional chemotherapy agent, was used in all parallel experiments. Moreover, the encapsulation of PtNPs in liposomes (LipoPtNPs) caused an approximately 2.4x higher of DNA damage in comparison with CisPt, LipoCisPt and PtNPs. The encapsulation of PtNPs in liposomes also increased their antibacterial, cytostatic and cytotoxic effect, which was determined by the method of growth curves on S. aureus and HFF cells. In addition, both the bare and encapsulated PtNPs caused lower oxidative stress (determined by GSH/GSSG ratio) in the human erythrocytes compared to the bare and encapsulated CisPt. CisPt was used in all parallel experiments as traditional chemotherapy agent.

Facile and green synthesis of phytochemicals capped platinum nanoparticles and in vitro their superior antibacterial activity.

PubMed

Tahir, Kamran; Nazir, Sadia; Ahmad, Aftab; Li, Baoshan; Khan, Arif Ullah; Khan, Zia Ul Haq; Khan, Faheem Ullah; Khan, Qudrat Ullah; Khan, Abrar; Rahman, Aziz Ur

2017-01-01

The increase in the severe infectious diseases and resistance of the majority of the bacterial pathogens to the available drug is a serious problem now a day. In order to overcome this problem it is necessary to develop new therapeutic agents which are non-toxic and more effective to inhibit these microbial pathogens. For this purpose the plant extract of highly active medicinal plant, Taraxacum laevigatum was used for the synthesis of platinum nanoparticles (PtNPs) to enhance its bio-activities. The surface plasmon resonance peak appeared at 283nm clearly represent the formation of PtNPs. The results illustrate that the bio-synthesized PtNPs were uniformly dispersed, small sized (2-7nm) and spherical in shape. The green synthesized PtNPs were characterized by UV-vis spectroscopy, XRD, TEM, SEM, EDX, DLS and FTIR. These nanoparticles were tested against gram positive bacteria (Bacillus subtilis) and gram negative bacteria (Pseudomonas aeruginosa). The bio-synthesized PtNPs were examined to be more effective against both of the bacteria. The results showed, that the zone of inhibition of PtNPs against P. aeruginosa was 15 (±0.5) mm and B. subtilis was 18 (±0.8) mm. The most significant outcome of this examination is that PtNPs exhibited strong antibacterial activity against P. aeruginosa and B. subtilis which have strong defensive system against several antibiotics. Copyright © 2016 Elsevier B.V. All rights reserved.

Identical Location Transmission Electron Microscopy Imaging of Site-Selective Pt Nanocatalysts: Electrochemical Activation and Surface Disordering.

PubMed

Arán-Ais, Rosa M; Yu, Yingchao; Hovden, Robert; Solla-Gullón, Jose; Herrero, Enrique; Feliu, Juan M; Abruña, Héctor D

2015-12-02

We have employed identical location transmission electron microscopy (IL-TEM) to study changes in the shape and morphology of faceted Pt nanoparticles as a result of electrochemical cycling; a procedure typically employed for activating platinum surfaces. We find that the shape and morphology of the as-prepared hexagonal nanoparticles are rapidly degraded as a result of potential cycling up to +1.3 V. As few as 25 potential cycles are sufficient to cause significant degradation, and after about 500-1000 cycles the particles are dramatically degraded. We also see clear evidence of particle migration during potential cycling. These finding suggest that great care must be exercised in the use and study of shaped Pt nanoparticles (and related systems) as electrocatlysts, especially for the oxygen reduction reaction where high positive potentials are typically employed.

Platinum-TM (TM = Fe, Co) alloy nanoparticles dispersed nitrogen doped (reduced graphene oxide-multiwalled carbon nanotube) hybrid structure cathode electrocatalysts for high performance PEMFC applications.

PubMed

Vinayan, B P; Ramaprabhu, S

2013-06-07

The efforts to push proton exchange membrane fuel cells (PEMFC) for commercial applications are being undertaken globally. In PEMFC, the sluggish kinetics of oxygen reduction reactions (ORR) at the cathode can be improved by the alloying of platinum with 3d-transition metals (TM = Fe, Co, etc.) and with nitrogen doping, and in the present work we have combined both of these aspects. We describe a facile method for the synthesis of a nitrogen doped (reduced graphene oxide (rGO)-multiwalled carbon nanotubes (MWNTs)) hybrid structure (N-(G-MWNTs)) by the uniform coating of a nitrogen containing polymer over the surface of the hybrid structure (positively surface charged rGO-negatively surface charged MWNTs) followed by the pyrolysis of these (rGO-MWNTs) hybrid structure-polymer composites. The N-(G-MWNTs) hybrid structure is used as a catalyst support for the dispersion of platinum (Pt), platinum-iron (Pt3Fe) and platinum-cobalt (Pt3Co) alloy nanoparticles. The PEMFC performances of Pt-TM alloy nanoparticle dispersed N-(G-MWNTs) hybrid structure electrocatalysts are 5.0 times higher than that of commercial Pt-C electrocatalysts along with very good stability under acidic environment conditions. This work demonstrates a considerable improvement in performance compared to existing cathode electrocatalysts being used in PEMFC and can be extended to the synthesis of metal, metal oxides or metal alloy nanoparticle decorated nitrogen doped carbon nanostructures for various electrochemical energy applications.

Engineered Biocompatible Nanoparticles for in Vivo Imaging Applications

PubMed Central

2010-01-01

Iron−platinum alloy nanoparticles (FePt NPs) are extremely promising candidates for the next generation of contrast agents for magnetic resonance (MR) diagnostic imaging and MR-guided interventions, including hyperthermic ablation of solid cancers. FePt has high Curie temperature, saturation magnetic moment, magneto-crystalline anisotropy, and chemical stability. We describe the synthesis and characterization of a family of biocompatible FePt NPs suitable for biomedical applications, showing and discussing that FePt NPs can exhibit low cytotoxicity. The importance of engineering the interface of strongly magnetic NPs using a coating allowing free aqueous permeation is demonstrated to be an essential parameter in the design of new generations of diagnostic and therapeutic MRI contrast agents. We report effective cell internalization of FePt NPs and demonstrate that they can be used for cellular imaging and in vivo MRI applications. This opens the way for several future applications of FePt NPs, including regenerative medicine and stem cell therapy in addition to enhanced MR diagnostic imaging. PMID:20919679

Tackling CO Poisoning with Single Atom Alloy Catalysts

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

Liu, Jilei; Lucci, Felicia R.; Yang, Ming

2016-05-01

Platinum (Pt) catalysts are extensively used in the chemical industry and as electrocatalysts in fuel cells. Pt is notorious for its sensitivity to poisoning by strong CO adsorption. Here we demonstrate that the single atom alloy (SAA) strat-egy applied to Pt reduces the binding strength of CO while maintaining catalytic performance. By using surface sensi-tive studies, we accurately determined the binding strength of CO to different Pt ensembles, and this in turn guided the preparation of PtCu alloy nanoparticles. The atomic ratio Pt:Cu = 1:120 yielded a SAA which exhibited excellent CO tolerance in H2 activation, the key elementary stepmore » for hy-drogenation and hydrogen electro-oxidation. As a probe reaction, the selective hydrogenation of acetylene to ethene was performed under flow conditions on the SAA nanopar-ticles supported on alumina without activity loss in the pres-ence of CO. The ability to maintain reactivity in the presence of CO is vital to other industrial reactions including fuel reforming and methanol/ethanol fuel cells.« less

Hydrogen Adsorption Properties of Carbon Nanotubes and Platinum Nanoparticles from a New Ammonium-Ethylimidazolium Chloroplatinate Salt.

PubMed

Tamburri, Emanuela; Cassani, Maria Cristina; Ballarin, Barbara; Tomellini, Massimo; Femoni, Cristina; Mignani, Adriana; Terranova, Maria Letizia; Orlanducci, Silvia

2016-05-23

Self-supporting membranes built entirely of carbon nanotubes have been prepared by wet methods and characterized by Raman spectroscopy. The membranes are used as supports for the electrodeposition of Pt nanoparticles without the use of additional additives and/or stabilizers. The Pt precursor is an ad hoc synthesized ammonium-ethylimidazolium chloroplatinate(IV) salt, [NH3 (CH2 )2 MIM)][PtCl6 ]. The Pt complex was characterized using NMR spectroscopy, XRD, ESI-MS, and FTIR spectroscopy. The interaction between the Pt-carbon nanotubes nanocomposites and hydrogen is analyzed using electrochemical and quartz microbalance measurements under near-ambient conditions. The contribution of the Pt phase to the hydrogen adsorption on nanotube is found and explained by a kinetic model that takes into account a spillover event. Such a phenomenon may be exploited conveniently for catalysis and electrocatalysis applications in which the hybrid systems could act as a hydrogen transfer agent in specific hydrogenation reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vertically aligned carbon nanotubes/carbon fiber paper composite to support Pt nanoparticles for direct methanol fuel cell application

NASA Astrophysics Data System (ADS)

Zhang, Jing; Yi, Xi-bin; Liu, Shuo; Fan, Hui-Li; Ju, Wei; Wang, Qi-Chun; Ma, Jie

2017-03-01

Vertically aligned carbon nanotubes (VACNTs) grown on carbon fiber paper (CFP) by plasma enhanced chemical vapor deposition is introduced as a catalyst support material for direct methanol fuel cells (DMFCs). Well dispersed Pt nanoparticles on VACNTs surface are prepared by impregnation-reduction method. The VACNTs on CFP possess well-maintained alignment, large surface area and good electrical conductivity, which leading to the formation of Pt particles with a smaller size and enhance the Pt utilization rate. The structure and nature of resulting Pt/VACNTs/CFP catalysts for methanol oxidation are investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD) and scanning electron microscope (SEM). With the aid of VACNTs, well-dispersed Pt catalysts enable the reversibly rapid redox kinetic since electron transport efficiently passes through a one-dimensional pathway, which leads to enhance the catalytic activity and Pt utilization rate. Compared with the Pt/XC-72/CFP electrode, the electrochemical measurements results display that the Pt/VACNTs/CFP catalyst shows much higher electrocatalytic activity and better stability for methanol oxidation. In addition, the oxidation current from 200 to 1200 s decayed more slowly for the Pt/VACNTs/CFP than that of the Pt/XC-72/CFP catalysts, indicating less accumulation of adsorbed CO species. All those results imply that the Pt/VACNTs/CFP has a great potential for applications in DMFCs.

Enhancing the methanol tolerance of platinum nanoparticles for the cathode reaction of direct methanol fuel cells through a geometric design.

PubMed

Feng, Yan; Ye, Feng; Liu, Hui; Yang, Jun

2015-11-18

Mastery over the structure of nanoparticles might be an effective way to enhance their performance for a given application. Herein we demonstrate the design of cage-bell nanostructures to enhance the methanol tolerance of platinum (Pt) nanoparticles while remaining their catalytic activity for oxygen reduction reaction. This strategy starts with the synthesis of core-shell-shell nanoparticles with Pt and silver (Ag) residing respectively in the core and inner shell regions, which are then agitated with saturated sodium chloride (NaCl) solution to eliminate the Ag component from the inner shell region, leading to the formation of bimetallic nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a metal shell with nano-channels, which exhibit superior methanol-tolerant property in catalyzing oxygen reduction reaction due to the different diffusion behaviour of methanol and oxygen in the porous metal shell of cage-bell structured nanoparticles. In particular, the use of remarkably inexpensive chemical agent (NaCl) to promote the formation of cage-bell structured particles containing a wide spectrum of metal shells highlights its engineering merit to produce highly selective electrocatalysts on a large scale for the cathode reaction of direct methanol fuel cells.

Oriented Pt Nanoparticles Supported on Few-Layers Graphene as Highly Active Catalyst for Aqueous-Phase Reforming of Ethylene Glycol.

PubMed

Esteve-Adell, Iván; Bakker, Nadia; Primo, Ana; Hensen, Emiel; García, Hermenegildo

2016-12-14

Pt nanoparticles (NPs) strongly grafted on few-layers graphene (G) have been prepared by pyrolysis under inert atmosphere at 900 °C of chitosan films (70-120 nm thickness) containing adsorbed H 2 PtCl 6 . Preferential orientation of exposed Pt facets was assessed by X-ray diffraction of films having high Pt loading where the 111 and 222 diffraction lines were observed and also by SEM imaging comparing elemental Pt mapping with the image of the 111 oriented particles. Characterization techniques allow determination of the Pt content (from 45 ng to 1 μg cm -2 , depending on the preparation conditions), particle size distribution (9 ± 2 nm), and thickness of the films (12-20 nm). Oriented Pt NPs on G exhibit at least 2 orders of magnitude higher catalytic activity for aqueous-phase reforming of ethylene glycol to H 2 and CO 2 compared to analogous samples of randomly oriented Pt NPs supported on preformed graphene. Oriented [Formula: see text]/fl-G undergoes deactivation upon reuse, the most probable cause being Pt particle growth, probably due to the presence of high concentrations of carboxylic acids acting as mobilizing agents during the course of the reaction.

Dicationic ionic liquid mediated fabrication of Au@Pt nanoparticles supported on reduced graphene oxide with highly catalytic activity for oxygen reduction and hydrogen evolution

NASA Astrophysics Data System (ADS)

Shi, Ya-Cheng; Chen, Sai-Sai; Feng, Jiu-Ju; Lin, Xiao-Xiao; Wang, Weiping; Wang, Ai-Jun

2018-05-01

Ionic liquids as templates or directing agents have attracted great attention for shaping-modulated synthesis of advanced nanomaterials. In this work, reduced graphene oxide supported uniform core-shell Au@Pt nanoparticles (Au@Pt NPs/rGO) were fabricated by a simple one-pot aqueous approach, using N-methylimidazolium-based dicationic ionic liquid (1,1-bis(3-methylimadazoilum-1-yl)butylene bromide, [C4(Mim)2]2Br) as the shape-directing agent. The morphology evolution, structural information and formation mechanism of Au@Pt NPs anchored on rGO were investigated by a series of characterization techniques. The obtained nanocomposites displayed superior electrocatalytic features toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) compared with commercial Pt/C catalyst. This approach provides a novel route for facile synthesis of nanocatalysts in fuel cells.

Screening metal nanoparticles using boron-doped diamond microelectrodes

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

Ivandini, Tribidasari A., E-mail: ivandini.tri@sci.ui.ac.id; Rangkuti, Prasmita K.; Einaga, Yasuaki

2016-04-19

Boron-doped diamond (BDD) microelectrodes were used to observe the correlation between electrocatalytic currents caused by individual Pt nanoparticle (Pt-np) collisions at the electrode. The BDD microelectrodes, ∼20 µm diameter and ∼2 µm particle size, were fabricated at the surface of tungsten wires. Pt-np with a size of 1 to 5 nm with agglomerations up to 20 nm was used for observation. The electrolytic currents were observed via catalytic reaction of 15 mM hydrazine in 50 mM phosphate buffer solution at Pt-np at 0.4 V when it collides with the surface of the microelectrodes. The low current noise and wider potential window in the measurements using BDD microelectrodemore » produced a better results, which represents a better correlation to the TEM result of the Pt-np, compared to when gold microelectrodes was used.« 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.

Ultrasonic-electrodeposition of PtPd alloy nanoparticles on ionic liquid-functionalized graphene paper: towards a flexible and versatile nanohybrid electrode

NASA Astrophysics Data System (ADS)

Sun, Yimin; Zheng, Huaming; Wang, Chenxu; Yang, Mengmeng; Zhou, Aijun; Duan, Hongwei

2016-01-01

Here we fabricate a new type of flexible and versatile nanohybrid paper electrode by ultrasonic-electrodeposition of PtPd alloy nanoparticles on freestanding ionic liquid (IL)-functionalized graphene paper, and explore its multifunctional applications in electrochemical catalysis and sensing systems. The graphene-based paper materials demonstrate intrinsic flexibility, exceptional mechanical strength and high electrical conductivity, and therefore can serve as an ideal freestanding flexible electrode for electrochemical devices. Furthermore, the functionalization of graphene with IL (i.e., 1-butyl-3-methylimidazolium tetrafluoroborate) not only increases the electroactive surface area of a graphene-based nanohybrid paper electrode, but also improves the adhesion and dispersion of metal nanoparticles on the paper surface. These unique attributes, combined with the merits of an ultrasonic-electrodeposition method, lead to the formation of PtPd alloy nanoparticles on IL-graphene paper with high loading, uniform distribution, controlled morphology and favourable size. Consequently, the resultant nanohybrid paper electrode exhibits remarkable catalytic activity as well as excellent cycle stability and improved anti-poisoning ability towards electrooxidation of fuel molecules such as methanol and ethanol. Furthermore, for nonenzymatic electrochemical sensing of some specific biomarkers such as glucose and reactive oxygen species, the nanohybrid paper electrode shows high selectivity, sensitivity and biocompatibility in these bio-catalytic processes, and can be used for real-time tracking hydrogen peroxide secretion by living human cells. All these features demonstrate its promising application as a versatile nanohybrid electrode material in flexible and lightweight electrochemical energy conversion and biosensing systems such as bendable on-chip power sources, wearable/implantable detectors and in vivo micro-biosensors.Here we fabricate a new type of flexible and versatile nanohybrid paper electrode by ultrasonic-electrodeposition of PtPd alloy nanoparticles on freestanding ionic liquid (IL)-functionalized graphene paper, and explore its multifunctional applications in electrochemical catalysis and sensing systems. The graphene-based paper materials demonstrate intrinsic flexibility, exceptional mechanical strength and high electrical conductivity, and therefore can serve as an ideal freestanding flexible electrode for electrochemical devices. Furthermore, the functionalization of graphene with IL (i.e., 1-butyl-3-methylimidazolium tetrafluoroborate) not only increases the electroactive surface area of a graphene-based nanohybrid paper electrode, but also improves the adhesion and dispersion of metal nanoparticles on the paper surface. These unique attributes, combined with the merits of an ultrasonic-electrodeposition method, lead to the formation of PtPd alloy nanoparticles on IL-graphene paper with high loading, uniform distribution, controlled morphology and favourable size. Consequently, the resultant nanohybrid paper electrode exhibits remarkable catalytic activity as well as excellent cycle stability and improved anti-poisoning ability towards electrooxidation of fuel molecules such as methanol and ethanol. Furthermore, for nonenzymatic electrochemical sensing of some specific biomarkers such as glucose and reactive oxygen species, the nanohybrid paper electrode shows high selectivity, sensitivity and biocompatibility in these bio-catalytic processes, and can be used for real-time tracking hydrogen peroxide secretion by living human cells. All these features demonstrate its promising application as a versatile nanohybrid electrode material in flexible and lightweight electrochemical energy conversion and biosensing systems such as bendable on-chip power sources, wearable/implantable detectors and in vivo micro-biosensors. Electronic supplementary information (ESI) available: The stress-strain curve of the IL-rGOP, EDX spectrum of PtPd/IL-rGOP, the particle size and size distribution of Pt, PtPd and Pd nanoparticles electrodeposited on IL-rGOP derived from SEM, and the structural parameters of Pt, PtPd and Pd nanoparticles electrodeposited on IL-rGOP derived from XRD, influence of the potential interfering species towards glucose detection. See DOI: 10.1039/c5nr06912b

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-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

Acute and chronic nephrotoxicity of platinum nanoparticles in mice

NASA Astrophysics Data System (ADS)

Yamagishi, Yoshiaki; Watari, Akihiro; Hayata, Yuya; Li, Xiangru; Kondoh, Masuo; Yoshioka, Yasuo; Tsutsumi, Yasuo; Yagi, Kiyohito

2013-09-01

Platinum nanoparticles are being utilized in various industrial applications, including in catalysis, cosmetics, and dietary supplements. Although reducing the size of the nanoparticles improves the physicochemical properties and provides useful performance characteristics, the safety of the material remains a major concern. The aim of the present study was to evaluate the biological effects of platinum particles less than 1 nm in size (snPt1). In mice administered with a single intravenous dose of snPt1, histological analysis revealed necrosis of tubular epithelial cells and urinary casts in the kidney, without obvious toxic effects in the lung, spleen, and heart. These mice exhibited dose-dependent elevation of blood urea nitrogen, an indicator of kidney damage. Direct application of snPt1 to in vitro cultures of renal cells induced significant cytotoxicity. In mice administered for 4 weeks with twice-weekly intraperitoneal snPt1, histological analysis of the kidney revealed urinary casts, tubular atrophy, and inflammatory cell accumulation. Notably, these toxic effects were not observed in mice injected with 8-nm platinum particles, either by single- or multiple-dose administration. Our findings suggest that exposure to platinum particles of less than 1 nm in size may induce nephrotoxicity and disrupt some kidney functions. However, this toxicity may be reduced by increasing the nanoparticle size.

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

Acute and chronic nephrotoxicity of platinum nanoparticles in mice

PubMed Central

2013-01-01

Platinum nanoparticles are being utilized in various industrial applications, including in catalysis, cosmetics, and dietary supplements. Although reducing the size of the nanoparticles improves the physicochemical properties and provides useful performance characteristics, the safety of the material remains a major concern. The aim of the present study was to evaluate the biological effects of platinum particles less than 1 nm in size (snPt1). In mice administered with a single intravenous dose of snPt1, histological analysis revealed necrosis of tubular epithelial cells and urinary casts in the kidney, without obvious toxic effects in the lung, spleen, and heart. These mice exhibited dose-dependent elevation of blood urea nitrogen, an indicator of kidney damage. Direct application of snPt1 to in vitro cultures of renal cells induced significant cytotoxicity. In mice administered for 4 weeks with twice-weekly intraperitoneal snPt1, histological analysis of the kidney revealed urinary casts, tubular atrophy, and inflammatory cell accumulation. Notably, these toxic effects were not observed in mice injected with 8-nm platinum particles, either by single- or multiple-dose administration. Our findings suggest that exposure to platinum particles of less than 1 nm in size may induce nephrotoxicity and disrupt some kidney functions. However, this toxicity may be reduced by increasing the nanoparticle size. PMID:24059288

Ultra-fine Pt nanoparticles on graphene aerogel as a porous electrode with high stability for microfluidic methanol fuel cell

NASA Astrophysics Data System (ADS)

Kwok, Y. H.; Tsang, Alpha C. H.; Wang, Yifei; Leung, Dennis Y. C.

2017-05-01

Platinum-decorated graphene aerogel as a porous electrode for flow-through direct methanol microfluidic fuel cell is introduced. Ultra-fine platinum nanoparticles with size ranged from diameter 1.5 nm-3 nm are evenly anchored on the graphene nanosheets without agglomeration. The electrode is characterized by scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray spectroscopy. Catalytic activity is confirmed by cyclic voltammetry. The electroactive surface area and catalytic activity of platinum on graphene oxide (Pt/GO) are much larger than commercial platinum on carbon black (Pt/C). A counterflow microfluidic fuel cell is designed for contrasting the cell performance between flow-over type and flow-through type electrodes using Pt/C on carbon paper and Pt/GO, respectively. The Pt/GO electrode shows 358% increment in specific power compared with Pt/C anode. Apart from catalytic activity, the effect of porous electrode conductivity to cell performance is also studied. The conductivity of the porous electrode should be further enhanced to achieve higher cell performance.

Metallopolymer precursors to L10-CoPt nanoparticles: synthesis, characterization, nanopatterning and potential application

NASA Astrophysics Data System (ADS)

Dong, Qingchen; Qu, Wenshan; Liang, Wenqing; Guo, Kunpeng; Xue, Haibin; Guo, Yuanyuan; Meng, Zhengong; Ho, Cheuk-Lam; Leung, Chi-Wah; Wong, Wai-Yeung

2016-03-01

Ferromagnetic (L10 phase) CoPt alloy nanoparticles (NPs) with extremely high magnetocrystalline anisotropy are promising candidates for the next generation of ultrahigh-density data storage systems. It is a challenge to generate L10 CoPt NPs with high coercivity, controllable size, and a narrow size distribution. We report here the fabrication of L10 CoPt NPs by employing a heterobimetallic CoPt-containing polymer as a single-source precursor. The average size of the resulting L10 CoPt NPs is 3.4 nm with a reasonably narrow size standard deviation of 0.58 nm. The coercivity of L10 CoPt NPs is 0.54 T which is suitable for practical application. We also fabricated the L10 CoPt NP-based nanoline and nanodot arrays through nanoimprinting the polymer blend of CoPt-containing metallopolymer and polystyrene followed by pyrolysis. The successful transfer of the pre-defined patterns of the stamps onto the surface of the polymer blend implies that this material holds great application potential as a data storage medium.Ferromagnetic (L10 phase) CoPt alloy nanoparticles (NPs) with extremely high magnetocrystalline anisotropy are promising candidates for the next generation of ultrahigh-density data storage systems. It is a challenge to generate L10 CoPt NPs with high coercivity, controllable size, and a narrow size distribution. We report here the fabrication of L10 CoPt NPs by employing a heterobimetallic CoPt-containing polymer as a single-source precursor. The average size of the resulting L10 CoPt NPs is 3.4 nm with a reasonably narrow size standard deviation of 0.58 nm. The coercivity of L10 CoPt NPs is 0.54 T which is suitable for practical application. We also fabricated the L10 CoPt NP-based nanoline and nanodot arrays through nanoimprinting the polymer blend of CoPt-containing metallopolymer and polystyrene followed by pyrolysis. The successful transfer of the pre-defined patterns of the stamps onto the surface of the polymer blend implies that this material holds great application potential as a data storage medium. Electronic supplementary information (ESI) available: PXRD, EDX and SEM original data. See DOI: 10.1039/c6nr00034g

Photoelectrochemistry by Design: Tailoring the Nanoscale Structure of Pt/NiO Composites Leads to Enhanced Photoelectrochemical Hydrogen Evolution Performance

PubMed Central

2017-01-01

Photoelectrochemical hydrogen evolution is a promising avenue to store the energy of sunlight in the form of chemical bonds. The recent rapid development of new synthetic approaches enables the nanoscale engineering of semiconductor photoelectrodes, thus tailoring their physicochemical properties toward efficient H2 formation. In this work, we carried out the parallel optimization of the morphological features of the semiconductor light absorber (NiO) and the cocatalyst (Pt). While nanoporous NiO films were obtained by electrochemical anodization, the monodisperse Pt nanoparticles were synthesized using wet chemical methods. The Pt/NiO nanocomposites were characterized by XRD, XPS, SEM, ED, TEM, cyclic voltammetry, photovoltammetry, EIS, etc. The relative enhancement of the photocurrent was demonstrated as a function of the nanoparticle size and loading. For mass-specific surface activity the smallest nanoparticles (2.0 and 4.8 nm) showed the best performance. After deconvoluting the trivial geometrical effects (stemming from the variation of Pt particle size and thus the electroactive surface area), however, the intermediate particle sizes (4.8 and 7.2 nm) were found to be optimal. Under optimized conditions, a 20-fold increase in the photocurrent (and thus the H2 evolution rates) was observed for the nanostructured Pt/NiO composite, compared to the benchmark nanoparticulate NiO film. PMID:28620447

Novel platinum–palladium bimetallic nanoparticles synthesized by Dioscorea bulbifera: anticancer and antioxidant activities

PubMed Central

Ghosh, Sougata; Nitnavare, Rahul; Dewle, Ankush; Tomar, Geetanjali B; Chippalkatti, Rohan; More, Piyush; Kitture, Rohini; Kale, Sangeeta; Bellare, Jayesh; Chopade, Balu A

2015-01-01

Medicinal plants serve as rich sources of diverse bioactive phytochemicals that might even take part in bioreduction and stabilization of phytogenic nanoparticles with immense therapeutic properties. Herein, we report for the first time the rapid efficient synthesis of novel platinum–palladium bimetallic nanoparticles (Pt–PdNPs) along with individual platinum (PtNPs) and palladium (PdNPs) nanoparticles using a medicinal plant, Dioscorea bulbifera tuber extract (DBTE). High-resolution transmission electron microscopy revealed monodispersed PtNPs of size 2–5 nm, while PdNPs and Pt–PdNPs between 10 and 25 nm. Energy dispersive spectroscopy analysis confirmed 30.88%±1.73% elemental Pt and 68.96%±1.48% elemental Pd in the bimetallic nanoparticles. Fourier transform infrared spectra indicated strong peaks at 3,373 cm−1, attributed to hydroxyl group of polyphenolic compounds in DBTE that might play a key role in bioreduction in addition to the sharp peaks at 2,937, 1,647, 1,518, and 1,024 cm−1, associated with C–H stretching, N–H bending in primary amines, N–O stretching in nitro group, and C–C stretch, respectively. Anticancer activity against HeLa cells showed that Pt–PdNPs exhibited more pronounced cell death of 74.25% compared to individual PtNPs (12.6%) or PdNPs (33.15%). Further, Pt–PdNPs showed an enhanced scavenging activity against 2,2-diphenyl-1-picrylhydrazyl, superoxide, nitric oxide, and hydroxyl radicals. PMID:26719690

Effect of valence state and particle size on NO oxidation in fresh and aged Pt-based diesel oxidation catalysts

NASA Astrophysics Data System (ADS)

Liang, Yanli; Ding, Xinmei; Zhao, Ming; Wang, Jianli; Chen, Yaoqiang

2018-06-01

To stabilize Pt, Magnesium-modified SiO2-Al2O3 materials was used to impregnate with Pt, which could strengthen the bonding effect between Pt and Mg. Before and after aging, both showed a higher dispersion. High valence state of Pt in fresh modified catalyst was unfavorable of NO oxidation, indicating that the valence state of Pt was the leader factor in fresh catalytic performance. While for the aged Mg-modified sample, its reaction temperature of 30% NO conversion lowered by around 30 °C. The Pt stabilization via interacting with Mg derives a relation that the variation of Pt valence state and its exposed sites played a significant role in fresh and aged catalytic NO activity, respectively.

Rapid synthesis of platinum-ruthenium bimetallic nanoparticles dispersed on carbon support as improved electrocatalysts for ethanol oxidation.

PubMed

Gu, Zhulan; Li, Shumin; Xiong, Zhiping; Xu, Hui; Gao, Fei; Du, Yukou

2018-07-01

Bimetallic nanocatalysts with small particle size benefit from markedly enhanced electrocatalytic activity and stability during small molecule oxidation. Herein, we report a facile method to synthesize binary Pt-Ru nanoparticles dispersed on a carbon support at an optimum temperature. Because of its monodispersed nanostructure, synergistic effects were observed between Pt and Ru and the PtRu/C electrocatalysts showed remarkably enhanced electrocatalytic activity towards ethanol oxidation. The peak current density of the Pt 1 Ru 1 /C electrocatalyst is 3731 mA mg -1 , which is 9.3 times higher than that of commercial Pt/C (401 mA mg -1 ). Furthermore, the synthesized Pt 1 Ru 1 /C catalyst exhibited higher stability during ethanol oxidation in an alkaline medium and maintained a significantly higher current density after successive cyclic voltammograms (CVs) of 500 cycles than commercial Pt/C. Our work highlights the significance of the reaction temperature during electrocatalyst synthesis, leading to enhanced catalytic performance towards ethanol oxidation. The Pt 1 Ru 1 /C electrocatalyst has great potential for application in direct ethanol fuel cells. Copyright © 2018 Elsevier Inc. All rights reserved.

A new method for mapping the three-dimensional atomic distribution within nanoparticles by atom probe tomography (APT).

PubMed

Kim, Se-Ho; Kang, Phil Woong; Park, O Ok; Seol, Jae-Bok; Ahn, Jae-Pyoung; Lee, Ji Yeong; Choi, Pyuck-Pa

2018-07-01

We present a new method of preparing needle-shaped specimens for atom probe tomography from freestanding Pd and C-supported Pt nanoparticles. The method consists of two steps, namely electrophoresis of nanoparticles on a flat Cu substrate followed by electrodeposition of a Ni film acting as an embedding matrix for the nanoparticles. Atom probe specimen preparation can be subsequently carried out by means of focused-ion-beam milling. Using this approach, we have been able to perform correlative atom probe tomography and transmission electron microscopy analyses on both nanoparticle systems. Reliable mass spectra and three-dimensional atom maps could be obtained for Pd nanoparticle specimens. In contrast, atom probe samples prepared from C-supported Pt nanoparticles showed uneven field evaporation and hence artifacts in the reconstructed atom maps. Our developed method is a viable means of mapping the three-dimensional atomic distribution within nanoparticles and is expected to contribute to an improved understanding of the structure-composition-property relationships of various nanoparticle systems. Copyright © 2018 Elsevier B.V. All rights reserved.

Fast Synthesis of Pt Nanocrystals and Pt/Microporous La2O3 Materials Using Acoustic Levitation.

PubMed

Yu, Yinkai; Qu, Shaohua; Zang, Duyang; Wang, Liuding; Wu, Hongjing

2018-02-13

Usually, we must use an appropriate support material to keep the metal species stable and finely dispersed as supported metal nanoparticles for industry application. Therefore, the choice of support material is a key factor in determining the dispersion and particle size of the noble metal species. Here, we report the synthesis of a single-atom Pt material in the solution and supported Pt nanoclusters on microporous La 2 O 3 by a one-step acoustic levitation method without any pretreatment/modification of raw oxide. We have strongly contributed to the synthetic methodology of the surface/interfacial heterogeneous catalysts in this study, and this finding could open another door for synthesis of supported metal nanoparticles on porous materials for environmental catalysis.

One-pot catalytic conversion of cellulose into polyols with Pt/CNTs catalysts.

PubMed

Yang, Li; Yan, Xiaopei; Wang, Qiwu; Wang, Qiong; Xia, Haian

2015-03-02

A series of Pt nanoparticles supported on carbon nanotubes (CNTs) were synthesized using the incipient-wetness impregnation method. These catalysts were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscope (TEM) techniques. The characterization results indicate that the Pt nanoparticles were highly dispersed on the surface of the CNTs, and the mean size was less than 5 nm. These catalysts were utilized to convert cellulose to hexitol, ethylene glycerol (EG), and 1,2-propylene glycol (1,2-PG) under low H2 pressure. The total yields were as high as 71.4% for EG and 1,2-PG using 1Pt/CNTs as the catalyst in the hydrolytic hydrogenation of cellulose under mild reaction conditions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Fast Synthesis of Pt Nanocrystals and Pt/Microporous La2O3 Materials Using Acoustic Levitation

NASA Astrophysics Data System (ADS)

Yu, Yinkai; Qu, Shaohua; Zang, Duyang; Wang, Liuding; Wu, Hongjing

2018-02-01

Usually, we must use an appropriate support material to keep the metal species stable and finely dispersed as supported metal nanoparticles for industry application. Therefore, the choice of support material is a key factor in determining the dispersion and particle size of the noble metal species. Here, we report the synthesis of a single-atom Pt material in the solution and supported Pt nanoclusters on microporous La2O3 by a one-step acoustic levitation method without any pretreatment/modification of raw oxide. We have strongly contributed to the synthetic methodology of the surface/interfacial heterogeneous catalysts in this study, and this finding could open another door for synthesis of supported metal nanoparticles on porous materials for environmental catalysis.

Non-Aqueous Sol-Gel Synthesis of FePt Nanoparticles in the Absence of In Situ Stabilizers

PubMed Central

Preller, Tobias; Knickmeier, Saskia; Porsiel, Julian Cedric; Temel, Bilal

2018-01-01

The synthesis of FePt nanocrystals is typically performed in an organic solvent at rather high temperatures, demanding the addition of the in situ stabilizers oleic acid and oleylamine to produce monomodal particles with well-defined morphologies. Replacing frequently-used solvents with organic media bearing functional moieties, the use of the stabilizers can be completely circumvented. In addition, various morphologies and sizes of the nanocrystals can be achieved by the choice of organic solvent. The kinetics of particle growth and the change in the magnetic behavior of the superparamagnetic FePt nanocrystals during the synthesis with a set of different solvents, as well as the resulting morphologies and stoichiometries of the nanoparticles were determined by powder X-ray diffraction (PXRD), small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP-OES)/mass spectrometry (ICP-MS), and superconducting quantum interference device (SQUID) measurements. Furthermore, annealing of the as-prepared FePt nanoparticles led to the ordered L10 phase and, thus, to hard magnetic materials with varying saturation magnetizations and magnetic coercivities. PMID:29751508

Platinum-Free Counter Electrode Comprised of Metal-Organic-Framework (MOF)-Derived Cobalt Sulfide Nanoparticles for Efficient Dye-Sensitized Solar Cells (DSSCs)

PubMed Central

Hsu, Shao-Hui; Li, Chun-Ting; Chien, Heng-Ta; Salunkhe, Rahul R.; Suzuki, Norihiro; Yamauchi, Yusuke; Ho, Kuo-Chuan; Wu, Kevin C.-W.

2014-01-01

We fabricated a highly efficient (with a solar-to-electricity conversion efficiency (η) of 8.1%) Pt-free dye-sensitized solar cell (DSSC). The counter electrode was made of cobalt sulfide (CoS) nanoparticles synthesized via surfactant-assisted preparation of a metal organic framework, ZIF-67, with controllable particle sizes (50 to 320 nm) and subsequent oxidation and sulfide conversion. In contrast to conventional Pt counter electrodes, the synthesized CoS nanoparticles exhibited higher external surface areas and roughness factors, as evidenced by X-ray diffraction (XRD), scanning electron microscopy (SEM) element mapping, and electrochemical analysis. Incident photon-to-current conversion efficiency (IPCE) results showed an increase in the open circuit voltage (VOC) and a decrease in the short-circuit photocurrent density (Jsc) for CoS-based DSSCs compared to Pt-based DSSCs, resulting in a similar power conversion efficiency. The CoS-based DSSC fabricated in the study show great potential for economically friendly production of Pt-free DSSCs. PMID:25382139

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

Rouleau, Christopher M.; Puretzky, Alexander A.; Geohegan, David B.

The slowing of Pt nanoparticles in argon background gas was characterized by Rayleigh scattering imaging using a plume of nanoparticles generated by femtosecond laser through thin film ablation (fs-TTFA) of 20 nanometers-thick Pt films. The ablation was performed at threshold laser energy fluences for complete film removal to provide a well-defined plume consisting almost entirely of nanoparticles traveling with a narrow velocity distribution, providing a unique system to unambiguously characterize the slowing of nanoparticles during interaction with background gases. Nanoparticles of ~200 nm diameter were found to decelerate in background Ar gas with pressures less than 50 Torr in goodmore » agreement with a linear drag model in the Epstein regime. Based on this model, the stopping distance of small nanoparticles in the plume was predicted and tested by particle collection in an off-axis geometry, and size distribution analysis by transmission electron microscopy. These results permit a basis to interpret nanoparticle propagation through background gases in laser ablation plumes that contain mixed components.« less

Controllable deposition of platinum nanoparticles on single-wall carbon nanohorns as catalyst for direct methanol fuel cells.

PubMed

Niu, Ben; Xu, Wei; Guo, Zhengduo; Zhou, Nengzhi; Liu, Yang; Shi, Zujin; Lian, Yongfu

2012-09-01

Uniform and well dispersed platinum nanoparticles were successfully deposited on single-walled carbon nanohorns with the assistance of 4,4-dipydine and ion liquids, respectively. In particular, the size of platinum nanoparticles could be controlled in a very narrow range (2.2 to 2.5 nm) when ion liquids were applied. The crystalline nature of these platinum nanoparticles was confirmed by high resolution transmission electron microscopy observation and X-ray power diffraction analysis, and two species of platinum Pt(0) and Pt(II) were detected by X-ray photoelectron spectroscopy. Electrochemical studies revealed that thus obtained nanocomposites had much better electrocatalytic activity for the methanol oxidation than those prepared with carbon nanotubes as supporter.

Toward a chemiresistive ammonia (NH3) gas sensor based on viral-templated gold nanoparticles embedded in polypyrrole nanowires

NASA Astrophysics Data System (ADS)

Yan, Yiran; Zhang, Miluo; Su, Heng Chia; Myung, Nosang V.; Haberer, Elaine D.

2014-08-01

Preliminary studies toward the assembly of a gold-polypyrrole (PPy) peapod-like chemiresistive ammonia (NH3) gas sensors are presented. The proposed synthesis process will use electropolymerization to embed gold nanoparticles in polypyrrole nanowires. Viral-templating of gold nanoparticles and PPy electrodeposition via cyclic voltammetry are the focus of this investigation. A gold-binding M13 bacteriophage was used as a bio-template to assemble continuous chains of gold nanoparticles on interdigitated Pt working electrodes. The dimensions of the resulting nanowire-like structures were examined and the electrical resistance measured. PPy films were electropolymerized using an interdigitated planar, Pt electrode integrated counter and reference electrode. Morphological characterization of the polymer films was completed.

Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2.

PubMed

DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly; Pham, Nicholas; Graham, George W; Pan, Xiaoqing; Christopher, Phillip

2017-10-11

Oxide-supported precious metal nanoparticles are widely used industrial catalysts. Due to expense and rarity, developing synthetic protocols that reduce precious metal nanoparticle size and stabilize dispersed species is essential. Supported atomically dispersed, single precious metal atoms represent the most efficient metal utilization geometry, although debate regarding the catalytic activity of supported single precious atom species has arisen from difficulty in synthesizing homogeneous and stable single atom dispersions, and a lack of site-specific characterization approaches. We propose a catalyst architecture and characterization approach to overcome these limitations, by depositing ∼1 precious metal atom per support particle and characterizing structures by correlating scanning transmission electron microscopy imaging and CO probe molecule infrared spectroscopy. This is demonstrated for Pt supported on anatase TiO 2 . In these structures, isolated Pt atoms, Pt iso , remain stable through various conditions, and spectroscopic evidence suggests Pt iso species exist in homogeneous local environments. Comparing Pt iso to ∼1 nm preoxidized (Pt ox ) and prereduced (Pt metal ) Pt clusters on TiO 2 , we identify unique spectroscopic signatures of CO bound to each site and find CO adsorption energy is ordered: Pt iso ≪ Pt metal < Pt ox . Pt iso species exhibited a 2-fold greater turnover frequency for CO oxidation than 1 nm Pt metal clusters but share an identical reaction mechanism. We propose the active catalytic sites are cationic interfacial Pt atoms bonded to TiO 2 and that Pt iso exhibits optimal reactivity because every atom is exposed for catalysis and forms an interfacial site with TiO 2 . This approach should be generally useful for studying the behavior of supported precious metal atoms.

Fe Stabilization by Intermetallic L1 0-FePt and Pt Catalysis Enhancement in L1 0-FePt/Pt Nanoparticles for Efficient Oxygen Reduction Reaction in Fuel Cells

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

Li, Junrui; Xi, Zheng; Pan, Yung -Tin

We report in this article a detailed study on how to stabilize a first-row transition metal (M) in an intermetallic L1 0-MPt alloy nanoparticle (NP) structure and how to surround the L1 0-MPt with an atomic layer of Pt to enhance the electrocatalysis of Pt for oxygen reduction reaction (ORR) in fuel cell operation conditions. Using 8 nm FePt NPs as an example, we demonstrate that Fe can be stabilized more efficiently in a core/shell structured L1 0-FePt/Pt with a 5 Å Pt shell. The presence of Fe in the alloy core induces the desired compression of the thin Ptmore » shell, especially the 2 atomic layers of Pt shell, further improving the ORR catalysis. This leads to much enhanced Pt catalysis for ORR in 0.1 M HClO 4 solution (both at room temperature and 60°C) and in the membrane electrode assembly (MEA) at 80°C. The L1 0-FePt/Pt catalyst has a mass activity of 0.7 A/mg Pt from the half-cell ORR test and shows no obvious mass activity loss after 30,000 potential cycles between 0.6 V and 0.95 V at 80°C in the MEA, meeting the DOE 2020 target (<40% loss in mass activity). Here, we are extending the concept and preparing other L1 0-MPt/Pt NPs, such as L1 0-CoPt/Pt NPs, with reduced NP size as a highly efficient ORR catalyst for automotive fuel cell applications.« less

Fe Stabilization by Intermetallic L1 0-FePt and Pt Catalysis Enhancement in L1 0-FePt/Pt Nanoparticles for Efficient Oxygen Reduction Reaction in Fuel Cells

DOE PAGES

Li, Junrui; Xi, Zheng; Pan, Yung -Tin; ...

2018-02-07

We report in this article a detailed study on how to stabilize a first-row transition metal (M) in an intermetallic L1 0-MPt alloy nanoparticle (NP) structure and how to surround the L1 0-MPt with an atomic layer of Pt to enhance the electrocatalysis of Pt for oxygen reduction reaction (ORR) in fuel cell operation conditions. Using 8 nm FePt NPs as an example, we demonstrate that Fe can be stabilized more efficiently in a core/shell structured L1 0-FePt/Pt with a 5 Å Pt shell. The presence of Fe in the alloy core induces the desired compression of the thin Ptmore » shell, especially the 2 atomic layers of Pt shell, further improving the ORR catalysis. This leads to much enhanced Pt catalysis for ORR in 0.1 M HClO 4 solution (both at room temperature and 60°C) and in the membrane electrode assembly (MEA) at 80°C. The L1 0-FePt/Pt catalyst has a mass activity of 0.7 A/mg Pt from the half-cell ORR test and shows no obvious mass activity loss after 30,000 potential cycles between 0.6 V and 0.95 V at 80°C in the MEA, meeting the DOE 2020 target (<40% loss in mass activity). Here, we are extending the concept and preparing other L1 0-MPt/Pt NPs, such as L1 0-CoPt/Pt NPs, with reduced NP size as a highly efficient ORR catalyst for automotive fuel cell applications.« less

Activity and Stability of Dispersed Multi Metallic Pt-based Catalysts for CO Tolerance in Proton Exchange Membrane Fuel Cell Anodes.

PubMed

Hassan, Ayaz; Ticianelli, Edson A

2018-01-01

Studies aiming at improving the activity and stability of dispersed W and Mo containing Pt catalysts for the CO tolerance in proton exchange membrane fuel cell (PEMFC) anodes are revised for the following catalyst systems: (1) a carbon supported PtMo electrocatalyst submitted to heat treatments; (2) Pt and PtMo nanoparticles deposited on carbon-supported molybdenum carbides (Mo2C/C); (3) ternary and quaternary materials formed by PtMoFe/C, PtMoRu/C and PtMoRuFe/C and; (4) Pt nanoparticles supported on tungsten carbide/carbon catalysts and its parallel evaluation with carbon supported PtW catalyst. The heat-treated (600 oC) Pt-Mo/C catalyst showed higher hydrogen oxidation activity in the absence and in the presence of CO and better stability, compared to all other Mo-containing catalysts. PtMoRuFe, PtMoFe, PtMoRu supported on carbon and Pt supported on Mo2C/C exhibited similar CO tolerances but better stability, as compared to as-prepared PtMo supported on carbon. Among the tungsten-based catalysts, tungsten carbide supported Pt catalyst showed reasonable performance and reliable stability in comparison to simple carbon supported PtW catalyst, though an uneven level of catalytic activity towards H2 oxidation in presence of CO is observed for the former as compared to Mo containing catalyst. However, a small dissolution of Mo, Ru, Fe and W from the anodes and their migration toward cathodes during the cell operation is observed. These results indicate that the fuel cell performance and stability has been improved but not yet totally resolved.

Roughening of Pt nanoparticles induced by surface-oxide formation.

PubMed

Zhu, Tianwei; Hensen, Emiel J M; van Santen, Rutger A; Tian, Na; Sun, Shi-Gang; Kaghazchi, Payam; Jacob, Timo

2013-02-21

Using density functional theory (DFT) and thermodynamic considerations we studied the equilibrium shape of Pt nanoparticles (NPs) under electrochemical conditions. We found that at very high oxygen coverage, obtained at high electrode potentials, the experimentally-observed tetrahexahedral (THH) NPs consist of high-index (520) faces. Since high-index surfaces often show higher (electro-)chemical activity in comparison to their close-packed counterparts, the THH NPs can be promising candidates for various (electro-)catalytic applications.

Ferrocenemonocarboxylic-HRP@Pt nanoparticles labeled RCA for multiple amplification of electro-immunosensing.

PubMed

Su, Huilan; Yuan, Ruo; Chai, Yaqin; Mao, Li; Zhuo, Ying

2011-07-15

A multiple amplification immunoassay was proposed to detect alpha-fetoprotein (AFP), which was based on ferrocenemonocarboxylic-HRP conjugated on Pt nanoparticles as labels for rolling circle amplification (RCA). Firstly, the capture antibody (anti-AFP) was immobilized on glass carbon electrode (GCE) deposited nano-sized gold particles. After a typical immuno-sandwich protocol, primary DNA was immobilized by labeling secondary antibody, which acted as a precursor to initiate RCA. The products of RCA provide large amount of sites to link detection DNAs, which were labeled by signal probes (ferrocenemonocarboxylic) and horseradish peroxidase (HRP). Moreover, the enzymatic amplification signals could be produced by the catalysis of HRP and Pt nanoparticles with the addition of H₂O₂. These lead to multiple amplification signals monitoring by electrochemical instrument and further resulted in high sensitivity of the immunoassay with the detection limit of 1.7 pg/mL. Copyright © 2011 Elsevier B.V. All rights reserved.

Crizotinib-loaded polymeric nanoparticles in lung cancer chemotherapy.

PubMed

Jiang, Zhi-Ming; Dai, Shou-Ping; Xu, Yong-Qing; Li, Tao; Xie, Jian; Li, Chong; Zhang, Zhong-Hui

2015-07-01

The study describes the development of polylactide-tocopheryl polyethylene glycol 1000 succinate (PLA-TPGS)-based nanosystem as a carrier of crizotinib (CZT) to achieve superior anticancer efficacy in lung cancer therapy. We have demonstrated that block copolymer and hydrophobic drug is capable of self-assembling into a very stable nanocarrier, with suitable properties that allow their application for cancer drug delivery. Drug release study showed a sustained release pattern as a result of entrapment in the hydrophobic core of micelles. CZT/PT NP showed a noticeable cytotoxic effect in NCIH3122 lung cancer cells in a dose-dependent manner. Furthermore, morphological imaging and Live/Dead assay revealed a superior anticancer efficacy for nanoformulations. The polymeric nanoparticle showed a predominant presence in the cytoplasmic region of cell, indicating a typical endocytosis-mediated cellular uptake. The annexin V/PI staining-based apoptosis assay showed a remarkable ~40 % apoptosis (early and late apoptosis cells) comparing to only ~25 % apoptosis by free CZT. Taken together, Vitamin E TPGS-modified PLA nanoparticles would be a potential drug delivery system to increase the chemotherapeutic efficacy of CZT in lung cancer chemotherapy.

Enhanced peroxidase-like properties of Au@Pt DNs/NG/Cu2+ and application of sandwich-type electrochemical immunosensor for highly sensitive detection of CEA.

PubMed

Lv, Hui; Li, Yueyun; Zhang, Xiaobo; Gao, Zengqiang; Zhang, Chunyan; Zhang, Shuan; Dong, Yunhui

2018-07-30

Effective treatment of cancer depends upon the early detection of the tumor marker. Here, we report on the development of a new immunosensor for early detection of carcinoembryonic antigen (CEA). Cubic Au@Pt dendritic nanomaterials functionalized nitrogen-doped graphene loaded with copper ion (Au@Pt DNs/NG/Cu 2+ ) with enhanced peroxidase-like properties was synthesized as labels to effectively capture and immobilize secondary anti-CEA. The Au@Pt DNs with more active surface area could efficiently enhance electrocatalysis for reduction of hydrogen peroxide (H 2 O 2 ). Meanwhile, with good conductivity and large specific surface area, NG can immobilize a large amount of Au@Pt DNs. Furthermore, after adsorbed Cu 2+ can further promote the redox of H 2 O 2 and amplify the signal of the immunosensor. For the immobilization of primary antibodies, Au nanoparticles functionalized polydopamine (Au@PDA) were used as transducing materials to modify glassy carbon electrodes and enhance the electron transfer efficiently. Under optimal conditions, the immunosensor exhibited a satisfactory response to CEA with a limit detection of 0.167 pg/mL and linear detection range from 0.5 pg/mL to 50 ng/mL. Based on the high sensitivity and specificity of the immunosensor, we propose this multiple amplified biosensor for early detection of CEA. Copyright © 2018 Elsevier B.V. All rights reserved.

Plain to point network reduced graphene oxide - activated carbon composites decorated with platinum nanoparticles for urine glucose detection

NASA Astrophysics Data System (ADS)

Hossain, Mohammad Faruk; Park, Jae Y.

2016-02-01

In this study, a hydrothermal technique was applied to synthesize glucose-treated reduced graphene oxide-activated carbon (GRGO/AC) composites. Platinum nanoparticles (PtNP) were electrochemically deposited on the modified GRGO/AC surface, and chitosan-glucose oxidase (Chit-GOx) composites and nafion were integrated onto the modified surface of the working electrode to prepare a highly sensitive glucose sensor. The fabricated biosensor exhibited a good amperometric response to glucose in the detection range from 0.002 mM to 10 mM, with a sensitivity of 61.06 μA/mMcm2, a short response time (4 s) and a low detection limit of 2 μM (signal to noise ratio is 3). The glucose sensor exhibited a negligible response to interference and good stability. In addition, the glucose levels in human urine were tested in order to conduct a practical assessment of the proposed sensor, and the results indicate that the sensor had superior urine glucose recognition. These results thus demonstrate that the noble nano-structured electrode with a high surface area and electrocatalytic activity offers great promise for use in urine glucose sensing applications.

Plain to point network reduced graphene oxide - activated carbon composites decorated with platinum nanoparticles for urine glucose detection

PubMed Central

Hossain, Mohammad Faruk; Park, Jae Y.

2016-01-01

In this study, a hydrothermal technique was applied to synthesize glucose-treated reduced graphene oxide-activated carbon (GRGO/AC) composites. Platinum nanoparticles (PtNP) were electrochemically deposited on the modified GRGO/AC surface, and chitosan-glucose oxidase (Chit-GOx) composites and nafion were integrated onto the modified surface of the working electrode to prepare a highly sensitive glucose sensor. The fabricated biosensor exhibited a good amperometric response to glucose in the detection range from 0.002 mM to 10 mM, with a sensitivity of 61.06 μA/mMcm2, a short response time (4 s) and a low detection limit of 2 μM (signal to noise ratio is 3). The glucose sensor exhibited a negligible response to interference and good stability. In addition, the glucose levels in human urine were tested in order to conduct a practical assessment of the proposed sensor, and the results indicate that the sensor had superior urine glucose recognition. These results thus demonstrate that the noble nano-structured electrode with a high surface area and electrocatalytic activity offers great promise for use in urine glucose sensing applications. PMID:26876368

Orientation of FePt nanoparticles on top of a-SiO2/Si(001), MgO(001) and sapphire(0001): effect of thermal treatments and influence of substrate and particle size.

PubMed

Schilling, Martin; Ziemann, Paul; Zhang, Zaoli; Biskupek, Johannes; Kaiser, Ute; Wiedwald, Ulf

2016-01-01

Texture formation and epitaxy of thin metal films and oriented growth of nanoparticles (NPs) on single crystal supports are of general interest for improved physical and chemical properties especially of anisotropic materials. In the case of FePt, the main focus lies on its highly anisotropic magnetic behavior and its catalytic activity, both due to the chemically ordered face-centered tetragonal (fct) L10 phase. If the c-axis of the tetragonal system can be aligned normal to the substrate plane, perpendicular magnetic recording could be achieved. Here, we study the orientation of FePt NPs and films on a-SiO2/Si(001), i.e., Si(001) with an amorphous (a-) native oxide layer on top, on MgO(001), and on sapphire(0001) substrates. For the NPs of an approximately equiatomic composition, two different sizes were chosen: "small" NPs with diameters in the range of 2-3 nm and "large" ones in the range of 5-8 nm. The 3 nm thick FePt films, deposited by pulsed laser deposition (PLD), served as reference samples. The structural properties were probed in situ, particularly texture formation and epitaxy of the specimens by reflection high-energy electron diffraction (RHEED) and, in case of 3 nm nanoparticles, additionally by high-resolution transmission electron microscopy (HRTEM) after different annealing steps between 200 and 650 °C. The L10 phase is obtained at annealing temperatures above 550 °C for films and 600 °C for nanoparticles in accordance with previous reports. On the amorphous surface of a-SiO2/Si substrates we find no preferential orientation neither for FePt films nor nanoparticles even after annealing at 630 °C. On sapphire(0001) supports, however, FePt nanoparticles exhibit a clearly preferred (111) orientation even in the as-prepared state, which can be slightly improved by annealing at 600-650 °C. This improvement depends on the size of NPs: Only the smaller NPs approach a fully developed (111) orientation. On top of MgO(001) the effect of annealing on particle orientation was found to be strongest. From a random orientation in the as-prepared state observed for both, small and large FePt NPs, annealing at 650 °C for 30 min reorients the small particles towards a cube-on-cube epitaxial orientation with a minor fraction of (111)-oriented particles. In contrast, large FePt NPs keep their as-prepared random orientation even after doubling the annealing period at 650 °C to 60 min.

Orientation of FePt nanoparticles on top of a-SiO2/Si(001), MgO(001) and sapphire(0001): effect of thermal treatments and influence of substrate and particle size

PubMed Central

Schilling, Martin; Ziemann, Paul; Zhang, Zaoli; Biskupek, Johannes; Kaiser, Ute

2016-01-01

Summary Texture formation and epitaxy of thin metal films and oriented growth of nanoparticles (NPs) on single crystal supports are of general interest for improved physical and chemical properties especially of anisotropic materials. In the case of FePt, the main focus lies on its highly anisotropic magnetic behavior and its catalytic activity, both due to the chemically ordered face-centered tetragonal (fct) L10 phase. If the c-axis of the tetragonal system can be aligned normal to the substrate plane, perpendicular magnetic recording could be achieved. Here, we study the orientation of FePt NPs and films on a-SiO2/Si(001), i.e., Si(001) with an amorphous (a-) native oxide layer on top, on MgO(001), and on sapphire(0001) substrates. For the NPs of an approximately equiatomic composition, two different sizes were chosen: “small” NPs with diameters in the range of 2–3 nm and “large” ones in the range of 5–8 nm. The 3 nm thick FePt films, deposited by pulsed laser deposition (PLD), served as reference samples. The structural properties were probed in situ, particularly texture formation and epitaxy of the specimens by reflection high-energy electron diffraction (RHEED) and, in case of 3 nm nanoparticles, additionally by high-resolution transmission electron microscopy (HRTEM) after different annealing steps between 200 and 650 °C. The L10 phase is obtained at annealing temperatures above 550 °C for films and 600 °C for nanoparticles in accordance with previous reports. On the amorphous surface of a-SiO2/Si substrates we find no preferential orientation neither for FePt films nor nanoparticles even after annealing at 630 °C. On sapphire(0001) supports, however, FePt nanoparticles exhibit a clearly preferred (111) orientation even in the as-prepared state, which can be slightly improved by annealing at 600–650 °C. This improvement depends on the size of NPs: Only the smaller NPs approach a fully developed (111) orientation. On top of MgO(001) the effect of annealing on particle orientation was found to be strongest. From a random orientation in the as-prepared state observed for both, small and large FePt NPs, annealing at 650 °C for 30 min reorients the small particles towards a cube-on-cube epitaxial orientation with a minor fraction of (111)-oriented particles. In contrast, large FePt NPs keep their as-prepared random orientation even after doubling the annealing period at 650 °C to 60 min. PMID:27335749

A nanocomposite-based electrochemical sensor for non-enzymatic detection of hydrogen peroxide

PubMed Central

Du, Xin; Chen, Yuan; Dong, Wenhao; Han, Bingkai; Liu, Min; Chen, Qiang; Zhou, Jun

2017-01-01

Hydrogen peroxide (H2O2) plays important signaling roles in normal physiology and disease. However, analyzing the actions of H2O2 is often impeded by the difficulty in detecting this molecule. Herein, we report a novel nanocomposite-based electrochemical sensor for non-enzymatic detection of H2O2. Graphene oxide (GO) was selected as the dopant for the synthesis of polyaniline (PANI), leading to the successful fabrication of a water-soluble and stable GO-PANI composite. GO-PANI was subsequently subject to cyclic voltammetry to generate reduced GO-PANI (rGO-PANI), enhancing the conductivity of the material. Platinum nanoparticles (PtNPs) were then electrodeposited on the surface of the rGO-PANI-modified glassy carbon electrode (GCE) to form an electrochemical H2O2 sensor. Compared to previously reported sensors, the rGO-PANI-PtNP/GCE exhibited an expanded linear range, higher sensitivity, and lower detection limit in the quantification of H2O2. In addition, the sensor displayed outstanding reproducibility and selectivity in real-sample examination. Our study suggests that the rGO-PANI-PtNP/GCE may have broad utility in H2O2 detection under physiological and pathological conditions. PMID:28035076

An extraordinarily stable catalyst: Pt NPs supported on two-dimensional Ti3C2X2 (X = OH, F) nanosheets for oxygen reduction reaction.

PubMed

Xie, Xiaohong; Chen, Siguo; Ding, Wei; Nie, Yao; Wei, Zidong

2013-10-03

High dispersion Pt nanoparticles supported on 2D Ti3C2X2 (X = OH, F) nanosheets are presented and electro-chemical measurements confirm that the Pt/Ti3C2X2 catalyst shows enhanced durability and improved ORR activity compared with the commercial Pt/C catalyst.

Effects of annealing temperature and duration on the morphological and optical evolution of self-assembled Pt nanostructures on c-plane sapphire.

PubMed

Sui, Mao; Li, Ming-Yu; Kunwar, Sundar; Pandey, Puran; Zhang, Quanzhen; Lee, Jihoon

2017-01-01

Metallic nanostructures (NSs) have been widely adapted in various applications and their physical, chemical, optical and catalytic properties are strongly dependent on their surface morphologies. In this work, the morphological and optical evolution of self-assembled Pt nanostructures on c-plane sapphire (0001) is demonstrated by the control of annealing temperature and dwelling duration with the distinct thickness of Pt films. The formation of Pt NSs is led by the surface diffusion, agglomeration and surface and interface energy minimization of Pt thin films, which relies on the growth parameters such as system temperature, film thickness and annealing duration. The Pt layer of 10 nm shows the formation of overlaying NPs below 650°C and isolated Pt nanoparticles above 700°C based on the enhanced surface diffusion and Volmer-Weber growth model whereas larger wiggly nanostructures are formed with 20 nm thick Pt layers based on the coalescence growth model. The morphologies of Pt nanostructures demonstrate a sharp distinction depending on the growth parameters applied. By the control of dwelling duration, the gradual transition from dense Pt nanoparticles to networks-like and large clusters is observed as correlated to the Rayleigh instability and Ostwald ripening. The various Pt NSs show a significant distinction in the reflectance spectra depending on the morphology evolution: i.e. the enhancement in UV-visible and NIR regions and the related optical properties are discussed in conjunction with the Pt NSs morphology and the surface coverage.

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports.

PubMed

Sneed, Brian T; Cullen, David A; Reeves, Kimberly S; Dyck, Ondrej E; Langlois, David A; Mukundan, Rangachary; Borup, Rodney L; More, Karren L

2017-09-06

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of the cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Furthermore, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports

DOE PAGES

Sneed, Brian T.; Cullen, David A.; Reeves, Kimberly S.; ...

2017-08-15

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of themore » cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Moreover, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.« less

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports

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

Sneed, Brian T.; Cullen, David A.; Reeves, Kimberly S.

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of themore » cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Moreover, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.« less

Visualization of interaction between inorganic nanoparticles and bacteria or fungi.

PubMed

Chwalibog, André; Sawosz, Ewa; Hotowy, Anna; Szeliga, Jacek; Mitura, Stanislaw; Mitura, Katarzyna; Grodzik, Marta; Orlowski, Piotr; Sokolowska, Aleksandra

2010-12-06

The objective of the present investigation was to evaluate the morphologic characteristics of self-assemblies of diamond (nano-D), silver (nano-Ag), gold (nano-Au), and platinum (nano-Pt) nanoparticles with Staphylococcus aureus (bacteria) and Candida albicans (fungi), to determine the possibility of constructing microorganism-nanoparticle vehicles. Hydrocolloids of individual nanoparticles were added to suspensions of S. aureus and C. albicans. Immediately after mixing, the samples were inspected by transmission electron microscopy. Visualization of the morphologic interaction between the nanoparticles and microorganisms showed that nano-D, which are dielectrics and exhibit a positive zeta potential, were very different from the membrane potentials of microorganisms, and uniformly surrounded the microorganisms, without causing visible damage and destruction of cells. All metal nanoparticles with negative zeta potential had cell damaging properties. Nano-Ag showed the properties of self-organization with the cells, disintegrating the cell walls and cytoplasmic membranes, and releasing a substance (probably cytoplasm) outside the cell. Arrangement of nano-Au with microorganisms did not create a system of self-organization, but instead a "noncontact" interaction between the nanoparticles and microorganisms was observed to cause damage to fungal cells. Nano-Pt caused both microorganisms to release a substance outside the cell and disintegrated the cytoplasmic membrane and cell wall. Nano-Ag, nano-Au, and nano-Pt (all metal nanoparticles) are harmful to bacteria and fungi. In contrast, nano-D bind closely to the surface of microorganisms without causing visible damage to cells, and demonstrating good self-assembling ability. The results indicate that both microorganisms could be used as potential carriers for nano-D.

Visualization of interaction between inorganic nanoparticles and bacteria or fungi

PubMed Central

Chwalibog, André; Sawosz, Ewa; Hotowy, Anna; Szeliga, Jacek; Mitura, Stanislaw; Mitura, Katarzyna; Grodzik, Marta; Orlowski, Piotr; Sokolowska, Aleksandra

2010-01-01

Purpose The objective of the present investigation was to evaluate the morphologic characteristics of self-assemblies of diamond (nano-D), silver (nano-Ag), gold (nano-Au), and platinum (nano-Pt) nanoparticles with Staphylococcus aureus (bacteria) and Candida albicans (fungi), to determine the possibility of constructing microorganism–nanoparticle vehicles. Methods Hydrocolloids of individual nanoparticles were added to suspensions of S. aureus and C. albicans. Immediately after mixing, the samples were inspected by transmission electron microscopy. Results Visualization of the morphologic interaction between the nanoparticles and microorganisms showed that nano-D, which are dielectrics and exhibit a positive zeta potential, were very different from the membrane potentials of microorganisms, and uniformly surrounded the microorganisms, without causing visible damage and destruction of cells. All metal nanoparticles with negative zeta potential had cell damaging properties. Nano-Ag showed the properties of self-organization with the cells, disintegrating the cell walls and cytoplasmic membranes, and releasing a substance (probably cytoplasm) outside the cell. Arrangement of nano-Au with microorganisms did not create a system of self-organization, but instead a “noncontact” interaction between the nanoparticles and microorganisms was observed to cause damage to fungal cells. Nano-Pt caused both microorganisms to release a substance outside the cell and disintegrated the cytoplasmic membrane and cell wall. Conclusion Nano-Ag, nano-Au, and nano-Pt (all metal nanoparticles) are harmful to bacteria and fungi. In contrast, nano-D bind closely to the surface of microorganisms without causing visible damage to cells, and demonstrating good self-assembling ability. The results indicate that both microorganisms could be used as potential carriers for nano-D. PMID:21270959

Composition distributions in FePt(Au) nanoparticles

NASA Astrophysics Data System (ADS)

Srivastava, C.; Nikles, D. E.; Harrell, J. W.; Thompson, G. B.

2010-08-01

Ternary alloy FePt(Au) nanoparticles were prepared by the co-reduction of platinum(II) acetylacetonate and gold(III) acetate and the thermal decomposition of iron pentacarbonyl in hot phenyl ether in the presence of oleic acid and oleylamine ligands. This gave spherical particles with an average diameter of 4.4 nm with a range of diameters from approximately 1.6-9 nm. The as-synthesized particles had a solid solution, face-centered-cubic structure. Though the average composition of the particles was Fe44Pt45Au11, individual particle analysis by Scanning Transmission Electron Microscopy-X-ray Energy Dispersive Spectroscopy showed a broad distribution in composition. In general, smaller-sized particles tended to have a lower amount of Au as compared to larger-sized particles. As the Au content increased, the ratio of Fe/Pt widened.

Development and Exploration of Nanoparticle Decorated Carbon Supports (Graphene and Graphene Oxide) for Energy Collection, Storage, and Conversion

DTIC Science & Technology

2012-12-17

hybrid films as an alternative to organic-based photoactive materials in flexible photodetectors and solar cells . Figure 3. Solution...a wide range of metal nanoparticle-decorated (Pt, Au, Ag, Pt/Ru) graphene oxide (GO) hybrids as well as inorganic particle-graphene ( TiO2 /PbSe/G... hybrids . These hybrids were then evaluated for their performance in energy conversion devices and two examples were chosen, namely stacked fuel cells

Sensing Characteristics of Flame-Spray-Made Pt/ZnO Thick Films as H2 Gas Sensor

PubMed Central

Tamaekong, Nittaya; Liewhiran, Chaikarn; Wisitsoraat, Anurat; Phanichphant, Sukon

2009-01-01

Hydrogen sensing of thick films of nanoparticles of pristine, 0.2, 1.0 and 2.0 atomic percentage of Pt concentration doped ZnO were investigated. ZnO nanoparticles doped with 0.2–2.0 at.% Pt were successfully produced in a single step by flame spray pyrolysis (FSP) technique using zinc naphthenate and platinum(II) acetylacetonate as precursors dissolved in xylene. The particle properties were analyzed by XRD, BET, SEM and TEM. Under the 5/5 (precursor/oxygen) flame condition, ZnO nanoparticles and nanorods were observed. The crystallite sizes of ZnO spheroidal and hexagonal particles were found to be ranging from 5 to 20 nm while ZnO nanorods were seen to be 5–20 nm wide and 20–40 nm long. ZnO nanoparticles paste composed of ethyl cellulose and terpineol as binder and solvent respectively was coated on Al2O3 substrate interdigitated with gold electrodes to form thin films by spin coating technique. The thin film morphology was analyzed by SEM technique. The gas sensing properties toward hydrogen (H2) was found that the 0.2 at.% Pt/ZnO sensing film showed an optimum H2 sensitivity of ∼164 at hydrogen concentration in air of 1 volume% at 300 °C and a low hydrogen detection limit of 50 ppm at 300 °C operating temperature. PMID:22399971

Pt/ZnO nanoarray nanogenerator as self-powered active gas sensor with linear ethanol sensing at room temperature.

PubMed

Zhao, Yayu; Lai, Xuan; Deng, Ping; Nie, Yuxin; Zhang, Yan; Xing, Lili; Xue, Xinyu

2014-03-21

A self-powered gas sensor that can actively detect ethanol at room temperature has been realized from a Pt/ZnO nanoarray nanogenerator. Pt nanoparticles are uniformly distributed on the whole surface of ZnO nanowires. The piezoelectric output of Pt/ZnO nanoarrays can act not only as a power source, but also as a response signal to ethanol at room temperature. Upon exposure to dry air and 1500 ppm ethanol at room temperature, the piezoelectric output of the device under the same compressive strain is 0.672 and 0.419 V, respectively. Moreover, a linear dependence of the sensitivity on the ethanol concentration is observed. Such a linear ethanol sensing at room temperature can be attributed to the atmosphere-dependent variety of the screen effect on the piezoelectric output of ZnO nanowires, the catalytic properties of Pt nanoparticles, and the Schottky barriers at Pt/ZnO interfaces. The present results can stimulate research in the direction of designing new material systems for self-powered room-temperature gas sensing.

Monodispersed porous flowerlike PtAu nanocrystals as effective electrocatalysts for ethanol oxidation

NASA Astrophysics Data System (ADS)

Li, Shumin; Xu, Hui; Xiong, Zhiping; Zhang, Ke; Wang, Caiqin; Yan, Bo; Guo, Jun; Du, Yukou

2017-11-01

Designing and tuning the bimetallic nanoparticles with desirable morphology and structure can embody them with greatly enhanced electrocatalytic activity and stability towards liquid fuel oxidation. We herein reported a facile one-pot method for the controlled synthesis of monodispersed binary PtAu nanoflowers with abundant exposed surface area. Owing to its fantastic structure, synergistic and electronic effect, such as-prepared PtAu nanoflowers exhibited outstandingly high electrocatalytic activity with the mass activity of 6482 mA mg-1 towards ethanol oxidation, which is 28.3 times higher than that of commercial Pt/C (227 mA mg-1). More interesting, the present PtAu nanoflower catalysts are more stable for the ethanol oxidation reaction in the alkaline with lower current density decay and retained a much higher current density after successive CVs of 500 cycles than that of commercial Pt/C. This work may open a new way for maximizing the catalytic performance of electrocatalysts towards ethanol oxidation by synthesizing shape-controlled alloy nanoparticles with more surface active sites to enhance the performances of direct fuel cells reaction, chemical conversion, and beyond.

Facile Photochemical Synthesis of Au/Pt/g-C3N4 with Plasmon-Enhanced Photocatalytic Activity for Antibiotic Degradation.

PubMed

Xue, Jinjuan; Ma, Shuaishuai; Zhou, Yuming; Zhang, Zewu; He, Man

2015-05-13

A novel plasmonic photocatalyst, Au/Pt/g-C3N4, was prepared by a facile calcination-photodeposition technique. The samples were characterized by X-ray diffraction, energy-dispersive spectroscopy, transmission electron microscopy, and UV-vis diffuse reflectance spectroscopy, and the results demonstrated that the Au and Pt nanoparticles (7-15 nm) were well-dispersed on the surfaces of g-C3N4. The Au/Pt codecorated g-C3N4 heterostructure displayed enhanced photocatalytic activity for antibiotic tetracycline hydrochloride (TC-HCl) degradation, and the degradation rate was 3.4 times higher than that of pure g-C3N4 under visible light irradiation. The enhancement of photocatalytic activity could be attributed to the surface plasmon resonance effect of Au and electron-sink function of Pt nanoparticles, which improve the optical absorption property and photogenerated charge carriers separation of g-C3N4, synergistically facilitating the photocatalysis process. Finally, a possible photocatalytic mechanism for degrading TC-HCl by Au/Pt/g-C3N4 heterostructure was tentatively proposed.

Enhanced electronic and electrochemical properties of core-shelled V2O5-Pt nanowires

NASA Astrophysics Data System (ADS)

Pan, Ko-Ying; Wei, Da-Hua

2018-01-01

Platinum nanoparticles (Pt NPs) were decorated on vanadium pentoxide nanowires (V2O5 NWs) to form the core-shelled vanadium-platinum nanowires (Pt@V2O5 NWs) and their electrochemical activities for methanol oxidation were investigated. The synthetic procedure involved the synthesis of abundant vanadium pentoxide nanowires (V2O5 NWs) by a direct vapor-solid growth process (VS method), followed by atomic layer depositions (ALD) of platinum nanoparticles (Pt NPs) onto the V2O5 NWs. After the physical examinations, three designed deposition parameters (50, 100 and 150 cycles) of Pt NPs onto the V2O5 NWs by ALD process were successful. From the measurements of current-voltage (I-V) and cyclic voltammetry (CV) curves respectively, both the conductivity and the ratio of the forward anodic peak current (IF) to the reverse anodic peak current (IR) are enhancing proportionately to the deposition cycles of ALD process, which denotes that coating Pt atomic layers onto V2O5 nanowires indeed improves the catalytic performances than that of pure V2O5 nanowires.

Surface-enhanced Raman spectroscopy of double-shell hollow nanoparticles: electromagnetic and chemical enhancements.

PubMed

Mahmoud, Mahmoud A

2013-05-28

Enhancements of the Raman signal by the newly prepared gold-palladium and gold-platinum double-shell hollow nanoparticles were examined and compared with those using gold nanocages (AuNCs). The surface-enhanced Raman spectra (SERS) of thiophenol adsorbed on the surface of AuNCs assembled into a Langmuir-Blodgett monolayer were 10-fold stronger than AuNCs with an inner Pt or Pd shell. The chemical and electromagnetic enhancement mechanisms for these hollow nanoparticles were further proved by comparing the Raman enhancement of nitrothiophenol and nitrotoulene. Nitrothiophenol binds to the surface of the nanoparticles by covalent interaction, and Raman enhancement by both the two mechanisms is possible, while nitrotoulene does not form any chemical bond with the surface of the nanoparticles and hence no chemical enhancement is expected. Based on discrete dipole approximation (DDA) calculations and the experimental SERS results, AuNCs introduced a high electromagnetic enhancement, while the nanocages with inner Pt or Pd shell have a strong chemical enhancement. The optical measurements of the localized surface plasmon resonance (LSPR) of the nanocages with an outer Au shell and an inner Pt or Pd shell were found, experimentally and theoretically, to be broad compared with AuNCs. The possible reason could be due to the decrease of the coherence time of Au oscillated free electrons and fast damping of the plasmon energy. This agreed well with the fact that a Pt or Pd inner nanoshell decreases the electromagnetic field of the outer Au nanoshell while increasing the SERS chemical enhancement.

Preparation and characterization of nanostructured Pt/TiO2 thin films treated using electron beam.

PubMed

Shin, Joong-Hyeok; Woo, Hee-Gweon; Kim, Bo-Hye; Lee, Byung Cheol; Jun, Jin

2010-05-01

Pt nanoparticle-doped titanium dioxide (Pt/TiO2) thin films were prepared on a silicon wafer substrate by sol-gel spin coating process. The prepared thin films were treated with electron beam (EB at 1.1 MeV, 100, 200, 300 kGy) at air atmosphere. The effect of EB-irradiation on the composition of the treated thin films, optical properties and morphology of thin films were investigated by various analytical techniques such as X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE), X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The crystal structure of the TiO2 layer was found to be an anatase phase and the size of TiO2 particles was determined to be about 13 nm. Pt nanoparticles with diameter of 5 nm were observed on surface of the films. A new layer (presumed to be Pt-Ti complex and/or PtO2 compound) was created in the Pt/TiO2 thin film treated with EB (300 kGy). The transmittance of thin film decreased with EB treatment whereas the refractive index increased.

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

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 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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07897k

Nanostructured aptamer-based sensing platform for highly sensitive recognition of myoglobin.

PubMed

Nia, Neda Ghafori; Azadbakht, Azadeh

2018-06-21

A composite was prepared from PtSn nanoparticles and carbon nanotubes (PtSnNP/CNTs) and applied to the electrochemical determination of myoglobin (Mb). An Mb-aptamer was immobilized on a glassy carbon electrode (GCE), and hexcyanoferrate was used as an electrochemical probe. The PtSnNP/CNTs were synthesized by a microwave-aided ethylene glycol reduction method. Detection is based on electron transfer inhibition that is caused by the folding and conformational change of the Mb-aptamer in the presence of Mb. The amperometric signal for hexacyanoferrate, best measured at 0.2 V vs. Ag/AgCl depends on the concentration of Mb that interacts with the aptamer on the GCE. This approach is selective and sensitive for Mb due to (a) the highly specific recognition ability of the aptamer for Mb, (b) the powerful electronic properties of carbon nanotubes, (c) the arranged decoration of CNTs with PtSnNPs, and (d), the superior electron transfer to hexacyanoferrate. The assay is highly selective, with linear relationships from 0.01-1 nM and 10 nM-200 nM, and a limit of detection as low as 2.2 ± 0.1 pM. The modified GCE was applied to the quantitation of Mb in spiked human serum samples. Graphical abstract Schematic illustration of the method for Mb detection.

Recent Advances in Developing Platinum Monolayer Electrocatalysts for the O2 Reduction Reaction

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

Vukmirovic,M.B.; Sasaki, K.; Zhou, W.-P.

2008-09-15

For Pt, the best single-element catalyst for many reactions, the question of content and loading is exceedingly important because of its price and availability. Using platinum as a fuel-cell catalyst in automotive applications will cause an unquantifiable increase in the demand for this metal. This big obstacle for using fuel cells in electric cars must be solved by decreasing the content of Pt, which is a great challenge of electrocatalysis Over the last several years we inaugurated a new class of electrocatalysts for the oxygen reduction reaction (ORR) based on a monolayer of Pt deposited on metal or alloy carbon-supportedmore » nanoparticles. The possibility of decreasing the Pt content in the ORR catalysts down to a monolayer level has a considerable importance because this reaction requires high loadings due to its slow kinetics. The Pt-monolayer approach has several unique features and some of them are: high Pt utilization, enhanced (or decreased) activity, enhanced stability, and direct activity correlations. The synthesis of Pt monolayer (ML) electrocatalysts was facilitated by our new synthesis method which allowed us to deposit a monolayer of Pt on various metals, or alloy nanoparticles [1, 2] for the cathode electrocatalyst. In this synthesis approach Pt is laid down by the galvanically displacing a Cu monolayer, which was deposited at underpotentials in a monolayer-limited reaction on appropriate metal substrate, with Pt after immersing the electrode in a K{sub 2}PtCl{sub 4} solution.« less

Realization of Both High-Performance and Enhanced Durability of Fuel Cells: Pt-Exoskeleton Structure Electrocatalysts.

PubMed

Kim, Ok-Hee; Cho, Yoon-Hwan; Jeon, Tae-Yeol; Kim, Jung Won; Cho, Yong-Hun; Sung, Yung-Eun

2015-07-01

Core-shell structure nanoparticles have been the subject of many studies over the past few years and continue to be studied as electrocatalysts for fuel cells. Therefore, many excellent core-shell catalysts have been fabricated, but few studies have reported the real application of these catalysts in a practical device actual application. In this paper, we demonstrate the use of platinum (Pt)-exoskeleton structure nanoparticles as cathode catalysts with high stability and remarkable Pt mass activity and report the outstanding performance of these materials when used in membrane-electrode assemblies (MEAs) within a polymer electrolyte membrane fuel cell. The stability and degradation characteristics of these materials were also investigated in single cells in an accelerated degradation test using load cycling, which is similar to the drive cycle of a polymer electrolyte membrane fuel cell used in vehicles. The MEAs with Pt-exoskeleton structure catalysts showed enhanced performance throughout the single cell test and exhibited improved degradation ability that differed from that of a commercial Pt/C catalyst.

Enhanced photoelectrochemical performance of TiO2 nanotube arrays with coexisted Pt nanoparticles and Co-Pi cocatalysts

NASA Astrophysics Data System (ADS)

Li, Yanfang; Cao, Chang; Xie, Xinxin; Zhang, Li; Lin, Shiwei

2018-04-01

Highly-ordered TiO2 nanotube arrays (TNTAs) were prepared by electrochemical anodization. Cobalt-phosphate (Co-Pi) film fabricated by electrodeposition and Pt nanoparticles (Pt NPs) fabricated by photochemical reduction were decorated onto TNTAs to enhance the photoelectrochemical (PEC) performance together. The photocurrent density of the TNTAs/Co-Pi/Pt photoelectrode could reach 0.185 mA/cm2 at 1.23 V versus reversible hydrogen electrode under UV lamp illumination (1 mW/cm2), which is 2.65 times compared to that of the pure TNTAs photoelectrode. Electrochemistry impedance spectroscopy and Mott-Schottky analysis were conducted to explore the reasons for the enhancement of the PEC performance. Pt NPs could promote the reduction of Co(Ⅳ)-oxo intermediate to Co(II) or Co(Ⅲ) which facilitated the charge transfer in the PEC performance. The result provides a promising guideline to design a simple and efficient photoelectrode for the PEC water-splitting system.

Glucose Biosensor Based on Immobilization of Glucose Oxidase in Platinum Nanoparticles/Graphene/Chitosan Nanocomposite Film

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

Wu, Hong; Wang, Jun; Kang, Xinhuang

2009-09-01

The bionanocomposite film consisting of glucose oxidase/Pt/functional graphene sheets/chitosan (GOD/Pt/FGS/chitosan) for glucose sensing was described. With the electrocatalytic synergy of FGS and Pt nanoparticles to hydrogen peroxide, a sensitive biosensor with detection limit of 0.6 µM glucose was achieved. The biosensor also had good reproducibility, long term stability and negligible interfering signals from ascorbic acid and uric acid comparing to the response to glucose. The large surface area and good conductivity of graphene suggests that graphene is a potential candidate for sensor material. The hybrid nanocomposite glucose sensor provides new opportunity for clinical diagnosis and point-of-care applications.

Loss compensation symmetry in dimers made of gain and lossy nanoparticles

NASA Astrophysics Data System (ADS)

Klimov, V. V.; Zabkov, I. V.; Guzatov, D. V.; Vinogradov, A. P.

2018-03-01

The eigenmodes in a two-dimensional dimer made of gain and lossy nanoparticles have been investigated within an exact analytical approach. It has been shown that there are eigenmodes for which all Joule losses are exactly compensated by the gain. Among such solutions there are solutions with a new type of symmetry, which we refer to as loss compensation symmetry, as well as well-known parity-time (PT) symmetric solutions. Unlike PT symmetric ones, the modes with loss compensation symmetry allow one to achieve full loss compensation with significantly less gain that in the case of PT symmetry. This effect paves the way to new loss compensation methods in optics.

Platinum nanoparticles encapsulated metal-organic frameworks for the electrochemical detection of telomerase activity.

PubMed

Ling, Pinghua; Lei, Jianping; Jia, Li; Ju, Huangxian

2016-01-21

A simple and rapid electrochemical sensor is constructed for the detection of telomerase activity based on the electrocatalysis of platinum nanoparticle (Pt NP) encapsulated metal-organic frameworks (MOFs), which are synthesized by one-pot encapsulation of Pt NPs into prototypal MOFs, UiO-66-NH2. Integrating with the efficient electrocatalysis of Pt@MOFs towards NaBH4 oxidation, this biosensor shows the wide dynamic correlation of telomerase activity from 5 × 10(2) to 10(7) HeLa cells mL(-1) and the telomerase activity in a single HeLa cell was calculated to be 2.0 × 10(-11) IU, providing a powerful platform for detecting telomerase activity.

High-coercivity FePt nanoparticle assemblies embedded in silica thin films.

PubMed

Yan, Q; Purkayastha, A; Singh, A P; Li, H; Li, A; Ramanujan, R V; Ramanath, G

2009-01-14

The ability to process assemblies using thin film techniques in a scalable fashion would be a key to transmuting the assemblies into manufacturable devices. Here, we embed FePt nanoparticle assemblies into a silica thin film by sol-gel processing. Annealing the thin film composite at 650 degrees C transforms the chemically disordered fcc FePt phase into the fct phase, yielding magnetic coercivity values H(c)>630 mT. The positional order of the particles is retained due to the protection offered by the silica host. Such films with assemblies of high-coercivity magnetic particles are attractive for realizing new types of ultra-high-density data storage devices and magneto-composites.

Novel galactosylated biodegradable nanoparticles for hepatocyte-delivery of oridonin.

PubMed

Wang, Ying; Liu, Xinquan; Liu, Guangpu; Guo, Hejian; Li, Caiyun; Zhang, Yongchun; Zhang, Fang; Zhao, Zhongxi; Cheng, Huiling

2016-04-11

Nanoparticles based on the newly synthesized copolymers of linear PLGA blocked with two TPGS ends and galactosylated TPGS were successfully constructed as carriers of oridonin for liver-targeting. The novel copolymers were characterized by (1)H-NMR and TGA. The drug-loaded nanoparticles were prepared by a nanoprecipitation technique and characterized in terms of physicochemical properties, such as particle size, zeta potential, morphology, encapsulation efficiency, in vitro drug release behavior and physical state of the entrapped drug. The ORI-Gal-PT NPs were found to have the highest antitumor efficacy in comparison with the oridonin solution and non-galactosylated nanoparticles and induced a higher apoptotic rate of tumor cells. The targeting nanoparticles could enhance the therapeutic effect of oridonin by increasing uptake of the nanoparticles through asialoglycoprotein receptor-mediated endocytosis. The ORI-Gal-PT NPs system could be a highly promising drug delivery system to be used in liver cancer therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

Photochemical Fabrication of Transition Metal Nanoparticles Using CdS Template and Their Co-Catalysis Effects for TiO2 Photocatalysis

NASA Astrophysics Data System (ADS)

Badhwar, Nidhi; Gupta, Nidhi; Pal, Bonamali

2013-09-01

Transition metal nanoparticles were prepared by chemical dissolution of CdS template from metal photodeposited CdS nanorod (length = 70-85 nm and width = 5-6 nm) heterocomposites. Size (9-10 nm) of metal nanoparticles obtained after CdS removal was larger than the size (4-6 nm) of metal nanodeposits over CdS template. The obtained Au nanoparticles displayed a broad red shifted absorption band at 660 nm, whereas Pt, Pd and Rh nanoparticles exhibit featureless absorption spectra. Elemental analysis confirms the complete removal of CdS template from Au-CdS (Au — 2.65 at.%) and Ag-CdS (Ag — 2.06 at.%) composites showing no Cd peak. These metal nanoparticles imparted dissimilar co-catalytic activity of TiO2 for photocatalytic degradation of salicylic acid in the order Au > Pt > Pd > Ag > Rh as a function of their nature, electronegativity, redox potential and work function.

Pt-Pd Bimetal Popcorn Nanocrystals: Enhancing the Catalytic Performance by Combination Effect of Stable Multipetals Nanostructure and Highly Accessible Active Sites.

PubMed

Ma, Yanxia; Yin, Lisi; Cao, Guojian; Huang, Qingli; He, Maoshuai; Wei, Wenxian; Zhao, Hong; Zhang, Dongen; Wang, Mingyan; Yang, Tao

2018-04-01

Exploration of highly efficient electrocatalysts is significantly urgent for the extensive adoption of the fuel cells. Because of their high activity and super stability, Pt-Pd bimetal nanocrystals have been widely recognized as one class of promising electrocatalysts for oxygen reduction. This article presents the synthesis of popcorn-shaped Pt-Pd bimetal nanoparticles with a wide composition range through a facile hydrothermal strategy. The hollow-centered nanoparticles are surrounded by several petals and concave surfaces. By exploring the oxygen reduction reaction on the carbon supported Pt-Pd popcorns in perchloric acid solution, it is found that compared with the commercial Pt/C catalyst the present catalysts display superior catalytic performances in aspects of catalytic activity and stability. More importantly, the Pt-Pd popcorns display minor performance degradations through prolonged potential cycling. The enhanced performances can be mainly attributed to the unique popcorn structure of the Pt-Pd components, which allows the appearance and long existence of the high active sites with more accessibility. The present work highlights the key roles of accessible high active sites in the oxygen reduction reaction, which will ultimately guide the design of highly durable Pt-Pd catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental and Theoretical Structural Investigation of AuPt Nanoparticles Synthesized using a Direct Electrochemical Method

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

Lapp, Aliya S.; Duan, Zhiyao; Marcella, Nicholas

In this report we examine the structure of bimetallic nanomaterials prepared by an electrochemical approach known as hydride-terminated (HT) electrodeposition. It has been shown previously that this method can lead to deposition of a single Pt monolayer on bulk-phase Au surfaces. Specifically, under appropriate electrochemical conditions and using a solution containing PtCl 4 2-, a monolayer of Pt atoms electrodeposits onto bulk-phase Au immediately followed by a monolayer of H atoms. The H-atom capping layer prevents deposition of Pt multilayers. We applied this method to ~1.6 nm Au nanoparticles (AuNPs) immobilized on an inert electrode surface. In contrast to themore » well-defined, segregated Au/Pt structure of the bulk-phase surface, we observe that HT electrodeposition leads to the formation of AuPt quasi-random alloy NPs rather than the core@shell structure anticipated from earlier reports relating to deposition onto bulk phases. The results provide a good example of how the phase behavior of macro materials does not always translate to the nano world. A key component of this study was the structure determination of the AuPt NPs, which required a combination of electrochemical methods, electron microscopy, X-ray absorption spectroscopy, and theory (DFT and MD).« less

Synthesis of honeycomb-like mesoporous nitrogen-doped carbon nanospheres as Pt catalyst supports for methanol oxidation in alkaline media

NASA Astrophysics Data System (ADS)

Zhang, Yunmao; Liu, Yong; Liu, Weihua; Li, Xiying; Mao, Liqun

2017-06-01

This paper reports the convenient synthesis of honeycomb-like mesoporous nitrogen-doped carbon spheres (MNCS) using a self-assembly strategy that employs dopamine (DA) as a carbon and nitrogen precursor and a polystyrene-b-poly(ethylene oxide) (PS173-b-PEO170) diblock copolymer as a soft template. The MNCS have large BET surface areas of up to 554 m2 g-1 and high nitrogen contents of up to 6.9 wt%. The obtained MNCS are used as a support for Pt catalysts, which promote methanol oxidation in alkaline media. The MNCS-supported Pt (Pt/MNCS) catalyst has a larger electrochemically active surface area (ESA) (89.2 m2 g-1) than does a commercially available Vulcan XC-72R supported Pt/C catalyst. Compared to the Pt/C catalyst, Pt/MNCS displays a higher peak current density (1007 mA mg-1) and is more stable during methanol oxidation. These improvements are attributed to the honeycomb-like porous structure of the MNCS and the introduction of nitrogen to the carbon support. The MNCS effectively stabilize Pt nanoparticles and assuage the agglomeration of the nanoparticles, suggesting that MNCS are potential and promising application as electrocatalyst supports in alkaline direct methanol fuel cells.

Experimental and Theoretical Structural Investigation of AuPt Nanoparticles Synthesized using a Direct Electrochemical Method

DOE PAGES

Lapp, Aliya S.; Duan, Zhiyao; Marcella, Nicholas; ...

2018-06-01

In this report we examine the structure of bimetallic nanomaterials prepared by an electrochemical approach known as hydride-terminated (HT) electrodeposition. It has been shown previously that this method can lead to deposition of a single Pt monolayer on bulk-phase Au surfaces. Specifically, under appropriate electrochemical conditions and using a solution containing PtCl 4 2-, a monolayer of Pt atoms electrodeposits onto bulk-phase Au immediately followed by a monolayer of H atoms. The H-atom capping layer prevents deposition of Pt multilayers. We applied this method to ~1.6 nm Au nanoparticles (AuNPs) immobilized on an inert electrode surface. In contrast to themore » well-defined, segregated Au/Pt structure of the bulk-phase surface, we observe that HT electrodeposition leads to the formation of AuPt quasi-random alloy NPs rather than the core@shell structure anticipated from earlier reports relating to deposition onto bulk phases. The results provide a good example of how the phase behavior of macro materials does not always translate to the nano world. A key component of this study was the structure determination of the AuPt NPs, which required a combination of electrochemical methods, electron microscopy, X-ray absorption spectroscopy, and theory (DFT and MD).« less

Experimental and Theoretical Structural Investigation of AuPt Nanoparticles Synthesized Using a Direct Electrochemical Method.

PubMed

Lapp, Aliya S; Duan, Zhiyao; Marcella, Nicholas; Luo, Long; Genc, Arda; Ringnalda, Jan; Frenkel, Anatoly I; Henkelman, Graeme; Crooks, Richard M

2018-05-11

In this report, we examine the structure of bimetallic nanomaterials prepared by an electrochemical approach known as hydride-terminated (HT) electrodeposition. It has been shown previously that this method can lead to deposition of a single Pt monolayer on bulk-phase Au surfaces. Specifically, under appropriate electrochemical conditions and using a solution containing PtCl 4 2- , a monolayer of Pt atoms electrodeposits onto bulk-phase Au immediately followed by a monolayer of H atoms. The H atom capping layer prevents deposition of Pt multilayers. We applied this method to ∼1.6 nm Au nanoparticles (AuNPs) immobilized on an inert electrode surface. In contrast to the well-defined, segregated Au/Pt structure of the bulk-phase surface, we observe that HT electrodeposition leads to the formation of AuPt quasi-random alloy NPs rather than the core@shell structure anticipated from earlier reports relating to deposition onto bulk phases. The results provide a good example of how the phase behavior of macro materials does not always translate to the nano world. A key component of this study was the structure determination of the AuPt NPs, which required a combination of electrochemical methods, electron microscopy, X-ray absorption spectroscopy, and theory (DFT and MD).

Effects triggered by platinum nanoparticles on primary keratinocytes.

PubMed

Konieczny, Piotr; Goralczyk, Anna Grazyna; Szmyd, Radoslaw; Skalniak, Lukasz; Koziel, Joanna; Filon, Francesca Larese; Crosera, Matteo; Cierniak, Agnieszka; Zuba-Surma, Ewa K; Borowczyk, Julia; Laczna, Eliza; Drukala, Justyna; Pyza, Elzbieta; Semik, Danuta; Woznicka, Olga; Klein, Andrzej; Jura, Jolanta

2013-01-01

The platinum (Pt)-group elements (PGEs) represent a new kind of environmental pollutant and a new hazard for human health. Since their introduction as vehicle-exhaust catalysts, their emissions into the environment have grown considerably compared with their low natural concentration in the earth crust. PGE emissions from vehicle catalysts can be also in the form of nanometer-sized particles (Pt nanoparticles [PtNPs]). These elements, both in their metallic form or as ions solubilized in biological media, are now recognized as potent allergens and sensitizers. Human skin is always exposed to toxic particles; therefore, in the present study we addressed the question of whether polyvinylpyrrolidone-coated PtNPs may have any negative effects on skin cells, including predominantly epidermal keratinocytes. In this study, PtNPs of two sizes were used: 5.8 nm and 57 nm, in concentrations of 6.25, 12.5, and 25 μg/mL. Both types of NPs were protected with polyvinylpyrrolidone. Primary keratinocytes were treated for 24 and 48 hours, then cytotoxicity, genotoxicity, morphology, metabolic activity, and changes in the activation of signaling pathways were investigated in PtNP-treated cells. We found that PtNPs trigger toxic effects on primary keratinocytes, decreasing cell metabolism, but these changes have no effects on cell viability or migration. Moreover, smaller NPs exhibited more deleterious effect on DNA stability than the big ones. Analyzing activation of caspases, we found changes in activity of caspase 9 and caspase 3/7 triggered mainly by smaller NPs. Changes were not so significant in the case of larger nanoparticles. Importantly, we found that PtNPs have antibacterial properties, as is the case with silver NPs (AgNPs). In comparison to our previous study regarding the effects of AgNPs on cell biology, we found that PtNPs do not exhibit such deleterious effects on primary keratinocytes as AgNPs and that they also can be used as potential antibacterial agents, especially in the treatment of Escherichia coli, representing a group of Gram-negative species.

Designed catalysts from Pt nanoparticles supported on macroporous oxides for selective isomerization of n-hexane.

PubMed

An, Kwangjin; Alayoglu, Selim; Musselwhite, Nathan; Na, Kyungsu; Somorjai, Gabor A

2014-05-14

Selective isomerization toward branched hydrocarbons is an important catalytic process in oil refining to obtain high-octane gasoline with minimal content of aromatic compounds. Colloidal Pt nanoparticles with controlled sizes of 1.7, 2.7, and 5.5 nm were deposited onto ordered macroporous oxides of SiO2, Al2O3, TiO2, Nb2O5, Ta2O5, and ZrO2 to investigate Pt size- and support-dependent catalytic selectivity in n-hexane isomerization. Among the macroporous oxides, Nb2O5 and Ta2O5 exhibited the highest product selectivity, yielding predominantly branched C6 isomers, including 2- or 3-methylpentane, as desired products of n-hexane isomerization (140 Torr n-hexane and 620 Torr H2 at 360 °C). In situ characterizations including X-ray diffraction and ambient-pressure X-ray photoelectron spectroscopy showed that the crystal structures of the oxides in Pt/oxide catalysts were not changed during the reaction and oxidation states of Nb2O5 were maintained under both H2 and O2 conditions. Fourier transform infrared spectra of pyridine adsorbed on the oxides showed that Lewis sites were the dominant acidic site of the oxides. Macroporous Nb2O5 and Ta2O5 were identified to play key roles in the selective isomerization by charge transfer at Pt-oxide interfaces. The selectivity was revealed to be Pt size-dependent, with improved isomer production as Pt sizes increased from 1.7 to 5.5 nm. When 5.5 nm Pt nanoparticles were supported on Nb2O5 or Ta2O5, the selectivity toward branched C6 isomers was further increased, reaching ca. 97% with a minimum content of benzene, due to the combined effects of the Pt size and the strong metal-support interaction.

Using the M13 Phage as a Biotemplate to Create Mesoporous Structures Decorated with Gold and Platinum Nanoparticles.

PubMed

Vera-Robles, L Irais; González-Gracida, Jaqueline; Hernández-Gordillo, Armin; Campero, Antonio

2015-08-25

By taking advantage of the physical and chemical properties of the M13 bacteriophage, we have used this virus to synthesize mesoporous silica structures. Major coat protein p8 was chemically modified by attaching thiol groups. As we show, the resulting thiolated phage can be used as a biotemplate able to direct the formation of mesoporous silica materials. Simultaneously, this thiol functionality acts as an anchor for binding metal ions, such as Au(3+) and Pt(4+), forming reactive M13-metal ionic complexes which evolve into metal nanoparticles (NPs) trapped in the mesoporous network. Interestingly, Au(3+) ions are reduced to Au(0) NPs by the protein residues without requiring an external reducing agent. Likewise, silica mesostructures decorated with Au and Pt NPs are prepared in a one-pot synthesis and characterized using different techniques. The obtained results allow us to propose a mechanism of formation. In addition, gold-containing mesoporous structures are tested for the reduction of 4-nitrophenol (4-NP) and methylene blue (MB) in the presence of NaBH4. Although all of the gold-containing catalysts exhibit catalytic activity, those obtained with thiolated phages present a better performance than that obtained with M13 alone. This behavior is ascribed to the position of the Au NPs, which are partially embedded in the wall of the final mesostructures.

Double heterojunction nanowire photocatalysts for hydrogen generation

NASA Astrophysics Data System (ADS)

Tongying, P.; Vietmeyer, F.; Aleksiuk, D.; Ferraudi, G. J.; Krylova, G.; Kuno, M.

2014-03-01

Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core/shell nanowires and their Pt nanoparticle-decorated counterparts. Femtosecond transient differential absorption measurements reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. In turn, we unravel the role of surface passivation, charge separation at semiconductor interfaces and charge transfer to metal co-catalysts in determining photocatalytic H2 generation efficiencies. This allows us to rationalize why Pt nanoparticle decorated CdSe/CdS NWs, a double heterojunction system, performs best with H2 generation rates of ~434.29 +/- 27.40 μmol h-1 g-1 under UV/Visible irradiation. In particular, we conclude that the CdS shell of this double heterojunction system serves two purposes. The first is to passivate CdSe NW surface defects, leading to long-lived charges at the CdSe/CdS interface capable of carrying out reduction chemistries. Upon photoexcitation, we also find that CdS selectively injects charges into Pt NPs, enabling simultaneous reduction chemistries at the Pt NP/solvent interface. Pt nanoparticle decorated CdSe/CdS NWs thus enable reduction chemistries at not one, but rather two interfaces, taking advantage of each junction's optimal catalytic activities.Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core/shell nanowires and their Pt nanoparticle-decorated counterparts. Femtosecond transient differential absorption measurements reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. In turn, we unravel the role of surface passivation, charge separation at semiconductor interfaces and charge transfer to metal co-catalysts in determining photocatalytic H2 generation efficiencies. This allows us to rationalize why Pt nanoparticle decorated CdSe/CdS NWs, a double heterojunction system, performs best with H2 generation rates of ~434.29 +/- 27.40 μmol h-1 g-1 under UV/Visible irradiation. In particular, we conclude that the CdS shell of this double heterojunction system serves two purposes. The first is to passivate CdSe NW surface defects, leading to long-lived charges at the CdSe/CdS interface capable of carrying out reduction chemistries. Upon photoexcitation, we also find that CdS selectively injects charges into Pt NPs, enabling simultaneous reduction chemistries at the Pt NP/solvent interface. Pt nanoparticle decorated CdSe/CdS NWs thus enable reduction chemistries at not one, but rather two interfaces, taking advantage of each junction's optimal catalytic activities. Electronic supplementary information (ESI) available: Details of NW syntheses, processing and characterization. Additional TEM images of CdS, CdSe and CdSe/CdS core/shell NWs. NW concentration and cross section estimates. Details of the Pt NP decoration. Additional TEM images of Pt NP decorated CdS, CdSe and CdSe/CdS core/shell NWs. Size distribution of Pt NPs for CdSe/Pt NP and CdSe/CdS/Pt NP NWs. Xe arc lamp spectrum. Details of H2 generation experiments. Estimated photon absorption rate. Details of TDA measurements. TDA spectra and kinetics of CdS and CdS/Pt NP NWs. Plot illustrating CdSe NW band edge bleach kinetics. Comparison of CdSe band edge bleach kinetics in CdSe/CdS core/shell NWs when excited at λexc = 387 nm and λexc = 560 nm. Comparison of CdSe band edge bleach kinetics in CdSe/Pt NP NWs when excited at λexc = 387 nm and λexc = 560 nm. Bar graph showing H2 generation efficiencies of CdS and CdS/Pt NP NWs. Bleach kinetics of CdSe/CdS/Pt NP NWs at λexc = 387 nm and λexc = 560 nm. Comparison of CdS band edge bleach kinetics in CdS/Pt NP, and CdSe/CdS core/shell NWs when excited at λexc = 387 nm. See DOI: 10.1039/c4nr00298a

Hemoglobin–Albumin Cluster Incorporating a Pt Nanoparticle: Artificial O2 Carrier with Antioxidant Activities

PubMed Central

Hosaka, Hitomi; Haruki, Risa; Yamada, Kana; Böttcher, Christoph; Komatsu, Teruyuki

2014-01-01

A covalent core–shell structured protein cluster composed of hemoglobin (Hb) at the center and human serum albumins (HSA) at the periphery, Hb-HSAm, is an artificial O2 carrier that can function as a red blood cell substitute. Here we described the preparation of a novel Hb-HSA3 cluster with antioxidant activities and its O2 complex stable in aqueous H2O2 solution. We used an approach of incorporating a Pt nanoparticle (PtNP) into the exterior HSA unit of the cluster. A citrate reduced PtNP (1.8 nm diameter) was bound tightly within the cleft of free HSA with a binding constant (K) of 1.1×107 M−1, generating a stable HSA-PtNP complex. This platinated protein showed high catalytic activities for dismutations of superoxide radical anions (O2 •–) and hydrogen peroxide (H2O2), i.e., superoxide dismutase and catalase activities. Also, Hb-HSA3 captured PtNP into the external albumin unit (K = 1.1×107 M−1), yielding an Hb-HSA3(PtNP) cluster. The association of PtNP caused no alteration of the protein surface net charge and O2 binding affinity. The peripheral HSA-PtNP shell prevents oxidation of the core Hb, which enables the formation of an extremely stable O2 complex, even in H2O2 solution. PMID:25310133

Pt- and Pd-decorated MWCNTs for vapour and gas detection at room temperature

PubMed Central

Baccar, Hamdi; Clément, Pierrick; Abdelghani, Adnane

2015-01-01

Summary Here we report on the gas sensing properties of multiwalled carbon nanotubes decorated with sputtered Pt or Pd nanoparticles. Sputtering allows for an oxygen plasma treatment that removes amorphous carbon from the surface of the carbon nanotubes and creates oxygenated surface defects in which metal nanoparticles nucleate within a few minutes. The decoration with the 2 nm Pt or the 3 nm Pd nanoparticles is very homogeneous. This procedure is performed at the device level (i.e., for carbon nanotubes deposited onto sensor substrates) for many devices in one batch, which illustrates the scalability for the mass production of affordable nanosensors. The response to selected aromatic and non-aromatic volatile organic compounds, as well as pollutant gases has been studied. Pt- and Pd-decorated multiwalled carbon nanotubes show a fully reversible response to the non-aromatic volatile organic compounds tested when operated at room temperature. In contrast, these nanomaterials were not responsive to the aromatic compounds studied (measured at concentrations up to 50 ppm). Therefore, these sensors could be useful in a small, battery-operated alarm detector, for example, which is able to discriminate aromatic from non-aromatic volatile organic compounds in ambient. PMID:25977863

Amplified cathodic electrochemiluminescence of luminol based on Pd and Pt nanoparticles and glucose oxidase decorated graphene as trace label for ultrasensitive detection of protein.

PubMed

Cao, Yaling; Yuan, Ruo; Chai, Yaqin; Liu, Huijing; Liao, Yuhong; Zhuo, Ying

2013-09-15

An ultrasensitive electrochemiluminescence (ECL) immunosensor was constructed for ultrasensitive detection of carcinoembryonic antigen (CEA) based on an amplified cathodic ECL of luminol at low potential. Firstly, Au nanoparticles (AuNPs) were electrodeposited onto single walled carbon nanotube-graphene composites (CNTs-Gra) coated glass carbon electrode (GCE) with enhanced surface area and good biocompatibility to capture primary antibody (Ab1) and then bind the antigen analytes. Secondly, Pd and Pt nanoparticles (Pd&PtNPs) decorated reduced graphene oxide (Pd&PtNPs@rGO) and glucose oxidase (GOD) labeled secondary antibody (Pd&PtNPs@ rGO-GOD-Ab2) could be captured onto the electrode surface by a sandwich immunoassay protocol to generate amplified cathodic ECL signals of luminol in the presence of glucose. The Pd&PtNPs@rGO composites and loaded GOD promoted luminol cathodic ECL response by efficiently catalyzing glucose to in-situ produce amount of hydrogen peroxide (H2O2) working as a coreactant of luminol. Then in turn Pd&PtNPs catalyzed H2O2 to generate various reactive oxygen species (ROSs), which accelerated the cathodic ECL reaction of luminol, enhanced the cathodic ECL intensity of luminol and improved the sensitivity of the immunosensor. The as-proposed ECL immunosensor exhibited sensitive response on the detection of CEA ranging from 0.0001 ng mL(-1) to 160 ng mL(-1) with a detection limit of 0.03 pg mL(-1) (S/N=3). Moreover, the stability, specificity, lifetime and reproducibility tests demonstrated the feasibility of the developed immunoassay, which can be further extended to the detection of other disease biomarkers. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis of platinum nanoparticles using seaweed Padina gymnospora and their catalytic activity as PVP/PtNPs nanocomposite towards biological applications.

PubMed

Ramkumar, V Sri; Pugazhendhi, A; Prakash, S; Ahila, N K; Vinoj, G; Selvam, S; Kumar, G; Kannapiran, E; Rajendran, R Babu

2017-08-01

In the recent years, synthesis of nanomaterials using seaweeds and their diverse applications is escalating research in modern era. Among the noble metals, platinum nanoparticles (PtNPs) are of great importance owing to their catalytic property and less toxicity. The significance of this work is a simple one-step synthesis of PtNPs using aqueous extract of Indian brown seaweed Padina gymnospora and their catalytic activity with a polymer Polyvinylpyrrolidone (PVP) as PVP/PtNPs nanocomposite towards antimicrobial, haemolytic, cytotoxic (Artemia salina) and antioxidant properties. Fourier Transform Infrared (FT-IR) spectrum results showed diversified functional groups (biomoeities such as carbohydrates and proteins) present in the seaweed extract is responsible for the reduction of platinum ions (Pt + ) to PtNPs. The seaweed mediated PtNPs was characterized by UV-vis spectrophotometer, X-ray diffraction (XRD) pattern, Field Emission Scanning Electron Microscopy (FESEM) equipped with Energy Dispersive X-ray (EDX) spectroscopy and High Resolution Transmission Electron Microscopy (HRTEM) analysis. The synthesized PtNPs was found to be truncated octahedral in shape with the range of 5-50nm. Crystalline nature of the nanoparticles was evidenced by Selected Area Electron Diffraction (SAED) pattern with bright circular spots corresponding to (111), (200), (220) and (311) Bragg's reflection planes. The size of the PtNPs was further evidenced by Dynamic Light Scattering (DLS) analysis and it is originate to be stable at -22.5mV through Zeta Potential (ZP) analysis. The present study shows that the catalytic behavior of PtNPs as polymer/metal nanocomposite (PVP/PtNPs) preparation for an antibacterial activity against seven disease causing pathogenic bacterial strains with the maximum activity against Escherichia coli (15.6mm) followed by Lactococcus lactis (14.8mm) and Klebsiella pneumoniae (14.4mm). But no haemolytic activity was seen at their effective bactericidal concentration, whereas increase in the haeomyltic activity was seen only in higher concentrations (600, 900 and 1200μgmL -1 ). On the other hand, PVP/PtNPs nanocomposite has shown cytotoxic activity at 100±4μgmL -1 (LC 50 ) against Artemia salina nauplii. Furthermore, PVP/PtNPs nanocomposite showed an enhanced scavenging activity against 2,2-diphenyl-1-picrylhydrazyl (DPPH), superoxide, nitric oxide and hydroxyl radicals. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Activity descriptor identification for oxygen reduction on platinum-based bimetallic nanoparticles: in situ observation of the linear composition-strain-activity relationship.

PubMed

Jia, Qingying; Liang, Wentao; Bates, Michael K; Mani, Prasanna; Lee, Wendy; Mukerjee, Sanjeev

2015-01-27

Despite recent progress in developing active and durable oxygen reduction catalysts with reduced Pt content, lack of elegant bottom-up synthesis procedures with knowledge over the control of atomic arrangement and morphology of the Pt-alloy catalysts still hinders fuel cell commercialization. To follow a less empirical synthesis path for improved Pt-based catalysts, it is essential to correlate catalytic performance to properties that can be easily controlled and measured experimentally. Herein, using Pt-Co alloy nanoparticles (NPs) with varying atomic composition as an example, we show that the atomic distribution of Pt-based bimetallic NPs under operating conditions is strongly dependent on the initial atomic ratio by employing microscopic and in situ spectroscopic techniques. The PtxCo/C NPs with high Co content possess a Co concentration gradient such that Co is concentrated in the core and gradually depletes in the near-surface region, whereas the PtxCo/C NPs with low Co content possess a relatively uniform distribution of Co with low Co population in the near-surface region. Despite their different atomic structure, the oxygen reduction reaction (ORR) activity of PtxCo/C and Pt/C NPs is linearly related to the bulk average Pt-Pt bond length (RPt-Pt). The RPt-Pt is further shown to contract linearly with the increase in Co/Pt composition. These linear correlations together demonstrate that (i) the improved ORR activity of PtxCo/C NPs over pure Pt NPs originates predominantly from the compressive strain and (ii) the RPt-Pt is a valid strain descriptor that bridges the activity and atomic composition of Pt-based bimetallic NPs.

Intraperitoneal delivery of platinum with in-situ crosslinkable hyaluronic acid gel for local therapy of ovarian cancer

PubMed Central

Cho, Eun Jung; Sun, Bo; Doh, Kyung-Oh; Wilson, Erin M.; Torregrosa-Allen, Sandra; Elzey, Bennett D.; Yeo, Yoon

2014-01-01

Intraperitoneal (IP) chemotherapy is a promising post-surgical therapy of solid carcinomas confined within the peritoneal cavity, with potential benefits in locoregional and systemic management of residual tumors. In this study, we intended to increase local retention of platinum in the peritoneal cavity over a prolonged period of time using a nanoparticle form of platinum and an in-situ crosslinkable hyaluronic acid gel. Hyaluronic acid was chosen as a carrier due to the biocompatibility and biodegradability. We confirmed a sustained release of platinum from the nanoparticles (PtNPs) and nanoparticle/gel hybrid (PtNP/gel), receptor-mediated endocytosis of PtNPs, and retention of the gel in the peritoneal cavity over 4 weeks--conditions desirable for a prolonged local delivery of platinum. However, PtNPs and PtNP/gel did not show a greater anti-tumor efficacy than CDDP solution administered at the same dose but rather caused a slight increase in tumor burdens at later time points, which suggests a potential involvement of empty carriers and degradation products in the growth of residual tumors. This study alerts that although several materials considered biocompatible and safe are used as drug carriers, they may have unwanted biological effects on the residual targets once the drug is exhausted; therefore, more attention should be paid to the selection of the drug carriers. PMID:25453960

Intraperitoneal delivery of platinum with in-situ crosslinkable hyaluronic acid gel for local therapy of ovarian cancer.

PubMed

Cho, Eun Jung; Sun, Bo; Doh, Kyung-Oh; Wilson, Erin M; Torregrosa-Allen, Sandra; Elzey, Bennett D; Yeo, Yoon

2015-01-01

Intraperitoneal (IP) chemotherapy is a promising post-surgical therapy of solid carcinomas confined within the peritoneal cavity, with potential benefits in locoregional and systemic management of residual tumors. In this study, we intended to increase local retention of platinum in the peritoneal cavity over a prolonged period of time using a nanoparticle form of platinum and an in-situ crosslinkable hyaluronic acid gel. Hyaluronic acid was chosen as a carrier due to the biocompatibility and biodegradability. We confirmed a sustained release of platinum from the nanoparticles (PtNPs) and nanoparticle/gel hybrid (PtNP/gel), receptor-mediated endocytosis of PtNPs, and retention of the gel in the peritoneal cavity over 4 weeks: conditions desirable for a prolonged local delivery of platinum. However, PtNPs and PtNP/gel did not show a greater anti-tumor efficacy than CDDP solution administered at the same dose but rather caused a slight increase in tumor burdens at later time points, which suggests a potential involvement of empty carriers and degradation products in the growth of residual tumors. This study alerts that although several materials considered biocompatible and safe are used as drug carriers, they may have unwanted biological effects on the residual targets once the drug is exhausted; therefore, more attention should be paid to the selection of drug carriers. Copyright © 2014 Elsevier Ltd. All rights reserved.

The Effect of PtRuIr Nanoparticle Crystallinity in Electrocatalytic Methanol Oxidation

PubMed Central

Ma, Yanjiao; Wang, Rongfang; Wang, Hui; Liao, Shijun; Key, Julian; Linkov, Vladimir; Ji, Shan

2013-01-01

Two structural forms of a ternary alloy PtRuIr/C catalyst, one amorphous and one highly crystalline, were synthesized and compared to determine the effect of their respective structures on their activity and stability as anodic catalysts in methanol oxidation. Characterization techniques included TEM, XRD, and EDX. Electrochemical analysis using a glassy carbon disk electrode for cyclic voltammogram and chronoamperometry were tested in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4. Amorphous PtRuIr/C catalyst was found to have a larger electrochemical surface area, while the crystalline PtRuIr/C catalyst had both a higher activity in methanol oxidation and increased CO poisoning rate. Crystallinity of the active alloy nanoparticles has a big impact on both methanol oxidation activity and in the CO poisoning rate. PMID:28809233

Investigation of follicular and non-follicular pathways for polyarginine and oleic acid modified nanoparticles

PubMed Central

Hayden, Patrick; Singh, Mandip

2013-01-01

Purpose The aim of the current study was to investigate the percutaneous permeation pathways of cell penetrating peptide modified lipid nanoparticles and oleic acid modified polymeric nanoparticles. Methods Confocal microscopy was performed on skin cultures (EpiDermFT™) for modified and un-modified nanoparticles. Differential stripping was performed following in vitro skin permeation of Ibuprofen (Ibu) encapsulated nanoparticles to estimate Ibu levels in different skin layers and receiver compartment. The hair follicles (HF) were blocked and in vitro skin permeation of nanoparticles was then compared with unblocked HF. The surface modified nanoparticles were investigated for response on allergic contact dermatitis (ACD). Results Surface modified nanoparticles showed a significant higher (p < 0.05) in fluorescence in EpiDermFT™ cultures compared to controls. The HF play less than 5% role in total nanoparticle permeation into the skin. The Ibu levels were significantly high (p<0.05) for surface modified nanoparticles compared to controls. The Ibu levels in skin and receiver compartment were not significantly different when HF were open or closed. Modified nanoparticles showed significant improvement in treatment of ACD compared to solution. Conclusions Our studies demonstrate that increased skin permeation of surface modified nanoparticles is not only dependent on a follicular pathway but also occur through non-follicular pathway(s). PMID:23187866

PtRu catalysts supported on heteropolyacid and chitosan functionalized carbon nanotubes for methanol oxidation reaction of fuel cells.

PubMed

Cui, Zhiming; Li, Chang Ming; Jiang, San Ping

2011-09-28

A simple self-assembly approach has been developed to functionalize carbon nanotubes (CNTs) with chitosan (CS) and heteropolyacids (HPAs) of phosphomolybdic acid (H(3)PMo(12)O(40), HPMo) and phosphotungstic acid (H(3)PW(12)O(40), HPW). The non-covalent functionalization method, which introduces homogenous surface functional groups with no detrimental effect on graphene structures of CNTs, can be carried out at room temperature without the use of corrosive acids. The PtRu nanoparticles supported on HPAs-CS-CNTs have a uniform distribution and much smaller size as compared to those of the PtRu nanoparticles supported on conventional acid treated CNTs (PtRu/AO-CNTs). The onset and peak potentials for CO(ad) oxidation on PtRu/HPAs-CS-CNTs catalysts are more negative than those on PtRu/AO-CNTs, indicating that HPAs facilitate the electro-oxidation of CO. The PtRu/HPMo-CS-CNTs catalyst has a higher electrocatalytic activity for methanol oxidation and higher tolerance toward CO poisoning than PtRu/HPW-CS-CNTs. The better electrocatalytic enhancement of HPMo on the PtRu/HPAs-CS-CNTs catalyst is most likely related to the fact that molybdenum-containing HPAs such as HPMo have more labile terminal oxygen to provide additional active oxygen sites while accelerating the CO and methanol oxidation in a similar way to that of Ru in the PtRu binary alloy system.