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.

Investigation of oxygen reduction and methanol oxidation reaction activity of PtAu nano-alloy on surface modified porous hybrid nanocarbon supports

NASA Astrophysics Data System (ADS)

Parambath Vinayan, Bhaghavathi; Nagar, Rupali; Ramaprabhu, Sundara

2016-09-01

We investigate the electrocatalytic activity of PtAu alloy nanoparticles supported on various chemically modified carbon morphologies towards oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). The surface-modification of graphene nanosheets (f-G), multi-walled carbon nanotubes (f-MWNTs) and (graphene nanosheets-carbon nanotubes) hybrid support (f-G-MWNTs) were carried out by soft functionalization method using a cationic polyelectrolyte poly-(diallyldimethyl ammonium chloride). The Pt and PtAu alloy nanoparticles were dispersed over chemically modified carbon supports by sodium-borohydride assisted modified polyol reduction method. The electrochemical performance of all electrocatalysts were studied by half- and full-cell proton exchange membrane fuel cell (PEMFC) measurements and PtAu/f-G-MWNTs catalyst comparatively yielded the best catalytic performance. PEMFC full cell measurements of PtAu/f-G-MWNTs cathode electrocatalyst yield a maximum power density of 319 mW cm-2 at 60 °C without any back pressure,which is 2.1 times higher than that of cathode electrocatalyst Pt on graphene support. The high ORR and MOR activity of PtAu/f-G-MWNTs electrocatalyst is due to the alloying effect and inherent beneficial properties of porous hybrid nanocarbon support.

Interface architecture determined electrocatalytic activity of Pt on vertically oriented TiO(2) nanotubes.

PubMed

Rettew, Robert E; Allam, Nageh K; Alamgir, Faisal M

2011-02-01

The surface atomic structure and chemical state of Pt is consequential in a variety of surface-intensive devices. Herein we present the direct interrelationship between the growth scheme of Pt films, the resulting atomic and electronic structure of Pt species, and the consequent activity for methanol electro-oxidation in Pt/TiO(2) nanotube hybrid electrodes. X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) measurements were performed to relate the observed electrocatalytic activity to the oxidation state and the atomic structure of the deposited Pt species. The atomic structure as well as the oxidation state of the deposited Pt was found to depend on the pretreatment of the TiO(2) nanotube surfaces with electrodeposited Cu. Pt growth through Cu replacement increases Pt dispersion, and a separation of surface Pt atoms beyond a threshold distance from the TiO(2) substrate renders them metallic, rather than cationic. The increased dispersion and the metallic character of Pt results in strongly enhanced electrocatalytic activity toward methanol oxidation. This study points to a general phenomenon whereby the growth scheme and the substrate-to-surface-Pt distance dictates the chemical state of the surface Pt atoms, and thereby, the performance of Pt-based surface-intensive devices.

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

Tin-oxide-coated single-walled carbon nanotube bundles supporting platinum electrocatalysts for direct ethanol fuel cells.

PubMed

Hsu, Ryan S; Higgins, Drew; Chen, Zhongwei

2010-04-23

Novel tin-oxide (SnO(2))-coated single-walled carbon nanotube (SWNT) bundles supporting platinum (Pt) electrocatalysts for ethanol oxidation were developed for direct ethanol fuel cells. SnO(2)-coated SWNT (SnO(2)-SWNT) bundles were synthesized by a simple chemical-solution route. SnO(2)-SWNT bundles supporting Pt (Pt/SnO(2)-SWNTs) electrocatalysts and SWNT-supported Pt (Pt/SWNT) electrocatalysts were prepared by an ethylene glycol reduction method. The catalysts were physically characterized using TGA, XRD and TEM and electrochemically evaluated through cyclic voltammetry experiments. The Pt/SnO(2)-SWNTs showed greatly enhanced electrocatalytic activity for ethanol oxidation in acid medium, compared to the Pt/SWNT. The optimal SnO(2) loading of Pt/SnO(2)-SWNT catalysts with respect to specific catalytic activity for ethanol oxidation was also investigated.

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.

Electronic properties and reactivity of Pt-doped carbon nanotubes.

PubMed

Tian, Wei Quan; Liu, Lei Vincent; Wang, Yan Alexander

2006-08-14

The structures of the (5,5) single-walled carbon nanotube (SWCNT) segments with hemispheric carbon cages capped at the ends (SWCNT rod) and the Pt-doped SWCNT rods have been studied within density functional theory. Our theoretical studies find that the hemispheric cages introduce localized states on the caps. The cap-Pt-doped SWCNT rods can be utilized as sensors because of the sensitivity of the doped Pt atom. The Pt-doped SWCNT rods can also be used as catalysts, where the doped Pt atom serves as the enhanced and localized active center on the SWCNT. The adsorptions of C(2)H(4) and H(2) on the Pt atom in the Pt-doped SWCNT rods reveal different adsorption characteristics. The adsorption of C(2)H(4) on the Pt atom in all of the three Pt-doped SWCNT rods studied (cap-end-doped, cap-doped, and wall-doped) is physisorption with the strongest interaction occurring in the middle of the sidewall of the SWCNT. On the other hand, the adsorption of H(2) on the Pt atom at the sidewall of the SWCNT is chemisorption resulting in the decomposition of H(2), and the adsorption of H(2) at the hemispheric caps is physisorption.

Ti Porous Film-Supported NiCo₂S₄ Nanotubes Counter Electrode for Quantum-Dot-Sensitized Solar Cells.

PubMed

Deng, Jianping; Wang, Minqiang; Song, Xiaohui; Yang, Zhi; Yuan, Zhaolin

2018-04-17

In this paper, a novel Ti porous film-supported NiCo₂S₄ nanotube was fabricated by the acid etching and two-step hydrothermal method and then used as a counter electrode in a CdS/CdSe quantum-dot-sensitized solar cell. Measurements of the cyclic voltammetry, Tafel polarization curves, and electrochemical impedance spectroscopy of the symmetric cells revealed that compared with the conventional FTO (fluorine doped tin oxide)/Pt counter electrode, Ti porous film-supported NiCo₂S₄ nanotubes counter electrode exhibited greater electrocatalytic activity toward polysulfide electrolyte and lower charge-transfer resistance at the interface between electrolyte and counter electrode, which remarkably improved the fill factor, short-circuit current density, and power conversion efficiency of the quantum-dot-sensitized solar cell. Under illumination of one sun (100 mW/cm²), the quantum-dot-sensitized solar cell based on Ti porous film-supported NiCo₂S₄ nanotubes counter electrode achieved a power conversion efficiency of 3.14%, which is superior to the cell based on FTO/Pt counter electrode (1.3%).

Non-carbon titanium cobalt nitride nanotubes supported platinum catalyst with high activity and durability for methanol oxidation reaction

NASA Astrophysics Data System (ADS)

Chen, Xiaoxiang; Li, Wuyi; Pan, Zhanchang; Xu, Yanbin; Liu, Gen; Hu, Guanghui; Wu, Shoukun; Li, Jinghong; Chen, Chun; Lin, Yingsheng

2018-05-01

Titanium cobalt nitride nanotubes (Ti0.95Co0.05N NTs) hybrid support, a novel robust non-carbon support material prepared by solvothermal and post-nitriding processes, is further decorated with Pt nanoparticles for the electrooxidation of methanol. The catalyst is characterized by X-ray diffraction (XRD), nitrogen adsorption/desorption, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The morphology, structure and composition of the synthesized Ti0.95Co0.05N NTs suggest that the nanotube wall is porous and consists of homogeneous cohesively attached nitrides nanocube particles. Notable, Ti0.95Co0.05N NTs supported Pt catalyst exhibits significantly improved catalytic activity and durability for methanol electrooxidation compared with the conventional JM Pt/C catalyst. The experimental data indicate that enhanced catalytic activity and stability of Pt/Ti0.95Co0.05N NTs towards methanol electrooxidation might be mainly attributed to the tubular nanostructures and synergistic effect introduced by the Co doping. Both of them are playing an important role in improving the activity and durability of the Ti0.95Co0.05N NTs catalyst.

Pt-Ru/CeO2/carbon nanotube nanocomposites: an efficient electrocatalyst for direct methanol fuel cells.

PubMed

Sun, Zhenyu; Wang, Xiang; Liu, Zhimin; Zhang, Hongye; Yu, Ping; Mao, Lanqun

2010-07-20

Pt-Ru/CeO(2)/multiwalled carbon nanotube (MWNT) electrocatalysts were prepared using a rapid sonication-facilitated deposition method and were characterized by X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and voltammetry. Morphological characterization by TEM revealed that CeO(2) nanoparticles (NPs) were in intimate contact with Pt-Ru NPs, and both were highly dispersed on the exteriors of nanotubes with a small size and a very narrow size distribution. Compared with the Pt-Ru/MWNT and Pt/MWNT electrocatalysts, the as-prepared Pt-Ru/CeO(2)/MWNT exhibited a significantly improved electrochemically active surface area (ECSA) and a remarkably enhanced activity toward methanol oxidation. The effects of the Pt-Ru loading and the Pt-to-Ru molar ratio on the electrocatalytic activity of Pt-Ru/CeO(2)/MWNT for methanol oxidation were investigated. We found that a maximum activity toward methanol oxidation reached at the 10 wt % of Pt-Ru loading and 1:1 of Pt-to-Ru ratio. Moreover, the role of CeO(2) in the catalysts for the enhancement of methanol oxidation was discussed in terms of both bifunctional mechanism and electronic effects.

Theoretical Calculation of the Gas-Sensing Properties of Pt-Decorated Carbon Nanotubes

PubMed Central

Zhang, Xiaoxing; Dai, Ziqiang; Wei, Li; Liang, Naifeng; Wu, Xiaoqing

2013-01-01

The gas-sensing properties of Pt-decorated carbon nanotubes (CNTs), which provide a foundation for the fabrication of sensors, have been evaluated. In this study, we calculated the gas adsorption of Pt-decorated (8,0) single-wall CNTs (Pt-SWCNTs) with SO2, H2S, and CO using GGA/PW91 method based on density functional theory. The adsorption energies and the changes in geometric and electronic structures after absorption were comprehensively analyzed to estimate the responses of Pt-SWCNTs. Results indicated that Pt-SWCNTs can respond to the three gases. The electrical characteristics of Pt-SWCNTs show different changes after adsorption. Pt-SWCNTs donate electrons and increase the number of hole carriers after adsorbing SO2, thereby enhancing its conductivity. When H2S is adsorbed on CNTs, electrons are transferred from H2S to Pt-SWCNTs, converting Pt-SWCNTs from p-type to n-type sensors with improved conductivity. However, Pt-SWCNTs obtain electrons and show decreased conductivity when reacted with CO gas. PMID:24201317

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.

Microfluidic Synthesis Enables Dense and Uniform Loading of Surfactant-Free PtSn Nanocrystals on Carbon Supports for Enhanced Ethanol Oxidation.

PubMed

Wu, Fuxiang; Zhang, Dongtang; Peng, Manhua; Yu, Zhihui; Wang, Xiayan; Guo, Guangsheng; Sun, Yugang

2016-04-11

Developing new synthetic methods for carbon supported catalysts with improved performance is of fundamental importance in advancing proton exchange membrane fuel cell (PEMFC) technology. Continuous-flow, microfluidic reactions in capillary tube reactors are described, which are capable of synthesizing surfactant-free, ultrafine PtSn alloyed nanoparticles (NPs) on various carbon supports (for example, commercial carbon black particles, carbon nanotubes, and graphene sheets). The PtSn NPs are highly crystalline with sizes smaller than 2 nm, and they are highly dispersed on the carbon supports with high loadings up to 33 wt%. These characteristics make the as-synthesized carbon-supported PtSn NPs more efficient than state of the art commercial Pt/C catalysts applied to the ethanol oxidation reaction (EOR). Significantly enhanced mass catalytic activity (two-times that of Pt/C) and improved stability are obtained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supported lipid bilayer/carbon nanotube hybrids

NASA Astrophysics Data System (ADS)

Zhou, Xinjian; Moran-Mirabal, Jose M.; Craighead, Harold G.; McEuen, Paul L.

2007-03-01

Carbon nanotube transistors combine molecular-scale dimensions with excellent electronic properties, offering unique opportunities for chemical and biological sensing. Here, we form supported lipid bilayers over single-walled carbon nanotube transistors. We first study the physical properties of the nanotube/supported lipid bilayer structure using fluorescence techniques. Whereas lipid molecules can diffuse freely across the nanotube, a membrane-bound protein (tetanus toxin) sees the nanotube as a barrier. Moreover, the size of the barrier depends on the diameter of the nanotube-with larger nanotubes presenting bigger obstacles to diffusion. We then demonstrate detection of protein binding (streptavidin) to the supported lipid bilayer using the nanotube transistor as a charge sensor. This system can be used as a platform to examine the interactions of single molecules with carbon nanotubes and has many potential applications for the study of molecular recognition and other biological processes occurring at cell membranes.

Forming a Highly Active, Homogeneously Alloyed AuPt Co-catalyst Decoration on TiO2 Nanotubes Directly During Anodic Growth.

PubMed

Bian, Haidong; Nguyen, Nhat Truong; Yoo, JeongEun; Hejazi, Seyedsina; Mohajernia, Shiva; Müller, Julian; Spiecker, Erdmann; Tsuchiya, Hiroaki; Tomanec, Ondrej; Sanabria-Arenas, Beatriz E; Zboril, Radek; Li, Yang Yang; Schmuki, Patrik

2018-05-30

Au and Pt do not form homogeneous bulk alloys as they are thermodynamically not miscible. However, we show that anodic TiO 2 nanotubes (NTs) can in situ be uniformly decorated with homogeneous AuPt alloy nanoparticles (NPs) during their anodic growth. For this, a metallic Ti substrate containing low amounts of dissolved Au (0.1 atom %) and Pt (0.1 atom %) is used for anodizing. The matrix metal (Ti) is converted to oxide, whereas at the oxide/metal interface direct noble metal particle formation and alloying of Au and Pt takes place; continuously these particles are then picked up by the growing nanotube wall. In our experiments, the AuPt alloy NPs have an average size of 4.2 nm, and at the end of the anodic process, these are regularly dispersed over the TiO 2 nanotubes. These alloyed AuPt particles act as excellent co-catalyst in photocatalytic H 2 generation, with a H 2 production rate of 12.04 μL h -1 under solar light. This represents a strongly enhanced activity as compared to TiO 2 NTs decorated with monometallic particles of Au (7 μL h -1 ) or Pt (9.96 μL h -1 ).

KOH-activated multi-walled carbon nanotubes as platinum supports for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

He, Chaoxiong; Song, Shuqin; Liu, Jinchao; Maragou, Vasiliki; Tsiakaras, Panagiotis

In the present investigation, multi-walled carbon nanotubes (MWCNTs) thermally treated by KOH were adopted as the platinum supporting material for the oxygen reduction reaction electrocatalysts. FTIR and Raman spectra were used to investigate the surface state of MWCNTs treated by KOH at different temperatures (700, 800, and 900 °C) and showed MWCNTs can be successfully functionalized. The structural properties of KOH-activated MWCNTs supported Pt were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their electrochemical performance was evaluated by the aid of cyclic voltammetry (CV) and rotating disk electrode (RDE) voltammetry. According to the experimental findings of the present work, the surrface of MWCNTs can be successfully functionalized with oxygen-containing groups after activation by KOH, favoring the good dispersion of Pt nanoparticles with narrow size distribution. The as-prepared Pt catalysts supported on KOH treated MWCNTs at higher temperature, possess higher electrochemical surface area and exhibit desirable activity towards oxygen reduction reaction (ORR). More precisely, it has been found that the electrochemical active area of Pt/MWCNTs-900 is approximately two times higher than that of Pt/MWCNTs. It can be concluded that KOH activation is an effective way to decorate MWCNTs' surface with oxygen-containing groups and bigger surface area, which makes them more suitable as electrocatalyst support materials.

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.

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

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.

Adsorption of HCN molecules on Ni, Pd and Pt-doped (7, 0) boron nitride nanotube: a DFT study

NASA Astrophysics Data System (ADS)

Habibi-Yangjeh, Aziz; Basharnavaz, Hadi

2018-05-01

We studied affinity of pure and Ni, Pd and Pt-doped (7, 0) boron nitride nanotubes (BNNTs) to toxic HCN molecules using density functional theory calculations. The results indicated that the pure (7, 0) BNNTs can weakly adsorb HCN molecules with adsorption energy of -0.2474 eV. Upon adsorption of HCN molecules on this nanotube, the band gap energy was decreased from 3.320 to 2.960 eV. The more negative adsorption energy between these transition metal-doped (7, 0) BNNTs and HCN molecules indicated that doping of (7, 0) BNNTs with Ni, Pd and Pt elements can significantly improve the affinity of BNNTs toward this gas. Additionally, it was found that the interaction energy between HCN molecules and Pt-doped BNNTs is more negative than those of the Ni and Pd-doped BNNTs. These observations suggested that the Pt-doped (7, 0) BNNTs are strongly sensitive to HCN molecules and therefore it may be used in gas sensor devices for detecting this toxic gas.

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.

Continuous preparation of carbon-nanotube-supported platinum catalysts in a flow reactor directly heated by electric current

PubMed Central

dos Santos, Antonio Rodolfo; Kunz, Ulrich; Turek, Thomas

2011-01-01

Summary In this contribution we present for the first time a continuous process for the production of highly active Pt catalysts supported by carbon nanotubes by use of an electrically heated tubular reactor. The synthesized catalysts show a high degree of dispersion and narrow distributions of cluster sizes. In comparison to catalysts synthesized by the conventional oil-bath method a significantly higher electrocatalytic activity was reached, which can be attributed to the higher metal loading and smaller and more uniformly distributed Pt particles on the carbon support. Our approach introduces a simple, time-saving and cost-efficient method for fuel cell catalyst preparation in a flow reactor which could be used at a large scale. PMID:22043252

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.

Electrochemical study of highly durable cathode with Pt supported on ITO-CNT composite for proton exchange membrane fuel cells

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

Park, Sehkyu; Shao, Yuyan; Viswanathan, Vilayanur V.

2016-10-01

In this paper, we describe a highly stable cathode containing a Pt catalyst supported on an indium tin oxide (ITO) and carbon nanotube (CNT) composite. The dependence of cathode performance and durability on the ITO content and the diameter of the CNTs were investigated by electrochemical techniques. The cathode with 30 wt% ITO and CNTs with diameters 10–20 nm in the composite offered preferred locations for Pt stabilization and was very resistant to carbon corrosion (i.e., 82.7% ESA retention and 105.7% mass activity retention after an accelerated stress test for 400 h).

Hydrogenotitanates nanotubes supported platinum anode for direct methanol fuel cell

NASA Astrophysics Data System (ADS)

Abida, Bochra; Chirchi, Lotfi; Baranton, Stève; Napporn, Teko Wilhelmin; Morais, Cláudia; Léger, Jean-Michel; Ghorbel, Abdelhamid

2013-11-01

Hydrogenotitanates nanotubes (HTNs) are prepared from TiO2 powder via hydrothermal processing in 11.25 M NaOH aq. The reaction temperature is 130 °C for 20 h. Afterward a heat treatment is done during 2 h at 500 °C in air, to obtain calcined HTNs (HTNs-cal). The structural change on the molecular TiO2 during the hydrothermal treatment is investigated in detail by various analytic techniques such as XRD and TEM, which reveal that the crystal structure of the HTNs materials is similar to that of H2Ti2O5·H2O nanotubes with 160 nm in length and 10 nm in diameter. Nitrogen adsorption-desorption isotherms indicate that synthesized solids are mesoporous materials with a multiwalled nanotubular structure and high specific surface area. Platinum nanoparticles are deposited on the HTNs by the impregnation method for a total noble metal loading of 10 wt%. The electrocatalytic activity of these electrocatalysts is evaluated by cyclic voltammetry in acid medium. Typical CO stripping voltammetry in acidic solutions is investigated. The results demonstrate that the HTNs can greatly enhance the catalytic activity of Pt for methanol oxidation. The CO stripping test shows that the Pt/HTNs can shift the CO oxidation potential to lower direction than Pt/C (XC72) and Pt/HTNs-cal catalysts.

Heterojunctions of mixed phase TiO2 nanotubes with Cu, CuPt, and Pt nanoparticles: interfacial band alignment and visible light photoelectrochemical activity

NASA Astrophysics Data System (ADS)

Kar, Piyush; Zhang, Yun; Mahdi, Najia; Thakur, Ujwal K.; Wiltshire, Benjamin D.; Kisslinger, Ryan; Shankar, Karthik

2018-01-01

Anodically formed, vertically oriented, self-organized cylindrical TiO2 nanotube arrays composed of the anatase phase undergo an interesting morphological and phase transition upon flame annealing to square-shaped nanotubes composed of both anatase and rutile phases. This is the first report on heterojunctions consisting of metal nanoparticles (NPs) deposited on square-shaped TiO2 nanotube arrays (STNAs) with mixed rutile and anatase phase content. A simple photochemical deposition process was used to form Cu, CuPt, and Pt NPs on the STNAs, and an enhancement in the visible light photoelectrochemical water splitting performance for the NP-decorated STNAs was observed over the bare STNAs. Under narrow band illumination by visible photons at 410 nm and 505 nm, Cu NP-decorated STNAs performed the best, producing photocurrents 80% higher and 50 times higher than bare STNAs, respectively. Probing the energy level structure at the NP-STNA interface using ultraviolet photoelectron spectroscopy revealed Schottky barrier formation in the NP-decorated STNAs, which assists in separating the photogenerated charge carriers, as also confirmed by longer charge carrier lifetimes in NP-decorated STNAs. While all the NP-decorated STNAs showed enhanced visible light absorption compared to the bare STNAs, only the Cu NPs exhibited a clear plasmonic behavior with an extinction cross section that peaked at 550 nm.

Heterojunctions of mixed phase TiO2 nanotubes with Cu, CuPt, and Pt nanoparticles: interfacial band alignment and visible light photoelectrochemical activity.

PubMed

Kar, Piyush; Zhang, Yun; Mahdi, Najia; Thakur, Ujwal K; Wiltshire, Benjamin D; Kisslinger, Ryan; Shankar, Karthik

2018-01-05

Anodically formed, vertically oriented, self-organized cylindrical TiO 2 nanotube arrays composed of the anatase phase undergo an interesting morphological and phase transition upon flame annealing to square-shaped nanotubes composed of both anatase and rutile phases. This is the first report on heterojunctions consisting of metal nanoparticles (NPs) deposited on square-shaped TiO 2 nanotube arrays (STNAs) with mixed rutile and anatase phase content. A simple photochemical deposition process was used to form Cu, CuPt, and Pt NPs on the STNAs, and an enhancement in the visible light photoelectrochemical water splitting performance for the NP-decorated STNAs was observed over the bare STNAs. Under narrow band illumination by visible photons at 410 nm and 505 nm, Cu NP-decorated STNAs performed the best, producing photocurrents 80% higher and 50 times higher than bare STNAs, respectively. Probing the energy level structure at the NP-STNA interface using ultraviolet photoelectron spectroscopy revealed Schottky barrier formation in the NP-decorated STNAs, which assists in separating the photogenerated charge carriers, as also confirmed by longer charge carrier lifetimes in NP-decorated STNAs. While all the NP-decorated STNAs showed enhanced visible light absorption compared to the bare STNAs, only the Cu NPs exhibited a clear plasmonic behavior with an extinction cross section that peaked at 550 nm.

Efficiently Visible-Light Driven Photoelectrocatalytic Oxidation of As(III) at Low Positive Biasing Using Pt/TiO2 Nanotube Electrode

NASA Astrophysics Data System (ADS)

Qin, Yanyan; Li, Yilian; Tian, Zhen; Wu, Yangling; Cui, Yanping

2016-01-01

A constant current deposition method was selected to load highly dispersed Pt nanoparticles on TiO2 nanotubes in this paper, to extend the excited spectrum range of TiO2-based photocatalysts to visible light. The morphology, elemental composition, and light absorption capability of as-obtained Pt/TiO2 nanotubes electrodes were characterized by FE-SEM, energy dispersive spectrometer (EDS), X-ray photoelectron spectrometer (XPS), and UV-vis spectrometer. The photocatalytic and photoelectrocatalytic oxidation of As(III) using a Pt/TiO2 nanotube arrays electrode under visible light ( λ > 420 nm) irradiation were investigated in a divided anode/cathode electrolytic tank. Compared with pure TiO2 which had no As(III) oxidation capacity under visible light, Pt/TiO2 nanotubes exhibited excellent visible-light photocatalytic performance toward As(III), even at dark condition. In anodic cell, As(III) could be oxidized with high efficiency by photoelectrochemical process with only 1.2 V positive biasing. Experimental results showed that photoelectrocatalytic oxidation process of As(III) could be well described by pseudo-first-order kinetic model. Rate constants depended on initial concentration of As(III), applied bias potential and solution pH. At the same time, it was interesting to find that in cathode cell, As(III) was also continuously oxidized to As(V). Furthermore, high-arsenic groundwater sample (25 m underground) with 0.32 mg/L As(III) and 0.35 mg/L As(V), which was collected from Daying Village, Datong basin, Northern China, could totally transform to As(V) after 200 min under visible light in this system.

Supported Lipid Bilayer/Carbon Nanotube Hybrids

NASA Astrophysics Data System (ADS)

Zhou, Xinjian; Moran-Mirabal, Jose; Craighead, Harold; McEuen, Paul

2007-03-01

We form supported lipid bilayers on single-walled carbon nanotubes and use this hybrid structure to probe the properties of lipid membranes and their functional constituents. We first demonstrate membrane continuity and lipid diffusion over the nanotube. A membrane-bound tetanus toxin protein, on the other hand, sees the nanotube as a diffusion barrier whose strength depends on the diameter of the nanotube. Finally, we present results on the electrical detection of specific binding of streptavidin to biotinylated lipids with nanotube field effect transistors. Possible techniques to extract dynamic information about the protein binding events will also be discussed.

The effect of titanium nickel nitride decorated carbon nanotubes-reduced graphene oxide hybrid support for methanol oxidation

NASA Astrophysics Data System (ADS)

Liu, Gen; Pan, Zhanchang; Li, Wuyi; Yu, Ke; Xia, Guowei; Zhao, Qixiang; Shi, Shikun; Hu, Guanghui; Xiao, Chumin; Wei, Zhigang

2017-07-01

Titanium nickel nitride (TiNiN) decorated three-dimensional (3D) carbon nanotubes-reduced graphene oxide (CNT-rGO), a fancy 3D platinum (Pt)-based catalyst hybrid support, is prepared by a solvothermal process followed by a nitriding process, which is tested as anodic catalyst support for the methanol oxidation reaction (MOR). The structure, morphology and composition of the synthesized TiNiN/CNT-rGO exhibits a uniform particle dispersion with high purity and interpenetrating 3D network structure. Notably, Pt/TiNiN/CNT-rGO catalyst exhibits significantly improved catalytic activity and durability for methanol oxidation in comparison with Pt/CNT-rGO and conventional Pt/C (JM). The outstanding electrochemical performance was attributed to structure and properties. That is, the 3D CNT-rGO provided a fast transport network for charge-transfer and mass-transfer as well as TiNiN NPs with good synergistic effect and the strong electronic coupling between different domains in TiNiN/CNT-rGO, thus the catalytic activity of the novel catalyst is greatly improved. These results evidences 3D TiNiN/CNT-rGO as a promising catalyst support for a wide range of applications in fuel cells.

Fuel cell electrocatalyst using polybenzimidazole-modified carbon nanotubes as support materials.

PubMed

Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2013-03-25

Toward the next generation fuel cell systems, the development of a novel electrocatalyst for the polymer electrolyte fuel cell (PEFC) is crucial to overcome the drawbacks of the present electrocatalyst. As a conductive supporting material for the catalyst, carbon nanotubes (CNTs) have emerged as a promising candidate, and many attempts have been carried out to introduce CNT, in place of carbon black. On the other hand, as a polymer electrolyte, polybenzimidazoles (PBIs) have been recognized as a powerful candidate due to the high proton conductivity above 100 °C under non-humid conditions. In 2008, we found that these two materials have a strong physical interaction and form a stable hybrid material, in which the PBIs uniformly wrap the surfaces of the CNTs. Furthermore, PBIs serve as effective binding sites for the formation of platinum (Pt) nanoparticles to fabricate a ternary composite (CNT/PBIs/Pt). In this review article, we summarize the fundamental properties of the CNT/PBIs/Pt and discuss their potential as a new electrocatalyst for the PEFC in comparison with the conventional ones. Furthermore, potential applications of CNT/PBIs including use of the materials for oxygen reduction catalysts and reinforcement of PBI films are summarized. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Surface tailored single walled carbon nanotubes as catalyst support for direct methanol fuel cell

NASA Astrophysics Data System (ADS)

Kireeti, Kota V. M. K.; Jha, Neetu

2017-10-01

A strategy for tuning the surface property of Single Walled Carbon Nanotubes (SWNTs) for enhanced methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) along with methanol tolerance is presented. The surface functionality is tailored using controlled acid and base treatment. Acid treatment leads to the attachment of carboxylic carbon (CC) fragments to SWNT making it hydrophilic (P3-SWNT). Base treatment of P3-SWNT with 0.05 M NaOH reduces the CCs and makes it hydrophobic (P33-SWNT). Pt catalyst supported on the P3-SWNT possesses enhanced MOR whereas that supported on P33-SWNT not only enhances ORR kinetics but also possess good tolerance towards methanol oxidation as verified by the electrochemical technique.

Supported noble metals on hydrogen-treated TiO2 nanotube arrays as highly ordered electrodes for fuel cells.

PubMed

Zhang, Changkun; Yu, Hongmei; Li, Yongkun; Gao, Yuan; Zhao, Yun; Song, Wei; Shao, Zhigang; Yi, Baolian

2013-04-01

Hydrogen-treated TiO2 nanotube (H-TNT) arrays serve as highly ordered nanostructured electrode supports, which are able to significantly improve the electrochemical performance and durability of fuel cells. The electrical conductivity of H-TNTs increases by approximately one order of magnitude in comparison to air-treated TNTs. The increase in the number of oxygen vacancies and hydroxyl groups on the H-TNTs help to anchor a greater number of Pt atoms during Pt electrodeposition. The H-TNTs are pretreated by using a successive ion adsorption and reaction (SIAR) method that enhances the loading and dispersion of Pt catalysts when electrodeposited. In the SIAR method a Pd activator can be used to provide uniform nucleation sites for Pt and leads to increased Pt loading on the H-TNTs. Furthermore, fabricated Pt nanoparticles with a diameter of 3.4 nm are located uniformly around the pretreated H-TNT support. The as-prepared and highly ordered electrodes exhibit excellent stability during accelerated durability tests, particularly for the H-TNT-loaded Pt catalysts that have been annealed in ultrahigh purity H2 for a second time. There is minimal decrease in the electrochemical surface area of the as-prepared electrode after 1000 cycles compared to a 68 % decrease for the commercial JM 20 % Pt/C electrode after 800 cycles. X-ray photoelectron spectroscopy shows that after the H-TNT-loaded Pt catalysts are annealed in H2 for the second time, the strong metal-support interaction between the H-TNTs and the Pt catalysts enhances the electrochemical stability of the electrodes. Fuel-cell testing shows that the power density reaches a maximum of 500 mWcm(-2) when this highly ordered electrode is used as the anode. When used as the cathode in a fuel cell with extra-low Pt loading, the new electrode generates a specific power density of 2.68 kWg(Pt) (-1) . It is indicated that H-TNT arrays, which have highly ordered nanostructures, could be used as ordered electrode supports

Reduced graphene oxide supported MnS nanotubes hybrid as a novel non-precious metal electrocatalyst for oxygen reduction reaction with high performance

NASA Astrophysics Data System (ADS)

Tang, Yongfu; Chen, Teng; Guo, Wenfeng; Chen, Shunji; Li, Yanshuai; Song, Jianzheng; Chang, Limin; Mu, Shichun; Zhao, Yufeng; Gao, Faming

2017-09-01

Electronic structure of Mn cations, electric conductivity of active materials and three dimensional structure for mass transport play vital roles in the electrocatalytic activity of Mn-based electrocatalysts for oxygen reduction reaction (ORR). To construct efficient and robust Mn-based electrocatalysts, MnS nanotubes anchored on reduced graphene oxide (MnS-NT@rGO) hybrid was synthesized and used as a novel non-precious metal electrocatalyst for ORR. The formation of nano-tubular structure, which offers more active sites and suitable channels for mass transport to enhance the electrocatalytic activity towards ORR, are carefully illustrated based on the core-dissolution/shell-recrystallization type Ostwald ripening effect. Tuned electronic structure of Mn cations, enhanced electric conductivity and suitable nano-tubular structure endow MnS-NT@rGO electrocatalyst comparative catalytic activity to commercial 20 wt % Pt/C in alkaline electrolyte. The MnS-NT@rGO electrocatalyst exhibits higher catalytic activity than rGO supported MnS nanoparticles (MnS-NP@rGO) and MnS nanotubes without rGO substrate (MnS-NT), as well as rGO supported Mn(OH)2 (Mn(OH)2@rGO) and rGO supported MnO (MnO@rGO). Moreover, the MnS-NT@rGO electrocatalyst shows superior durability and methanol tolerance to commercial Pt/C.

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.

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.

Single-wall carbon nanotube-based proton exchange membrane assembly for hydrogen fuel cells.

PubMed

Girishkumar, G; Rettker, Matthew; Underhile, Robert; Binz, David; Vinodgopal, K; McGinn, Paul; Kamat, Prashant

2005-08-30

A membrane electrode assembly (MEA) for hydrogen fuel cells has been fabricated using single-walled carbon nanotubes (SWCNTs) support and platinum catalyst. Films of SWCNTs and commercial platinum (Pt) black were sequentially cast on a carbon fiber electrode (CFE) using a simple electrophoretic deposition procedure. Scanning electron microscopy and Raman spectroscopy showed that the nanotubes and the platinum retained their nanostructure morphology on the carbon fiber surface. Electrochemical impedance spectroscopy (EIS) revealed that the carbon nanotube-based electrodes exhibited an order of magnitude lower charge-transfer reaction resistance (R(ct)) for the hydrogen evolution reaction (HER) than did the commercial carbon black (CB)-based electrodes. The proton exchange membrane (PEM) assembly fabricated using the CFE/SWCNT/Pt electrodes was evaluated using a fuel cell testing unit operating with H(2) and O(2) as input fuels at 25 and 60 degrees C. The maximum power density obtained using CFE/SWCNT/Pt electrodes as both the anode and the cathode was approximately 20% better than that using the CFE/CB/Pt electrodes.

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

Vapor Synthesis and Thermal Modification of Supportless Platinum–Ruthenium Nanotubes and Application as Methanol Electrooxidation Catalysts

DOE PAGES

Atkinson III, Robert W.; Unocic, Raymond R.; Unocic, Kinga A.; ...

2015-04-23

Metallic, mixed-phase, and alloyed bimetallic Pt-Ru nanotubes were synthesized by a novel route based on the sublimation of metal acetylacetonate precursors and their subsequent vapor deposition within anodic alumina templates. Nanotube architectures were tuned by thermal annealing treatments. As-synthesized nanotubes are composed of nanoparticulate, metallic platinum and hydrous ruthenium oxide whose respective thicknesses depend on the sample chemical composition. The Pt-decorated, hydrous Ru oxide nanotubes may be thermally annealed to promote a series of chemical and physical changes to the nanotube structures including alloy formation, crystallite growth and morphological evolution. Annealed Pt-Ru alloy nanotubes and their as-synthesized analogs demonstrate relativelymore » high specific activities for the oxidation of methanol. As-synthesized, mixed-phase Pt-Ru nanotubes (0.39 mA/cm2) and metallic alloyed Pt64Ru36NTs (0.33 mA/cm2) have considerably higher area-normalized activities than PtRu black (0.22 mA/cm2) at 0.65 V vs. RHE.« less

Carbon Nanotubes as Support in the Platinum-Catalyzed Hydrolytic Dehydrogenation of Ammonia Borane.

PubMed

Chen, Wenyao; Duan, Xuezhi; Qian, Gang; Chen, De; Zhou, Xinggui

2015-09-07

We report remarkable support effects for carbon nanotubes (CNTs) in the Pt/CNT-catalyzed hydrolytic dehydrogenation of ammonia borane. The origin of the support-dependent activity and durability is elucidated by combining the catalytic and durability testing with characterization by a range of spectroscopy and high-angle annular dark-field scanning transmission electron microscopy techniques and ICP analysis. The effects mainly arise from different electronic properties and different abilities for the adsorption of boron-containing species on platinum surfaces and changes in size and shape of the platinum particles during the reaction. Defect-rich CNTs in particular are a promising support material, as it not only enhances the platinum binding energy, leading to the highest hydrogen generation rate, but also inhibits the adsorption of boron-containing species and stabilizes the platinum nanoparticles to resist the agglomeration during the reaction, leading to the highest durability. The insights revealed herein may pave the way for the rational design of highly active and durable metal/carbon catalysts for the hydrolytic dehydrogenation of ammonia borane. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microwave decoration of Pt nanoparticles on entangled 3D carbon nanotube architectures as PEM fuel cell cathode.

PubMed

Sherrell, Peter C; Zhang, Weimin; Zhao, Jie; Wallace, Gordon G; Chen, Jun; Minett, Andrew I

2012-07-01

Proton-exchange membrane fuel cells (PEMFCs) are expected to provide a complementary power supply to fossil fuels in the near future. The current reliance of fuel cells on platinum catalysts is undesirable. However, even the best-performing non-noble metal catalysts are not as efficient. To drive commercial viability of fuel cells forward in the short term, increased utilization of Pt catalysts is paramount. We have demonstrated improved power and energy densities in a single PEMFC using a designed cathode with a Pt loading of 0.1 mg cm(-2) on a mesoporous conductive entangled carbon nanotube (CNT)-based architecture. This electrode allows for rapid transfer of both fuel and waste to and from the electrode, respectively. Pt particles are bound tightly, directly to CNT sidewalls by a microwave-reduction technique, which provided increased charge transport at this interface. The Pt entangled CNT cathode, in combination with an E-TEK 0.2 mg cm(-2) anode, has a maximum power and energy density of 940 mW cm(-2) and 2700 mA cm(-2), respectively, and a power and energy density of 4.01 W mg(Pt)(-1) and 6.35 A mg(Pt)(-1) at 0.65 V. These power densities correspond to a specific mass activity of 0.81 g Pt per kW for the combined mass of both anode and cathode electrodes, approaching the current US Department of Energy efficiency target. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of structural H 2O in TiO 2 nanotubes in enhancing Pt/C direct ethanol fuel cell anode electro-catalysts

NASA Astrophysics Data System (ADS)

Song, Huanqiao; Qiu, Xinping; Guo, Daojun; Li, Fushen

TiO 2 nanotubes (TNTs) with different structural water were obtained by heat treatment under different temperatures. The role of the structural water in TNTs co-catalyzing ethanol oxidation with Pt/C catalyst was studied systematically. Electrochemical studies using cyclic voltammetry and CO stripping voltammetry indicated that more structural water in TNTs was favorable for improving the tolerance of Pt/C to poisoning species; while chronoamperometry curves and repeated cyclic voltammograms showed that slightly less structural water in TNTs actually led to higher catalytic activity and better stability of Pt/C catalysts for ethanol oxidation. This strange result has been analyzed and was ascribed to the appropriate balance of bi-functional mechanism and ethanol transfer in the catalyst layer with less structural water.

Ultrathin Coating of Confined Pt Nanocatalysts by Atomic Layer Deposition for Enhanced Catalytic Performance in Hydrogenation Reactions.

PubMed

Wang, Meihua; Gao, Zhe; Zhang, Bin; Yang, Huimin; Qiao, Yan; Chen, Shuai; Ge, Huibin; Zhang, Jiankang; Qin, Yong

2016-06-13

Metal-support interfaces play a prominent role in heterogeneous catalysis. However, tailoring the metal-support interfaces to realize full utilization remains a major challenge. In this work, we propose a graceful strategy to maximize the metal-oxide interfaces by coating confined nanoparticles with an ultrathin oxide layer. This is achieved by sequential deposition of ultrathin Al2 O3 coats, Pt, and a thick Al2 O3 layer on carbon nanocoils templates by atomic layer deposition (ALD), followed by removal of the templates. Compared with the Pt catalysts confined in Al2 O3 nanotubes without the ultrathin coats, the ultrathin coated samples have larger Pt-Al2 O3 interfaces. The maximized interfaces significantly improve the activity and the protecting Al2 O3 nanotubes retain the stability for hydrogenation reactions of 4-nitrophenol. We believe that applying ALD ultrathin coats on confined catalysts is a promising way to achieve enhanced performance for other catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of SWNT/Pt nanocomposites for their effective role in hydrogen storage applications

NASA Astrophysics Data System (ADS)

Sharma, Anshu; Andreas, Rossos; Nehra, S. P.

2018-05-01

Single Wall Carbon Nanotubes (SWNTs) decorated with platinum were synthesized for hydrogen storage applications. Platinum was deposited on the nanotubes using hexachloroplatinic acid (H2PtCl6.6H2O) as a precursor. Commercial SWNTs were also used to compare the results. The obtained SWNTs/Pt nanocomposite was characterized by various techniques such as powder X-ray diffractrometry (XRD), Raman Spectroscopy and Scanning Electron Microscopy (SEM). Furthermore, in the case of SWNTs/Pt, Pt nanoparticles are found to be uniformly dispersed and bound to the SWNTs acting like a single atom catalyst.

Flutter and divergence instability of supported piezoelectric nanotubes conveying fluid

NASA Astrophysics Data System (ADS)

Bahaadini, Reza; Hosseini, Mohammad; Jamali, Behnam

2018-01-01

In this paper, divergence and flutter instabilities of supported piezoelectric nanotubes containing flowing fluid are investigated. To take the size effects into account, the nonlocal elasticity theory is implemented in conjunction with the Euler-Bernoulli beam theory incorporating surface stress effects. The Knudsen number is applied to investigate the slip boundary conditions between the flow and wall of nanotube. The nonlocal governing equations of nanotube are obtained using Newtonian method, including the influence of piezoelectric voltage, surface effects, Knudsen number and nonlocal parameter. Applying Galerkin approach to transform resulting equations into a set of eigenvalue equations under the simple-simple (S-S) and clamped-clamped (C-C) boundary conditions. The effects of the piezoelectric voltage, surface effects, Knudsen number, nonlocal parameter and boundary conditions on the divergence and flutter boundaries of nanotubes are discussed. It is observed that the fluid-conveying nanotubes with both ends supported lose their stability by divergence first and then by flutter with increase in fluid velocity. Results indicate the importance of using piezoelectric voltage, nonlocal parameter and Knudsen number in decrease of critical flow velocities of system. Moreover, the surface effects have a significant role on the eigenfrequencies and critical fluid velocity.

Study of different nanostructured carbon supports for fuel cell catalysts

NASA Astrophysics Data System (ADS)

Mirabile Gattia, Daniele; Antisari, Marco Vittori; Giorgi, Leonardo; Marazzi, Renzo; Piscopiello, Emanuela; Montone, Amelia; Bellitto, Serafina; Licoccia, Silvia; Traversa, Enrico

Pt clusters were deposited by an impregnation process on three carbon supports: multi-wall carbon nanotubes (MWNT), single-wall carbon nanohorns (SWNH), and Vulcan XC-72 carbon black to investigate the effect of the carbon support structure on the possibility of reducing Pt loading on electrodes for direct methanol (DMFC) fuel cells without impairing performance. MWNT and SWNH were in-house synthesised by a DC and an AC arc discharge process between pure graphite electrodes, respectively. UV-vis spectrophotometry, scanning and transmission electron microscopy, X-ray diffraction, and cyclic voltammetry measurements were used to characterize the Pt particles deposited on the three carbon supports. A differential yield for Pt deposition, not strictly related to the surface area of the carbon support, was observed. SWNH showed the highest surface chemical activity toward Pt deposition. Pt deposited in different forms depending on the carbon support. Electrochemical characterizations showed that the Pt nanostructures deposited on MWNT are particularly efficient in the methanol oxidation reaction.

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.

TePtFe Nanotubes as High-Performing Bifunctional Electrocatalysts for the Oxygen Reduction Reaction and Hydrogen Evolution Reaction.

PubMed

Li, Wenqiang; Amiinu, Ibrahim Saana; Ye, Bei; Wang, Zhe; Zhu, Jiawei; Kou, Zongkui; Mu, Shichun

2018-04-25

Currently, a multicomponent platinum-based alloy has been applied as a promising electrocatalyst to improve catalysis and lower the usage of the noble metal platinum. Herein, a tellurium nanowire (NW)-derived ternary TePtFe nanotube (NT) electrocatalyst has been prepared by the Kirkendall effect. The TePtFe NT formed consists of small single-crystal nanoparticles and voids with an open-end and hollow structure. The TePtFe NT electrocatalyst presents an impressive catalytic activity and stability for both the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Its ORR specific activity and mass activity are 8.5 and 2.4 times, respectively, improved relative to those of commercial platinum catalysts. It is also impressive that, for the HER, a very low overpotential of 28.1 mV at 10 mA cm -2 can be achieved; this is lower than that of platinum (51.8 mV) catalysts in 0.1 m HClO 4 , and the activity is improved, even after 5000 cycles. This work reveals that TePtFe NTs can be employed as nanocatalysts with an impressive catalytic activity and stability for application in fuel cells and hydrogen production. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical vapor deposited carbon nanotubes for aqueous H2-Cl2 fuel cells.

PubMed

Suryavanshi, U B; Bhosale, C H

2010-06-01

Carbon nanotubes having large surface area is an interesting material to develop H2-Cl2 fuel cell electrodes. The attempts were made to deposit carbon nanotubes on porous substrates by chemical vapour deposition. Turpentine oil (C10H16) was used as a precursor, decomposed at 1100 degrees C reactor temperature. Nickel, platinum, tin, Ni-Pt, Ni-Sn, Pt-Sn, Ni-Pt-Sn catalysts were used to grow carbon nanotubes. Nickel was deposited with electrodeposition, platinum with sputter coater and tin with vacuum deposition technique. The developed electrodes were characterized by XRD, SEM, TEM, FTIR, and resistivity by van-der Pauw method. Carbon nanotubes have been formed for 0.25 N nickel deposited for 45 and 60 min; 0.5 N, 0.75 N and 1 N nickel deposited for 15 to 60 min, at the interval of 15. Ni-Pt, Ni-Sn, Pt-Sn and Ni-Pt-Sn activated carbon also shows the well grown CNTs. Aqueous H2-Cl2 fuel cell performance was tested with these grown carbon nanotubes. 40% KCl with 1067 mohm(-1) cm(-1) conductivity was used as electrolyte. Linear sweep voltametry shows reduction potential for hydrogen gas. Chronoamperometry results show better half cell performance for nickel, deposited with 1 N, 45 min deposition time period; and combination of Ni-Pt-Sn with 140, and 110-100 mA/cm2 stable current density respectively.

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.

CO 2 hydrogenation on Pt, Pt/SiO 2 and Pt/TiO 2: Importance of synergy between Pt and oxide support

DOE PAGES

Kattel, Shyam; Yan, Binhang; Chen, Jingguang G.; ...

2016-01-27

In this paper we combined density functional theory (DFT), kinetic Monte Carlo (KMC) simulations and experimental measurements to gain insight into the mechanisms of CO 2 conversion by hydrogen on the Pt nanoparticle (NP). The results show that in spite of the presence of active, low-coordinated sites, Pt NP alone is not able to catalyze the reaction due to the weak CO 2 binding on the catalyst. Once CO 2 is stabilized, the hydrogenation of CO 2 to CO via the reverse-water–gas shift (RWGS) reaction is promoted; in contrast, the enhancement for further *CO hydrogenation to CH 4 is lessmore » significant and no CH 3OH is observed. The selectivity to CO is mainly determined by CO binding energy and the energetics of *CO hydrogenation to *HCO, while that for CH 4 and CH 3OH is determined by the competition between hydrogenation and C–O bond scission reactions of the *H 2COH species. Using SiO 2 and TiO 2 as the support, Pt NP is able to promote the overall CO 2 conversion, while the impact on the selectivity is rather small. The theoretically predicted trend in activity and selectivity is in good agreement with the experimental results. Finally, the enhanced activity of Pt/oxide over Pt is originated from the sites at the Pt–oxide interface, where the synergy between Pt and oxide plays an important role.« less

CO 2 hydrogenation on Pt, Pt/SiO 2 and Pt/TiO 2: Importance of synergy between Pt and oxide support

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

Kattel, Shyam; Yan, Binhang; Chen, Jingguang G.

In this paper we combined density functional theory (DFT), kinetic Monte Carlo (KMC) simulations and experimental measurements to gain insight into the mechanisms of CO 2 conversion by hydrogen on the Pt nanoparticle (NP). The results show that in spite of the presence of active, low-coordinated sites, Pt NP alone is not able to catalyze the reaction due to the weak CO 2 binding on the catalyst. Once CO 2 is stabilized, the hydrogenation of CO 2 to CO via the reverse-water–gas shift (RWGS) reaction is promoted; in contrast, the enhancement for further *CO hydrogenation to CH 4 is lessmore » significant and no CH 3OH is observed. The selectivity to CO is mainly determined by CO binding energy and the energetics of *CO hydrogenation to *HCO, while that for CH 4 and CH 3OH is determined by the competition between hydrogenation and C–O bond scission reactions of the *H 2COH species. Using SiO 2 and TiO 2 as the support, Pt NP is able to promote the overall CO 2 conversion, while the impact on the selectivity is rather small. The theoretically predicted trend in activity and selectivity is in good agreement with the experimental results. Finally, the enhanced activity of Pt/oxide over Pt is originated from the sites at the Pt–oxide interface, where the synergy between Pt and oxide plays an important role.« less

Growth of vertically aligned single-walled carbon nanotubes with metallic chirality through faceted FePt-Au catalysts

NASA Astrophysics Data System (ADS)

Ohashi, Toshiyuki; Iwama, Hiroki; Shima, Toshiyuki

2016-02-01

Direct synthesis of vertically aligned metallic single-walled carbon nanotubes (m-SWCNT forests) is a difficult challenge. We have successfully synthesized m-SWCNT forests using faceted iron platinum-gold catalysts epitaxially grown on a single crystalline magnesium oxide substrate. The metallic content of the forests estimated by Raman spectroscopy reaches 90%. From the standpoint of growth rate of the forests, the growth mechanism is probably based on the catalyst of solid state. It is suggested that preferential growth of m-SWCNTs is achieved when both factors are satisfied, namely, {111} dominant octahedral facet and ideal size (fine particles) of FePt particles.

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

Partially unzipped carbon nanotubes as a superior catalyst support for PEM fuel cells.

PubMed

Long, Donghui; Li, Wei; Qiao, Wenming; Miyawaki, Jin; Yoon, Seong-Ho; Mochida, Isao; Ling, Licheng

2011-09-07

Partially unzipped carbon nanotubes prepared by strong oxidation and thermal expansion of carbon nanotubes were explored as an advanced catalyst support for PEM fuel cells. The unique hybrid structure of 1D nanotube and 2D double-side graphene resulted in an outstanding electrocatalytic performance. This journal is © The Royal Society of Chemistry 2011

Synthesis and properties of platinum on multiwall carbon nanotube modified by chitosan

NASA Astrophysics Data System (ADS)

Fikriyyah, A. K.; Chaldun, E. R.; Indriyati

2018-03-01

Platinum nanoparticles on multiwall carbon nanotubes (Pt/MWCNT) play an important role in fuel cell to convert the chemical energy from a fuel into electricity. In this study, Pt/MWCNT electrocatalysts were prepared by chemical reduction of the metal salts in chitosan as the support. Firstly, commercial MWCNTs were functionalized by oxidative process using a mixture of nitric acid and sulfuric acid. Then, functionalized MWCNTs were mixed with chitosan-acetic acid solution to conduct grafting reaction with NH2 groups in chitosan by solution polymerization method. Platinum nanoparticles were loaded onto the surface of the MWCNTs after hexachloroplatinic acid was reduced by sodium hydroxide solution. The result showed that Pt was attached on MWCNT based on analysis from EDS, XRD, and UV Vis Spectroscopy. UV Vis analysis indicates the plasmon absorbance band of Pt nanoparticles in Pt/MWCNT, while XRD analysis confirmed the size of Pt particle in nanometer. This elucidates the potential procedure to synthesize Pt/MWCNT using chitosan.

An enhanced sensing platform for ultrasensitive impedimetric detection of target genes based on ordered FePt nanoparticles decorated carbon nanotubes.

PubMed

Zhang, Wei; Zong, Peisong; Zheng, Xiuwen; Wang, Libin

2013-04-15

We demonstrate a novel high-performance DNA hybridization biosensor with a carbon nanotubes (CNTs)-based nanocomposite membrane as the enhanced sensing platform. The platform was constructed by homogenously distributing ordered FePt nanoparticles (NPs) onto the CNTs matrix. The surface structure and electrochemical performance of the FePt/CNTs nanocomposite membrane were systematically investigated. Such a nanostructured composite membrane platform could combine with the advantages of FePt NPs and CNTs, greatly facilitate the electron-transfer process and the sensing behavior for DNA detection, leading to excellent sensitivity and selectivity. The complementary target genes from acute promyelocytic leukemia could be quantified in a wide range of 1.0×10⁻¹² mol/L to 1.0×10⁻⁶ mol/L using electrochemical impedance spectroscopy, and the detection limit was 2.1×10⁻¹³ mol/L under the optimal conditions. In addition, the DNA electrochemical biosensor was highly selective to discriminate single-base or double-base mismatched sequences. Copyright © 2012 Elsevier B.V. All rights reserved.

Sustainable Hypersaline Microbial Fuel Cells: Inexpensive Recyclable Polymer Supports for Carbon Nanotube Conductive Paint Anodes.

PubMed

Grattieri, Matteo; Shivel, Nelson D; Sifat, Iram; Bestetti, Massimiliano; Minteer, Shelley D

2017-05-09

Microbial fuel cells are an emerging technology for wastewater treatment, but to be commercially viable and sustainable, the electrode materials must be inexpensive, recyclable, and reliable. In this study, recyclable polymeric supports were explored for the development of anode electrodes to be applied in single-chamber microbial fuel cells operated in field under hypersaline conditions. The support was covered with a carbon nanotube (CNT) based conductive paint, and biofilms were able to colonize the electrodes. The single-chamber microbial fuel cells with Pt-free cathodes delivered a reproducible power output after 15 days of operation to achieve 12±1 mW m -2 at a current density of 69±7 mA m -2 . The decrease of the performance in long-term experiments was mostly related to inorganic precipitates on the cathode electrode and did not affect the performance of the anode, as shown by experiments in which the cathode was replaced and the fuel cell performance was regenerated. The results of these studies show the feasibility of polymeric supports coated with CNT-based paint for microbial fuel cell applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

Pt nanocatalysts supported on reduced graphene oxide for selective conversion of cellulose or cellobiose to sorbitol.

PubMed

Wang, Ding; Niu, Wenqi; Tan, Minghui; Wu, Mingbo; Zheng, Xuejun; Li, Yanpeng; Tsubaki, Noritatsu

2014-05-01

Pt nanocatalysts loaded on reduced graphene oxide (Pt/RGO) were prepared by means of a convenient microwave-assisted reduction approach with ethylene glycol as reductant. The conversion of cellulose or cellobiose into sorbitol was used as an application reaction to investigate their catalytic performance. Various metal nanocatalysts loaded on RGO were compared and RGO-supported Pt exhibited the highest catalytic activity with 91.5 % of sorbitol yield from cellobiose. The catalytic performances of Pt nanocatalysts supported on different carbon materials or on silica support were also compared. The results showed that RGO was the best catalyst support, and the yield of sorbitol was as high as 91.5 % from cellobiose and 58.9 % from cellulose, respectively. The improvement of catalytic activity was attributed to the appropriate Pt particle size and hydrogen spillover effect of Pt/RGO catalyst. Interestingly, the size and dispersion of supported Pt particles could be easily regulated by convenient adjustment of the microwave heating temperature. The catalytic performance was found to initially increase and then decrease with increasing particle size. The optimum Pt particle size was 3.6 nm. These findings may offer useful guidelines for designing novel catalysts with beneficial catalytic performance for biomass conversion. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Architecture-dependent surface chemistry for Pt monolayers on carbon-supported Au.

PubMed

Cheng, Shuang; Rettew, Robert E; Sauerbrey, Marc; Alamgir, Faisal M

2011-10-01

Pt monolayers were grown by surface-limited redox replacement (SLRR) on two types of Au nanostructures. The Au nanostructures were fabricated electrochemically on carbon fiber paper (CFP) by either potentiostatic deposition (PSD) or potential square wave deposition (PSWD). The morphology of the Au/CFP heterostructures, examined using scanning electron microscopy (SEM), was found to depend on the type of Au growth method employed. The properties of the Pt deposit, as studied using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and cyclic voltammetry (CV), were found to depend strongly on the morphology of the support. Specifically, it was found that smaller Au morphologies led to a higher degree of cationicity in the resulting Pt deposit, with Pt(4+) and Pt(2+) species being identified using XPS and XAS. For fuel-cell catalysts, the resistance of ultrathin catalyst deposits to surface area loss through dissolution, poisoning, and agglomeration is critical. This study shows that an equivalent of two monolayers (ML) is the low-loading limit of Pt on Au. At 1 ML or below, the Pt film decreases in activity and durability very rapidly due to presence of cationic Pt. © 2011 American Chemical Society

Cross-beam pulsed laser fabrication of Free-Standing Nanostructured Carbon Nanotubes-Pt-Ceria Anode with unprecedented electroactivity and durability for ethanol oxidation

NASA Astrophysics Data System (ADS)

Wang, Youling; Tabet-Aoul, Amel; Gougis, Maxime; Mohamedi, Mohamed

2015-01-01

Owing to its inherent properties such as great capacity to store and release oxygen, lattice oxygen that has a key role in removing the CO poisoning effect, non-toxicity, abundance, low cost and low temperature processing, CeO2 is emerging as a unique class of electrode material for low temperature polymer electrolyte fuel cells such as direct ethanol fuel cells (DEFCs). However, the maximal exploitation of its functional properties is strictly reliant on the availability of optimized synthesis routes that allow tailor-designing, architecturing and manipulation of CeO2 in a precise manner when it is combined with other functional materials. Here we use the cross-beam pulsed laser deposition (CBPLD) technique to synthesize free-standing (binderless) Pt-CeO2 nanostructured thin films onto carbon nanotubes as anodes for ethanol oxidation reaction. Further significance of this work is that it establishes the importance in the design of the catalyst layer architecture. Indeed, we demonstrate here that when CeO2 material is beneath or when it is mixed with Pt, the interactions between Pt with CeO2 are not similar leading inevitably to different electrocatalytic performances. Given proper tailoring synthesis conditions, CBPLD-developed Pt-CeO2 thin films are remarkably stable and provide electrochemical performance much greater than the layer onto layer CeO2/Pt architecture.

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

Co3O4 nanorod-supported Pt with enhanced performance for catalytic HCHO oxidation at room temperature

NASA Astrophysics Data System (ADS)

Yan, Zhaoxiong; Xu, Zhihua; Cheng, Bei; Jiang, Chuanjia

2017-05-01

Formaldehyde (HCHO) removal from air at room (ambient) temperature by effective catalysts is of significance for improving indoor air quality, and catalysts with high efficiency and good recyclability are highly desirable. In this study, platinum (Pt) supported on nanorod-shaped Co3O4 (Pt/Co3O4) was prepared by calcination of microwave-assisted synthesized Co3O4 precursor followed by NaBH4-reduction of Pt precursor. The as-prepared Co3O4 exhibited a morphology of nanorods with lengths of 400-700 nm and diameters of approximately 40-50 nm, which were self-assembled by nanoparticles. The Pt/Co3O4 catalyst exhibited a superior catalytic performance for HCHO oxidation at room temperature compared to Pt supported on commercial Co3O4 (Pt/Co3O4-c) and Pt supported on commercial TiO2 (Pt/TiO2), which is mainly due to the high oxygen mobility resulting from its distinct nanorod morphology, strong metal-support interaction between Pt and Co3O4, and the intrinsic redox nature of the Co3O4 support. This study provides new insights into the fabrication of high-performance catalysts for indoor air purification.

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.

Bimetallic Ag-Pt Sub-nanometer Supported Clusters as Highly Efficient and Robust Oxidation Catalysts

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

Negreiros, Fabio R.; Halder, Avik; Yin, Chunrong

A combined experimental and theoretical investigation of Ag-Pt sub-nanometer clusters as heterogeneous catalysts in the CO -> CO2 reaction (COox) is presented. Ag9Pt2 and Ag9Pt3 clusters are size-selected in the gas phase, deposited on an ultrathin amorphous alumina support, and tested as catalysts experimentally under realistic conditions and by first-principles simulations at realistic coverage. Insitu GISAXS/TPRx demonstrates that the clusters do not sinter or deactivate even after prolonged exposure to reactants at high temperature, and present comparable, extremely high COox catalytic efficiency. Such high activity and stability are ascribed to a synergic role of Ag and Pt in ultranano-aggregates, inmore » which Pt anchors the clusters to the support and binds and activates two CO molecules, while Ag binds and activates O-2, and Ag/Pt surface proximity disfavors poisoning by CO or oxidized species.« less

Hydrogen adsorption in metal-decorated silicon carbide nanotubes

NASA Astrophysics Data System (ADS)

Singh, Ram Sevak; Solanki, Ankit

2016-09-01

Hydrogen storage for fuel cell is an active area of research and appropriate materials with excellent hydrogen adsorption properties are highly demanded. Nanotubes, having high surface to volume ratio, are promising storage materials for hydrogen. Recently, silicon carbide nanotubes have been predicted as potential materials for future hydrogen storage application, and studies in this area are ongoing. Here, we report a systematic study on hydrogen adsorption properties in metal (Pt, Ni and Al) decorated silicon carbide nanotubes (SiCNTs) using first principles calculations based on density functional theory. The hydrogen adsorption properties are investigated by calculations of adsorption energy, electronic band structure, density of states (DOS) and Mulliken charge population analysis. Our findings show that hydrogen adsorptions on Pt, Ni and Al-decorated SiCNTs undergo spontaneous exothermic reactions with significant modulation of electronic structure of SiCNTs in all cases. Importantly, according to the Mulliken charge population analysis, dipole-dipole interaction causes chemisorptions of hydrogen in Pt, Ni and Al decorated SiCNTs with formation of chemical bonds. The study is a platform for the development of metal decorated SiCNTs for hydrogen adsorption or hydrogen storage application.

Advantages of electrodes with dendrimer-protected platinum nanoparticles and carbon nanotubes for electrochemical methanol oxidation.

PubMed

Siriviriyanun, Ampornphan; Imae, Toyoko

2013-04-14

Electrochemical sensors consisting of electrodes loaded with carbon nanotubes and Pt nanoparticles (PtNPs) protected by dendrimers have been developed using a facile method to fabricate them on two types of disposable electrochemical printed chips with a screen-printed circular gold or a screen-printed circular glassy carbon working electrode. The electrochemical performance of these sensors in the oxidation of methanol was investigated by cyclic voltammetry. It was revealed that such sensors possess stable durability and high electrocatalytic activity: the potential and the current density of an anodic peak in the oxidation of methanol increased with increasing content of PtNPs on the electrodes, indicating the promotion of electrocatalytic activity in relation to the amount of catalyst. The low anodic potential suggests the easy electrochemical reaction, and the high catalyst tolerance supports the almost complete oxidation of methanol to carbon dioxide. The significant performance of these sensors in the detection of methanol oxidation comes from the high electrocatalytic ability of PtNPs, excellent energy transfer of carbon nanotubes and the remarkable ability of dendrimers to act as binders. Thus these systems are effective for a wide range of applications as chemical, biomedical, energy and environmental sensors and as units of direct methanol fuel cells.

Engineering catalytic activity via ion beam bombardment of catalyst supports for vertically aligned carbon nanotube growth

NASA Astrophysics Data System (ADS)

Islam, A. E.; Nikolaev, P.; Amama, P. B.; Zakharov, D.; Sargent, G.; Saber, S.; Huffman, D.; Erford, M.; Semiatin, S. L.; Stach, E. A.; Maruyama, B.

2015-09-01

Carbon nanotube growth depends on the catalytic activity of metal nanoparticles on alumina or silica supports. The control on catalytic activity is generally achieved by variations in water concentration, carbon feed, and sample placement on a few types of alumina or silica catalyst supports obtained via thin film deposition. We have recently expanded the choice of catalyst supports by engineering inactive substrates like c-cut sapphire via ion beam bombardment. The deterministic control on the structure and chemistry of catalyst supports obtained by tuning the degree of beam-induced damage have enabled better regulation of the activity of Fe catalysts only in the ion beam bombarded areas and hence enabled controllable super growth of carbon nanotubes. A wide range of surface characterization techniques were used to monitor the catalytically active surface engineered via ion beam bombardment. The proposed method offers a versatile way to control carbon nanotube growth in patterned areas and also enhances the current understanding of the growth process. With the right choice of water concentration, carbon feed and sample placement, engineered catalyst supports may extend the carbon nanotube growth yield to a level that is even higher than the ones reported here, and thus offers promising applications of carbon nanotubes in electronics, heat exchanger, and energy storage.

Enhancement of ethanol oxidation at Pt and PtRu nanoparticles dispersed over hybrid zirconia-rhodium supports

NASA Astrophysics Data System (ADS)

Rutkowska, Iwona A.; Koster, Margaretta D.; Blanchard, Gary J.; Kulesza, Pawel J.

2014-12-01

A catalytic material for electrooxidation of ethanol that utilizes PtRu nanoparticles dispersed over thin films of rhodium-free and rhodium-containing zirconia (ZrO2) supports is described here. The enhancement of electrocatalytic activity (particularly in the potential range as low as 0.25-0.5 V vs. RHE), that has been achieved by dispersing PtRu nanoparticles (loading, 100 μg cm-2) over the hybrid Rh-ZrO2 support composed of nanostructured zirconia and metallic rhodium particles, is clearly evident from comparison of the respective voltammetric and chronoamperometric current densities recorded at room temperature (22 °C) in 0.5 mol dm-3 H2SO4 containing 0.5 mol dm-3 ethanol. Porous ZrO2 nanostructures, that provide a large population of hydroxyl groups in acidic medium in the vicinity of PtRu sites, are expected to facilitate the ruthenium-induced removal of passivating CO adsorbates from platinum, as is apparent from the diagnostic experiments with a small organic molecule such as methanol. Although Rh itself does not show directly any activity toward ethanol oxidation, the metal is expected to facilitate C-C bond splitting in C2H5OH. It has also been found during parallel voltammetric and chronoamperometric measurements that the hybrid Rh-ZrO2 support increases activity of the platinum component itself toward ethanol oxidation in the low potential range.

Interaction of bimetallic PtCo layers with bare and graphene-covered ZnO(0001) supports

NASA Astrophysics Data System (ADS)

Luo, Wen; Mélart, Christophe; Rach, Alain; Sutter, Christophe; Zafeiratos, Spyridon

2018-03-01

PtCo bimetallic overlayers supported on bare and graphene covered ZnO(0001) substrates have been successfully prepared and used to investigate the effect of graphene interlayer on the arrangement and the redox behaviour of PtCo. We found that Co is readily oxidized at the PtCo/ZnO interface during annealing in ultra-high vacuum (UHV) and low pressure O2 atmosphere, while after inserting a layer of graphene in-between, the oxidation of Co is restricted. In addition, the reduction of Co oxides by H2 is more pronounced when PtCo is supported on graphene covered ZnO. Apart from the cobalt oxidation state, graphene insertion at the interface also influences the PtCo arrangement by favouring their intermixing. Raman spectra show that low intensity defects are introduced into graphene layer after the deposition of PtCo and are enhanced by high temperature annealing. This study highlights the prospect of using graphene to tune the interaction between alloys and oxide supports which finds potential applications in catalysis.

Efficiency of bimetallic PtPd on polydopamine modified on various carbon supports for alcohol oxidations

NASA Astrophysics Data System (ADS)

Pinithchaisakula, A.; Ounnunkad, K.; Themsirimongkon, S.; Promsawan, N.; Waenkaew, P.; Saipanya, S.

2017-02-01

In this work, the preparation, characterization, and electrocatalytic analysis of the catalysts on various carbon substrates for direct alcohol fuel cells were studied. Selected carbons were modified with/without polydopamine (labelled as PDA-C and C) and further metal electrodeposited incorporated onto the glassy carbon (labelled as 5Pt1Pd/PDA-C and 5Pt1Pd/C). Four various carbon materials were used e.g. graphite (G), carbon nanotube (CNT), graphene (GP) and graphene oxide (GO) and the carbons were modified with PDA denoted as PDA-G, PDA-CNT, PDA-GP and PDA-GO, respectively. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) experimental observation showed narrow size distribution of metal anchored on the PDA-C and C materials. Chemical compositions and oxidation states of the catalysts were determined by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX). The catalytic performances for small organic electro-oxidation (e.g. methanol and ethanol) were measured by cyclic voltammetry (CV). Among different PDA-C and C catalysts, monometallic Pt showed less activity than the bimetallic catalysts. Among catalysts with PDA, the 5Pt1Pd/PDA-GO catalyst facilitated methanol and ethanol oxidations with high oxidation currents and If/Ib value and stability with low potentials while among catalysts without PDA, the 5Pt1Pd/CNT provides highest activity and stability. It was found that the catalysts with PDA provided high activity and stability than the catalysts without PDA. The improved catalytic performance of the prepared catalysts could be related to the higher active surface area from polymer modification and bimetallic catalyst system in the catalyst composites.

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.

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.

Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells.

PubMed

Gentil, Solène; Lalaoui, Noémie; Dutta, Arnab; Nedellec, Yannig; Cosnier, Serge; Shaw, Wendy J; Artero, Vincent; Le Goff, Alan

2017-02-06

A biomimetic nickel bis-diphosphine complex incorporating the amino acid arginine in the outer coordination sphere was immobilized on modified carbon nanotubes (CNTs) through electrostatic interactions. The functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H 2 /2 H + interconversion from pH 0 to 9, with catalytic preference for H 2 oxidation at all pH values. The high activity of the complex over a wide pH range allows us to integrate this bio-inspired nanomaterial either in an enzymatic fuel cell together with a multicopper oxidase at the cathode, or in a proton exchange membrane fuel cell (PEMFC) using Pt/C at the cathode. The Ni-based PEMFC reaches 14 mW cm -2 , only six-times-less as compared to full-Pt conventional PEMFC. The Pt-free enzyme-based fuel cell delivers ≈2 mW cm -2 , a new efficiency record for a hydrogen biofuel cell with base metal catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-Supported Mesostructured Pt-Based Bimetallic Nanospheres Containing an Intermetallic Phase as Ultrastable Oxygen Reduction Electrocatalysts.

PubMed

Kim, Ho Young; Cho, Seonghun; Sa, Young Jin; Hwang, Sun-Mi; Park, Gu-Gon; Shin, Tae Joo; Jeong, Hu Young; Yim, Sung-Dae; Joo, Sang Hoon

2016-10-01

Developing highly active and stable cathode catalysts is of pivotal importance for proton exchange membrane fuel cells (PEMFCs). While carbon-supported nanostructured Pt-based catalysts have so far been the most active cathode catalysts, their durability and single-cell performance are yet to be improved. Herein, self-supported mesostructured Pt-based bimetallic (Meso-PtM; M = Ni, Fe, Co, Cu) nanospheres containing an intermetallic phase are reported, which can combine the beneficial effects of transition metals (M), an intermetallic phase, a 3D interconnected framework, and a mesoporous structure. Meso-PtM nanospheres show enhanced oxygen reduction reaction (ORR) activity, compared to Pt black and Pt/C catalysts. Notably, Meso-PtNi containing an intermetallic phase exhibits ultrahigh stability, showing enhanced ORR activity even after 50 000 potential cycles, whereas Pt black and Pt/C undergo dramatic degradation. Importantly, Meso-PtNi with an intermetallic phase also demonstrated superior activity and durability when used in a PEMFC single-cell, with record-high initial mass and specific activities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Engineering catalytic activity via ion beam bombardment of catalyst supports for vertically aligned carbon nanotube growth

DOE PAGES

Islam, A. E.; Zakharov, D.; Stach, E. A.; ...

2015-09-16

Carbon nanotube growth depends on the catalytic activity of metal nanoparticles on alumina or silica supports. The control on catalytic activity is generally achieved by variations in water concentration, carbon feed, and sample placement on a few types of alumina or silica catalyst supports obtained via thin film deposition. We have recently expanded the choice of catalyst supports by engineering inactive substrates like c-cut sapphire via ion beam bombardment. The deterministic control on the structure and chemistry of catalyst supports obtained by tuning the degree of beam-induced damage have enabled better regulation of the activity of Fe catalysts only inmore » the ion beam bombarded areas and hence enabled controllable super growth of carbon nanotubes. A wide range of surface characterization techniques were used to monitor the catalytically active surface engineered via ion beam bombardment. The proposed method offers a versatile way to control carbon nanotube growth in patterned areas and also enhances the current understanding of the growth process. As a result, with the right choice of water concentration, carbon feed and sample placement, engineered catalyst supports may extend the carbon nanotube growth yield to a level that is even higher than the ones reported here, and thus offers promising applications of carbon nanotubes in electronics, heat exchanger, and energy storage.« less

Carbon nanotube synthesis with different support materials and catalysts

NASA Astrophysics Data System (ADS)

Gümüş, Fatih; Yuca, Neslihan; Karatepe, Nilgün

2013-09-01

Having remarkable characteristics, carbon nanotubes (CNTs) have attracted a lot of interest. Their mechanical, electrical, thermal and chemical properties make CNTs suitable for several applications such as electronic devices, hydrogen storage, textile, drug delivery etc. CNTs have been synthesized by various methods, such as arc discharge, laser ablation and catalytic chemical vapor deposition (CCVD). In comparison with the other techniques, CCVD is widely used as it offers a promising route for mass production. High capability of decomposing hydrocarbon formation is desired for the selected catalysts. Therefore, transition metals which are in the nanometer scale are the most effective catalysts. The common transition metals that are being used are Fe, Co, Ni and their binary alloys. The impregnation of the catalysts over the support material has a crucial importance for the CNT production. In this study, the influence of the support materials on the catalytic activity of metals was investigated. CNTs have been synthesized over alumina (Al2O3), silica (SiO2) and magnesium oxide (MgO) supported Fe, Co, Fe-Co catalysts. Catalyst - support material combinations have been investigated and optimum values for each were compared. Single walled carbon nanotubes (SWCNTs) were produced at 800°C. The duration of synthesis was 30 minutes for all support materials. The synthesized materials were characterized by thermal gravimetric analysis (TGA), Raman spectroscopy and transmission electron microscopy.

Platinum-ruthenium nanotubes and platinum-ruthenium coated copper nanowires as efficient catalysts for electro-oxidation of methanol

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

Zheng, Jie; Cullen, David A.; Forest, Robert V.

2015-01-15

The sluggish kinetics of methanol oxidation reaction (MOR) is a major barrier to the commercialization of direct methanol fuel cells (DMFCs). In this study, we report a facile synthesis of platinum–ruthenium nanotubes (PtRuNTs) and platinum–ruthenium-coated copper nanowires (PtRu/CuNWs) by galvanic displacement reaction using copper nanowires as a template. The PtRu compositional effect on MOR is investigated; the optimum Pt/Ru bulk atomic ratio is about 4 and surface atomic ratio about 1 for both PtRuNTs and PtRu/CuNWs. Enhanced specific MOR activities are observed on both PtRuNTs and PtRu/CuNWs compared with the benchmark commercial carbon-supported PtRu catalyst (PtRu/C, Hispec 12100). Finally, x-raymore » photoelectron spectroscopy (XPS) reveals a larger extent of electron transfer from Ru to Pt on PtRu/CuNWs, which may lead to a modification of the d-band center of Pt and consequently a weaker bonding of CO (the poisoning intermediate) on Pt and a higher MOR activity on PtRu/CuNWs.« less

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

CoMn2O4-supported functionalized carbon nanotube: efficient catalyst for oxygen reduction in microbial fuel cells

NASA Astrophysics Data System (ADS)

Zhu, Nengwu; Lu, Yu; Liu, Bowen; Zhang, Taiping; Huang, Jianjian; Shi, Chaohong; Wu, Pingxiao; Dang, Zhi; Wang, Ruixin

2017-10-01

Recently, the synthesis of nonprecious metal catalysts with low cost and high oxygen reduction reaction (ORR) efficiency is paid much attention in field of microbial fuel cells (MFCs). Transition metal oxides (AMn2O4, A = Co、Ni, and Zn) supported on carbon materials such as graphene and carbon nanotube exhibit stronger electroconductivity and more active sites comparing to bare AMn2O4. Herein, we demonstrate an easy operating Hummer's method to functionalize carbon nanotubes (CNTs) with poly (diallyldimethylammonium chloride) in order to achieve effective loading of CoMn2O4 nanoparticles, named CoMn2O4/PDDA-CNTs (CMODT). After solvothermal treatment, nanoscale CoMn2O4 particles ( 80 nm) were successfully attached on the noncovalent functionalized carbon nanotube. Results show that such composites possess an outstanding electrocatalytic activity towards ORR comparable to the commercial Pt/C catalyst in neutral media. Electrochemical detections as cyclic voltammogram (CV) and rotating ring-disk electrode tests (RRDE) showed that the potential of oxygen reduction peak of 30% CMODT was at - 0.3 V (vs Ag/AgCl), onset potential was at + 0.4 V. Among them, 30% CMODT composite appeared the best candidate of oxygen reduction via 3.9 electron transfer pathway. When 30% CMODT composite was utilized as cathode catalyst in air cathode MFC, the reactor obtained 1020 mW m-2 of the highest maximum power density and 0.781 V of open circuit voltage. The excellent activity and low cost (0.2 g-1) of the hybrid materials demonstrate the potential of transition metal oxide/carbon as effective cathode ORR catalyst for microbial fuel cells. [Figure not available: see fulltext.

Preparation of supported electrocatalyst comprising multiwalled carbon nanotubes

DOEpatents

Wu, Gang; Zelenay, Piotr

2013-08-27

A process for preparing a durable non-precious metal oxygen reduction electrocatalyst involves heat treatment of a ball-milled mixture of polyaniline and multiwalled carbon nanotubes in the presence of a Fe species. The catalyst is more durable than catalysts that use carbon black supports. Performance degradation was minimal or absent after 500 hours of operation at constant cell voltage of 0.40 V.

Functionalized Single-Walled Carbon Nanotube-Based Fuel Cell Benchmarked Against US DOE 2017 Technical Targets

PubMed Central

Jha, Neetu; Ramesh, Palanisamy; Bekyarova, Elena; Tian, Xiaojuan; Wang, Feihu; Itkis, Mikhail E.; Haddon, Robert C.

2013-01-01

Chemically modified single-walled carbon nanotubes (SWNTs) with varying degrees of functionalization were utilized for the fabrication of SWNT thin film catalyst support layers (CSLs) in polymer electrolyte membrane fuel cells (PEMFCs), which were suitable for benchmarking against the US DOE 2017 targets. Use of the optimum level of SWNT -COOH functionality allowed the construction of a prototype SWNT-based PEMFC with total Pt loading of 0.06 mgPt/cm2 - well below the value of 0.125 mgPt/cm2 set as the US DOE 2017 technical target for total Pt group metals (PGM) loading. This prototype PEMFC also approaches the technical target for the total Pt content per kW of power (<0.125 gPGM/kW) at cell potential 0.65 V: a value of 0.15 gPt/kW was achieved at 80°C/22 psig testing conditions, which was further reduced to 0.12 gPt/kW at 35 psig back pressure. PMID:23877112

Functionalized single-walled carbon nanotube-based fuel cell benchmarked against US DOE 2017 technical targets.

PubMed

Jha, Neetu; Ramesh, Palanisamy; Bekyarova, Elena; Tian, Xiaojuan; Wang, Feihu; Itkis, Mikhail E; Haddon, Robert C

2013-01-01

Chemically modified single-walled carbon nanotubes (SWNTs) with varying degrees of functionalization were utilized for the fabrication of SWNT thin film catalyst support layers (CSLs) in polymer electrolyte membrane fuel cells (PEMFCs), which were suitable for benchmarking against the US DOE 2017 targets. Use of the optimum level of SWNT -COOH functionality allowed the construction of a prototype SWNT-based PEMFC with total Pt loading of 0.06 mg(Pt)/cm²--well below the value of 0.125 mg(Pt)/cm² set as the US DOE 2017 technical target for total Pt group metals (PGM) loading. This prototype PEMFC also approaches the technical target for the total Pt content per kW of power (<0.125 g(PGM)/kW) at cell potential 0.65 V: a value of 0.15 g(Pt)/kW was achieved at 80°C/22 psig testing conditions, which was further reduced to 0.12 g(Pt)/kW at 35 psig back pressure.

Electrochemical Glucose Biosensor of Platinum Nanospheres Connected by Carbon Nanotubes

PubMed Central

Claussen, Jonathan C.; Kim, Sungwon S.; Haque, Aeraj ul; Artiles, Mayra S.; Porterfield, D. Marshall; Fisher, Timothy S.

2010-01-01

Background Glucose biosensors comprised of nanomaterials such as carbon nanotubes (CNTs) and metallic nanoparticles offer enhanced electrochemical performance that produces highly sensitive glucose sensing. This article presents a facile biosensor fabrication and biofunctionalization procedure that utilizes CNTs electrochemically decorated with platinum (Pt) nanospheres to sense glucose amperometrically with high sensitivity. Method Carbon nanotubes are grown in situ by microwave plasma chemical vapor deposition (MPCVD) and electro-chemically decorated with Pt nanospheres to form a CNT/Pt nanosphere composite biosensor. Carbon nanotube electrodes are immobilized with fluorescently labeled bovine serum albumin (BSA) and analyzed with fluorescence microscopy to demonstrate their biocompatibility. The enzyme glucose oxidase (GOX) is immobilized onto the CNT/Pt nanosphere biosensor by a simple drop-coat method for amperometric glucose sensing. Results Fluorescence microscopy demonstrates the biofunctionalization capability of the sensor by portraying adsorption of fluorescently labeled BSA unto MPCVD-grown CNT electrodes. The subsequent GOX–CNT/Pt nanosphere biosensor demonstrates a high sensitivity toward H2O2 (7.4 μA/mM/cm2) and glucose (70 μA/mM/cm2), with a glucose detection limit and response time of 380 nM (signal-to-noise ratio = 3) and 8 s (t90%), respectively. The apparent Michaelis–Menten constant (0.64 mM) of the biosensor also reflects the improved sensitivity of the immobilized GOX/nanomaterial complexes. Conclusions The GOX–CNT/Pt nanosphere biosensor outperforms similar CNT, metallic nanoparticle, and more conventional carbon-based biosensors in terms of glucose sensitivity and detection limit. The biosensor fabrication and biofunctionalization scheme can easily be scaled and adapted for microsensors for physiological research applications that require highly sensitive glucose sensing. PMID:20307391

Electrochemical glucose biosensor of platinum nanospheres connected by carbon nanotubes.

PubMed

Claussen, Jonathan C; Kim, Sungwon S; Haque, Aeraj Ul; Artiles, Mayra S; Porterfield, D Marshall; Fisher, Timothy S

2010-03-01

Glucose biosensors comprised of nanomaterials such as carbon nanotubes (CNTs) and metallic nanoparticles offer enhanced electrochemical performance that produces highly sensitive glucose sensing. This article presents a facile biosensor fabrication and biofunctionalization procedure that utilizes CNTs electrochemically decorated with platinum (Pt) nanospheres to sense glucose amperometrically with high sensitivity. Carbon nanotubes are grown in situ by microwave plasma chemical vapor deposition (MPCVD) and electro-chemically decorated with Pt nanospheres to form a CNT/Pt nanosphere composite biosensor. Carbon nanotube electrodes are immobilized with fluorescently labeled bovine serum albumin (BSA) and analyzed with fluorescence microscopy to demonstrate their biocompatibility. The enzyme glucose oxidase (GO(X)) is immobilized onto the CNT/Pt nanosphere biosensor by a simple drop-coat method for amperometric glucose sensing. Fluorescence microscopy demonstrates the biofunctionalization capability of the sensor by portraying adsorption of fluorescently labeled BSA unto MPCVD-grown CNT electrodes. The subsequent GO(X)-CNT/Pt nanosphere biosensor demonstrates a high sensitivity toward H(2)O(2) (7.4 microA/mM/cm(2)) and glucose (70 microA/mM/cm(2)), with a glucose detection limit and response time of 380 nM (signal-to-noise ratio = 3) and 8 s (t(90%)), respectively. The apparent Michaelis-Menten constant (0.64 mM) of the biosensor also reflects the improved sensitivity of the immobilized GO(X)/nanomaterial complexes. The GO(X)-CNT/Pt nanosphere biosensor outperforms similar CNT, metallic nanoparticle, and more conventional carbon-based biosensors in terms of glucose sensitivity and detection limit. The biosensor fabrication and biofunctionalization scheme can easily be scaled and adapted for microsensors for physiological research applications that require highly sensitive glucose sensing. (c) 2010 Diabetes Technology Society.

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

PubMed

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

2014-12-15

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

Citric acid induced promoted dispersion of Pt on the support and enhanced catalytic activities for a Pt-based catalyst

NASA Astrophysics Data System (ADS)

Cheng, Tianqiong; Wang, Jianli; Wang, Suning; Cui, Yajuan; Zhang, Hailong; Yan, Shuang; Yuan, Shandong; Chen, Yaoqiang

2017-12-01

Citric acid (CA), as the chelating agent, was introduced to obtain the enhanced Pt dispersion and catalytic activities for the Pt-based catalysts supported on oxygen-storage material. The role and content of CA were investigated systematically. It was found that the citric acid-assisted catalysts showed better Pt dispersion and smaller nanoparticle size of Pt. Thus, the catalyst had lower reduction temperature, preferable thermostability and possessed more oxidation state of Pt species under the oxidation atmosphere. The citric acid-induced fresh catalysts were excellent to convert CO and the corresponding aged ones exhibited higher activities for the elimination of all the target pollutants. Among the aged catalysts, P2-a (the mole ratio of Pt/CA is 2:1) presented the best performance. Particularly, compared with the reference sample (Pc-a), the light-off temperatures (T50) of NO, HC and CO for P2-a decreased by 39 °C, 42 °C and 72 °C, respectively, and the full-conversion temperatures (T90) of NO, HC and CO for P2-a decreased by 44 °C, 44 °C and 48 °C, respectively. Therefore, this work provides a facile and valid method to manufacture advanced catalysts for purification of the vehicle exhaust in the future.

Development of Metal-impregnated Single Walled Carbon Nanotubes for Toxic Gas Contaminant Control in Advanced Life Support Systems

NASA Technical Reports Server (NTRS)

Pisharody, Suresh A.; Fisher, John W.; Wignarajah, K.

2002-01-01

The success of physico-chemical waste processing and resource recovery technologies for life support application depends partly on the ability of gas clean-up systems to efficiently remove trace contaminants generated during the process with minimal use of expendables. Carbon nanotubes promise superior performance over conventional approaches to gas clean-up due to their ability to direct the selective uptake of gaseous species based on their controlled pore size, high surface area, ordered chemical structure that allows functionalization and their effectiveness also as catalyst support materials for toxic gas conversion. We present results and findings from a preliminary study on the effectiveness of metal impregnated single walled nanotubes as catalyst/catalyst support materials for toxic gas contaminate control. The study included the purification of single walled nanotubes, the catalyst impregnation of the purified nanotubes, the experimental characterization of the surface properties of purified single walled nanotubes and the characterization of physisorption and chemisorption of uptake molecules.

n-Hexane conversion over supported Pt catalysts: Reply to Zoltan Paal

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

Sharma, S.B.; Dumesic, J.A.

In the accompanying letter to the Journal of Catalysis, Paal has questioned the findings and conclusions of the author`s recently published paper. It is important to stress that many of these conclusions are based on the combined interpretation of the data from the author`s recently published paper with results form spectroscopic and microcalorimetric studies of various supported platinum catalysts. In short, the authors have shown that highly dispersed, cluster-sized platinum particles supported in L-zeolite have the same heats of H{sub 2} and CO adsorption as larger platinum particles supported on silica; however, Pt/L-zeolite catalysts are more resistant to self-poisoning reactions,more » exhibit higher turnover frequencies, and show enhanced formation of benzene and methylcyclopentane (MCP) compared to larger particles of Pt supported on silica during n-hexane conversion at total pressures of 3 atm and hydrogen pressures near 276 kPa. 13 refs., 1 tab.« less

Role of the Support and Reaction Conditions on the Vapor-Phase Deoxygenation of m-Cresol over Pt/C and Pt/TiO 2 Catalysts

DOE PAGES

Griffin, Michael B.; Ferguson, Glen A.; Ruddy, Daniel A.; ...

2016-03-23

The catalytic deoxygenation of biomass fast pyrolysis vapors offers a promising route for the sustainable production of liquid transportation fuels. However, a clear understanding of the mechanistic details involved in this process has yet to be achieved, and questions remain regarding the role of the catalyst support and the influence of reaction conditions. In order to gain insight into these questions, the deoxygenation of m-cresol was investigated over Pt/C and Pt/TiO 2 catalysts using experimental and computational techniques. The performance of each catalyst was evaluated in a packed-bed reactor under two conditions (523 K, 2.0 MPa and 623 K, 0.5more » MPa), and the energetics of the ring hydrogenation, direct deoxygenation, and tautomerization mechanisms were calculated over hydrogen-covered Pt(111) and oxygen vacancies on the surface of TiO 2(101). Over Pt(111), ring hydrogenation to 3-methylcyclohexanone and 3-methylcyclohexanol was found to be the most energetically favorable pathway. Over TiO 2(101), tautomerization and direct deoxygenation to toluene were identified as additional energetically favorable routes. These calculations are consistent with the experimental data, in which Pt/TiO 2 was more active on a metal site basis and exhibited higher selectivity to toluene at 623 K relative to Pt/C. On the basis of these results, it is likely that the reactivity of Pt/TiO 2 and Pt/C is driven by the metallic phase at 523 K, while contributions from the TiO 2 support enhance deoxygenation at 623 K. These results highlight the synergistic effects between hydrogenation catalysts and reducible metal oxide supports and provide insight into the reaction pathways responsible for their enhanced deoxygenation performance.« less

Glucose sensing based on Pt-MWCNT and MWCNT

NASA Astrophysics Data System (ADS)

Aryasomayajula, Lavanya; Xie, Jining; Wang, Shouyan; Varadan, Vijay K.

2007-04-01

It is known that multi walled carbon nanotubes (MWCNTs) is an excellent materials for biosensing applications and with the introduction of Pt nanoparticles (Pt-MWCNTs) of about 3nm in diameter in MWCNTs greatly increases the current sensitivity and also the signal to noise ratio. We fabricated the CNT- based glucose sensor by immobilization the bio enzyme, glucose oxidase (GoX), on the Pt-MWCNT and electrode were prepared. The sensor has been tested effectively for both the abnormal blood glucose levels- greater than 6.9 mM and less than 3.5 mM which are the prediabetic and diabetic glucose levels, respectively. The current signal obtained from the Pt-MWCNT was much higher compared to the MWCNT based sensors.

Alumina-supported sub-nanometer Pt 10 clusters: Amorphization and role of the support material in a highly active CO oxidation catalyst

DOE PAGES

Yin, Chunrong; Negreiros, Fabio R.; Barcaro, Giovanni; ...

2017-02-03

Catalytic CO oxidation is unveiled on size-selected Pt 10 clusters deposited on two very different ultrathin (≈0.5–0.7 nm thick) alumina films: (i) a highly ordered alumina obtained under ultra-high vacuum (UHV) by oxidation of the NiAl(110) surface and (ii) amorphous alumina obtained by atomic layer deposition (ALD) on a silicon chip that is a close model of real-world supports. Notably, when exposed to realistic reaction conditions, the Pt 10/UHV-alumina system undergoes a morphological transition in both the clusters and the substrate, and becomes closely akin to Pt 10/ALD-alumina, thus reconciling UHV-type surface-science and real-world experiments. The Pt 10 clusters, thoroughlymore » characterized via combined experimental techniques and theoretical analysis, exhibit among the highest CO oxidation activity per Pt atom reported for CO oxidation catalysts, due to the interplay of ultra-small size and support effects. Lastly, a coherent interdisciplinary picture then emerges for this catalytic system.« less

Electrochemical and Morphological Investigations of Ga Addition to Pt Electrocatalyst Supported on Carbon

PubMed Central

Paganoto, Giordano T.; Santos, Deise M.; Guimarães, Marco C. C.; Carneiro, Maria Tereza W. D.

2017-01-01

This paper is consisted in the synthesis of platinum-based electrocatalysts supported on carbon (Vulcan XC-72) and investigation of the addition of gallium in their physicochemical and electrochemical properties toward ethanol oxidation reaction (EOR). PtGa/C electrocatalysts were prepared through thermal decomposition of polymeric precursor method at a temperature of 350°C. Six different compositions were homemade: Pt50Ga50/C, Pt60Ga40/C, Pt70Ga30/C, Pt80Ga20/C, Pt90Ga10/C, and Pt100/C. These electrocatalysts were electrochemically characterized by cyclic voltammetry (CV), chronoamperometry (CA), chronopotentiometry (CP), and electrochemical impedance spectroscopy (EIS) in the presence and absence of ethanol 1.0 mol L−1. Thermogravimetric analysis (TGA), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and transmission electron microscopy (TEM) were also carried out for a physicochemical characterization of those materials. XRD results showed the main peaks of face-centered cubic Pt. The particle sizes obtained from XRD and TEM analysis range from 7.2 nm to 12.9 nm. The CV results indicate behavior typical of Pt-based electrocatalysts in acid medium. The CV, EIS, and CA data reveal that the addition of up to 31% of gallium to the Pt highly improves catalytic activity on EOR response when compared to Pt100/C. PMID:28466065

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

NASA Astrophysics Data System (ADS)

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

2017-10-01

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

Boosted surface acidity in TiO2 and Al2O3-TiO2 nanotubes as catalytic supports

NASA Astrophysics Data System (ADS)

Camposeco, R.; Castillo, S.; Mejía-Centeno, Isidro; Navarrete, J.; Nava, N.

2015-11-01

In this study, titanate nanotubes (NT) and titanate nanotubes with alumina (NT-Al) were studied as solid acid catalytic supports to show the relationship between the kind of acidity and catalytic activity. The supports were characterized by XRD, TEM, FTIR, XPS, and tested in the SCR-NO with NH3. It was found that the amount of Brönsted acid sites was maintained and the Lewis acid sites were significantly affected by the addition of alumina (1, 3, 5 and 10 wt.%); such acidity was higher than that of the titanate nanotubes (NT) by two-fold. To confirm the formation of titanate nanotubes and titanate nanotubes with alumina, transmission electron microscopy (TEM) was used. X-ray diffraction (XRD) revealed the formation of the H2Ti4O9·H2O phase. All NT and NT-Al supports presented catalytic activity to remove NO with NH3 under lean conditions, confirming the presence of an important amount of Brönsted and Lewis acid sites in both NT and NT-Al supports.

CO 2 hydrogenation over oxide-supported PtCo catalysts: The role of the oxide support in determining the product selectivity

DOE PAGES

Kattel, Shyam; Yu, Weiting; Yang, Xiaofang; ...

2016-05-09

By simply changing the oxide support, the selectivity of a metal–oxide catalysts can be tuned. For the CO 2 hydrogenation over PtCo bimetallic catalysts supported on different reducible oxides (CeO 2, ZrO 2, and TiO 2), replacing a TiO 2 support by CeO 2 or ZrO 2 selectively strengthens the binding of C,O-bound and O-bound species at the PtCo–oxide interface, leading to a different product selectivity. Lastly, these results reveal mechanistic insights into how the catalytic performance of metal–oxide catalysts can be fine-tuned.

Halloysite nanotube-based electrospun ceramic nanofibre mat: a novel support for zeolite membranes

PubMed Central

Chen, Zhuwen; Zeng, Jiaying; Lv, Dong; Gao, Jinqiang; Zhang, Jian; Bai, Shan; Li, Ruili; Wu, Jingshen

2016-01-01

Some key parameters of supports such as porosity, pore shape and size are of great importance for fabrication and performance of zeolite membranes. In this study, we fabricated millimetre-thick, self-standing electrospun ceramic nanofibre mats and employed them as a novel support for zeolite membranes. The nanofibre mats were prepared by electrospinning a halloysite nanotubes/polyvinyl pyrrolidone composite followed by a programmed sintering process. The interwoven nanofibre mats possess up to 80% porosity, narrow pore size distribution, low pore tortuosity and highly interconnected pore structure. Compared with the commercial α-Al2O3 supports prepared by powder compaction and sintering, the halloysite nanotube-based mats (HNMs) show higher flux, better adsorption of zeolite seeds, adhesion of zeolite membranes and lower Al leaching. Four types of zeolite membranes supported on HNMs have been successfully synthesized with either in situ crystallization or a secondary growth method, demonstrating good universality of HNMs for supporting zeolite membranes. PMID:28083098

Halloysite nanotube-based electrospun ceramic nanofibre mat: a novel support for zeolite membranes

NASA Astrophysics Data System (ADS)

Chen, Zhuwen; Zeng, Jiaying; Lv, Dong; Gao, Jinqiang; Zhang, Jian; Bai, Shan; Li, Ruili; Hong, Mei; Wu, Jingshen

2016-12-01

Some key parameters of supports such as porosity, pore shape and size are of great importance for fabrication and performance of zeolite membranes. In this study, we fabricated millimetre-thick, self-standing electrospun ceramic nanofibre mats and employed them as a novel support for zeolite membranes. The nanofibre mats were prepared by electrospinning a halloysite nanotubes/polyvinyl pyrrolidone composite followed by a programmed sintering process. The interwoven nanofibre mats possess up to 80% porosity, narrow pore size distribution, low pore tortuosity and highly interconnected pore structure. Compared with the commercial α-Al2O3 supports prepared by powder compaction and sintering, the halloysite nanotube-based mats (HNMs) show higher flux, better adsorption of zeolite seeds, adhesion of zeolite membranes and lower Al leaching. Four types of zeolite membranes supported on HNMs have been successfully synthesized with either in situ crystallization or a secondary growth method, demonstrating good universality of HNMs for supporting zeolite membranes.

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.

Control of Electron Flow Direction in Photoexcited Cycloplatinated Complex Containing Conjugated Polymer-Single Walled Carbon Nanotube Hybrids.

PubMed

Xiong, Wenjuan; Du, Lili; Lo, Kin Cheung; Shi, Haiting; Takaya, Tomohisa; Iwata, Koichi; Chan, Wai Kin; Phillips, David Lee

2018-06-25

Conjugated polymers incorporated with cycloplatinated complexes (P1-Pt and P2-Pt) were used as dispersants for single walled carbon nanotubes (SWCNTs). Significant changes in the UV-vis absorption spectra were observed after the formation of the polymer/SWCNT hybrids. Molecular dynamics (MD) simulations revealed the presence of a strong interaction between the cycloplatinated complex moieties and the SWCNT surface. The photoinduced electron transfer processes in these hybrids were strongly dependent on the type of the comonomer unit. Upon photoexcitation, the excited P1-Pt donates electrons to the SWCNT, while P2-Pt accepts electrons from the photoexcited SWCNT. These observations were supported by results from Raman and femtosecond time-resolved transient absorption spectroscopy experiments. The strong electronic interaction between the Pt complexes and the SWCNT gives rise to a new hybrid system that has a controllable photo-induced electron transfer flow, which are important in regulating the charge transport processes SWCNT-based optoelectronic devices.

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.

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.

Development of Metal-impregnated Single Walled Carbon Nanotubes for Toxic Gas Contaminant Control in Advanced Life Support Systems

NASA Technical Reports Server (NTRS)

Cinke, Martin; Li, Jing; Chen, Bin; Wignarajah, Kanapathipillai; Pisharody, Suresh A.; Fisher, John W.; Delzeit, Lance; Meyyappan, Meyya; Partridge, Harry; Clark, Kimberlee

2003-01-01

The success of physico-chemical waste processing and resource recovery technologies for life support application depends partly on the ability of gas clean-up systems to efficiently remove trace contaminants generated during the process with minimal use of expendables. Highly purified metal-impregnated carbon nanotubes promise superior performance over conventional approaches to gas clean-up due to their ability to direct the selective uptake gaseous species based both on the nanotube s controlled pore size, high surface area, and ordered chemical structure that allows functionalization and on the nanotube s effectiveness as a catalyst support material for toxic contaminants removal. We present results on the purification of single walled carbon nanotubes (SWCNT) and efforts at metal impregnation of the SWCNT's.

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.

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.

Remarkable support effect on the reactivity of Pt/In2O3/MOx catalysts for methanol steam reforming

NASA Astrophysics Data System (ADS)

Liu, Xin; Men, Yong; Wang, Jinguo; He, Rong; Wang, Yuanqiang

2017-10-01

Effects of supports over Pt/In2O3/MOx catalysts with extremely low loading of Pt (1 wt%) and In2O3 loadings (3 wt%) are investigated for the hydrogen production of methanol steam reforming (MSR) in the temperature range of 250-400 °C. Under practical conditions without the pre-reduction, the 1Pt/3In2O3/CeO2 catalyst shows the highly efficient catalytic performance, achieving almost complete methanol conversion (98.7%) and very low CO selectivity of 2.6% at 325 °C. The supported Pt/In2O3 catalysts are characterized by means of Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), high-resolution transmission microscopy (HRTEM), temperature programmed reduction with hydrogen (H2-TPR), CO pulse chemisorption, temperature programmed desorption of methanol and water (CH3OH-TPD and H2O-TPD). These demonstrate that the nature of catalyst support of Pt/In2O3/MOx plays crucial roles in the Pt dispersion associated by the strong interaction among Pt, In2O3 and supporting materials and the surface redox properties at low temperature, and thus affects their capability to activate the reactants and determines the catalytic activity of methanol steam reforming. The superior 1Pt/3In2O3/CeO2 catalyst, exhibiting a remarkable reactivity and stability for 32 h on stream, demonstrates its potential for efficient hydrogen production of methanol steam reforming in mobile and de-centralized H2-fueled PEMFC systems.

Negligible degradation upon in situ voltage cycling of a PEMFC using an electrospun niobium-doped tin oxide supported Pt cathode.

PubMed

Savych, Iuliia; Subianto, Surya; Nabil, Yannick; Cavaliere, Sara; Jones, Deborah; Rozière, Jacques

2015-07-14

Novel platinum-catalysed, corrosion-resistant, loose-tube-structured electrocatalysts for proton exchange membrane fuel cells have been obtained using single-needle electrospinning associated with a microwave-assisted polyol method. Monodisperse platinum particles supported on Nb-SnO2 demonstrated higher electrochemical stability than conventional Pt/C electrodes during ex situ potential cycling and comparable activity in the oxygen reduction reaction. In situ fuel cell operation under accelerated stress test conditions of a membrane electrode assembly elaborated using a Pt/C anode and Pt/Nb-SnO2 cathode confirmed that the voltage loss is significantly lower for the novel cathode than for an MEA prepared using conventional Pt/C supported electrocatalysts. Furthermore, the Nb-SnO2 stabilised the supported platinum nanoparticles against dissolution, migration and reprecipitation in the membrane. Pt/Nb-SnO2 loose-tubes constitute a mitigation strategy for two known degradation mechanisms in PEMFC: corrosion of the carbon support at the cathode, and dissolution of Pt at high cell voltages.

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.

Tailoring Silica-alumina Supported Pt-Pd As Poison Tolerant Catalyst For Aromatics Hydrogenation

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

Yu, Yanzhe; Gutierrez, Oliver Y.; Haller, Gary L.

2013-08-01

The tailoring of the physicochemical and catalytic properties of mono- and bimetallic Pt-Pd catalysts supported on amorphous silica-alumina is studied. Electron energy loss spectroscopy and extended X-ray absorption fine structure analyses indicated that bimetallic Pt-Pd and relatively large monometallic Pd particles were formed, whereas the X-ray absorption near edge structure provided direct evidence for the electronic deficiency of the Pt atoms. The heterogeneous distribution of metal particles was also shown by high resolution transmission electron microscopy. The average structure of the bimetallic particles (Pt-rich core and Pd-rich shell) and the presence of Pd particles led to surface Pd enrichment, whichmore » was independently shown by IR spectra of adsorbed CO. The specific metal distribution, average size, and surface composition of the Pt-Pd particles depend to a large extent on the metal precursors. In the presence of NH3 ligands, Pt-Pd particles with a fairly homogeneous bulk and surface metal distribution were formed. Also high Lewis acid site concentration of the carrier leads to more homogeneous bimetallic particles. All catalysts were active for the hydrogenation of tetralin in the absence and presence of quinoline and dibenzothiophene (DBT). Monometallic Pt catalysts had the highest hydrogenation activity in poison-free and quinoline-containing feed. When DBT was present, bimetallic Pt-Pd catalysts with the most homogenous metal distribution showed the highest activity. The higher resistance of bimetallic catalysts towards sulfur poisoning compared to their monometallic Pt counterparts results from the weakened metal-sulfur bond on the electron deficient Pt atoms. Thus, increasing the fraction of electron deficient Pt on the surface of the bimetallic particles increases the efficiency of the catalyst in the presence of sulfur.« less

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.

Improvement of energy conversion efficiency and power generation in direct borohydride-hydrogen peroxide fuel cell: The effect of Ni-M core-shell nanoparticles (M = Pt, Pd, Ru)/Multiwalled Carbon Nanotubes on the cell performance

NASA Astrophysics Data System (ADS)

Hosseini, M. G.; Mahmoodi, R.

2017-12-01

In this study, core@shell nanoparticles with Ni as a core material and Pt, Pd and Ru as shell materials are synthesized on multiwalled carbon nanotube (MWCNT) as catalyst support using the sequence reduction method. The influence of Ni@Pt, Ni@Pd and Ni@Ru core@shell nanoparticles on MWCNT toward borohydride oxidation in alkaline solution is investigated by various three-electrode electrochemical techniques. Also, the impact of these anodic electrocatalysts on the performance of direct borohydride-hydrogen peroxide fuel cell (DBHPFC) is evaluated. The structural and morphological properties of electrocatalysts are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). The results of three electrode investigations show that Ni@Pd/MWCNT has excellent catalytic activity since borohydride oxidation current density on Ni@Pd/MWCNT (34773.27 A g-1) is 1.37 and 9.19 times higher than those of Ni@Pt/MWCNT (25347.27 A g-1) and Ni@Ru/MWCNT (3782.83 A g-1), respectively. Also, the energy conversion efficiency and power density of DBHPFC with Ni@Pd/MWCNT (246.82 mW cm-2) increase to 34.27% and 51.53% respect to Ni@Pt/MWCNT (162.24 mW cm-2) and Ni@Ru/MWCNT (119.62 mW cm-2), respectively. This study reveals that Ni@Pd/MWCNT has highest activity toward borohydride oxidation and stability in fuel cell.

Double-side illuminated titania nanotubes for high volume hydrogen generation by water splitting

NASA Astrophysics Data System (ADS)

Mohapatra, Susanta K.; Mahajan, Vishal K.; Misra, Mano

2007-11-01

A sonoelectrochemical anodization method is proposed to synthesize TiO2 nanotubular arrays on both sides of a titanium foil (TiO2/Ti/TiO2). Highly ordered TiO2 nanotubular arrays of 16 cm2 area with uniform surface distribution can be obtained using this anodization procedure. These double-sided TiO2/Ti/TiO2 materials are used as both photoanode (carbon-doped titania nanotubes) and cathode (Pt nanoparticles dispersed on TiO2 nanotubes; PtTiO2/Ti/PtTiO2) in a specially designed photoelectrochemical cell to generate hydrogen by water splitting at a rate of 38 ml h-1. The nanomaterials are characterized by FESEM, HRTEM, STEM, EDS, FFT, SAED and XPS techniques. The present approach can be used for large-scale hydrogen generation using renewable energy sources.

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.

Platinum atomic wire encapsulated in gold nanotubes: A first principle study

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

Nigam, Sandeep, E-mail: snigam@barc.gov.in; Majumder, Chiranjib; Sahoo, Suman K.

2014-04-24

The nanotubes of gold incorporated with platinum atomic wire have been investigated by means of firstprinciples density functional theory with plane wave pseudopotential approximation. The structure with zig-zag chain of Pt atoms in side gold is found to be 0.73 eV lower in energy in comparison to straight chain of platinum atoms. The Fermi level of the composite tube was consisting of d-orbitals of Pt atoms. Further interaction of oxygen with these tubes reveals that while tube with zig-zag Pt prefers dissociative adsorption of oxygen molecule, the gold tube with linear Pt wire favors molecular adsorption.

PEO-b-P4VP/Yttrium Hydroxide Hybrid Nanotubes as Supporter for Catalyst Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Yang, Qian; Chen, Dao-yong

2012-06-01

The adsorption of poly (ethylene oxide)-b-poly(4-vinylpyridine)(PEO-b-P4VP) micelles onto the surface of yttrium hydroxide nanotubes (YNTs) resulted in the hybrid nanotubes with a dense P4VP inner layer and a stretched PEO outer layer surrounding YNTs. The dense P4VP layer was further stabilized by the crosslinking using 1,4-dibromobutane as the crosslinker. Then, the crosslinked hybrid nanotubes (CHNTs) were used as a novel nano supporter for loading the catalyst gold nanoparticles (GNPs) within the crosslinked P4VP layer. The resultant GNPs/CHNTs (GNTs loaded on CHNTs) were applied to catalyze the reduction reaction of p-nitrophenol. The results indicate that this novel nano supporter has advantages such as good dispersity in the suspension, high capacity in loading GNPs (0.87 mmol/g), high catalytic activity of the loaded GNPs (12.9 μmol-1min-1), and good reusability of GNTs/CHNTs.

Calorimetry, activity, and micro-FTIR analysis of CO chemisorption, titration, and oxidation on supported Pt

NASA Technical Reports Server (NTRS)

Sermon, Paul A.; Self, Valerie A.; Vong, Mariana S. W.; Wurie, Alpha T.

1990-01-01

The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.

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

Computational Spectroscopy of Structured Carbon Nanotube Interfaces for Biochemical Sensing

DTIC Science & Technology

2010-04-01

oxidized layer of SiCh served as a diffusion barrier to prevent Pt silicide formation and was shown to aide the formation of well dispersed catalytic nano...Three types of fluorescent mi- crospheres (Fluospheres) from Invitrogen were tested. The fluorescent microspheres were prepared in a 10:1 solution with...spectral channels for a given pixel location. Carbon Nanotube Growth on Pt Sample preparation involved cleaving silicon (100) wafers to desired

N, P-codoped Mesoporous Carbon Supported PtCox Nanoparticles and Their Superior Electrochemical toward Methanol Oxidation

NASA Astrophysics Data System (ADS)

Cui, Hangjun; Li, Yueming; Liu, Shimin

2018-03-01

In this report, a novel strategy by using the N, P co-doped mesoporous carbon structure as catalyst support to enhance the electrochemical catalytic activity of Pt-based catalysts is proposed. The as-synthesized PtCox@N, P-doped mesoporous carbon nanocomposties have been studied as an anode catalyst toward methanol oxidation, exhibiting greatly improved electrochemical activity and stability compared with Pt@mesoporous carbon. The synergistic effects of N, P dual-doping and porous carbon structure help to achieve better electron transport at the electrode surface, which eventually leads to greatly enhanced catalytic activity compared to the pristine Pt/mesoporous carbon.…

Facile synthesis of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide with enhanced electrocatalytic properties

NASA Astrophysics Data System (ADS)

Li, Shan-Shan; Zheng, Jie-Ning; Ma, Xiaohong; Hu, Yuan-Yuan; Wang, Ai-Jun; Chen, Jian-Rong; Feng, Jiu-Ju

2014-05-01

A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media.A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media. Electronic supplementary information (ESI) available: Experimental section, Fig. S1-S12 and Tables S1 and S2. See DOI: 10.1039/c3nr06808k

Facile approach to prepare Pt decorated SWNT/graphene hybrid catalytic ink

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

Mayavan, Sundar, E-mail: sundarmayavan@cecri.res.in; Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology, Daejeon, 305-701; Mandalam, Aditya

Highlights: • Pt NPs were in situ synthesized onto CNT–graphene support in aqueous solution. • The as-prepared material was used directly as a catalyst ink without further treatment. • Catalyst ink is active toward methanol oxidation. • This approach realizes both scalable and greener production of hybrid catalysts. - Abstract: Platinum nanoparticles were in situ synthesized onto hybrid support involving graphene and single walled carbon nanotube in aqueous solution. We investigate the reduction of graphene oxide, and platinum nanoparticle functionalization on hybrid support by X-ray photoelectron spectroscopy, Raman spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The as-preparedmore » platinum on hybrid support was used directly as a catalyst ink without further treatment and is active toward methanol oxidation. This work realizes both scalable and greener production of highly efficient hybrid catalysts, and would be valuable for practical applications of graphene based fuel cell catalysts.« less

Thin-walled SnO2 nanotubes functionalized with Pt and Au catalysts via the protein templating route and their selective detection of acetone and hydrogen sulfide molecules

NASA Astrophysics Data System (ADS)

Jang, Ji-Soo; Kim, Sang-Joon; Choi, Seon-Jin; Kim, Nam-Hoon; Hakim, Meggie; Rothschild, Avner; Kim, Il-Doo

2015-10-01

Bio-inspired Pt (~2 nm) and Au (~2.7 nm) catalysts encapsulated by a protein shell, i.e., Pt-apoferritin (Pt@AF) and Au-apoferriten (Au@AF), were synthesized via the hollow protein nanocage (apoferritin) templating route and directly functionalized on the interior and exterior walls of electrospun SnO2 nanotubes (NTs) during controlled single-nozzle electrospinning followed by high temperature calcination with heating rate control. Fast crystallization of the exterior shell and outward diffusion of the interior Sn precursors and crystallites result in the continued growth of a tubular wall, which is related to rapid heating driven Ostwald-ripening behavior. Very importantly, the Pt and Au nanoparticles (NPs) were immobilized onto thin-walled SnO2 NTs with a diameter of ~350 nm and a shell thickness of ~40 nm without any aggregation of catalysts due to high dispersibility, which originated from repulsive electrostatic (Coulombic) forces acting on the surface charged protein shells, leading to an enhanced catalytic effect and outstanding gas sensing properties. Pt-loaded SnO2 NTs exhibited superior acetone response (Rair/Rgas = 92 at 5 ppm) compared to pure SnO2 NFs (Rair/Rgas = 4.8 at 5 ppm) and SnO2 NTs (Rair/Rgas = 11 at 5 ppm) while Au-loaded SnO2 NTs showed a high response when exposed to hydrogen sulfide (Rair/Rgas = 34 at 5 ppm), offering selective gas detection with minimal cross-sensitivity against other interfering gases such as NH3, CO, NO, C6H5CH3, and C5H12. Our results provide a new insight into facile, cost-effective, and highly dispersible catalyst loading on the interior and exterior walls of hollow metal oxide NTs via simple electrospinning as a potential breath analyzer.Bio-inspired Pt (~2 nm) and Au (~2.7 nm) catalysts encapsulated by a protein shell, i.e., Pt-apoferritin (Pt@AF) and Au-apoferriten (Au@AF), were synthesized via the hollow protein nanocage (apoferritin) templating route and directly functionalized on the interior and exterior walls

Surface chemistry of aromatic reactants on Pt- and Mo-modified Pt catalysts

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

Robinson, Allison M.; Mark, Lesli; Rasmussen, Mathew J.

Supported catalysts containing an oxophilic metal such as Mo and a noble metal such as Pt have shown promising activity and selectivity for deoxygenation of biomass-derived compounds. Here, we report that PtMo catalysts also promote hydrogenolysis of the model compound benzyl alcohol, while decarbonylation is most prevalent over unmodified Pt. A combination of single crystal surface science studies, density functional theory (DFT) calculations, and vapor phase upgrading experiments using supported catalysts was carried out to better understand the mechanism by which Mo promotes deoxygenation. Molybdenum was deposited in submonolayer quantities on a Pt(111) surface and reduced at high temperature. Temperature-programmedmore » desorption (TPD) experiments using benzyl alcohol as a reactant showed greatly enhanced yields of the deoxygenation product toluene at moderate Mo coverages. To understand how the interaction of the aromatic group with the surface influenced this reactivity, we investigated the adsorption of toluene as a probe molecule. We found that the addition of Mo to Pt(111) resulted in a significant decrease in toluene decomposition. DFT calculations indicated that this decrease was consistent with decreased aromatic adsorption strengths that accompany incorporation of Mo into the Pt subsurface. The weaker aromatic-surface interaction on Pt/Mo surfaces led to a tilted adsorption geometry for benzyl alcohol, which presumably promotes hydrogenolysis to produce toluene instead of decarbonylation to produce benzene and CO. Alumina-supported Pt and PtMo catalysts were also tested for benzyl alcohol deoxygenation. PtMo catalysts had a higher rate of toluene production and lower rates of benzene and benzaldehyde production. Additionally, when benzaldehyde was used as the reactant to measure decarbonylation activity the mass-normalized rate of benzene production was 2.5 times higher on Pt than PtMo. Altogether, the results of TPD, DFT, and supported catalyst

Surface chemistry of aromatic reactants on Pt- and Mo-modified Pt catalysts

DOE PAGES

Robinson, Allison M.; Mark, Lesli; Rasmussen, Mathew J.; ...

2016-11-01

Supported catalysts containing an oxophilic metal such as Mo and a noble metal such as Pt have shown promising activity and selectivity for deoxygenation of biomass-derived compounds. Here, we report that PtMo catalysts also promote hydrogenolysis of the model compound benzyl alcohol, while decarbonylation is most prevalent over unmodified Pt. A combination of single crystal surface science studies, density functional theory (DFT) calculations, and vapor phase upgrading experiments using supported catalysts was carried out to better understand the mechanism by which Mo promotes deoxygenation. Molybdenum was deposited in submonolayer quantities on a Pt(111) surface and reduced at high temperature. Temperature-programmedmore » desorption (TPD) experiments using benzyl alcohol as a reactant showed greatly enhanced yields of the deoxygenation product toluene at moderate Mo coverages. To understand how the interaction of the aromatic group with the surface influenced this reactivity, we investigated the adsorption of toluene as a probe molecule. We found that the addition of Mo to Pt(111) resulted in a significant decrease in toluene decomposition. DFT calculations indicated that this decrease was consistent with decreased aromatic adsorption strengths that accompany incorporation of Mo into the Pt subsurface. The weaker aromatic-surface interaction on Pt/Mo surfaces led to a tilted adsorption geometry for benzyl alcohol, which presumably promotes hydrogenolysis to produce toluene instead of decarbonylation to produce benzene and CO. Alumina-supported Pt and PtMo catalysts were also tested for benzyl alcohol deoxygenation. PtMo catalysts had a higher rate of toluene production and lower rates of benzene and benzaldehyde production. Additionally, when benzaldehyde was used as the reactant to measure decarbonylation activity the mass-normalized rate of benzene production was 2.5 times higher on Pt than PtMo. Altogether, the results of TPD, DFT, and supported catalyst

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.

High-performance electrochemical mercury aptasensor based on synergistic amplification of Pt nanotube arrays and Fe3O4/rGO nanoprobes.

PubMed

Luo, Jingyi; Jiang, Danfeng; Liu, Tao; Peng, Jingmeng; Chu, Zhenyu; Jin, Wanqin

2018-05-01

In this work, a novel sandwich-type aptasensor was designed for the ultrasensitive recognition of trace mercury ions in water. Numerous oriented platinum nanotube arrays (PtNAs) were in-situ crystallized on a flexible electrode as a sensing interface, while thionine labelled Fe 3 O 4 /rGO nanocomposites as signal amplifiers. Both PtNAs/CF and nanocomposites were synthesized by easy hydrothermal processes. With their large surface area, it was favorable for electrochemical performance and immobilization of capture DNAs (cDNA) and report DNAs (rDNA). Upon the existence of Hg 2+ , partial linker DNAs were tightly bound with cDNAs through thymine-Hg 2+ -thymine pairing (T-Hg 2+ -T). Then rDNAs attached Fe 3 O 4 /rGO nanoprobes were fixed on the electrode through the match of remaining linker DNAs and rDNAs. Under the optimal conditions, the Hg 2+ aptasensor showed a synergistic amplification performance with a wide linear range from 0.1nM to 100nM, as well as a low detection limit of 30pM. Moreover, the as-prepared aptasensor also exhibited reliable performance for assay in real lake water samples. Copyright © 2017. Published by Elsevier B.V.

Facile Synthesis of Highly Aligned Multiwalled Carbon Nanotubes from Polymer Precursors

DOE PAGES

Han, Catherine Y.; Xiao, Zhi-Li; Wang, H. Hau; ...

2009-01-01

We report a facile one-step approach which involves no flammable gas, no catalyst, and no in situ polymerization for the preparation of well-aligned carbon nanotube array. A polymer precursor is placed on top of an anodized aluminum oxide (AAO) membrane containing regular nanopore arrays, and slow heating under Ar flow allows the molten polymer to wet the template through adhesive force. The polymer spread into the nanopores of the template to form polymer nanotubes. Upon carbonization the resulting multi-walled carbon nanotubes duplicate the nanopores morphology precisely. The process is demonstrated for 230, 50, and 20 nm pore membranes. The synthesized carbonmore » nanotubes are characterized with scanning/transmission electron microscopies, Raman spectroscopy, and resistive measurements. Convenient functionalization of the nanotubes with this method is demonstrated through premixing CoPt nanoparticles in the polymer precursors.« less

Carbon nanocages: a new support material for Pt catalyst with remarkably high durability.

PubMed

Wang, Xiao Xia; Tan, Zhe Hua; Zeng, Min; Wang, Jian Nong

2014-03-24

Low durability is the major challenge hindering the large-scale implementation of proton exchange membrane fuel cell (PEMFC) technology, and corrosion of carbon support materials of current catalysts is the main cause. Here, we describe the finding of remarkably high durability with the use of a novel support material. This material is based on hollow carbon nanocages developed with a high degree of graphitization and concurrent nitrogen doping for oxidation resistance enhancement, uniform deposition of fine Pt particles, and strong Pt-support interaction. Accelerated degradation testing shows that such designed catalyst possesses a superior electrochemical activity and long-term stability for both hydrogen oxidation and oxygen reduction relative to industry benchmarks of current catalysts. Further testing under conditions of practical fuel cell operation reveals almost no degradation over long-term cycling. Such a catalyst of high activity, particularly, high durability, opens the door for the next-generation PEMFC for "real world" application.

Carbon nanocages: A new support material for Pt catalyst with remarkably high durability

PubMed Central

Wang, Xiao Xia; Tan, Zhe Hua; Zeng, Min; Wang, Jian Nong

2014-01-01

Low durability is the major challenge hindering the large-scale implementation of proton exchange membrane fuel cell (PEMFC) technology, and corrosion of carbon support materials of current catalysts is the main cause. Here, we describe the finding of remarkably high durability with the use of a novel support material. This material is based on hollow carbon nanocages developed with a high degree of graphitization and concurrent nitrogen doping for oxidation resistance enhancement, uniform deposition of fine Pt particles, and strong Pt-support interaction. Accelerated degradation testing shows that such designed catalyst possesses a superior electrochemical activity and long-term stability for both hydrogen oxidation and oxygen reduction relative to industry benchmarks of current catalysts. Further testing under conditions of practical fuel cell operation reveals almost no degradation over long-term cycling. Such a catalyst of high activity, particularly, high durability, opens the door for the next-generation PEMFC for “real world” application. PMID:24658614

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).

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.

Synthesis of Pt-Ni-Fe/CNT/CP nanocomposite as an electrocatalytic electrode for PEM fuel cell cathode

NASA Astrophysics Data System (ADS)

Litkohi, Hajar Rajaei; Bahari, Ali; Ojani, Reza

2017-08-01

In order to use carbon nanotube (CNT)-supported catalyst as fuel cell electrodes, Pt-Ni-Fe/CNT/carbon paper (CP) electrode was prepared using an ethylene glycol reduction method. CNTs were directly synthesized on Ni-impregnated carbon paper, plain carbon cloth, and Teflonized carbon cloth using chemical vapor deposition. FESEM and TEM images and thermogravimetric analysis indicated that in situ CNT on carbon paper (ICNT/CP) possesses more appropriate structural quality and stronger adhesion to the substrate than other substrates. The contact angle analysis demonstrated that the degree of ICNT/CP surface hydrophobicity encountered a 24% increase in comparison to CP and promoted to superhydrophobicity from hydrophobicity. The polarization curves and electrochemical impedance spectroscopy results of the loaded Pt-Ni-Fe on in situ and ex situ CNT/CP illustrated that the power density increased and charge transfer resistance reduced compared to commercial Pt/C loaded on CP. The results can be attributed to the outstanding properties of CNTs and high catalytic activity of triple catalysts causing alloying of Pt with Ni and Fe, which makes them a proper candidate to be used as cathode electrodes in proton exchange membrane fuel cells.

Preparation and characterization of Pt/C and Pt sbnd Ru/C electrocatalysts for direct ethanol fuel cells

NASA Astrophysics Data System (ADS)

Liu, Zhaolin; Ling, Xing Yi; Su, Xiaodi; Lee, Jim Yang; Gan, Leong Ming

Nano-sized Pt and Pt sbnd Ru colloids are prepared by a microwave-assisted polyol process, and transferred to a toluene solution of decanthiol. Vulcan XC-72 is then added to the toluene solution to adsorb the thiolated Pt and Pt sbnd Ru colloids. Transmission electron microscopy examinations show nearly spherical particles and narrow size distributions for both supported and unsupported metals. The carbon-supported Pt and Pt sbnd Ru nanoparticles are activated by thermal treatment to remove the thiol stabilizing shell. All Pt and Pt sbnd Ru catalysts (except Pt 23sbnd Ru 77) give the X-ray diffraction pattern of a face-centered cubic (fcc) crystal structure, whereas the Pt 23sbnd Ru 77 alloy is more typical of the hexagonal close packed (hcp) structure. The electro-oxidation of liquid ethanol on these catalysts is investigated at room temperature by cyclic voltammetry. The results demonstrate that the alloy catalyst is catalytically more active than pure platinum. Preliminary tests on a single cell of a direct ethanol fuel cell (DEFC) indicate that a Pt 52sbnd Ru 48/C anode catalyst gives the best electrocatalytic performance among all the carbon-supported Pt and Pt sbnd Ru catalysts.

Radiochemical synthesis of a carbon-supported Pt-SnO2 bicomponent nanostructure exhibiting enhanced catalysis of ethanol oxidation

NASA Astrophysics Data System (ADS)

Okazaki, Tomohisa; Seino, Satoshi; Nakagawa, Takashi; Kugai, Junichiro; Ohkubo, Yuji; Akita, Tomoki; Nitani, Hiroaki; Yamamoto, Takao A.

2015-03-01

Carbon-supported Pt-SnO2 electrocatalysts with various Sn/Pt molar ratios were prepared by an electron beam irradiation method. These catalysts were composed of metallic Pt particles approximately 5 nm in diameter together with low crystalline SnO2. The contact between the Pt and SnO2 in these materials varied with the amount of dissolved oxygen in the precursor solutions and it was determined that intimate contact between the Pt and SnO2 significantly enhanced the catalytic activity of these materials during the ethanol oxidation reaction. The mechanism by which the contact varies is discussed based on the radiochemical reduction process.

Nanotube Sensors

NASA Technical Reports Server (NTRS)

McEuen, Paul L.

2002-01-01

Under this project, we explored the feasibility of utilizing carbon nanotubes in sensing applications. The grant primarily supported a graduate student, who worked on a number of aspects of the electrical properties of carbon nanotubes in collaboration with other researchers in my group. The two major research accomplishments are described below. The first accomplishment is the demonstration that solution carbon nanotube transistors functioned well in an electrolyte environment. This was important for two reasons. First, it allowed us to explore the ultimate limits of nanotube electronic performance by using the electrolyte as a highly effective gate, with a dielectric constant of approximately 80 and an effective insulator thickness of approximately 1 nm. Second, it showed that nanotubes function well under biologically relevant conditions (salty water) and therefore offer great promise as biological sensors. The second accomplishment was the demonstration that a voltage pulse applied to an AFM tip could be used to electrically cut carbon nanotubes. We also showed that a carefully applied pulse could also 'nick' a nanotube, creating a tunnel barrier without completely breaking the tube. Nicking was employed to make, for example, a quantum dot within a nanotube.

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.

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

Aqueous synthesis of porous platinum nanotubes at room temperature and their intrinsic peroxidase-like activity.

PubMed

Cai, Kai; Lv, Zhicheng; Chen, Kun; Huang, Liang; Wang, Jing; Shao, Feng; Wang, Yanjun; Han, Heyou

2013-07-11

Platinum nanotubes (PtNTs) exhibiting high porosity were constructed by sacrificing the exterior of tellurium nanowires (TeNWs) and disintegrating the inner part spontaneously in aqueous solution at room temperature, in which the Kirkendall effect may play an important role. The present PtNTs exhibited intrinsic peroxidase-like activity in the presence of H2O2.

Optical properties of breast tumor phantoms containing carbon nanotubes and nanohorns

PubMed Central

Sarkar, Saugata; Gurjarpadhye, Abhijit A.; Rylander, Christopher G.; Nichole Rylander, Marissa

2011-01-01

The degree by which optical properties of tumors are altered following introduction of carbon nanotubes (CNTs) of varying concentration and type is poorly understood, making it difficult to predict the impact of CNT inclusion on the photothermal response to laser therapies. Optical properties were measured of phantoms representative of breast tumor tissue incorporated with multiwalled carbon nanotubes (MWNTs), single-walled carbon nanotubes (SWNTs), and single-walled carbon nanohorns (SWNHs) of varying concentration (0.01–0.1 mg/ml). Tissue phantoms were made from sodium alginate (3 g/ml) incorporated with polystyrene microbeads (3 μm diam and 1 mg/ml) and talc-France powder (40 mg/ml). Absorption (μa) and reduced scattering (\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{upgreek} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} \\begin{equation*}\\mu^\\prime _s\\end{equation*} \\end{document}μs′) coefficients of phantoms containing CNTs were determined by the inverse adding-doubling algorithm for the wavelength range of 400–1300 nm. Optical properties of phantoms without CNTs were in the range of μa = 1.04–0.06 mm−1 and \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{upgreek} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} \\begin{equation*}\\mu^\\prime _s\\end{equation*} \\end{document}μs′ = 0.05–0.07 mm−1 at a wavelength of 900 nm, which corresponds with published data for human breast tumor tissue. Incorporating MWNTs, SWNTs, and SWNHs in phantoms with a concentration of 0.1 mg/ml increased (μa) by 20- to 30-fold, 5- to 6-fold, and 9- to 14-fold, respectively, for the wavelength range of 800–1100 nm with minimal change in \\documentclass[12pt]{minimal} \\usepackage

Synthesis of Highly Dispersed and Highly Stable Supported Au–Pt Bimetallic Catalysts by a Two-Step Method

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

Wang, Xiaofeng; Zhao, Haiyan; Wu, Tianpin

2016-11-01

Highly dispersed and highly stable supported bimetallic catalysts were prepared using a two-step process. Pt nanoparticles (NPs) were first deposited on porous γ-Al2O3 particles by atomic layer deposition (ALD). Au NPs were synthesized by using gold(III) chloride as the Au precursor, and then immobilized on ALD Pt/γ-Al2O3 particles. The Au–Pt bimetallic catalysts were highly active and highly stable in a vigorously stirred liquid phase reaction of glucose oxidation.

Dislocation Onset and Glide in Carbon Nanotubes under Torsion

NASA Astrophysics Data System (ADS)

Dumitrica, Traian; Zhang, Dong-Bo; James, Richard

2009-03-01

The torsional plastic response of carbon nanotubes is comprehensively described in the objective molecular dynamics framework [1-3]. It is shown that an (n,m) tube is prone to slip along a nearly-axial helical path, which introduces a distinct (+1,-1) change in the wrapping index. The low energy realization occurs without loss of mass, via nucleation of a 5-7-7-5 dislocation dipole, followed by a nearly-axial glide of the 5-7 dislocation. The onset of plasticity depends not only on chirality but also on handedness. For a given handedness of the applied twist, chiral tubes of opposed handedness are most susceptible to yield. A right-handed applied twist on an armchair (zig-zag) tube leads to a right- (left-) handed tube. [4pt] [1] T. Dumitrica and R.D. James, Objective Molecular Dynamics, Journal of the Mechanics and Physics of Solids 55, 2206 (2007). [0pt] [2] D.-B. Zhang, M. Hua, and T. Dumitrica, Stability of Polycrystalline and Wurtzite Si Nanowires via Symmetry-Adapted Tight-Binding Objective Molecular Dynamics, Journal of Chemical Physics 128, 084104 (2008). [0pt] [3] D.-B. Zhang and T. Dumitrica, Elasticity of Ideal Single-Walled Carbon Nanotubes via Symmetry-Adapted Tight-Binding Objective Modeling, Applied Physics Letters 93, 031919 (2008).

Theoretical analysis of hydrogen spillover mechanism on carbon nanotubes

PubMed Central

Juarez-Mosqueda, Rosalba; Mavrandonakis, Andreas; Kuc, Agnieszka B.; Pettersson, Lars G. M.; Heine, Thomas

2015-01-01

The spillover mechanism of molecular hydrogen on carbon nanotubes in the presence of catalytically active platinum clusters was critically and systematically investigated by using density-functional theory. Our simulation model includes a Pt4 cluster for the catalyst nanoparticle and curved and planar circumcoronene for two exemplary single-walled carbon nanotubes (CNT), the (10,10) CNT and one of large diameter, respectively. Our results show that the H2 molecule dissociates spontaneously on the Pt4 cluster. However, the dissociated H atoms have to overcome a barrier of more than 2 eV to migrate from the catalyst to the CNT, even if the Pt4 cluster is at full saturation with six adsorbed and dissociated hydrogen molecules. Previous investigations have shown that the mobility of hydrogen atoms on the CNT surface is hindered by a barrier. We find that instead the Pt4 catalyst may move along the outer surface of the CNT with activation energy of only 0.16 eV, and that this effect offers the possibility of full hydrogenation of the CNT. Thus, although we have not found a low-energy pathway to spillover onto the CNT, we suggest, based on our calculations and calculated data reported in the literature, that in the hydrogen-spillover process the observed saturation of the CNT at hydrogen background pressure occurs through mobile Pt nanoclusters, which move on the substrate more easily than the substrate-chemisorbed hydrogens, and deposit or reattach hydrogens in the process. Initial hydrogenation of the carbon substrate, however, is thermodynamically unfavoured, suggesting that defects should play a significant role. PMID:25699250

Solvothermal synthesis of N-doped graphene supported PtCo nanodendrites with highly catalytic activity for 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Zhang, Xiao-Fang; Zhu, Xiao-Yan; Feng, Jiu-Ju; Wang, Ai-Jun

2018-01-01

A simple solvothermal method was developed to prepare N-doped reduced graphene oxide supported homogeneous PtCo nanodendrites (PtCo NDs/N-rGO), where ethylene glycol (EG) served as the reducing agent and the solvent, and linagliptin as the structure-directing and stabilizing agent for PtCo NDs and dopant for rGO, respectively. Controlled researches showed that the dosage of linagliptin and the ratios of the two metal precursors were important in the current synthesis. The PtCo NDs/N-rGO nanocomposite exhibited higher catalytic activity towards the reduction of 4-nitrophnol (4-NP) in contrast with the referenced Pt1Co3 NCs/N-rGO, Pt3Co1 NCs/N-rGO and commercial Pt/C catalysts. More importantly, the constructed catalyst exhibited the superior stability without sacrificing the catalytic activity, showing great prospect for the reduction of 4-NP in practice.

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

DOE PAGES

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

2016-01-14

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

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

PubMed Central

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

2016-01-01

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

Isolated Pt Atoms Stabilized by Amorphous Tungstenic Acid for Metal-Support Synergistic Oxygen Activation.

PubMed

Zhang, Qian; Qin, Xixi; Duanmu, Fanpeng; Ji, Huiming; Shen, Zhurui; Han, Xiaopeng; Hu, Wenbin

2018-06-05

Oxygen activation plays a crucial role in many important chemical reactions such as organics oxidation and oxygen reduction. For developing highly active materials for oxygen activation, herein, we report an atomically dispersed Pt on WO3 nanoplates stabilized by in-situ formed amorphous H2WO4 out-layer and the mechanism for activating molecular oxygen. Experimental and theoretical studies demonstrate that the isolated Pt atoms coordinated with oxygen atoms from [WO6] and water of H2WO4, consequently leading to optimized surface electronic configuration and strong metal support interaction (SMSI). In exemplified reactions of butanone oxidation sensing and oxygen reduction, the atomic Pt/WO3 hybrid exhibits superior activity than those of Pt nanoclusters/WO3 and bare WO3 as well as enhanced long-term durability. This work will provide insight on the origin of activity and stability for atomically dispersed materials, thus promoting the development of highly efficient and durable single atom-based catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-wire dye-sensitized solar cells wrapped by carbon nanotube film electrodes.

PubMed

Zhang, Sen; Ji, Chunyan; Bian, Zhuqiang; Liu, Runhua; Xia, Xinyuan; Yun, Daqin; Zhang, Luhui; Huang, Chunhui; Cao, Anyuan

2011-08-10

Conventional fiber-shaped polymeric or dye-sensitized solar cells (DSSCs) are usually made into a double-wire structure, in which a secondary electrode wire (e.g., Pt) was twisted along the primary core wire consisting of active layers. Here, we report highly flexible DSSCs based on a single wire, by wrapping a carbon nanotube film around Ti wire-supported TiO(2) tube arrays as the transparent electrode. Unlike a twisted Pt electrode, the CNT film ensures full contact with the underlying active layer, as well as uniform illumination along circumference through the entire DSSC. The single-wire DSSC shows a power conversion efficiency of 1.6% under standard illumination (AM 1.5, 100 mW/cm(2)), which is further improved to more than 2.6% assisted by a second conventional metal wire (Ag or Cu). Our DSSC wires are stable and can be bent to large angles up to 90° reversibly without performance degradation.

Purification of carbon nanotubes via selective heating

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

Rogers, John A.; Wilson, William L.; Jin, Sung Hun

The present invention provides methods for purifying a layer of carbon nanotubes comprising providing a precursor layer of substantially aligned carbon nanotubes supported by a substrate, wherein the precursor layer comprises a mixture of first carbon nanotubes and second carbon nanotubes; selectively heating the first carbon nanotubes; and separating the first carbon nanotubes from the second carbon nanotubes, thereby generating a purified layer of carbon nanotubes. Devices benefiting from enhanced electrical properties enabled by the purified layer of carbon nanotubes are also described.

Facile synthesis of porous Pt-Pd nanospheres supported on reduced graphene oxide nanosheets for enhanced methanol electrooxidation

NASA Astrophysics Data System (ADS)

Li, Shan-Shan; Lv, Jing-Jing; Hu, Yuan-Yuan; Zheng, Jie-Ning; Chen, Jian-Rong; Wang, Ai-Jun; Feng, Jiu-Ju

2014-02-01

In this study, a simple, facile, and effective wet-chemical strategy was developed in the synthesis of uniform porous Pt-Pd nanospheres (Pt-Pd NSs) supported on reduced graphene oxide nanosheets (RGOs) under ambient temperature, where octylphenoxypolye thoxyethanol (NP-40) is used as a soft template, without any seed, organic solvent or special instruments. The as-prepared nanocomposites display enhanced electrocatalytic activity and good stability toward methanol oxidation, compared with commercial Pd/C and Pt/C catalysts. This strategy may open a new route to design and prepare advanced electrocatalysts for fuel cells.

Free vibration of functionally graded carbon nanotube reinforced composite cylindrical panels with general elastic supports

NASA Astrophysics Data System (ADS)

Xie, Fei; Tang, Jinyuan; Wang, Ailun; Shuai, Cijun; Wang, Qingshan

2018-05-01

In this paper, a unified solution for vibration analysis of the functionally graded carbon nanotube reinforced composite (FG-CNTRC) cylindrical panels with general elastic supports is carried out via using the Ritz method. The excellent accuracy and reliability of the present method are compared with the results of the classical boundary cases found in the literature. New results are given for vibration characteristics of FG-CNTRC cylindrical panels with various boundary conditions. The effects of the elastic restraint parameters, thickness, subtended angle and volume fraction of carbon nanotubes on the free vibration characteristic of the cylindrical panels are also reported.

Self-Assembled Fe-N-Doped Carbon Nanotube Aerogels with Single-Atom Catalyst Feature as High-Efficiency Oxygen Reduction Electrocatalysts

DOE PAGES

Zhu, Chengzhou; Fu, Shaofang; Song, Junhua; ...

2017-02-06

In this study, self-assembled M–N-doped carbon nanotube aerogels with single-atom catalyst feature are for the first time reported through one-step hydrothermal route and subsequent facile annealing treatment. By taking advantage of the porous nanostructures, 1D nanotubes as well as single-atom catalyst feature, the resultant Fe–N-doped carbon nanotube aerogels exhibit excellent oxygen reduction reaction electrocatalytic performance even better than commercial Pt/C in alkaline solution.

Performance improvement in PEMFC using aligned carbon nanotubes as electrode catalyst support.

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

Liu, D. J.; Yang, J.; Kariuki, N.

2008-01-01

A novel membrane electrode assembly (MEA) using aligned carbon nanotubes (ACNT) as the electrocatalyst support was developed for proton exchange membrane fuel cell (PEMFC) application. A multiple-step process of preparing ACNT-PEMFC including ACNT layer growth and catalyzing, MEA fabrication, and single cell packaging is reported. Single cell polarization studies demonstrated improved fuel utilization and higher power density in comparison with the conventional, ink based MEA.

Tunable and selective hydrogenation of furfural to furfuryl alcohol and cyclopentanone over Pt supported on biomass-derived porous heteroatom doped carbon.

PubMed

Liu, Xiuyun; Zhang, Bo; Fei, Benhua; Chen, Xiufang; Zhang, Junyi; Mu, Xindong

2017-09-21

The search for and exploitation of efficient catalytic systems for selective conversion of furfural into various high value-added chemicals remains a huge challenge for green synthesis in the chemical industry. Here, novel Pt nanoparticles supported on bamboo shoot-derived porous heteroatom doped carbon materials were designed as highly active catalysts for controlled hydrogenation of furfural in aqueous media. The porous heteroatom doped carbon supported Pt catalysts were endowed with a large surface area with a hierarchical porous structure, a high content of nitrogen and oxygen functionalities, a high dispersion of the Pt nanoparticles, good water dispersibility and reaction stability. Benefiting from these features, the novel Pt catalysts displayed a high activity and controlled tunable selectivity for furfural hydrogenation to produce furfuryl alcohol and cyclopentanone in water. The product selectivity could be easily modulated by controlling the carbonization temperature of the porous heteroatom doped carbon support and the reaction conditions (temperature and H 2 pressure). Under mild conditions (100 °C, 1 MPa H 2 ), furfuryl alcohol was obtained in water with complete conversion of the furfural and an impressive furfuryl alcohol selectivity of >99% in the presence of Pt/NC-BS-500. A higher reaction temperature, in water, favored rearrangement of the furfural (FFA) with Pt/NC-BS-800 as the catalyst, which resulted in a high cyclopentanone yield of >76% at 150 °C and 3 MPa H 2 . The surface properties and pore structure of the heteroatom doped carbon support, adjusted using the carbonization temperature, might determine the interactions between the Pt nanoparticles, carbon support and catalytic reactants in water, which in turn could have led to a good selectivity control. The effect of different reaction temperatures and reaction times on the product selectivity was also explored. Combined with exploration of the distribution of the reaction products, a

High activity of cubic PtRh alloys supported on graphene towards ethanol electrooxidation.

PubMed

Rao, Lu; Jiang, Yan-Xia; Zhang, Bin-Wei; Cai, Yuan-Rong; Sun, Shi-Gang

2014-07-21

Cubic PtRh alloys supported on graphene (PtxRhy/GN) with different atomic ratio of Pt and Rh were directly synthesized for the first time using the modified polyol method with Br(-) for the shape-directing agents. The process didn't use surface-capping agents such as PVP that easily occupy the active sites of electrocatalysts and are difficult to remove. Graphene is the key factor for cubic shape besides Br(-) and keeping catalysts high-dispersed. The X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to characterize the structure and morphology of these electrocatalysts. The results showed that they were composed of homogeneous cubic PtRh alloys. Traditional electrochemical methods, such as cyclic voltammetry and chronoamperometry, were used to investigate the electrocatalytic properties of PtxRhy/GN towards ethanol electrooxidation. It can be seen that PtxRhy/GN with all atomic ratios exhibited high catalytic activity, and the most active one has a composition with Pt : Rh = 9 : 1 atomic ratio. Electrochemical in situ FTIR spectroscopy was used to evaluate the cleavage of C-C bond in ethanol at room temperature in acidic solutions, the results illustrated that Rh in an alloy can promote the split of C-C bond in ethanol, and the alloy catalyst with atomic ratio Pt : Rh = 1 : 1 showed obviously better performance for the C-C bond breaking in ethanol and higher selectivity for the enhanced activity of ethanol complete oxidation to CO2 than alloys with other ratios of Pt and Rh. The investigation indicates that high activity of PtxRhy/GN electrocatalyst towards ethanol oxidation is due to the specific shape of alloys and the synergistic effect of two metal elements as well as graphene support.

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.

Anomalous Structural Disorder in Supported Pt Nanoparticles

DOE PAGES

Vila, Fernando D.; Rehr, John J.; Nuzzo, Ralph G.; ...

2017-07-02

Supported Pt nanocatalysts generally exhibit anomalous behavior, including negative thermal expansion and large structural disorder. Finite temperature DFT/MD simulations reproduce these properties, showing that they are largely explained by a combination of thermal vibrations and low-frequency disorder. We show in this paper that a full interpretation is more complex and that the DFT/MD mean-square relative displacements (MSRD) can be further separated into vibrational disorder, “dynamic structural disorder” (DSD), and long-time equilibrium fluctuations of the structure dubbed “anomalous structural disorder” (ASD). We find that the vibrational and DSD components behave normally, increasing linearly with temperature while the ASD decreases, reflecting themore » evolution of mean nanoparticle geometry. Finally, as a consequence the usual procedure of fitting the MSRD to normal vibrations plus temperature-independent static disorder results in unphysical bond strengths and Grüneisen parameters.« less

Phase investigation in Pt supported off-stoichiometric iron-platinum thin films

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

Gupta, Rekha; Medwal, Rohit; Annapoorni, S., E-mail: annapoornis@yahoo.co.in

2013-10-15

Graphical abstract: - Highlights: • Low temperature FePt L1{sub 0} phase transformation using Pt/Fe{sub 3}Pt/Pt structure. • Temperature dependent FCC to FCT phase investigation using Rietveld refinement. • Estimation of soft and hard ferromagnetic contribution from demagnetization curve. • Interlayer diffusion and stoichiometry conformation of L1{sub 0} phase using RBS. • Correlation of structural, magnetic and RBS studies were successfully understood. - Abstract: The structural and magnetic phase transformation of Pt/Fe{sub 3}Pt/Pt films on Si <1 0 0> substrates prepared by DC magnetron sputtering is investigated as a function of annealing temperature. Pt diffusion driven low temperature phase transformation frommore » A1 to L1{sub 0} phase is achieved at 300 °C, attaining a very high coercivity of 9 kOe. At 300 °C, 85% L1{sub 0} phase transformation is observed using the X-ray diffraction profile fitting. The estimated phase content is also further verified by fitting the demagnetization curve. The underlayer promotes the ordering at lower temperature while overlayer induces growth along (0 0 1) preferred orientation. Rutherford back scattering study reveals interlayer diffusion and confirms the desired stoichiometry for L1{sub 0} phase. The presence of Pt under-overlayer provides the Pt source and further facilitates the Pt diffusion, which makes it effective in promoting the phase ordering at a lower temperature.« 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

Saccharide-based graphitic carbon nanocoils as supports for PtRu nanoparticles for methanol electrooxidation

NASA Astrophysics Data System (ADS)

Sevilla, Marta; Lota, Grzegorz; Fuertes, Antonio B.

Highly graphitic carbon nanocoils were synthesised from the catalytic graphitization of carbon spherules obtained by the hydrothemal treatment of different saccharides (sucrose, glucose and starch). This nanostructured carbon was characterized by X-ray power diffraction, N 2 adsorption and microscopy techniques (SEM and TEM). The carbon nanocoils were used as a support for PtRu nanoparticles, which were well-dispersed over the carbon surface. This catalytic system was investigated for use as an electrocatalyst for methanol electrooxidation in an acid medium. The experiments were carried out at two working temperatures (25 °C and 60 °C). It was found that the carbon nanocoils supporting PtRu nanoparticles exhibit a high catalytic activity, which is even higher than that of conventional carbon supports (Vulcan XC-72R). We believe that the high electrocatalytic activity of the carbon nanocoils presented here is due to the combination of a good electrical conductivity, derived from their graphitic structure, and a wide porosity that allows the diffusional resistances of reactants/products to be minimized.

High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

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

Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.

2016-12-01

High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group bymore » dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.« less

Electro-catalytic activity of multiwall carbon nanotube-metal (Pt or Pd) nanohybrid materials synthesized using microwave-induced reactions and their possible use in fuel cells.

PubMed

V, Lakshman Kumar; Ntim, Susana Addo; Sae-Khow, Ornthida; Janardhana, Chelli; Lakshminarayanan, V; Mitra, Somenath

2012-11-30

Microwave induced reactions for immobilizing platinum and palladium nanoparticles on multiwall carbon nanotubes are presented. The resulting hybrid materials were used as catalysts for direct methanol, ethanol and formic acid oxidation in acidic as well as alkaline media. The electrodes are formed by simply mixing the hybrids with graphite paste, thus using a relatively small quantity of the precious metal. We report Tafel slopes and apparent activation energies at different potentials and temperatures. Ethanol electro-oxidation with the palladium hybrid showed an activation energy of 7.64 kJmol(-1) which is lower than those observed for other systems. This system is economically attractive because Pd is significantly less expensive than Pt and ethanol is fast evolving as a commercial biofuel.

Electro-catalytic activity of multiwall carbon nanotube-metal (Pt or Pd) nanohybrid materials synthesized using microwave-induced reactions and their possible use in fuel cells

PubMed Central

V, Lakshman Kumar; Ntim, Susana Addo; Sae-Khow, Ornthida; Janardhana, Chelli; Lakshminarayanan, V.; Mitra, Somenath

2012-01-01

Microwave induced reactions for immobilizing platinum and palladium nanoparticles on multiwall carbon nanotubes are presented. The resulting hybrid materials were used as catalysts for direct methanol, ethanol and formic acid oxidation in acidic as well as alkaline media. The electrodes are formed by simply mixing the hybrids with graphite paste, thus using a relatively small quantity of the precious metal. We report Tafel slopes and apparent activation energies at different potentials and temperatures. Ethanol electro-oxidation with the palladium hybrid showed an activation energy of 7.64 kJmol−1 which is lower than those observed for other systems. This system is economically attractive because Pd is significantly less expensive than Pt and ethanol is fast evolving as a commercial biofuel. PMID:23118490

Carbon nanotubes based methanol sensor for fuel cells application.

PubMed

Kim, D W; Lee, J S; Lee, G S; Overzet, L; Kozlov, M; Aliev, A E; Park, Y W; Yang, D J

2006-11-01

An electrochemical sensor is built using vertically grown multi-walled carbon nanotubes (MWNTs) micro-array to detect methanol concentration in water. This study is done for the potential use of the array as methanol sensor for portable units of direct methanol fuel cells (DMFCs). Platinum (Pt) nanoparticles electro-deposited CNTs (Pt/CNTs) electrode shows high sensitivity in the measurement of methanol concentration in water with cyclic voltammetry (CV) measurement at room temperature. Further investigation has also been undertaken to measure the concentration by changing the amount of the mixture of methanol and formic acid in water. We compared the performance of our micro array sensor built with Pt/CNTs electrodes versus that of Pt wire electrode using CV measurement. We found that our Pt/CNTs array sensor shows high sensitivity and detects methanol concentrations in the range of 0.04 M to 0.10 M. In addition, we found that co-use of formic acid as electrolyte enables us to measure up to 1.0 M methanol concentration.

Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

NASA Astrophysics Data System (ADS)

Bauer, Alex; Gyenge, Előd L.; Oloman, Colin W.

Pressed graphite felt (thickness ∼350 μm) with electrodeposited PtRu (43 g m -2, 1.4:1 atomic ratio) or PtRuMo (52 g m -2, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m -2 with PtRuMo at 5500 A m -2 and 353 K while under the same conditions PtRu yielded 1925 W m -2. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation.

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

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.

Single Molecule Detection in Living Biological Cells using Carbon Nanotube Optical Probes

NASA Astrophysics Data System (ADS)

Strano, Michael

2009-03-01

osmotic pressure gradients will be discussed, as well as its potential as a unique transduction mechanism for a new class of implantable sensors. [4pt] [1] Saito, R., Dresselhaus, G. & Dresselhaus, M. S. Physical Properties of Carbon Nanotubes (Imperial College Press, London, 1998). [0pt] [2] Barone, P. W., Baik, S., Heller, D. A. & Strano, M. S. Near-Infrared Optical Sensors Based on Single-Walled Carbon Nanotubes. Nature Materials 4, 86-92 (2005). [0pt] [3] Jeng, E. S., Moll, A. E., Roy, A. C., Gastala, J. B. & Strano, M. S. Detection of DNA hybridization using the near infrared band-gap fluorescence of single-walled carbon nanotubes. Nano Letters 6, 371-375 (2006). [0pt] [4] Heller, D. A. et al. Optical detection of DNA conformational polymorphism on single-walled carbon nanotubes. Science 311, 508-511 (2006).

Development of an ultra-thin film comprised of a graphene membrane and carbon nanotube vein support.

PubMed

Lin, Xiaoyang; Liu, Peng; Wei, Yang; Li, Qunqing; Wang, Jiaping; Wu, Yang; Feng, Chen; Zhang, Lina; Fan, Shoushan; Jiang, Kaili

2013-01-01

Graphene, exhibiting superior mechanical, thermal, optical and electronic properties, has attracted great interest. Considering it being one-atom-thick, and the reduced mechanical strength at grain boundaries, the fabrication of large-area suspended chemical vapour deposition graphene remains a challenge. Here we report the fabrication of an ultra-thin free-standing carbon nanotube/graphene hybrid film, inspired by the vein-membrane structure found in nature. Such a square-centimetre-sized hybrid film can realize the overlaying of large-area single-layer chemical vapour deposition graphene on to a porous vein-like carbon nanotube network. The vein-membrane-like hybrid film, with graphene suspended on the carbon nanotube meshes, possesses excellent mechanical performance, optical transparency and good electrical conductivity. The ultra-thin hybrid film features an electron transparency close to 90%, which makes it an ideal gate electrode in vacuum electronics and a high-performance sample support in transmission electron microscopy.

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.

Dual-functional Pt-on-Pd supported on reduced graphene oxide hybrids: peroxidase-mimic activity and an enhanced electrocatalytic oxidation characteristic.

PubMed

Zhang, Xiahong; Wu, Genghuang; Cai, Zhixiong; Chen, Xi

2015-03-01

In this study, a facile hydrothermal method was developed to synthesize Pt-on-Pd supported on reduced graphene oxide (Pt-on-Pd/RGO) hybrids. Because of the synergistic effect between Pt-on-Pd and RGO, the obtained Pt-on-Pd/RGO had superior peroxidase-mimic activities in H2O2 reduction and TMB oxidation. The reaction medium was optimized and a sensing approach for H2O2 was developed with a linear range from 0.98 to 130.7 μM of H2O2. In addition, the characteristic of electrocatalytic oxidation of methanol was investigated. The peak current density value, j(f), for the Pt-on-Pd/RGO hybrid (328 mA mg(Pt)(-1)) was about 1.85 fold higher than that of commercial Pt black (177 mA mg(Pt)(-1)) and, also, more durable electrocatalytic activity could be obtained. For the first time, the dual-functional Pt-on-Pd/RGO with peroxidase-mimic activity and an enhanced electrocatalytic oxidation characteristic was reported. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Nitrogen Doped Graphene Supported Pt Nanoflowers as Electrocatalysts for Oxidation of Formaldehyde.

PubMed

Xie, Aijuan; Zhou, Wenting; Luo, Shiping; Chen, Yu; Zhou, Xiaoqing; Chao, Yao

2017-02-01

A facile Pt nanoflowers/nitrogen-doped graphene (PtNFs/NG) electrocatalyst was prepared via depositing Pt nanoflowers (PtNFs) onto the nitrogen-doped graphene (NG) matrix with urea as the nitrogen source and PtNFs/NG modified glassy carbon electrode (GCE) was prepared by electro-chemical method. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscope, X-ray photoelectron spectroscopy (XPS) and Scanning electron microscope (SEM) were used to characterize the resulting composites. Also oxidation of formaldehyde on the resulting PtNFs/NG modified electrode was investigated. The influence of deposition time, electrodeposition potential and formaldehyde concentration on electrooxidation of formaldehyde was detected, the experimental results indicate the high performance of PtNFs/NG catalyst for formaldehyde oxidation is at electrodeposition time of 300 s with the applied potential of −0.3 V. Electrochemical process, electrocatalytic stability and chronoamperometry were also inspected, it was indicated that formalde-hyde oxidation reaction on the PtNFs/NG electrode is diffusion-controlled and PtNFs/NG exhibits a high catalytic activity, stability as well as excellent poisoning-tolerance towards formaldehyde oxidation, which is attributed to the synergistic effect of PtNFs and NG. It turns out that PtNFs/NG can be used in direct liquid-feed fuel cells as a promising alternative catalyst.

Electro-oxidation of methanol and ethanol using PtRu/C, PtSn/C and PtSnRu/C electrocatalysts prepared by an alcohol-reduction process

NASA Astrophysics Data System (ADS)

Neto, Almir Oliveira; Dias, Ricardo R.; Tusi, Marcelo M.; Linardi, Marcelo; Spinacé, Estevam V.

PtRu/C, PtSn/C and PtSnRu/C electrocatalysts were prepared by the alcohol reduction process using ethylene glycol as the solvent and reduction agent and Vulcan Carbon XC72 as the support. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electrochemical oxidation of methanol and ethanol were studied by chronoamperometry using a thin porous coating technique. The PtSn/C electrocatalyst prepared by this methodology showed superior performance compared to the PtRu/C and PtSnRu/C electrocatalysts for methanol and ethanol oxidation at room temperature.

Nitrogen-Doped Carbon Nanotube-Supported Pd Catalyst for Improved Electrocatalytic Performance toward Ethanol Electrooxidation

NASA Astrophysics Data System (ADS)

Wei, Ying; Zhang, Xinyuan; Luo, Zhiyong; Tang, Dian; Chen, Changxin; Zhang, Teng; Xie, Zailai

2017-07-01

In this study, hydrothermal carbonization (HTC) was applied for surface functionalization of carbon nanotubes (CNTs) in the presence of glucose and urea. The HTC process allowed the deposition of thin nitrogen-doped carbon layers on the surface of the CNTs. By controlling the ratio of glucose to urea, nitrogen contents of up to 1.7 wt% were achieved. The nitrogen-doped carbon nanotube-supported Pd catalysts exhibited superior electrochemical activity for ethanol oxidation relative to the pristine CNTs. Importantly, a 1.5-fold increase in the specific activity was observed for the Pd/HTC-N1.67%CNTs relative to the catalyst without nitrogen doping (Pd/HTC-CNTs). Further experiments indicated that the introduction of nitrogen species on the surface of the CNTs improved the Pd(0) loading and increased the binding energy.

Dynamic Structural Changes of SiO₂ Supported Pt-Ni Bimetallic Catalysts over Redox Treatments Revealed by NMR and EPR

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

Xu, Suochang; Walter, Eric D.; Zhao, Zhenchao

2015-08-18

SiO 2 supported Pt-Ni bimetallic catalysts with different nickel loadings were prepared and their structural changes after redox treatments were studied by XRD, NMR, and EPR. It is found that the paramagnetic Ni species are mainly located on the surface of silica lattice. The relaxation of detected 29Si nuclei in our samples is mainly governed by a spin-diffusion mechanism. The paramagnetic effects are reflected in the spin-lattice relaxation of Q 4 species, with the oxidized samples presenting faster relaxation rates than the corresponding reduced ones. Meanwhile the Q 3 species, which are in close contact with the paramagnetic nickel ions,more » are “spectrally invisible”. In reducing atmosphere Ni gradually diffuses into Pt NPs to form PtNi alloys. While under oxidization treatment, the alloyed Ni atoms migrate outward from the core of Pt NPs and are oxidized. The main EPR spectrum results from reduced nickel species, and the reduced samples show stronger EPR signal than the corresponding oxidized ones. However, in the reduced samples, the superparamagnetic or ferromagnetic metallic Ni particles were inside the PtNi NPs, making their influence on the 29Si relaxation in the SiO 2 support weaker than the oxidized samples.« less

Impregnation of Catalytic Metals in Single-Walled Carbon Nanotubes for Toxic Gas Conversion in Life Support System

NASA Technical Reports Server (NTRS)

Li, Jing; Wignarajah, Kanapathipillai; Cinke, Marty; Partridge, Harry; Fisher, John

2004-01-01

Carbon nanotubes (CNTs) possess extraordinary properties such as high surface area, ordered chemical structure that allows functionalization, larger pore volume, and very narrow pore size distribution that have attracted considerable research attention from around the world since their discovery in 1991. The development and characterization of an original and innovative approach for the control and elimination of gaseous toxins using single walled carbon nanotubes (SWNTs) promise superior performance over conventional approaches due to the ability to direct the selective uptake of gaseous species based on their controlled pore size, increased adsorptive capacity due to their increased surface area and the effectiveness of carbon nanotubes as catalyst supports for gaseous conversion. We present our recent investigation of using SWNTs as catalytic supporting materials to impregnate metals, such as rhodium (Rh), palladium (Pd) and other catalysts. A protocol has been developed to oxidize the SWNTs first and then impregnate the Rh in aqueous rhodium chloride solution, according to unique surface properties of SWNTs. The Rh has been successfully impregnated in SWNTs. The Rh-SWNTs have been characterized by various techniques, such as TGA, XPS, TEM, and FTIR. The project is funded by a NASA Research Announcement Grant to find applications of single walled nanocarbons in eliminating toxic gas Contaminant in life support system. This knowledge will be utilized in the development of a prototype SWNT KO, gas purification system that would represent a significant step in the development of high efficiency systems capable of selectively removing specific gaseous for use in regenerative life support system for human exploration missions.

Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

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

Zabidi, Noor Asmawati Mohd, E-mail: noorasmawati-mzabidi@petronas.com.my; Ali, Sardar, E-mail: alikhan-635@yahoo.com; Subbarao, Duvvuri, E-mail: duvvuri-subbarao@petronas.com.my

2014-10-24

This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H{sub 2}-temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H{sub 2}/CO = 2v/v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances comparedmore » to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C{sub 5+} selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum.« less

Effects of K and Pt promoters on the performance of cobalt catalyst supported on CNTs

NASA Astrophysics Data System (ADS)

Zabidi, Noor Asmawati Mohd; Ali, Sardar; Subbarao, Duvvuri

2014-10-01

This paper presents a comparative study on the effects of incorporation of potassium (K) and platinum (Pt) as promoters on the physicochemical properties of cobalt catalyst. The catalyst was prepared by a wet impregnation method on a CNTs support. Samples were characterized using transmission electron microscopy (TEM), H2-temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) techniques. Fischer-Tropsch Synthesis (FTS) was carried out in a fixed-bed microreactor at 543 K and 1 atm, with H2/ CO = 2v / v and space velocity, SV of 12 L/g.h for 5 hours. The K-promoted and Pt-promoted Co catalysts have different physicochemical properties and catalytic performances compared to that of the un-promoted Co catalyst. XPS analysis revealed that K and Pt promoters induced electronic modifications as exhibited by the shifts in the Co binding energies. Incorporation of 0.06 wt% K and 0.06 wt% Pt in Co/CNTs catalyst resulted in an increase in the CO conversion and C5+ selectivity and a decrease in methane selectivity. Potassium was found to be a better promoter for Co/CNTs catalyst compared to platinum.

Study on the failure temperature of Ti/Pt/Au and Pt5Si2-Ti/Pt/Au metallization systems

NASA Astrophysics Data System (ADS)

Zhang, Jie; Han, Jianqiang; Yin, Yijun; Dong, Lizhen; Niu, Wenju

2017-09-01

The Ti/Pt/Au metallization system has an advantage of resisting KOH or TMAH solution etching. To form a good ohmic contact, the Ti/Pt/Au metallization system must be alloyed at 400 °C. However, the process temperatures of typical MEMS packaging technologies, such as anodic bonding, glass solder bonding and eutectic bonding, generally exceed 400 °C. It is puzzling if the Ti/Pt/Au system is destroyed during the subsequent packaging process. In the present work, the resistance of doped polysilicon resistors contacted by the Ti/Pt/Au metallization system that have undergone different temperatures and time are measured. The experimental results show that the ohmic contacts will be destroyed if heated to 500 °C. But if a 20 nm Pt film is sputtered on heavily doped polysilicon and alloyed at 700 °C before sputtering Ti/Pt/Au films, the Pt5Si2-Ti/Pt/Au metallization system has a higher service temperature of 500 °C, which exceeds process temperatures of most typical MEMS packaging technologies. Project supported by the National Natural Science Foundation of China (No. 61376114).

Photo-induced thermoelectric response in suspended single-walled carbon nanotube films

NASA Astrophysics Data System (ADS)

St-Antoine, Benoit; Menard, David; Martel, Richard

2010-03-01

A study was carried out on the position dependent photovoltage of suspended single-walled carbon nanotube films in vacuum. The photoresponse of such films was found to be driven by a thermal mechanism, rather than by direct photoexcitation of carriers. [1] A model was developed which establishes a relation between the photoresponse profile and the local Seebeck coefficient of the film, thus opening up new perspectives for material characterization. The technique was demonstrated by monitoring the doping changes in the nanotube films obtained by successive current conditioning steps. Since the Seebeck coefficient of carbon nanotubes spans a considerable range depending on their doping state, the photovoltage amplitude can be tuned and large responses have been measured (up to 0.75mV for 1.2mW). [4pt] [1] B. St-Antoine et al. Nano Lett. 9, 3503 (2009)

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.

Adsorption Behavior, Thermodynamics, and Kinetics of the Methanol Decomposition Reaction on defective graphene-supported Pt13

NASA Astrophysics Data System (ADS)

Gasper, Raymond; Ramasubramaniam, Ashwin

Defective graphene has been shown experimentally to be an excellent support for transition-metal electrocatalysts in direct methanol fuel cells. Prior computational modeling has shown that the improved catalytic activity of graphene-supported metal clusters is in part due to increased resistance to catalyst sintering and CO poisoning, but the increased reaction rate for the methanol decomposition reaction (MDR) is not yet fully explained. Using DFT, we investigate the adsorption of MDR intermediates and reaction thermodynamics on defective graphene-supported Pt13 nanoclusters with realistic, low-symmetry morphologies. We find that the support-induced shifts in Pt13 electronic structure correlate well with a rigid shift in adsorption of MDR intermediates, and that adsorption energy scaling relationships perform well on the low-symmetry surface. We investigate the reaction kinetics and thermodynamics, including testing the effectiveness of scaling relationships for predicting reaction barriers on the nanoclusters. Using these fundamental data, we perform microkinetic modeling to quantify the effect of the support on the MDR, and to understand how the support influences surface coverages, CO poisoning, and the relationships between reaction pathways. Funded by U.S. Department of Energy under Award Number DE-SC0010610. Computational resources were provided by National Energy Research Scientific Computing Center.

Growing Aligned Carbon Nanotubes for Interconnections in ICs

NASA Technical Reports Server (NTRS)

Li, Jun; Ye, Qi; Cassell, Alan; Ng, Hou Tee; Stevens, Ramsey; Han, Jie; Meyyappan, M.

2005-01-01

A process for growing multiwalled carbon nanotubes anchored at specified locations and aligned along specified directions has been invented. Typically, one would grow a number of the nanotubes oriented perpendicularly to a silicon integrated-circuit (IC) substrate, starting from (and anchored on) patterned catalytic spots on the substrate. Such arrays of perpendicular carbon nanotubes could be used as electrical interconnections between levels of multilevel ICs. The process (see Figure 1) begins with the formation of a layer, a few hundred nanometers thick, of a compatible electrically insulating material (e.g., SiO(x) or Si(y)N(z) on the silicon substrate. A patterned film of a suitable electrical conductor (Al, Mo, Cr, Ti, Ta, Pt, Ir, or doped Si), having a thickness between 1 nm and 2 m, is deposited on the insulating layer to form the IC conductor pattern. Next, a catalytic material (usually, Ni, Fe, or Co) is deposited to a thickness between 1 and 30 nm on the spots from which it is desired to grow carbon nanotubes. The carbon nanotubes are grown by plasma-enhanced chemical vapor deposition (PECVD). Unlike the matted and tangled carbon nanotubes grown by thermal CVD, the carbon nanotubes grown by PECVD are perpendicular and freestanding because an electric field perpendicular to the substrate is used in PECVD. Next, the free space between the carbon nanotubes is filled with SiO2 by means of CVD from tetraethylorthosilicate (TEOS), thereby forming an array of carbon nanotubes embedded in SiO2. Chemical mechanical polishing (CMP) is then performed to remove excess SiO2 and form a flat-top surface in which the outer ends of the carbon nanotubes are exposed. Optionally, depending on the application, metal lines to connect selected ends of carbon nanotubes may be deposited on the top surface. The top part of Figure 2 is a scanning electron micrograph (SEM) of carbon nanotubes grown, as described above, on catalytic spots of about 100 nm diameter patterned by

Telescopic nanotube device for hot nanolithography

DOEpatents

Popescu, Adrian; Woods, Lilia M

2014-12-30

A device for maintaining a constant tip-surface distance for producing nanolithography patterns on a surface using a telescopic nanotube for hot nanolithography. An outer nanotube is attached to an AFM cantilever opposite a support end. An inner nanotube is telescopically disposed within the outer nanotube. The tip of the inner nanotube is heated to a sufficiently high temperature and brought in the vicinity of the surface. Heat is transmitted to the surface for thermal imprinting. Because the inner tube moves telescopically along the outer nanotube axis, a tip-surface distance is maintained constant due to the vdW force interaction, which in turn eliminates the need of an active feedback loop.

Three-dimensional carbon nanotube networks with a supported nickel oxide nanonet for high-performance supercapacitors.

PubMed

Wu, Mao-Sung; Zheng, Yo-Ru; Lin, Guan-Wei

2014-08-04

A three-dimensional porous carbon nanotube film with a supported NiO nanonet was prepared by simple electrophoretic deposition and hydrothermal synthesis, which could deliver a high specific capacitance of 1511 F g(-1) at a high discharge current of 50 A g(-1) due to the significantly improved transport of the electrolyte and electrons.

Preparation of micelle supported magnetic hydroxylated multi-walled carbon nanotubes based DSPE for determination of PAHs

NASA Astrophysics Data System (ADS)

Wang, Mingyu; Zhang, Shaojun; Zhang, Xiao; Li, Deyu

2017-06-01

A micelle supported Fe3O4 magnetic nanoparticles decorated hydroxylated multi-walled carbon nanotubes material was synthesized. The material was facilely synthesized between carbon nanotubes and Fe2+. The synthesized nanomaterial served as an excellent support for micelles, exhibiting high loading capacity and selectivity. The prepared material used in dispersive solid-phase extraction (DSPE) for investigation of gaseous phase polycyclic aromatic hydrocarbons (PAHs) emitted from marine diesel engine for the first time. The application showed good response (R2 > 0.9981) in the range of 0.02 - 1.0 μg/L, satisfactory reproducibility (variation less than ± 10%) and high precision. Limits of detection of sixteen PAHs ranged from 0.009 to 0.018 μg/L (S/N=3). The spiked recovery of proposed method (72.65-96.54 %) was 1.01 - 2.32 times higher than that of the conventional method. The enrichment factors reached to 39.65-121.32 that exhibited good enrichment ability.

Carbon nanotube substrates and catalyzed hot stamp for polishing and patterning the substrates

DOEpatents

Wang, Yuhuang [Evanston, IL; Hauge, Robert H [Houston, TX; Schmidt, Howard K [Houston, TX; Kim, Myung Jong [Houston, TX; Kittrell, W Carter [Houston, TX

2009-09-08

The present invention is generally directed to catalyzed hot stamp methods for polishing and/or patterning carbon nanotube-containing substrates. In some embodiments, the substrate, as a carbon nanotube fiber end, is brought into contact with a hot stamp (typically at 200-800.degree. C.), and is kept in contact with the hot stamp until the morphology/patterns on the hot stamp have been transferred to the substrate. In some embodiments, the hot stamp is made of material comprising one or more transition metals (Fe, Ni, Co, Pt, Ag, Au, etc.), which can catalyze the etching reaction of carbon with H.sub.2, CO.sub.2, H.sub.2O, and/or O.sub.2. Such methods can (1) polish the carbon nanotube-containing substrate with a microscopically smooth finish, and/or (2) transfer pre-defined patterns from the hot stamp to the substrate. Such polished or patterned carbon nanotube substrates can find application as carbon nanotube electrodes, field emitters, and field emitter arrays for displays and electron sources.

Methane Conversion to Ethylene and Aromatics on PtSn Catalysts

DOE PAGES

Gerceker, Duygu; Motagamwala, Ali Hussain; Rivera-Dones, Keishla R.; ...

2017-02-03

Pt and PtSn catalysts supported on SiO 2 and H-ZSM-5 were studied for methane conversion under nonoxidative conditions. Addition of Sn to Pt/SiO 2 increased the turnover frequency for production of ethylene by a factor of 3, and pretreatment of the catalyst at 1123 K reduced the extent of coke formation. Pt and PtSn catalysts supported on H-ZSM-5 zeolite were prepared to improve the activity and selectivity to non-coke products. Ethylene formation rates were 20 times faster over a PtSn(1:3)/H-ZSM-5 catalyst with SiO 2:Al 2O 3 = 280 in comparison to those over PtSn(3:1)/SiO 2. H-ZSM-5-supported catalysts were also activemore » for the formation of aromatics, and the rates of benzene and naphthalene formation were increased by using more acidic H-ZSM-5 supports. These catalysts operate through a bifunctional mechanism, in which ethylene is first produced on highly dispersed PtSn nanoparticles and then is subsequently converted to benzene and naphthalene on Brønsted acid sites within the zeolite support. The most active and stable PtSn catalyst forms carbon products at a rate, 2.5 mmol of C/((mol of Pt) s), which is comparable to that of state-of-the-art Mo/H-ZSM-5 catalysts with same metal loading operated under similar conditions (1.8 mmol of C/((mol of Mo) s)). Scanning transmission electron microscopy measurements suggest the presence of smaller Pt nanoparticles on H-ZSM-5-supported catalysts, in comparison to SiO 2-supported catalysts, as a possible source of their high activity. As a result, a microkinetic model of methane conversion on Pt and PtSn surfaces, built using results from density functional theory calculations, predicts higher coupling rates on bimetallic and stepped surfaces, supporting the experimental observations that relate the high catalytic activity to small PtSn particles.« less

CO oxidation on Ru-Pt bimetallic nanoclusters supported on TiO2(101): The effect of charge polarization

NASA Astrophysics Data System (ADS)

Jia, Chuanyi; Zhong, Wenhui; Deng, Mingsen; Jiang, Jun

2018-03-01

Pt-based catalyst is widely used in CO oxidation, while its catalytic activity is often undermined because of the CO poisoning effect. Here, using density functional theory, we propose the use of a Ru-Pt bimetallic cluster supported on TiO2 for CO oxidation, to achieve both high activity and low CO poisoning effect. Excellent catalytic activity is obtained in a Ru1Pt7/TiO2(101) system, which is ascribed to strong electric fields induced by charge polarization between one Ru atom and its neighboring Pt atoms. Because of its lower electronegativity, the Ru atom donates electrons to neighboring Pt. This induces strong electric fields around the top-layered Ru, substantially promoting the adsorption of O2/CO + O2 and eliminating the CO poisoning effect. In addition, the charge polarization also drives the d-band center of the Ru1Pt7 cluster to up-shift to the Fermi level. For surface O2 activation/CO oxidation, the strong electric field and d-band center close to the Fermi level can promote the adsorption of O2 and CO as well as reduce the reaction barrier of the rate-determining step. Meanwhile, since O2 easily dissociates on Ru1Pt7/TiO2(101) resulting in unwanted oxidation of Ru and Pt, a CO-rich condition is necessary to protect the catalyst at high temperature.

A Kinetic and DRIFTS Study of Supported Pt Catalysts for NO Oxidation

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

Toops, Todd J; Ji, Yaying; Graham, Uschi

NO oxidation was studied over Pt/CeO2 and Pt/SiO2 catalysts. Apparent activation energies (Ea) of 31.4 and 40.6 kJ/mole were determined for Pt/CeO2 and Pt/SiO2, respectively, while reaction orders for NO and O2 were fractional and positive for both catalysts. Pre-treatment of the catalysts with SO2 caused a decrease in the Ea values, while the reaction orders were only slightly changed. In situ DRIFTS measurements indicated that high concentrations of nitrate species were formed on the surface of Pt/CeO2 during NO oxidation, while almost no surface species could be detected on Pt/SiO2. The addition of SO2 resulted in the formation ofmore » a highly stable sulfate at the expense of nitrate species and caused an irreversible loss of catalytic activity for Pt/CeO2.« less

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.

V-doped TiO2 supported Pt as a promising oxygen reduction reaction catalyst: Synthesis, characterization and in-situ evaluation in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Bharti, Abha; Cheruvally, Gouri

2017-09-01

This study deals with the synthesis and characterization of V-doped, TiO2 supported Pt catalyst (Pt/V-TiO2) for oxygen reduction reaction (ORR) and its in-situ performance investigation in proton exchange membrane (PEM) fuel cell. Pt/V-TiO2 nanocomposite catalyst is prepared via a facile sol-gel and microwave assisted, modified chemical reduction route and its performance is compared with the undoped TiO2 supported catalyst, Pt/TiO2 prepared in an identical way. The prepared Pt/V-TiO2 and Pt/TiO2 catalysts are employed as cathode catalyst in PEM fuel cell and compared with standard Pt/C catalyst. Their comparative studies are conducted with physical and electrochemical techniques. In-situ electrochemical characterization studies show improved ORR catalytic activity of Pt/V-TiO2 compared to Pt/TiO2. Furthermore, both Pt/TiO2 and Pt/V-TiO2 are more stable than Pt/C when subjected to 6000 voltammetric cycles in the range of 0.2-1.2 V vs. standard hydrogen electrode in operating fuel cell conditions, losing only <20% of its electrochemical surface area as compared to 50% loss exhibited by Pt/C. This study thus demonstrates Pt/V-TiO2 nanocomposite material as a potential cathode catalyst for PEM fuel cell with immense scope for further investigation.

Well-dispersed NiO nanoparticles supported on nitrogen-doped carbon nanotube for methanol electrocatalytic oxidation in alkaline media

NASA Astrophysics Data System (ADS)

Wang, Pengcheng; Zhou, Yingke; Hu, Min; Chen, Jian

2017-01-01

Nitrogen-doped carbon nanotube supporting NiO nanoparticles were synthesized by a chemical precipitation process coupled with subsequent calcination. The morphology and structure of the composites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and the electrochemical performance was evaluated using cyclic voltammetry and chronoamperometric technique. The effects of nitrogen doping, calcination temperature and content of NiO nanoparticles on the electrocatalytic activity toward methanol oxidation were systematically studied. The results show that the uniformly dispersed ultrafine NiO nanoparticles supported on nitrogen-doped carbon nanotube are obtained after calcination at 400 °C. The optimized composite catalysts present high electrocatalytic activity, fast charge-transfer process, excellent accessibility and stability for methanol oxidation reaction, which are promising for application in the alkaline direct methanol fuel cells.

Soluble organic nanotubes for catalytic systems

NASA Astrophysics Data System (ADS)

Xiong, Linfeng; Yang, Kunran; Zhang, Hui; Liao, Xiaojuan; Huang, Kun

2016-03-01

In this paper, we report a novel method for constructing a soluble organic nanotube supported catalyst system based on single-molecule templating of core-shell bottlebrush copolymers. Various organic or metal catalysts, such as sodium prop-2-yne-1-sulfonate (SPS), 1-(2-(prop-2-yn-1-yloxy)ethyl)-1H-imidazole (PEI) and Pd(OAc)2 were anchored onto the tube walls to functionalize the organic nanotubes via copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Depending on the ‘confined effect’ and the accessible cavity microenvironments of tubular structures, the organic nanotube catalysts showed high catalytic efficiency and site-isolation features. We believe that the soluble organic nanotubes will be very useful for the development of high performance catalyst systems due to their high stability of support, facile functionalization and attractive textural properties.

Soluble organic nanotubes for catalytic systems.

PubMed

Xiong, Linfeng; Yang, Kunran; Zhang, Hui; Liao, Xiaojuan; Huang, Kun

2016-03-18

In this paper, we report a novel method for constructing a soluble organic nanotube supported catalyst system based on single-molecule templating of core–shell bottlebrush copolymers. Various organic or metal catalysts, such as sodium prop-2-yne-1-sulfonate (SPS), 1-(2-(prop-2-yn-1-yloxy)ethyl)-1H-imidazole (PEI) and Pd(OAc)2 were anchored onto the tube walls to functionalize the organic nanotubes via copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Depending on the 'confined effect' and the accessible cavity microenvironments of tubular structures, the organic nanotube catalysts showed high catalytic efficiency and site-isolation features. We believe that the soluble organic nanotubes will be very useful for the development of high performance catalyst systems due to their high stability of support, facile functionalization and attractive textural properties.

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.

Catalytic behavior of ‘Pt-atomic chain encapsulated gold nanotube’: A density functional study

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

Nigam, Sandeep, E-mail: snigam@barc.gov.in; Majumder, Chiranjib

2016-05-23

With an aim to design novel material and explore its catalytic performance towards CO oxidation, Pt atomic chain was introduced inside gold nanotube (Au-NT). Theoretical calculations at the level of first principles formalism was carried out to investigate the atomic and electronic properties of the composite. Geometrically Pt atoms prefer to align in zig-zag fashion. Significant electronic charge transfer from inside Pt atoms to the outer wall Au atoms is observed. Interaction of O{sub 2} with Au-NT wall follows by injection of additional electronic charge in the anti-bonding orbital of oxygen molecule leading to activation of the O-O bond. Furthermore » interaction of CO molecule with the activated oxygen molecule leads to spontaneous oxidation reaction and formation of CO{sub 2}.« less

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

NASA Astrophysics Data System (ADS)

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

2013-08-01

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

Application of green chemistry techniques to prepare electrocatalysts for direct methanol fuel cells.

PubMed

Shimizu, Kenichi; Wang, Joanna S; Wai, Chien M

2010-03-25

A series of green techniques for synthesizing carbon nanotube-supported platinum nanoparticles and their high electrocatalytic activity toward methanol fuel cell applications are reported. The techniques utilize either the supercritical fluid carbon dioxide or water as a medium for depositing platinum nanoparticles on surfaces of multiwalled or single-walled carbon nanotubes. The catalytic properties of the carbon nanotubes-supported Pt nanoparticle catalysts prepared by four different techniques are compared for anodic oxidation of methanol and cathodic reduction of oxygen using cyclic voltammetry. One technique using galvanic exchange of Pt(2+) in water with zerovalent iron present on the surfaces of as-grown single-walled carbon nanotubes produces a Pt catalyst that shows an unusually high catalytic activity for reduction of oxygen but a negligible activity for oxidation of methanol. This fuel-selective catalyst may have a unique application as a cathode catalyst in methanol fuel cells to alleviate the problems caused by crossover of methanol through the polymer electrolyte membrane.

Metallized Nanotube Polymer Composite (MNPC) and Methods for Making Same

NASA Technical Reports Server (NTRS)

Harrison, Joycelyn S. (Inventor); Lowther, Sharon E. (Inventor); Lillehei, Peter T. (Inventor); Park, Cheol (Inventor); Taylor, Larry (Inventor); Kang, Jin Ho (Inventor); Nazem, Negin (Inventor); Kim, Jae-Woo (Inventor); Sauti, Godfrey (Inventor)

2017-01-01

A novel method to develop highly conductive functional materials which can effectively shield various electromagnetic effects (EMEs) and harmful radiations. Metallized nanotube polymer composites (MNPC) are composed of a lightweight polymer matrix, superstrong nanotubes (NT), and functional nanoparticle inclusions. MNPC is prepared by supercritical fluid infusion of various metal precursors (Au, Pt, Fe, and Ni salts), incorporated simultaneously or sequentially, into a solid NT-polymer composite followed by thermal reduction. The infused metal precursor tends to diffuse toward the nanotube surface preferentially as well as the surfaces of the NT-polymer matrix, and is reduced to form nanometer-scale metal particles or metal coatings. The conductivity of the MNPC increases with the metallization, which provides better shielding capabilities against various EMEs and radiations by reflecting and absorbing EM waves more efficiently. Furthermore, the supercritical fluid infusion process aids to improve the toughness of the composite films significantly regardless of the existence of metal.

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

PubMed

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

2010-07-01

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

Constructing hierarchical interfaces: TiO 2-supported PtFe-FeO x nanowires for room temperature CO oxidation

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

Zhu, Huiyuan; Wu, Zili; Dong, Su

2015-08-05

This is a report of a facile approach to constructing catalytic active hierarchical interfaces in one-dimensional (1D) nanostructure, exemplified by the synthesis of TiO 2-supported PtFe–FeO x nanowires (NWs). The hierarchical interface, constituting atomic level interactions between PtFe and FeO x within each NW and the interactions between NWs and support (TiO 2), enables CO oxidation with 100% conversion at room temperature. We identify the role of the two interfaces by probing the CO oxidation reaction with isotopic labeling experiments. Both the oxygen atoms (Os) in FeO x and TiO 2 participate in the initial CO oxidation, facilitating the reactionmore » through a redox pathway. Moreover, the intact 1D structure leads to the high stability of the catalyst. After 30 h in the reaction stream, the PtFe–FeO x/TiO2 catalyst exhibits no activity decay. These results provide a general approach and new insights into the construction of hierarchical interfaces for advanced catalysis.« less

Production of carbon nanotubes: Chemical vapor deposition synthesis from liquefied petroleum gas over Fe-Co-Mo tri-metallic catalyst supported on MgO

NASA Astrophysics Data System (ADS)

Setyopratomo, P.; Wulan, Praswasti P. D. K.; Sudibandriyo, M.

2016-06-01

Carbon nanotubes were produced by chemical vapor deposition method to meet the specifications for hydrogen storage. So far, the various catalyst had been studied outlining their activities, performances, and efficiencies. In this work, tri-metallic catalyst consist of Fe-Co-Mo supported on MgO was used. The catalyst was prepared by wet-impregnation method. Liquefied Petroleum Gas (LPG) was used as carbon source. The synthesis was conducted in atmospheric fixed bed reactor at reaction temperature range 750 - 850 °C for 30 minutes. The impregnation method applied in this study successfully deposed metal component on the MgO support surface. It found that the deposited metal components might partially replace Mg(OH)2 or MgO molecules in their crystal lattice. Compare to the original MgO powder; it was significant increases in pore volume and surface area has occurred during catalyst preparation stages. The size of obtained carbon nanotubes is ranging from about 10.83 nm OD/4.09 nm ID up to 21.84 nm OD/6.51 nm ID, which means that multiwall carbon nanotubes were formed during the synthesis. Yield as much as 2.35 g.CNT/g.catalyst was obtained during 30 minutes synthesis and correspond to carbon nanotubes growth rate of 0.2 μm/min. The BET surface area of the obtained carbon nanotubes is 181.13 m2/g and around 50 % of which is contributed by mesopores. Micropore with half pore width less than 1 nm contribute about 10% volume of total micro and mesopores volume of the carbon nanotubes. The existence of these micropores is very important to increase the hydrogen storage capacity of the carbon nanotubes.

Effect of Enhanced Thermal Stability of Alumina Support Layer on Growth of Vertically Aligned Single-Walled Carbon Nanotubes and Their Application in Nanofiltration Membranes

NASA Astrophysics Data System (ADS)

In, Jung Bin; Cho, Kang Rae; Tran, Tung Xuan; Kim, Seok-Min; Wang, Yinmin; Grigoropoulos, Costas P.; Noy, Aleksandr; Fornasiero, Francesco

2018-06-01

We investigate the thermal stability of alumina supporting layers sputtered at different conditions and its effect on the growth of aligned single-walled carbon nanotube arrays. Radio frequency magnetron sputtering of alumina under oxygen-argon atmosphere produces a Si-rich alumina alloy film on a silicon substrate. Atomic force microscopy on the annealed catalysts reveals that Si-rich alumina films are more stable than alumina layers with low Si content at the elevated temperatures at which the growth of single-walled carbon nanotubes is initiated. The enhanced thermal stability of the Si-rich alumina layer results in a narrower (< 2.2 nm) diameter distribution of the single-walled carbon nanotubes. Thanks to the smaller diameters of their nanotube pores, membranes fabricated with vertically aligned nanotubes grown on the stable layers display improved ion selectivity.

Pt/Au nanoalloy supported on alumina and chlorided alumina: DFT and experimental analysis

NASA Astrophysics Data System (ADS)

Sharifi, N.; Falamaki, C.; Ghorbanzadeh Ahangari, M.

2018-04-01

Density functional theory (DFT) was used to explore the adsorption of Pt/Au nanoalloy onto a pure and chlorided γ-Al2O3(110) surface, which has been applied in numerous catalytic reactions. First, we considered the adsorption properties of Pt clusters (n ≤ 5) onto the Al2O3(110) surface to determine the most stable Pt cluster on alumina surface in reforming processes. After full structural relaxations of Pt clusters at various configurations on alumina, our computed results expressed that the minimum binding energy (‑5.67 eV) is accrued for Pt4 cluster and the distance between the nearest Pt atom in the cluster to the alumina surface is equal to 1.13 Å. Then, we investigated the binding energies, geometries, and electronic properties of adsorbed Aun clusters (n ≤ 6) on the γ-Al2O3(110) surface. Our studied showed that Au5 was the most thermodynamically stable structure on γ-Al2O3. Finally, we inspected these properties for adsorbed Au clusters onto the Pt4-decorated alumina (Aun/Pt4-alumina) system. The binding energy of the Au4/Pt4-alumina system was ‑5.01 eV, and the distance between Au4 cluster and Pt4-alumina was 1.33 Å. The Au4/Pt4alumina system was found to be the most stable nanometer-sized catalyst design. At last, our first-principles calculations predicted that the best position of embedment Cl on the Au4/Pt4-alumina.

Pt-Ni and Pt-Co Catalyst Synthesis Route for Fuel Cell Applications

NASA Technical Reports Server (NTRS)

Firdosy, Samad A.; Ravi, Vilupanur A.; Valdez, Thomas I.; Kisor, Adam; Narayan, Sri R.

2013-01-01

Oxygen reduction reactions (ORRs) at the cathode are the rate-limiting step in fuel cell performance. The ORR is 100 times slower than the corresponding hydrogen oxidation at the anode. Speeding up the reaction at the cathode will improve fuel cell efficiency. The cathode material is generally Pt powder painted onto a substrate (e.g., graphite paper). Recent efforts in the fuel cell area have focused on replacing Pt with Pt-X alloys (where X = Co, Ni, Zr, etc.) in order to (a) reduce cost, and (b) increase ORR rates. One of these strategies is to increase ORR rates by reducing the powder size, which would result in an increase in the surface area, thereby facilitating faster reaction rates. In this work, a process has been developed that creates Pt-Ni or Pt-Co alloys that are finely divided (on the nano scale) and provide equivalent performance at lower Pt loadings. Lower Pt loadings will translate to lower cost. Precursor salts of the metals are dissolved in water and mixed. Next, the salt mixtures are dried on a hot plate. Finally, the dried salt mixture is heattreated in a furnace under flowing reducing gas. The catalyst powder is then used to fabricate a membrane electrode assembly (MEA) for electrochemical performance testing. The Pt- Co catalyst-based MEA showed comparable performance to an MEA fabri cated using a standard Pt black fuel cell catalyst. The main objective of this program has been to increase the overall efficiencies of fuel cell systems to support power for manned lunar bases. This work may also have an impact on terrestrial programs, possibly to support the effort to develop a carbon-free energy source. This catalyst can be used to fabricate high-efficiency fuel cell units that can be used in space as regenerative fuel cell systems, and terrestrially as primary fuel cells. Terrestrially, this technology will become increasingly important when transition to a hydrogen economy occurs.

Electrochemical oxidation of 4-chlorophenol for wastewater treatment using highly active UV treated TiO2 nanotubes.

PubMed

Tian, Min; Thind, Sapanbir S; Dondapati, Jesse S; Li, Xinyong; Chen, Aicheng

2018-06-07

In the present work, we report on a facile UV treatment approach for enhancing the electrocatalytic activity of TiO 2 nanotubes. The TiO 2 nanotubes were prepared using an anodization oxidation method by applying a voltage of 40 V for 8 h in a DMSO + 2% HF solution, and further treated under UV light irradiation. Compared with Pt and untreated TiO 2 nanotubes, the UV treated electrode exhibited a superior electrocatalytic activity toward the oxidation of 4-chlorophenol (4-ClPh). The effects of current density and temperature on the electrochemical oxidation of the 4-ClPh were also systematically investigated. The high electrocatalytic activity of the UV treated TiO 2 nanotubes was further confirmed by the electrochemical oxidation of other persistent organic pollutants including phenol, 2-, 3-, 4-nitrophenol, and 4-aminophenol. The total organic carbon (TOC) analysis revealed that over 90% 4-ClPh was removed when the UV treated TiO 2 electrode was employed and the rate constant was 16 times faster than that of the untreated TiO 2 electrode; whereas only 60% 4-ClPh was eliminated at the Pt electrode under the same conditions. This dramatically improved electrocatalytic activity might be attributed to the enhanced donor density, conductivity, and high overpotential for oxygen evolution. Our results demonstrated that the application of the UV treatment to the TiO 2 nanotubes enhanced their electrochemical activity and energy consumption efficiency significantly, which is highly desirable for the abatement of persistent organic pollutants. Copyright © 2018 Elsevier Ltd. All rights reserved.

Sintering of Pt nanoparticles via volatile PtO 2: Simulation and comparison with experiments

DOE PAGES

Plessow, Philipp N.; Abild-Pedersen, Frank

2016-09-23

It is a longstanding question whether sintering of platinum under oxidizing conditions is mediated by surface migration of Pt species or through the gas phase, by PtO 2(g). Clearly, a rational approach to avoid sintering requires understanding the underlying mechanism. A basic theory for the simulation of ripening through the vapor phase has been derived by Wynblatt and Gjostein. Recent modeling efforts, however, have focused entirely on surface-mediated ripening. In this work, we explicitly model ripening through PtO 2(g) and study how oxygen pressure, temperature, and shape of the particle size distribution affect sintering. On the basis of the availablemore » data on α-quartz, adsorption of monomeric Pt species on the support is extremely weak and has therefore not been explicitly simulated, while this may be important for more strongly interacting supports. Our simulations clearly show that ripening through the gas phase is predicted to be relevant. Assuming clean Pt particles, sintering is generally overestimated. This can be remedied by explicitly including oxygen coverage effects that lower both surface free energies and the sticking coefficient of PtO 2(g). Additionally, mass-transport limitations in the gas phase may play a role. Using a parameterization that accounts for these effects, we can quantitatively reproduce a number of experiments from the literature, including pressure and temperature dependence. Lastly, this substantiates the hypothesis of ripening via PtO 2(g) as an alternative to surface-mediated ripening.« less

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.

Role of Pt during hydrodeoxygenation of biomass pyrolysis vapors over Pt/HBEA

DOE PAGES

Yung, Matthew M.; Foo, Guo Shiou; Sievers, Carsten

2017-03-27

1.3 wt% Pt/HBEA and HBEA were studied as catalysts for the hydrodeoxygenation of pine pyrolysis vapors at 500 °C. Both catalysts showed high initial conversion of oxygenated pyrolysis products into aromatic hydrocarbons, while Pt/HBEA showed higher stability in terms of hydrocarbon productivity and deferred breakthrough of oxygenated compounds. Among 1-, 2- and 3-ring aromatic hydrocarbons, Pt/HBEA had a significantly higher selectivity than HBEA towards unalkylated aromatics (e.g., benzene) as compared to the corresponding alkylated aromatics (e.g., toluene and xylene). Additionally, Pt addition to HBEA decreased coke deposition and improved resistance to pore and acid site blockage as determined by TPO,more » N 2 physisorption, and NH 3 TPD. The ability of Pt to promote cleavage and hydrogenation of methoxy and methyl groups was observed by increased methane production over Pt/HBEA relative to HBEA. A progressive decrease in the methane production over Pt/HBEA correlated with deactivation in terms of reduced benzene formation, breakthrough of oxygenated products, and increased formation of polynuclear aromatics and their degree of substitution, which indicate coke formation. In conclusion, the increased methane yield and suppressed coke formation with the addition of Pt is attributed to hydrogen spillover, through which hydrogen activated on Pt can subsequently migrate to the HBEA support to reverse the coke-forming hydrogen abstraction reaction.« less

Role of Pt during hydrodeoxygenation of biomass pyrolysis vapors over Pt/HBEA

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

Yung, Matthew M.; Foo, Guo Shiou; Sievers, Carsten

1.3 wt% Pt/HBEA and HBEA were studied as catalysts for the hydrodeoxygenation of pine pyrolysis vapors at 500 °C. Both catalysts showed high initial conversion of oxygenated pyrolysis products into aromatic hydrocarbons, while Pt/HBEA showed higher stability in terms of hydrocarbon productivity and deferred breakthrough of oxygenated compounds. Among 1-, 2- and 3-ring aromatic hydrocarbons, Pt/HBEA had a significantly higher selectivity than HBEA towards unalkylated aromatics (e.g., benzene) as compared to the corresponding alkylated aromatics (e.g., toluene and xylene). Additionally, Pt addition to HBEA decreased coke deposition and improved resistance to pore and acid site blockage as determined by TPO,more » N 2 physisorption, and NH 3 TPD. The ability of Pt to promote cleavage and hydrogenation of methoxy and methyl groups was observed by increased methane production over Pt/HBEA relative to HBEA. A progressive decrease in the methane production over Pt/HBEA correlated with deactivation in terms of reduced benzene formation, breakthrough of oxygenated products, and increased formation of polynuclear aromatics and their degree of substitution, which indicate coke formation. In conclusion, the increased methane yield and suppressed coke formation with the addition of Pt is attributed to hydrogen spillover, through which hydrogen activated on Pt can subsequently migrate to the HBEA support to reverse the coke-forming hydrogen abstraction reaction.« less

Effect of Enhanced Thermal Stability of Alumina Support Layer on Growth of Vertically Aligned Single-Walled Carbon Nanotubes and Their Application in Nanofiltration Membranes.

PubMed

In, Jung Bin; Cho, Kang Rae; Tran, Tung Xuan; Kim, Seok-Min; Wang, Yinmin; Grigoropoulos, Costas P; Noy, Aleksandr; Fornasiero, Francesco

2018-06-07

We investigate the thermal stability of alumina supporting layers sputtered at different conditions and its effect on the growth of aligned single-walled carbon nanotube arrays. Radio frequency magnetron sputtering of alumina under oxygen-argon atmosphere produces a Si-rich alumina alloy film on a silicon substrate. Atomic force microscopy on the annealed catalysts reveals that Si-rich alumina films are more stable than alumina layers with low Si content at the elevated temperatures at which the growth of single-walled carbon nanotubes is initiated. The enhanced thermal stability of the Si-rich alumina layer results in a narrower (< 2.2 nm) diameter distribution of the single-walled carbon nanotubes. Thanks to the smaller diameters of their nanotube pores, membranes fabricated with vertically aligned nanotubes grown on the stable layers display improved ion selectivity.

Fabrication of Au nanoparticles supported on CoFe2O4 nanotubes by polyaniline assisted self-assembly strategy and their magnetically recoverable catalytic properties

NASA Astrophysics Data System (ADS)

Zhang, Zhen; Jiang, Yanzhou; Chi, Maoqiang; Yang, Zezhou; Nie, Guangdi; Lu, Xiaofeng; Wang, Ce

2016-02-01

This article reports the fabrication of magnetically responsive Au nanoparticles supported on CoFe2O4 nanotubes through polyaniline (PANI) assisted self-assembly strategy which can be used as an efficient magnetically recoverable nanocatalyst. The central magnetic CoFe2O4 nanotubes possess a strong magnetic response under an externally magnetic field, enabling an easy and efficient separation from the reaction system for reuse. The thorn-like PANI layer on the surface of CoFe2O4 nanotubes provides large surface area for supporting Au nanocatalysts due to the electrostatic interactions. The as-prepared CoFe2O4/PANI/Au nanotube assemblies exhibit a high catalytic activity for the hydrogenation of 4-nitrophenol by sodium borohydride (NaBH4) at room temperature, with an apparent kinetic rate constant (Kapp) of about 7.8 × 10-3 s-1. Furthermore, the composite nanocatalyst shows a good recoverable property during the catalytic process. This work affords a reliable way in developing multifunctional nanocomposite for catalysis and other potential applications in many fields.

Structurally distinct membrane nanotubes between human macrophages support long-distance vesicular traffic or surfing of bacteria.

PubMed

Onfelt, Björn; Nedvetzki, Shlomo; Benninger, Richard K P; Purbhoo, Marco A; Sowinski, Stefanie; Hume, Alistair N; Seabra, Miguel C; Neil, Mark A A; French, Paul M W; Davis, Daniel M

2006-12-15

We report that two classes of membrane nanotubes between human monocyte-derived macrophages can be distinguished by their cytoskeletal structure and their functional properties. Thin membrane nanotubes contained only F-actin, whereas thicker nanotubes, i.e., those > approximately 0.7 microm in diameter, contained both F-actin and microtubules. Bacteria could be trapped and surf along thin, but not thick, membrane nanotubes toward connected macrophage cell bodies. Once at the cell body, bacteria could then be phagocytosed. The movement of bacteria is aided by a constitutive flow of the nanotube surface because streptavidin-coated beads were similarly able to traffic along nanotubes between surface-biotinylated macrophages. Mitochondria and intracellular vesicles, including late endosomes and lysosomes, could be detected within thick, but not thin, membrane nanotubes. Analysis from kymographs demonstrated that vesicles moved in a stepwise, bidirectional manner at approximately 1 microm/s, consistent with their traffic being mediated by the microtubules found only in thick nanotubes. Vesicular traffic in thick nanotubes and surfing of beads along thin nanotubes were both stopped upon the addition of azide, demonstrating that both processes require ATP. However, microtubule destabilizing agents colchicine or nocodazole abrogated vesicular transport but not the flow of the nanotube surface, confirming that distinct cytoskeletal structures of nanotubes give rise to different functional properties. Thus, membrane nanotubes between macrophages are more complex than unvarying ubiquitous membrane tethers and facilitate several means for distal interactions between immune cells.

Environmental Electrometry with Luminescent Carbon Nanotubes.

PubMed

Noé, Jonathan C; Nutz, Manuel; Reschauer, Jonathan; Morell, Nicolas; Tsioutsios, Ioannis; Reserbat-Plantey, Antoine; Watanabe, Kenji; Taniguchi, Takashi; Bachtold, Adrian; Högele, Alexander

2018-06-25

We demonstrate that localized excitons in luminescent carbon nanotubes can be utilized to study electrostatic fluctuations in the nanotube environment with sensitivity down to the elementary charge. By monitoring the temporal evolution of the cryogenic photoluminescence from individual carbon nanotubes grown on silicon oxide and hexagonal boron nitride, we characterize the dynamics of charge trap defects for both dielectric supports. We find a one order of magnitude reduction in the photoluminescence spectral wandering for nanotubes on extended atomically flat terraces of hexagonal boron nitride. For nanotubes on hexagonal boron nitride with pronounced spectral fluctuations, our analysis suggests proximity to terrace ridges where charge fluctuators agglomerate to exhibit areal densities exceeding those of silicon oxide. Our results establish carbon nanotubes as sensitive probes of environmental charge fluctuations and highlight their potential for applications in electrometric nanodevices with all-optical readout.

Purification of Carbon Nanotubes: Alternative Methods

NASA Technical Reports Server (NTRS)

Files, Bradley; Scott, Carl; Gorelik, Olga; Nikolaev, Pasha; Hulse, Lou; Arepalli, Sivaram

2000-01-01

Traditional carbon nanotube purification process involves nitric acid refluxing and cross flow filtration using surfactant TritonX. This is believed to result in damage to nanotubes and surfactant residue on nanotube surface. Alternative purification procedures involving solvent extraction, thermal zone refining and nitric acid refiuxing are used in the current study. The effect of duration and type of solvent to dissolve impurities including fullerenes and P ACs (polyaromatic compounds) are monitored by nuclear magnetic reasonance, high performance liquid chromatography, and thermogravimetric analysis. Thermal zone refining yielded sample areas rich in nanotubes as seen by scanning electric microscopy. Refluxing in boiling nitric acid seem to improve the nanotube content. Different procedural steps are needed to purify samples produced by laser process compared to arc process. These alternative methods of nanotube purification will be presented along with results from supporting analytical techniques.

Carbon nanotube-containing structures, methods of making, and processes using same

DOEpatents

Wang, Yong [Richland, WA; Chin, Ya-Huei [Richland, WA; Gao, Yufei [Blue Bell, PA; Aardahl, Christopher L [Richland, WA; Stewart, Terri L [Richland, WA

2006-03-14

Carbon nanotube structures are disclosed in which nanotubes are disposed over a porous support such as a foam, felt, mesh, or membrane. Techniques of making these structures are also disclosed. In some of these techniques, a support is pretreated with a templated surfactant composition to assist with the formation of a nanotube layer.

Carbon Nanotube-Containing Structures, Methods Of Making, And Processes Using Same

DOEpatents

Wang, Yong; Chin, Ya-Huei; Gao, Yufei; Aardahl, Christopher L.; Stewart, Terri L.

2004-11-30

Carbon nanotube structures are disclosed in which nanotubes are disposed over a porous support such as a foam, felt, mesh, or membrane. Techniques of making these structures are also disclosed. In some of these techniques, a support is pretreated with a templated surfactant composition to assist with the formation of a nanotube layer.

Growth kinetics and growth mechanism of ultrahigh mass density carbon nanotube forests on conductive Ti/Cu supports.

PubMed

Sugime, Hisashi; Esconjauregui, Santiago; D'Arsié, Lorenzo; Yang, Junwei; Makaryan, Taron; Robertson, John

2014-09-10

We evaluate the growth kinetics and growth mechanism of ultrahigh mass density carbon nanotube forests. They are synthesized by chemical vapor deposition at 450 °C using a conductive Ti/Cu support and Co-Mo catalyst system. We find that Mo stabilizes Co particles preventing lift off during the initial growth stage, thus promoting the growth of ultrahigh mass density nanotube forests by the base growth mechanism. The morphology of the forest gradually changes with growth time, mostly because of a structural change of the catalyst particles. After 100 min growth, toward the bottom of the forest, the area density decreases from ∼ 3-6 × 10(11) cm(-2) to ∼ 5 × 10(10) cm(-2) and the mass density decreases from 1.6 to 0.38 g cm(-3). We also observe part of catalyst particles detached and embedded within nanotubes. The progressive detachment of catalyst particles results in the depletion of the catalyst metals on the substrate surfaces. This is one of the crucial reasons for growth termination and may apply to other catalyst systems where the same features are observed. Using the packed forest morphology, we demonstrate patterned forest growth with a pitch of ∼ 300 nm and a line width of ∼ 150 nm. This is one of the smallest patterning of the carbon nanotube forests to date.

Synthesis and catalytic activity of electrospun NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation

NASA Astrophysics Data System (ADS)

Kim, Il Hee; Lee, Hyerim; Yu, Areum; Jeong, Jae Hwan; Lee, Youngmi; Kim, Myung Hwa; Lee, Chongmok; Dok Kim, Young

2018-04-01

NiO/NiCo2O4 nanotubes with a diameter of approximately 100 nm are synthesized using Ni and Co precursors via electro-spinning and subsequent calcination processes. The tubular structure is confirmed via transmission electron microscopy imaging, whereas the structures and elemental compositions of the nanotubes are determined using x-ray diffraction, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. N2 adsorption isotherm data reveal that the surface of the nanotubes consists of micropores, thereby resulting in a significantly higher surface area (˜20 m2 g-1) than expected for a flat-surface structure (<15 m2 g-1). Herein, we present a study of the catalytic activity of our novel NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation. The catalytic activity of NiO/NiCo2O4 is superior to Pt below 100 °C for CO oxidation. For acetaldehyde oxidation, the total oxidation activity of NiO/NiCo2O4 for acetaldehyde is comparable with that of Pt. Coexistence of many under-coordinated Co and Ni active sites in our structure is suggested be related to the high catalytic activity. It is suggested that our novel NiO/NiCo2O4 tubular structures with surface microporosity can be of interest for a variety of applications, including the catalytic oxidation of harmful gases.

Synthesis and catalytic activity of electrospun NiO/NiCo2O4 nanotubes for CO and acetaldehyde oxidation.

PubMed

Kim, Il Hee; Lee, Hyerim; Yu, Areum; Jeong, Jae Hwan; Lee, Youngmi; Kim, Myung Hwa; Lee, Chongmok; Kim, Young Dok

2018-04-27

NiO/NiCo 2 O 4 nanotubes with a diameter of approximately 100 nm are synthesized using Ni and Co precursors via electro-spinning and subsequent calcination processes. The tubular structure is confirmed via transmission electron microscopy imaging, whereas the structures and elemental compositions of the nanotubes are determined using x-ray diffraction, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. N 2 adsorption isotherm data reveal that the surface of the nanotubes consists of micropores, thereby resulting in a significantly higher surface area (∼20 m 2 g -1 ) than expected for a flat-surface structure (<15 m 2 g -1 ). Herein, we present a study of the catalytic activity of our novel NiO/NiCo 2 O 4 nanotubes for CO and acetaldehyde oxidation. The catalytic activity of NiO/NiCo 2 O 4 is superior to Pt below 100 °C for CO oxidation. For acetaldehyde oxidation, the total oxidation activity of NiO/NiCo 2 O 4 for acetaldehyde is comparable with that of Pt. Coexistence of many under-coordinated Co and Ni active sites in our structure is suggested be related to the high catalytic activity. It is suggested that our novel NiO/NiCo 2 O 4 tubular structures with surface microporosity can be of interest for a variety of applications, including the catalytic oxidation of harmful gases.

Synthesis of noble metal/carbon nanotube composites in supercritical methanol.

PubMed

Sun, Zhenyu; Fu, Lei; Liu, Zhimin; Han, Buxing; Liu, Yunqi; Du, Jimin

2006-03-01

A simple and efficient route has been employed to deposit noble metal nanoparticles (Pt, Ru, Pt-Ru, Rh, Ru-Sn) onto carbon nanotubes (CNTs) in supercritical methanol solution. In this method, the inorganic metallic salts acted as metal precursors, and methanol as solvent as well as reductant for the precursors. The as-prepared nanocomposites were structurally and morphologically characterized by X-ray diffraction spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy, and X-ray photoelectron spectroscopy analyses. It was demonstrated that the CNTs were decorated by crystalline metal nanoparticles with uniform sizes and a narrow particle size distribution. The size and loading content of the nanoparticles on CNTs could be tuned by manipulating reaction parameters. Furthermore, the formation mechanism of the composites was also discussed.

Is n-Hexane conversion on supported pt catalysts so simple (or can we learn more about the active sites from this reaction)?

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

Paal, Z.

A paper in which some very refined techniques (such as microcalorimetry and {sup 13}C NMR study) were used to characterize Pt catalysts on zeolitic and SiO{sub 2} supports has appeared in the Journal of Catalysis. That work-as well as its companion paper presenting {sup 13}CNMR results for fresh catalysts-supplies important new information on the changes of surface energetics of supported Pt samples, giving unquestionable evidence that the adsorption properties of a Pt/zeolite-as indicated by the differential heats of CO adsorption-after catalytic runs with n-hexane at 673 K are much closer to those of the initial state than are those ofmore » Pt/SiO{sub 2}. The authors must agree with the approach of the authors that no surface physical information has real value unless it is compared with catalytic propensities; the authors also include results of n-hexane test reactions. The discussion of catalytic results is oversimplified, however, and may suggest false ideas as far as the reaction pathways and their evaluation are concerned. 22 refs., 1 tab.« less

Synthesis of Metal Nanoparticle-decorated Carbon Nanotubes under Ambient Conditions

NASA Technical Reports Server (NTRS)

Lin, Yi; Watson, Kent A.; Ghose, Sayata; Smith, Joseph G.; Connell, John W.

2008-01-01

This viewgraph presentation reviews the production of Metal Nanoparticle-decorated carbon Nanotubes. Multi-walled carbon nanotubes (MWCNTs) were efficiently decorated with metal nanoparticles (e.g. Ag, Pt, etc.) using the corresponding metal acetate in a simple mixing process without the need of chemical reagents or further processing. The conversion of acetate compounds to the corresponding metal reached over 90%, forming nanoparticles with average diameters less than 10 nm under certain conditions. The process was readily scalable allowing for the convenient preparation of multi-gram quantities of metal nanoparticle-decorated MWCNTs in a matter of a few minutes. These materials are under evaluation for a variety of electrical and catalytic applications. The preparation and characterization of these materials will be presented. The microscopic views of the processed MWCNTs are shown

Synthesis of Pt@TiO2@CNTs Hierarchical Structure Catalyst by Atomic Layer Deposition and Their Photocatalytic and Photoelectrochemical Activity.

PubMed

Liao, Shih-Yun; Yang, Ya-Chu; Huang, Sheng-Hsin; Gan, Jon-Yiew

2017-04-29

Pt@TiO2@CNTs hierarchical structures were prepared by first functionalizing carbon nanotubes (CNTs) with nitric acid at 140 °C. Coating of TiO2 particles on the CNTs at 300 °C was then conducted by atomic layer deposition (ALD). After the TiO2@CNTs structure was fabricated, Pt particles were deposited on the TiO2 surface as co-catalyst by plasma-enhanced ALD. The saturated deposition rates of TiO2 on a-CNTs were 1.5 Å/cycle and 0.4 Å/cycle for substrate-enhanced process and linear process, respectively. The saturated deposition rate of Pt on TiO2 was 0.39 Å/cycle. The photocatalytic activities of Pt@TiO2@CNTs hierarchical structures were higher than those without Pt co-catalyst. The particle size of Pt on TiO2@CNTs was a key factor to determine the efficiency of methylene blue (MB) degradation. The Pt@TiO2@CNTs of 2.41 ± 0.27 nm exhibited the best efficiency of MB degradation.

Synthesis of Pt@TiO2@CNTs Hierarchical Structure Catalyst by Atomic Layer Deposition and Their Photocatalytic and Photoelectrochemical Activity

PubMed Central

Liao, Shih-Yun; Yang, Ya-Chu; Huang, Sheng-Hsin; Gan, Jon-Yiew

2017-01-01

Pt@TiO2@CNTs hierarchical structures were prepared by first functionalizing carbon nanotubes (CNTs) with nitric acid at 140 °C. Coating of TiO2 particles on the CNTs at 300 °C was then conducted by atomic layer deposition (ALD). After the TiO2@CNTs structure was fabricated, Pt particles were deposited on the TiO2 surface as co-catalyst by plasma-enhanced ALD. The saturated deposition rates of TiO2 on a-CNTs were 1.5 Å/cycle and 0.4 Å/cycle for substrate-enhanced process and linear process, respectively. The saturated deposition rate of Pt on TiO2 was 0.39 Å/cycle. The photocatalytic activities of Pt@TiO2@CNTs hierarchical structures were higher than those without Pt co-catalyst. The particle size of Pt on TiO2@CNTs was a key factor to determine the efficiency of methylene blue (MB) degradation. The Pt@TiO2@CNTs of 2.41 ± 0.27 nm exhibited the best efficiency of MB degradation. PMID:28468248

Carbon nanotubes/carbon fiber hybrid material: a super support material for sludge biofilms.

PubMed

Liu, Qijie; Dai, Guangze; Bao, Yanling

2017-07-16

Carbon fiber (CF) is widely used as a sludge biofilm support material for wastewater treatment. Carbon nanotubes/carbon fiber (CNTs/CF) hybrid material was prepared by ultrasonically assisted electrophoretic deposition (EPD). CF supports (CF without handling, CF oxidized by nitric acid, CNTs/CF hybrid material) were evaluated by sludge immobilization tests, bacterial cell adsorption tests and Derjaguin -Landau -Verwey -Overbeek (DLVO) theory. We found that the CNTs/CF hybrid material has a high capacity for adsorbing activated sludge, nitrifying bacterial sludge and pure strains (Escherichia coli and Staphylococcus aureus). CNTs deposited on CF surface easily wound around the curved surface of bacterial cell which resulted in capturing more bacterial cells. DLVO theory indicated the lowest total interaction energy of CNTs/CF hybrid material, which resulted in the highest bacteria cell adsorption velocity. Experiments and DLVO theory results proved that CNTs/CF hybrid material is a super support material for sludge biofilms.

Experimental and DFT study of thiol-stabilized Pt/CNTs catalysts.

PubMed

Li, L; Chen, S G; Wei, Z D; Qi, X Q; Xia, M R; Wang, Y Q

2012-12-28

Using a combination of experiments and density functional theory (DFT) calculations, we explored the mechanisms of the stabilization effect of the thiolized (-SH) group on the Pt/SH-CNTs catalyst. Pt particles supported on the hydroxyl functionalized CNTs (Pt/OH-CNTs) are synthesized as a baseline for comparison. Experimentally, the platinum on OH-CNTs has a stronger tendency for aggregation than that on SH-CNTs. The differences in the oxidation resistance, migration activation energy, and corrosion resistance between the Pt/SH-CNTs and Pt/OH-CNTs are calculated using DFT. The DFT calculations indicate that the -SH group enhances the oxidation resistance of the Pt cluster and CNTs and restricts Pt migration on the CNTs. DFT calculations also suggest that the enhanced stability of Pt/SH-CNTs originates from the increased interaction between Pt and SH-CNTs and the depressed d-band center of the Pt NPs. Thus, the functional groups on the CNTs used for stabilization of supported Pt NPs should provide a deposit and anchor site for Pt NPs and maintain the perfect structure of CNTs rather than destroying it.

Carbon nanotube aerogel-CoS2 hybrid catalytic counter electrodes for enhanced photovoltaic performance dye-sensitized solar cells.

PubMed

Liu, Tao; Mai, Xianmin; Chen, Haijun; Ren, Jing; Liu, Zheting; Li, Yingxiang; Gao, Lina; Wang, Ning; Zhang, Jiaoxia; He, Hongcai; Guo, Zhanhu

2018-03-01

The carbon nanotube aerogel (CNA) with an ultra-low density, three-dimensional network nanostructure, superior electronic conductivity and large surface area is being widely employed as a catalytic electrode and catalytic support. Impressively, dye-sensitized solar cells (DSSCs) assembled with a CNA counter electrode (CE) achieved a maximum power conversion efficiency (PCE) of 8.28%, which exceeded that of the conventional platinum (Pt)-based DSSC (7.20%) under the same conditions. Furthermore, highly dispersed CoS 2 nanoparticles endowed with excellent intrinsic catalytic activity were hydrothermally incorporated to form a CNA-supported CoS 2 (CNA-CoS 2 ) CE, which was due to the large number of catalytically active sites and sufficient connections between CoS 2 and the CNA. The electrocatalytic ability and stability were systematically evaluated by cyclic voltammetry (CV), electrochemical impedance spectra (EIS) and Tafel polarization, which confirmed that the resultant CNA-CoS 2 hybrid CE exhibited a remarkably higher electrocatalytic activity toward I 3 - reduction, and faster ion diffusion and electron transfer than the pure CNA CE. Such cost-effective DSSCs assembled with an optimized CNA-CoS 2 CE yielded an enhanced PCE of 8.92%, comparable to that of the cell fabricated with the CNA-Pt hybrid CE reported in our published literature (9.04%). These results indicate that the CNA-CoS 2 CE can be considered as a promising candidate for Pt-free CEs used in low-cost and high-performance DSSCs.

Carbon Nanotube Membranes for Water Purification

NASA Astrophysics Data System (ADS)

Bakajin, Olgica

2009-03-01

Carbon nanotubes are an excellent platform for the fundamental studies of transport through channels commensurate with molecular size. Water transport through carbon nanotubes is also believed to be similar to transport in biological channels such as aquaporins. I will discuss the transport of gas, water and ions through microfabricated membranes with sub-2 nanometer aligned carbon nanotubes as ideal atomically-smooth pores. The measured gas flow through carbon nanotubes exceeded predictions of the Knudsen diffusion model by more than an order of magnitude. The measured water flow exceeded values calculated from continuum hydrodynamics models by more than three orders of magnitude and is comparable to flow rates extrapolated from molecular dynamics simulations and measured for aquaporins. More recent reverse osmosis experiments reveal ion rejection by our membranes. Based on our experimental findings, the current understanding of the fundamentals of water and gas transport and of ion rejection will be discussed. The potential application space that exploits these unique nanofluidic phenomena will be explored. The extremely high permeabilities of these membranes, combined with their small pore size will enable energy efficient filtration and eventually decrease the cost of water purification.[4pt] In collaboration with Francesco Fornasiero, Biosciences and Biotechnology Division, PLS, LLNL, Livermore, CA 94550; Sangil Kim, NSF Center for Biophotonics Science & Technology, University of California at Davis, Sacramento CA 95817; Jung Bin In, Mechanical Engineering Department, UC Berkeley, Berkeley CA 94720; Hyung Gyu Park, Jason K Holt, and Michael Stadermann, Biosciences and Biotechnology Division, PLS, LLNL; Costas P. Grigoropoulos, Mechanical Engineering Department, UC Berkeley; Aleksandr Noy, Biosciences and Biotechnology Division, PLS, LLNL and School of Natural Sciences, University of California at Merced.

Mesoporous graphene-like nanobowls as Pt electrocatalyst support for highly active and stable methanol oxidation

NASA Astrophysics Data System (ADS)

Yan, Zaoxue; He, Guoqiang; Jiang, Zhifeng; Wei, Wei; Gao, Lina; Xie, Jimin

2015-06-01

Mesoporous graphene-like nanobowls (GLBs) with high surface area of 1091 m2 g-1, high pore volume of 2.7 cm3 g-1 and average pore diameter of 9.8 nm are synthesized through template method. The GLBs with inherent excellent electrical conductivity and chemical inertia show the properties of well mass transfer, poison resistance and stable loading of smaller Pt particles. Therefore, the Pt/GLB catalyst shows much higher activity and stability than that of commercial Pt/C (TKK) for methanol oxidation reaction (MOR). Therein, the peak current density on Pt/GLB (2075 mA mgPt-1) for MOR is 2.87 times that of commercial Pt/C (723 mA mgPt-1); and the onset potential for the MOR on the former is negatively shifted about 160 mV compared with that on the latter. The catalytic performances of the Pt/GLB are also better than those of the Pt loading on mesoporous amorphous carbon nanobowls (Pt/BLC), indicating promotion effect of graphite on Pt catalytic performance.

Water-gas shift reaction on alumina-supported Pt-CeO x catalysts prepared by supercritical fluid deposition

DOE PAGES

Deal, Jacob W.; Le, Phong; Corey, C. Blake; ...

2016-08-25

Alumina-supported platinum catalysts, both with and without ceria, were prepared by supercritical fluid deposition and evaluated for activity for water-gas shift reaction. The organometallic precursor, platinum(II) acetylacetonate, was deposited from solution in supercritical carbon dioxide. Analysis of the catalysts by high resolution scanning transmission electron microscopy indicated that platinum was present in the form of highly dispersed metal nanoparticles. Pretreatment of the alumina-supported ceria in hydrogen prior to the deposition of the platinum precursor resulted in more platinum nucleated on ceria than non-pretreated alumina-supported ceria but varied in both particle size and structure. The ceria-containing catalyst that was not pretreatedmore » exhibited a more uniform particle size, and the Pt particles were encapsulated in crystalline ceria. Reaction rate measurements showed that the catalyst was more active for water-gas shift, with reaction rates per mass of platinum that exceeded most literature values for water-gas shift reaction on Pt-CeO x catalysts. The high activity was attributed to the significant fraction of platinum/ceria interfacial contact. We found that these results show the promise of supercritical fluid deposition as a scalable means of synthesizing highly active supported metal catalysts that offer efficient utilization of precious metals.« less

Investigation of carbon supported PtW catalysts as CO tolerant anodes at high temperature in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Hassan, Ayaz; Paganin, Valdecir A.; Ticianelli, Edson A.

2016-09-01

The CO tolerance mechanism and the stability of carbon supported PtW electrocatalysts are evaluated in the anode of a proton exchange membrane fuel cell (PEMFC) at two different temperatures. The electrocatalysts are characterized by energy dispersive spectroscopy, X-ray diffraction, and transmission electron spectroscopy. Employed electrochemical techniques include cyclic voltammetry, CO stripping, fuel cell polarization, and online mass spectrometry. At a cell temperature of 85 °C, the PtW/C catalyst shows higher CO tolerance compared to Pt/C due an electronic effect of WOx in the Pt 5d band, which reduces the CO adsorption. An increase in hydrogen oxidation activity in the presence of CO is observed for both the catalysts at a higher temperature, due to the decrease of the Pt-CO coverage. A reduction in the current densities occurs for the PtW/C catalyst in both polarization curves and cyclic voltammograms after 5000 cycles of the anode in the range of 0.1-0.7 V vs. RHE at 50 mVs-1. This decrease in performance is assigned to the dissolution of W, with a consequent increase in the membrane resistivity. However, the observed decline of performance is small either in the presence of pure H2 or in the presence of H2/CO.

Electrochemical oxidation of hydrolyzed poly oxymethylene-dimethyl ether by PtRu catalysts on Nb-doped SnO(2-δ) supports for direct oxidation fuel cells.

PubMed

Kakinuma, Katsuyoshi; Kim, In-Tae; Senoo, Yuichi; Yano, Hiroshi; Watanabe, Masahiro; Uchida, Makoto

2014-12-24

We synthesized Pt and PtRu catalysts supported on Nb-doped SnO(2-δ) (Pt/Sn0.99Nb0.01O(2-δ), PtRu/Sn0.99Nb0.01O(2-δ)) for direct oxidation fuel cells (DOFCs) using poly oxymethylene-dimethyl ether (POMMn, n = 2, 3) as a fuel. The onset potential for the oxidation of simulated fuels of POMMn (methanol-formaldehyde mixtures; n = 2, 3) for Pt/Sn0.99Nb0.01O(2-δ) and PtRu/Sn0.99Nb0.01O(2-δ) was less than 0.3 V vs RHE, which was much lower than those of two commercial catalysts (PtRu black and Pt2Ru3/carbon black). In particular, the onset potential of the oxidation reaction of simulated fuels of POMMn (n = 2, 3) for PtRu/Sn0.99Nb0.01O(2-δ) sintered at 800 °C in nitrogen atmosphere was less than 0.1 V vs RHE and is thus considered to be a promising anode catalyst for DOFCs. The mass activity (MA) of PtRu/Sn0.99Nb0.01O(2-δ) sintered at 800 °C was more than five times larger than those of the commercial catalysts in the measurement temperature range from 25 to 80 °C. Even though the MA for the methanol oxidation reaction was of the same order as those of the commercial catalysts, the MA for the formaldehyde oxidation reaction was more than five times larger than those of the commercial catalysts. Sn from the Sn0.99Nb0.01O(2-δ) support was found to have diffused into the Pt catalyst during the sintering process. The Sn on the top surface of the Pt catalyst accelerated the oxidation of carbon monoxide by a bifunctional mechanism, similar to that for Pt-Ru catalysts.

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.

Biofunctionalization of multiwalled carbon nanotubes by irradiation of electropolymerized poly(pyrrole-diazirine) films.

PubMed

Papper, Vladislav; Gorgy, Karine; Elouarzaki, Kamal; Sukharaharja, Ayrine; Cosnier, Serge; Marks, Robert S

2013-07-15

A photoactivatable poly(pyrrole-diazirine) film was synthesized and electropolymerized as a versatile tool for covalent binding of laccase and glucose oxidase on multiwalled carbon nanotube coatings and Pt, respectively. Irradiation of the functionalized nanotubes allowed photochemical grafting of laccase and its subsequent direct electrical wiring, as illustrated by the electrocatalytic reduction of oxygen. Moreover, covalent binding of glucose oxidase as model enzyme, achieved by UV activation of electropolymerized pyrrole-diazirine, allowed a glucose biosensor to be realized. This original method to graft biomolecules combines electrochemical and photochemical techniques. The simplicity of this new method allows it to be extended easily to other biological systems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gram-Scale Synthesized Pd2Co-Supported PtMonolayers Electrocatalysts for Oxygen Reduction Reaction

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

Zhou, W.P.; Sasaki, K.; Su, D.

2010-04-21

Gram-scale synthesis of Pt{sub ML} electrocatalysts with a well-defined core-shell structure has been carried out using method involving galvanic displacement of an underpotential deposition Cu layer. The Pt shell thickness can be controlled by stepwise deposition. The Pt{at}Pd{sub 2}Co/C nanoparticles were characterized by X-ray powder diffraction, aberration-corrected scanning transmission electron microscopy, high-resolution energy-loss spectrometry, and in situ X-ray absorption spectroscopy. A complete Pt shell of 0.6 nm on a Pd{sub 2}Co core has been confirmed. The Pt{at}Pd{sub 2}Co/C core-shell electrocatalysts showed a very high activity for the oxygen reduction reaction; the Pt mass and specific activity were 0.72 A mg{supmore » -1}{sub Pt} and 0.5 mA cm{sup -2}, respectively (3.5 and 2.5 times higher than the corresponding values for commercial Pt catalysts), at 0.9 V in 0.1 M HClO{sub 4} at room temperature. In an accelerated potential cycling test, a loss in active surface area and a decrease in catalytic activity for gram-scale-synthesized Pt{sub ML} catalysts were also determined.« less

The effect of the morphology of supported subnanometer Pt clusters on the first and key step of CO 2 photoreduction [Morphology effect of supported subnanometer Pt clusters on first and key step of CO 2 photoreduction

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

Yang, Chi -Ta; Wood, Brandon C.; Bhethanabotla, Venkat R.

2015-09-04

In this study, using density functional theory calculations, we investigate the influence of size-dependent cluster morphology on the synergistic catalytic properties of anatase TiO 2(101) surfaces decorated with subnanometer Pt clusters. Focusing on the formation of the key precursor in the CO 2 photoreduction reaction (bent CO 2 –), we find that flatter (2D-like) Pt clusters that “wet” the TiO 2 surface offer significantly less benefit than 3D-like Pt clusters. We attribute the differences to three factors. First, the 3D clusters provide a greater number of accessible Pt–TiO 2 interfacial sites with geometries that can aid CO 2 bond bendingmore » and charge transfer processes. Second, binding competition among each Pt–CO 2 bonding interaction mitigates maximum orbital overlaps, leading to insufficient CO 2 binding. Third and also most interestingly, the 3D clusters tend to possess higher structural fluxionality than the flatter clusters, which is shown to correlate positively with CO2 binding strength. The preferred morphology adopted by the clusters depends on several factors, including the cluster size and the presence of oxygen vacancies on the TiO 2 surface; this suggests a strategy for optimizing the synergistic effect between Pt clusters and TiO 2 surfaces for CO 2 photocatalysis. Clusters of ~6–8 atoms should provide the largest benefit, since they retain the desired 3D morphology, yet are small enough to exhibit high structural fluxionality. Electronic structure analysis provides additional insight into the electronic motivations for the enhanced binding of CO 2 on TiO 2-supported 3D Pt clusters, as well as suppressed binding on flattened, 2D-like clusters.« less

Carbon-Nanotubes-Supported Pd Nanoparticles for Alcohol Oxidations in Fuel Cells: Effect of Number of Nanotube Walls on Activity.

PubMed

Zhang, Jin; Lu, Shanfu; Xiang, Yan; Shen, Pei Kang; Liu, Jian; Jiang, San Ping

2015-09-07

Carbon nanotubes (CNTs) are well known electrocatalyst supports due to their high electrical conductivity, structural stability, and high surface area. Here, we demonstrate that the number of inner tubes or walls of CNTs also have a significant promotion effect on the activity of supported Pd nanoparticles (NPs) for alcohol oxidation reactions of direct alcohol fuel cells (DAFCs). Pd NPs with similar particle size (2.1-2.8 nm) were uniformly assembled on CNTs with different number of walls. The results indicate that Pd NPs supported on triple-walled CNTs (TWNTs) have the highest mass activity and stability for methanol, ethanol, and ethylene glycol oxidation reactions, as compared to Pd NPs supported on single-walled and multi-walled CNTs. Such a specific promotion effect of TWNTs on the electrocatalytic activity of Pd NPs is not related to the contribution of metal impurities in CNTs, oxygen-functional groups of CNTs or surface area of CNTs and Pd NPs. A facile charge transfer mechanism via electron tunneling between the outer wall and inner tubes of CNTs under electrochemical driving force is proposed for the significant promotion effect of TWNTs for the alcohol oxidation reactions in alkaline solutions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tuning Nanowires and Nanotubes for Efficient Fuel-Cell Electrocatalysis.

PubMed

Wang, Wei; Lv, Fan; Lei, Bo; Wan, Sheng; Luo, Mingchuan; Guo, Shaojun

2016-12-01

Developing new synthetic methods for the controlled synthesis of Pt-based or non-Pt nanocatalysts with low or no Pt loading to facilitate sluggish cathodic oxygen reduction reaction (ORR) and organics oxidation reactions is the key in the development of fuel-cell technology. Various nanoparticles (NPs), with a range of size, shape, composition, and structure, have shown good potential to catalyze the sluggish cathodic and anodic reactions. In contrast to NPs, one-dimensional (1D) nanomaterials such as nanowires (NWs), and nanotubes (NTs), exhibit additional advantages associated with their anisotropy, unique structure, and surface properties. The prominent characteristics of NWs and NTs include fewer lattice boundaries, a lower number of surface defect sites, and easier electron and mass transport for better electrocatalytic activity and lower vulnerability to dissolution, Ostwald ripening, and aggregation than Pt NPs for enhanced stability. An overview of recent advances in tuning 1D nanostructured Pt-based, Pd-based, or 1D metal-free nanomaterials as advanced electrocatalysts is provided here, for boosting fuel-cell reactions with high activity and stability, including the oxygen reduction reaction (ORR), methanol oxidation reaction (MOR), and ethanol oxidation reaction (EOR). After highlighting the different strategies developed so far for the synthesis of Pt-based 1D nanomaterials with controlled size, shape, and composition, special emphasis is placed on the rational design of diverse NWs and NTs catalysts such as Pt-based NWs or NTs, non-Pt NTs, and carbon NTs with molecular engineering, etc. for enhancing the ORR, MOR, and EOR. Finally, some perspectives are highlighted on the development of more efficient fuel-cell electrocatalysts featuring high stability, low cost, and enhanced performance, which are the key factors in accelerating the commercialization of fuel-cell technology. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vertically Aligned Carbon Nanotube Arrays as Efficient Supports for Faradaic Capacitive Electrodes

NASA Astrophysics Data System (ADS)

Oguntoye, Moses; Holleran, Mary-Kate; Roberts, Katherine; Pesika, Noshir

Supercapacitors are notable for their ability to deliver energy at higher power (compared to batteries) and store energy at higher density (compared to capacitors) as well as exhibit a long cycle life. In our efforts to further the development of supercapacitors, our focus is on using vertically aligned carbon nanotubes (VACNT) as supports for faradaic capacitive electrode materials. The objective is to develop electrodes functioning in an inexpensive aqueous environment with small potential windows, that store energy at a higher density than carbon materials alone. We describe the different approaches explored to overcome the challenges of non-uniform deposition, poor wetting and array collapse. Materials that are electrochemically anchored to VACNT supports include NiCo2O4, VOx, Fe2O3 and Co-Mn mixed oxides. In each case, the specific capacitance obtained using the VACNT arrays as supports is significantly more than that obtained by direct deposition onto current collectors or by using VACNT alone. The ease of VACNT growth and the degree of coating control achievable using electrodeposition means there is much potential in exploring them as supports for capacitive electrode materials.

Deposition of platinum nanoparticles on carbon nanotubes by supercritical fluid method.

PubMed

Yen, Clive H; Cui, Xiaoli; Pan, Horng-Bin; Wang, Shaofen; Lin, Yuehe; Wai, Chien M

2005-11-01

Carbon nanotube-supported platinum nanoparticles with a 5-15 nm diameter size range can be synthesized by hydrogen reduction of platinum(ll) acetylacetonate in methanol modified supercritical carbon dioxide. X-ray photoelectron spectroscopy and X-ray diffraction spectra indicate that the carbon nanotubes contain zero-valent platinum metal and high-resolution transmission electron microscopy images show that the visible lattice fringes of platinum nanoparticles are crystallites. Carbon nanotubes synthesized with 25% by weight of platinum nanoparticles exhibit a higher activity for hydrogenation of benzene compared with a commercial carbon black platinum catalyst. The carbon nanotube-supported platinum nanocatalyst can be reused at least six times for the hydrogenation reaction without losing activity. The carbon nanotube-supported platinum nanoparticles are also highly active for electrochemical oxidation of methanol and for reduction of oxygen suggesting their potential use as a new electrocatalyst for proton exchange membrane fuel cell applications.

Carbon Nanotubes for Human Space Flight

NASA Technical Reports Server (NTRS)

Scott, Carl D.; Files, Brad; Yowell, Leonard

2003-01-01

Single-wall carbon nanotubes offer the promise of a new class of revolutionary materials for space applications. The Carbon Nanotube Project at NASA Johnson Space Center has been actively researching this new technology by investigating nanotube production methods (arc, laser, and HiPCO) and gaining a comprehensive understanding of raw and purified material using a wide range of characterization techniques. After production and purification, single wall carbon nanotubes are processed into composites for the enhancement of mechanical, electrical, and thermal properties. This "cradle-to-grave" approach to nanotube composites has given our team unique insights into the impact of post-production processing and dispersion on the resulting material properties. We are applying our experience and lessons-learned to developing new approaches toward nanotube material characterization, structural composite fabrication, and are also making advances in developing thermal management materials and electrically conductive materials in various polymer-nanotube systems. Some initial work has also been conducted with the goal of using carbon nanotubes in the creation of new ceramic materials for high temperature applications in thermal protection systems. Human space flight applications such as advanced life support and fuel cell technologies are also being investigated. This discussion will focus on the variety of applications under investigation.

Carbon nanotubes grown on bulk materials and methods for fabrication

DOEpatents

Menchhofer, Paul A [Clinton, TN; Montgomery, Frederick C [Oak Ridge, TN; Baker, Frederick S [Oak Ridge, TN

2011-11-08

Disclosed are structures formed as bulk support media having carbon nanotubes formed therewith. The bulk support media may comprise fibers or particles and the fibers or particles may be formed from such materials as quartz, carbon, or activated carbon. Metal catalyst species are formed adjacent the surfaces of the bulk support material, and carbon nanotubes are grown adjacent the surfaces of the metal catalyst species. Methods employ metal salt solutions that may comprise iron salts such as iron chloride, aluminum salts such as aluminum chloride, or nickel salts such as nickel chloride. Carbon nanotubes may be separated from the carbon-based bulk support media and the metal catalyst species by using concentrated acids to oxidize the carbon-based bulk support media and the metal catalyst species.

Single Wall Nanotube Type-Specific Functionalization and Separation

NASA Technical Reports Server (NTRS)

Boul, Peter; Nikolaev, Pavel; Sosa, Edward; Arepalli, Sivaram; Yowell, Leonard

2008-01-01

Metallic single-wall carbon nanotubes were selectively solubilized in THF and separated from semiconducting nanotubes. Once separated, the functionalized metallic tubes were de-functionalized to restore their metallic band structure. Absorption and Raman spectroscopy of the enriched samples support conclusions of the enrichment of nanotube samples by metallic type. A scalable method for enriching nanotube conductive type has been developed. Raman and UV-Vis data indicate SWCNT reaction with dodecylbenzenediazonium results in metallic enrichment. It is expected that further refinement of this techniques will lead to more dramatic separations of types and diameters.

Chitin and carbon nanotube composites as biocompatible scaffolds for neuron growth

NASA Astrophysics Data System (ADS)

Singh, Nandita; Chen, Jinhu; Koziol, Krzysztof K.; Hallam, Keith R.; Janas, Dawid; Patil, Avinash J.; Strachan, Ally; G. Hanley, Jonathan; Rahatekar, Sameer S.

2016-04-01

The design of biocompatible implants for neuron repair/regeneration ideally requires high cell adhesion as well as good electrical conductivity. Here, we have shown that plasma-treated chitin carbon nanotube composite scaffolds show very good neuron adhesion as well as support of synaptic function of neurons. The addition of carbon nanotubes to a chitin biopolymer improved the electrical conductivity and the assisted oxygen plasma treatment introduced more oxygen species onto the chitin nanotube scaffold surface. Neuron viability experiments showed excellent neuron attachment onto plasma-treated chitin nanotube composite scaffolds. The support of synaptic function was evident on chitin/nanotube composites, as confirmed by PSD-95 staining. The biocompatible and electrically-conducting chitin nanotube composite scaffold prepared in this study can be used for in vitro tissue engineering of neurons and, potentially, as an implantable electrode for stimulation and repair of neurons.

Chitin and carbon nanotube composites as biocompatible scaffolds for neuron growth.

PubMed

Singh, Nandita; Chen, Jinhu; Koziol, Krzysztof K; Hallam, Keith R; Janas, Dawid; Patil, Avinash J; Strachan, Ally; G Hanley, Jonathan; Rahatekar, Sameer S

2016-04-21

The design of biocompatible implants for neuron repair/regeneration ideally requires high cell adhesion as well as good electrical conductivity. Here, we have shown that plasma-treated chitin carbon nanotube composite scaffolds show very good neuron adhesion as well as support of synaptic function of neurons. The addition of carbon nanotubes to a chitin biopolymer improved the electrical conductivity and the assisted oxygen plasma treatment introduced more oxygen species onto the chitin nanotube scaffold surface. Neuron viability experiments showed excellent neuron attachment onto plasma-treated chitin nanotube composite scaffolds. The support of synaptic function was evident on chitin/nanotube composites, as confirmed by PSD-95 staining. The biocompatible and electrically-conducting chitin nanotube composite scaffold prepared in this study can be used for in vitro tissue engineering of neurons and, potentially, as an implantable electrode for stimulation and repair of neurons.

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.

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.

A highly durable fuel cell electrocatalyst based on double-polymer-coated carbon nanotubes.

PubMed

Berber, Mohamed R; Hafez, Inas H; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2015-11-23

Driven by the demand for the commercialization of fuel cell (FC) technology, we describe the design and fabrication of a highly durable FC electrocatalyst based on double-polymer-coated carbon nanotubes for use in polymer electrolyte membrane fuel cells. The fabricated electrocatalyst is composed of Pt-deposited polybenzimidazole-coated carbon nanotubes, which are further coated with Nafion. By using this electrocatalyst, a high FC performance with a power density of 375 mW/cm(2) (at 70 ˚C, 50% relative humidity using air (cathode)/H2(anode)) was obtained, and a remarkable durability of 500,000 accelerated potential cycles was recorded with only a 5% loss of the initial FC potential and 20% loss of the maximum power density, which were far superior properties compared to those of the membrane electrode assembly prepared using carbon black in place of the carbon nanotubes. The present study indicates that the prepared highly durable fuel cell electrocatalyst is a promising material for the next generation of PEMFCs.

Graphene as an atomically thin interface for growth of vertically aligned carbon nanotubes.

PubMed

Rao, Rahul; Chen, Gugang; Arava, Leela Mohana Reddy; Kalaga, Kaushik; Ishigami, Masahiro; Heinz, Tony F; Ajayan, Pulickel M; Harutyunyan, Avetik R

2013-01-01

Growth of vertically aligned carbon nanotube (CNT) forests is highly sensitive to the nature of the substrate. This constraint narrows the range of available materials to just a few oxide-based dielectrics and presents a major obstacle for applications. Using a suspended monolayer, we show here that graphene is an excellent conductive substrate for CNT forest growth. Furthermore, graphene is shown to intermediate growth on key substrates, such as Cu, Pt, and diamond, which had not previously been compatible with nanotube forest growth. We find that growth depends on the degree of crystallinity of graphene and is best on mono- or few-layer graphene. The synergistic effects of graphene are revealed by its endurance after CNT growth and low contact resistances between the nanotubes and Cu. Our results establish graphene as a unique interface that extends the class of substrate materials for CNT growth and opens up important new prospects for applications.

Graphene as an atomically thin interface for growth of vertically aligned carbon nanotubes

PubMed Central

Rao, Rahul; Chen, Gugang; Arava, Leela Mohana Reddy; Kalaga, Kaushik; Ishigami, Masahiro; Heinz, Tony F.; Ajayan, Pulickel M.; Harutyunyan, Avetik R.

2013-01-01

Growth of vertically aligned carbon nanotube (CNT) forests is highly sensitive to the nature of the substrate. This constraint narrows the range of available materials to just a few oxide-based dielectrics and presents a major obstacle for applications. Using a suspended monolayer, we show here that graphene is an excellent conductive substrate for CNT forest growth. Furthermore, graphene is shown to intermediate growth on key substrates, such as Cu, Pt, and diamond, which had not previously been compatible with nanotube forest growth. We find that growth depends on the degree of crystallinity of graphene and is best on mono- or few-layer graphene. The synergistic effects of graphene are revealed by its endurance after CNT growth and low contact resistances between the nanotubes and Cu. Our results establish graphene as a unique interface that extends the class of substrate materials for CNT growth and opens up important new prospects for applications. PMID:23712556

Xe adsorption site distributions on Pt(111), Pt(221) and Pt(531)

NASA Astrophysics Data System (ADS)

Gellman, Andrew J.; Baker, L.; Holsclaw, B. S.

2016-04-01

The ideal structures of the Pt(111), Pt(221) and Pt(531) surfaces expose adsorption sites that can be qualitatively described as terrace sites on Pt(111), both step and terrace sites on Pt(221), and kink sites on Pt(531). The real surface structures of these surfaces can be complicated by imperfections such as misorientation, reconstruction and thermal roughening, all of which will influence their distributions of adsorption sites. Xe adsorption sites on the Pt(111), Pt(221) and Pt(531) surfaces have been probed using both photoemission of adsorbed Xe (PAX) and temperature programmed desorption (TPD) of Xe. Both PAX and Xe TPD are sensitive to the adsorption sites of the Xe and serve as complementary means of assessing the distributions of adsorption sites on these three Pt surfaces. The adsorption of Xe is sufficiently sensitive to detect the presence of residual steps on the Pt(111) surface at a density of 1.5% step atoms per Pt atom. On the Pt(221) surface, PAX and Xe TPD reveal adsorption at both terrace and step sites simultaneously. Although the ideal structure of the Pt(531) surface has no well-defined steps or terraces, Xe adsorption indicates that its adsorption sites are best described as a distribution of both step and kink sites with roughly twice as many steps sites as kinks.

In situ {sup 13}C MAS NMR study of n-hexane conversion on Pt and Pd supported on basic materials

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

Ivanova, I.I.; Pasau-Claerbout, A.; Seivert, M.

n-Hexane conversion was studied in situ on Pt and Pd supported on aluminum-stabilized magnesium oxide and Pt on Zeolite KL catalysts (Pt/Mg(Al)O, Pd/Mg(Al)O and Pt/KL) by means of {sup 13}C MAS NMR spectroscopy. n-Hexane 1-{sup 13}C was used as a labelled reactant. Forty NMR lines corresponding to 14 different products were resolved and identified. The NMR line assignments were confirmed by adsorption of model compounds. The NMR results were further quantified and compared with continuous flow microreactor tests. Four parallel reaction pathways were identified under flow conditions: isomerization, cracking, dehydrocyclization, and dehydrogenation. Aromatization occurs via two reaction routes: (1) n-hexanemore » dehydrogenation towards hexadienes and hexatrienes, followed by dehydrogenation of a cyclic intermediate. The former reaction pathway is prevented under NMR batch conditions. High pressures induced in the NMR cells at high reaction temperatures (573, 653 K) shift the reaction equilibrium towards hydrogenation. NMR experiments showed that on Pt catalysts aromatization occurs via a cyclohexane intermediate, whereas on Pd it takes place via methylcyclopentane ring enlargement. 54 refs., 15 figs., 3 tabs.« less

Friction on a single MoS2 nanotube

PubMed Central

2012-01-01

Friction was measured on a single molybdenum disulfide (MoS2) nanotube and on a single MoS2 nano-onion for the first time. We used atomic force microscopy (AFM) operating in ultra-high vacuum at room temperature. The average coefficient of friction between the AFM tip and MoS2 nanotubes was found considerably below the corresponding values obtained from an air-cleaved MoS2 single crystal or graphite. We revealed a nontrivial dependency of friction on interaction strength between the nanotube and the underlying substrate. Friction on detached or weakly supported nanotubes by the substrate was several times smaller (0.023 ± 0.005) than that on well-supported nanotubes (0.08 ± 0.02). We propose an explanation of a quarter of a century old phenomena of higher friction found for intracrystalline (0.06) than for intercrystalline slip (0.025) in MoS2. Friction test on a single MoS2 nano-onion revealed a combined gliding-rolling process. PACS, 62.20, 61.46.Fg, 68.37 Ps PMID:22490562

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.

Low temperature growth of ultra-high mass density carbon nanotube forests on conductive supports

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

Sugime, Hisashi; Esconjauregui, Santiago; Yang, Junwei

2013-08-12

We grow ultra-high mass density carbon nanotube forests at 450 °C on Ti-coated Cu supports using Co-Mo co-catalyst. X-ray photoelectron spectroscopy shows Mo strongly interacts with Ti and Co, suppressing both aggregation and lifting off of Co particles and, thus, promoting the root growth mechanism. The forests average a height of 0.38 μm and a mass density of 1.6 g cm{sup −3}. This mass density is the highest reported so far, even at higher temperatures or on insulators. The forests and Cu supports show ohmic conductivity (lowest resistance ∼22 kΩ), suggesting Co-Mo is useful for applications requiring forest growth onmore » conductors.« less

Mirror Support

NASA Technical Reports Server (NTRS)

Baron, Richard L. (Inventor)

2013-01-01

Disclosed herein is a method of making a mirror support comprising a composite, the composite comprising a plurality of carbon nanotubes, wherein at least two of the plurality of carbon nanotubes are bonded to each other through a bridging moiety bound to each of the two carbon nanotubes, and a laminate comprising the composite.

Novel carbon nanostructures as catalyst support for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Natarajan, Sadesh Kumar

Polymer electrolyte membrane fuel cell (PEMFC) technology has advanced rapidly in recent years, with one of active area focused on improving the long-term performance of carbon supported catalysts, which has been recognized as one of the most important issues to be addressed for the commercialization of PEMFCs. The central part of a PEMFC is the membrane electrode assembly (MEA) which consists of two electrodes (anode and cathode) and a cation exchange membrane. These electrodes are commonly made of carbon black (most often, Vulcan XC-72) supported on carbon paper or carbon cloth backings. It is the primary objective of this thesis to prepare and investigate carbon nanostructures (CNS, licensed to Hydrogen Research Institute -- IRH, Quebec, Canada), the carbon material with more graphite component like carbon nanotubes (CNTs) for use as catalyst support in PEMFCs. High energy ball-milling of activated carbon along with transition metal catalysts under hydrogen atmosphere, followed by heat-treatment leads to nanocrystalline structures of carbon called CNS. However, CNS formed in the quartz tube after heat-treatment is inevitably accompanied by many impurities such as metal particles, amorphous carbon and other carbon nanoparticules. Such impurities are a serious impediment to detailed characterization of the properties of nanostructures. In addition, since the surface of CNS is itself rather inert, it is difficult to control the homogeneity and size distribution of Pt nanoparticules. In this thesis work, we demonstrated a novel mean to purify and functionalize CNS via acid-oxidation under reflux conditions. To investigate and quantify these nanostructures X-ray diffraction, electrical conductivity measurements, specific surface area measurements, thermogravimetric analysis, X-ray photoelectron spectroscopy and transmission electron microscopy studies were used. Cyclic voltammetry studies were performed on different samples to derive estimates for the relationship

Electrochemical biosensors for biocontaminant detection consisting of carbon nanotubes, platinum nanoparticles, dendrimers, and enzymes.

PubMed

Siriviriyanun, Ampornphan; Imae, Toyoko; Nagatani, Naoki

2013-12-15

The presented approach provides the advanced development of effective, rapid, and versatile electrochemical sensors for a small amount of analytes on potential, cheap, and disposable printed chips. The electrocatalytic activity of this biosensor revealed the feasible detection of hydrogen peroxide at low potential (~0.09 V) and the detection of a biocontaminant inhibitor (organophosphorus pesticide) in a wide range of concentrations. This efficiency comes from the chemical immobilization of catalysts (Pt nanoparticles) and electron transfer-enlarging materials (carbon nanotubes) on an electrode. Especially, dendrimers raise the stable conjugation of enzymes (acetylcholinesterase/choline oxidase/peroxidase) as well as nanoparticles and carbon nanotubes on an electrode. Copyright © 2013 Elsevier Inc. All rights reserved.

Enhanced electrochemical degradation of ibuprofen in aqueous solution by PtRu alloy catalyst.

PubMed

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

2017-05-01

Electrochemical advanced oxidation processes (EAOPs) regarded as a green technology for aqueous ibuprofen treatment was investigated in this study. Multi-walled carbon nanotubes (MWCNTs), Pt nanoparticles (Pt NPs), and PtRu alloy, of which physicochemical properties were characterized by XRD and X-ray absorption spectroscopy, were used to synthesize three types of cheap and effective anodes based on commercial conductive glass. Furthermore, the operating parameters, such as the current densities, initial concentrations, and solution pH were also investigated. The intermediates determined by a UPLC-Q-TOF/MS system were used to evaluate the possible reaction pathway of ibuprofen (IBU). The results revealed that the usage of MWCNTs and PtRu alloy can effectively reduce the grain size of electrocatalysts and increase the surface activity from the XRD and XANES analysis. The results of CV analysis, degradation and mineralization efficiencies revealed that the EAOPs with PtRu-FTO anode were very effective due to advantages of the higher capacitance, CO tolerance, catalytic ability at less positive voltage and stability. The concentration trend of intermediates indicated that the potential cytotoxic to human caused by 1-(1-hydroxyenthyl)-4-isobutylbenzene was completely eliminated as the reaction time reaches 60 min. Therefore, EAOPs combined with synthesized anodes can be feasibly applied on the electrochemical degradation of ibuprofen. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of Carbon Nanotube Reinforced Nickel

NASA Technical Reports Server (NTRS)

Gill, Hansel; Hudson, Steve; Bhat, Biliyar; Munafo, Paul M. (Technical Monitor)

2002-01-01

Carbon nanotubes are cylindrical molecules composed of carbon atoms in a regular hexagonal arrangement. If nanotubes can be uniformly dispersed in a supporting matrix to form structural materials, the resulting structures could be significantly lighter and stronger than current aerospace materials. Work is currently being done to develop an electrolyte-based self-assembly process that produces a Carbon Nanotube/Nickel composite material with high specific strength. This process is expected to produce a lightweight metal matrix composite material, which maintains it's thermal and electrical conductivities, and is potentially suitable for applications such as advanced structures, space based optics, and cryogenic tanks.

Vibration characteristics of functionally graded carbon nanotube reinforced composite rectangular plates on Pasternak foundation with arbitrary boundary conditions and internal line supports

NASA Astrophysics Data System (ADS)

Zhong, Rui; Wang, Qingshan; Tang, Jinyuan; Shuai, Cijun; Liang, Qian

2018-02-01

This paper presents the first known vibration characteristics of moderately thick functionally graded carbon nanotube reinforced composite rectangular plates on Pasternak foundation with arbitrary boundary conditions and internal line supports on the basis of the firstorder shear deformation theory. Different distributions of single walled carbon nanotubes (SWCNTs) along the thickness are considered. Uniform and other three kinds of functionally graded distributions of carbon nanotubes along the thickness direction of plates are studied. The solutions carried out using an enhanced Ritz method mainly include the following three points: Firstly, create the Lagrange energy function by the energy principle; Secondly, as the main innovation point, the modified Fourier series are chosen as the basic functions of the admissible functions of the plates to eliminate all the relevant discontinuities of the displacements and their derivatives at the edges; Lastly, solve the natural frequencies as well as the associated mode shapes by means of the Ritz-variational energy method. In this study, the influences of the volume fraction of CNTs, distribution type of CNTs, boundary restrain parameters, location of the internal line supports, foundation coefficients on the natural frequencies and mode shapes of the FG-CNT reinforced composite rectangular plates are presented.

Magnetic nanotubes

DOEpatents

Matsui, Hiroshi; Matsunaga, Tadashi

2010-11-16

A magnetic nanotube includes bacterial magnetic nanocrystals contacted onto a nanotube which absorbs the nanocrystals. The nanocrystals are contacted on at least one surface of the nanotube. A method of fabricating a magnetic nanotube includes synthesizing the bacterial magnetic nanocrystals, which have an outer layer of proteins. A nanotube provided is capable of absorbing the nanocrystals and contacting the nanotube with the nanocrystals. The nanotube is preferably a peptide bolaamphiphile. A nanotube solution and a nanocrystal solution including a buffer and a concentration of nanocrystals are mixed. The concentration of nanocrystals is optimized, resulting in a nanocrystal to nanotube ratio for which bacterial magnetic nanocrystals are immobilized on at least one surface of the nanotubes. The ratio controls whether the nanocrystals bind only to the interior or to the exterior surfaces of the nanotubes. Uses include cell manipulation and separation, biological assay, enzyme recovery, and biosensors.

Carbon nanotube fiber spun from wetted ribbon

DOEpatents

Zhu, Yuntian T; Arendt, Paul; Zhang, Xiefei; Li, Qingwen; Fu, Lei; Zheng, Lianxi

2014-04-29

A fiber of carbon nanotubes was prepared by a wet-spinning method involving drawing carbon nanotubes away from a substantially aligned, supported array of carbon nanotubes to form a ribbon, wetting the ribbon with a liquid, and spinning a fiber from the wetted ribbon. The liquid can be a polymer solution and after forming the fiber, the polymer can be cured. The resulting fiber has a higher tensile strength and higher conductivity compared to dry-spun fibers and to wet-spun fibers prepared by other methods.

Plasma-Etching of Spray-Coated Single-Walled Carbon Nanotube Films for Biointerfaces

NASA Astrophysics Data System (ADS)

Kim, Joon Hyub; Lee, Jun-Yong; Min, Nam Ki

2012-08-01

We present an effective method for the batch fabrication of miniaturized single-walled carbon nanotube (SWCNT) film electrodes using oxygen plasma etching. We adopted the approach of spray-coating for good adhesion of the SWCNT film onto a pre-patterned Pt support and used O2 plasma patterning of the coated films to realize efficient biointerfaces between SWCNT surfaces and biomolecules. By these approaches, the SWCNT film can be easily integrated into miniaturized electrode systems. To demonstrate the effectiveness of plasma-etched SWCNT film electrodes as biointerfaces, Legionella antibody was selected as analysis model owing to its considerable importance to electrochemical biosensors and was detected using plasma-etched SWCNT film electrodes and a 3,3',5,5'-tetramethyl-benzidine dihydrochloride/horseradish peroxidase (TMB/HRP) catalytic system. The response currents increased with increasing concentration of Legionella antibody. This result indicates that antibodies were effectively immobilized on plasma-etched and activated SWCNT surfaces.

In situ {sup 13}C MAS NMR study of n-hexane conversion on Pt and Pd supported on basic materials. II. On the mechanism of isomerization and hydrocracking

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

Ivanova, I.I.; Seirvert, M.; Pasau-Claerbout, A.

{sup 13}C MAS NMR spectroscopy was performed in situ to investigate the mechanisms of n-hexane isomerization and hydrocracking on Pt and Pd supported on Al-stabilized magnesia (Pt/Mg(Al)O and Pd/Mg(Al)O), and Pt on KL zeolite (Pt/KL). All the catalysts had high metal dispersion, the metal particle sizes being 13, 11, and 18 {Angstrom}, respectively. n-Hexane 1-{sup 13}C was used for in situ label tracer experiments. {sup 13}C MAS NMR spectra were obtained during the time course of the reaction at 573 and 653 K. The NMR results were then quantified, and the reaction kinetics were studied. Identification of the primary andmore » secondary labeled reaction products led to the conclusion that both cyclic and bond-shift isomerization mechanisms operate on the three catalysts. In the case of Pt/Mg(Al)O, the cyclic mechanism accounts for 80% of the isomerization products. In the case of Pt/KL and Pd/Mg(Al)O, the contribution of bond-shift reactions increases due to restricted formation of the methylcyclopentane intermediate on the former and to suppressed hydrogenolysis of methylcyclopentane on the latter. A nonselective cyclic isomerization mechanism operates on magnesia catalysts, while on Pt/KL selective bisecondary bond rupturing occurs. Mechanistic pathways of bond-shift and hydrocracking reactions involve both 1,3- and 2,4-metallocyclobutane intermediates in the case of magnesia-supported catalysts, while in the case of the Pt/KL catalyst a 1,3-metallocyclobutane intermediate is preferentially formed. Only terminal scission occurs on Pt/KL. The Pd catalyst demonstrates enhanced activity in demethylation. The observed differences in the mechanistic pathways are explained on the basis of the specific properties of the metal and support. 64 refs., 14 figs., 6 tabs.« 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

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

Modification of Glucose Oxidase biofuel cell by multi-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Lotfi, Ladan; Farahbakhsh, Afshin; Aghili, Sina

2018-01-01

Biofuel cells are a subset of fuel cells that employ biocatalysts. Enzyme-based biofuel cells (EBFCs) generate electrical energy from biofuels such as glucose and ethanol, which are renewable and sustainable energy sources. Glucose biofuel cells (GBFCs) are particularly interesting nowadays due to continuous harvesting of oxygen and glucose from bioavailable substrates, activity inside the human body, and environmental benign, which generate electricity through oxidation of glucose on the anode and reduction of oxygen on the cathode. Promoting the electron transfer of redox enzymes at modified electrode utilizing Nano size materials, such as carbon nanotubes (CNT), to achieve the direct electrochemistry of enzymes has been reported. The polypyrrole-MWCNTs-glucose oxidase (PY-CNT-GOx) electrode has been investigated in the present work. Cyclic voltammetry tests were performed in a three-electrode electrochemical set-up with modified electrode (Pt/PPy/MWCNTs/GOx) was used as working electrode. Platinum flat and Ag/AgCl (saturated KCl) were used as counter electrode and the reference electrode, respectively. The biofuel cells probe was prepared by immobilizing MWCNTs at the tip of a platinum (Pt) electrode (0.5 cm2) with PPy as the support matrix We have demonstrated a well-dispersed nanomaterial PPy/MWNT, which is able to immobilize GOx firmly under the condition of the absence of any other cross-linking agent.

Effects of single-walled carbon nanotubes on lysozyme gelation.

PubMed

Tardani, Franco; La Mesa, Camillo

2014-09-01

The possibility to disperse carbon nanotubes in biocompatible matrices has got substantial interest from the scientific community. Along this research line, the inclusion of single walled carbon nanotubes in lysozyme-based hydrogels was investigated. Experiments were performed at different nanotube/lysozyme weight ratios. Carbon nanotubes were dispersed in protein solutions, in conditions suitable for thermal gelation. The state of the dispersions was determined before and after thermal treatment. Rheology, dynamic light scattering and different microscopies investigated the effect that carbon nanotubes exert on gelation. The gelation kinetics and changes in gelation temperature were determined. The effect of carbon and lysozyme content on the gel properties was, therefore, determined. At fixed lysozyme content, moderate amounts of carbon nanotubes do not disturb the properties of hydrogel composites. At moderately high volume fractions in carbon nanotubes, the gels become continuous in both lysozyme and nanotubes. This is because percolating networks are presumably formed. Support to the above statements comes by rheology. Copyright © 2014 Elsevier B.V. All rights reserved.

Biointerfacial Property of Plasma-Treated Single-Walled Carbon Nanotube Film Electrodes for Electrochemical Biosensors

NASA Astrophysics Data System (ADS)

Kim, Joon Hyub; Lee, Jun-Yong; Jin, Joon-Hyung; Park, Eun Jin; Min, Nam Ki

2013-01-01

The single-walled carbon nanotube (SWCNT)-based thin film was spray-coated on the Pt support and functionalized using O2 plasma. The effects of plasma treatment on the biointerfacial properties of the SWCNT films were analyzed by cyclic voltammogram (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). The plasma-functionalized (pf) SWCNT electrodes modified with Legionella pneumophila-specific probe DNA strands showed a much higher peak current and a smaller peak separation in differential pulse voltammetry and a lower charge transfer resistance, compared to the untreated samples. These results suggest that the pf-SWCNT films have a better electrocatalytic character and an electron transfer capability faster than the untreated SWCNTs, due to the fact that the oxygen-containing functional groups promote direct electron transfer in the biointerfacial region of the electrocatalytic activity of redox-active biomolecules.

Embedded arrays of vertically aligned carbon nanotube carpets and methods for making them

DOEpatents

Kim, Myung Jong; Nicholas, Nolan Walker; Kittrell, W. Carter; Schmidt, Howard K.

2015-06-30

According to some embodiments, the present invention provides a system and method for supporting a carbon nanotube array that involve an entangled carbon nanotube mat integral with the array, where the mat is embedded in an embedding material. The embedding material may be depositable on a carbon nanotube. A depositable material may be metallic or nonmetallic. The embedding material may be an adhesive material. The adhesive material may optionally be mixed with a metal powder. The embedding material may be supported by a substrate or self-supportive. The embedding material may be conductive or nonconductive. The system and method provide superior mechanical and, when applicable, electrical, contact between the carbon nanotubes in the array and the embedding material. The optional use of a conductive material for the embedding material provides a mechanism useful for integration of carbon nanotube arrays into electronic devices.

One-pot synthesis of ethylenediamine-connected graphene/carbon nanotube composite material for isolation of clenbuterol from pork.

PubMed

Yuan, Yanan; Jiao, Xiaoyan; Han, Yehong; Bai, Ligai; Liu, Haiyan; Qiao, Fengxia; Yan, Hongyuan

2017-09-01

A fluffy porous ethylenediamine-connected graphene/carbon nanotube composite (EGC), prepared by a simple and time-saving one-pot synthesis, was successfully applied as an adsorbent in pipette-tip solid-phase extraction (PT-SPE) for the rapid extraction and determination of clenbuterol (CLB) from pork. In the one-pot synthesis, carbon nanotubes were inserted into graphene sheets and then connected with ethylenediamine through chemical modification to form a three-dimensional framework structure to prevent agglomeration of the graphene sheets. Under the optimum conditions for extraction and determination, good linearity was achieved for CLB in the range of 15.0-1000.0ngg -1 (r=0.9998) and the recoveries at three spiked levels were in the range of 92.2-96.2% with relative standard deviation ≤9.2% (n=3). In comparison with other adsorbents, including silica, NH 2 , C 18 , and Al 2 O 3 , EGC showed higher extraction and purification efficiency for CLB from pork samples. This analytical method combines excellent adsorption performance of EGC and high extraction efficiency of PT-SPE. Copyright © 2017 Elsevier Ltd. All rights reserved.

Diameter-dependent release of a cisplatin pro-drug from small and large functionalized carbon nanotubes

NASA Astrophysics Data System (ADS)

Muzi, Laura; Ménard-Moyon, Cécilia; Russier, Julie; Li, Jian; Chin, Chee Fei; Ang, Wee Han; Pastorin, Giorgia; Risuleo, Gianfranco; Bianco, Alberto

2015-03-01

The use of platinum-based chemotherapeutic drugs in cancer therapy still suffers from severe disadvantages, such as lack of appropriate selectivity for tumor tissues and insurgence of multi-drug resistance. Moreover, drug efficacy can be attenuated by several mechanisms such as premature drug inactivation, reduced drug uptake inside cells and increased drug efflux once internalized. The use of functionalized carbon nanotubes (CNTs) as chemotherapeutic drug delivery systems is a promising strategy to overcome such limitations due to their ability to enhance cellular internalization of poorly permeable drugs and thus increase the drug bioavailability at the diseased site, compared to the free drug. Furthermore, the possibility to encapsulate agents in the nanotubes' inner cavity can protect the drug from early inactivation and their external functionalizable surface is useful for selective targeting. In this study, a hydrophobic platinum(iv) complex was encapsulated within the inner space of two different diameter functionalized multi-walled CNTs (Pt(iv)@CNTs). The behavior of the complexes, compared to the free drug, was investigated on both HeLa human cancer cells and RAW 264.7 murine macrophages. Both CNT samples efficiently induced cell death in HeLa cancer cells 72 hours after the end of exposure to CNTs. Although the larger diameter CNTs were more cytotoxic on HeLa cells compared to both the free drug and the smaller diameter nanotubes, the latter allowed a prolonged release of the encapsulated drug, thus increasing its anticancer efficacy. In contrast, both Pt(iv)@CNT constructs were poorly cytotoxic on macrophages and induced negligible cell activation and no pro-inflammatory cytokine production. Both CNT samples were efficiently internalized by the two types of cells, as demonstrated by transmission electron microscopy observations and flow cytometry analysis. Finally, the platinum levels found in the cells after Pt(iv)@CNT exposure demonstrate that they can

Single-walled carbon nanotube electromechanical switching behavior with shoulder slip

NASA Astrophysics Data System (ADS)

Ryan, Peter; Wu, Yu-Chiao; Somu, Sivasubramanian; Adams, George; McGruer, Nicol

2011-04-01

Several electromechanical devices, each consisting of a small bundle of single-walled carbon nanotubes suspended over an actuation electrode, have been fabricated and operated electrically. The nanotubes are assembled on the electrodes using dielectrophoresis, a potential high-rate nanomanufacturing process. A large decrease in the threshold voltage was seen after the first actuation. This is a result of the nanotubes sliding inward on their supports as they are pulled down toward the actuation electrode, leaving slack in the nanotube bundle for subsequent actuations. The electrical measurements agree well with an electromechanical model that uses a literature-reported value of the shear stress between the nanotubes and the SiO2 shoulders. Electrical measurements were performed in dry nitrogen as a large build-up of contamination was seen when the measurements were performed in lab air. We present measurements as well as a detailed mechanics model that support the interpretation of the data.

Flame Synthesis Used to Create Metal-Catalyzed Carbon Nanotubes

NASA Technical Reports Server (NTRS)

VanderWal, Randy L.

2001-01-01

Metal-catalyzed carbon nanotubes are highly ordered carbon structures of nanoscale dimensions. They may be thought of as hollow cylinders whose walls are formed by single atomic layers of graphite. Such cylinders may be composed of many nested, concentric atomic layers of carbon or only a single layer, the latter forming a single-walled carbon nanotube. This article reports unique results using a flame for their synthesis. Only recently were carbon nanotubes discovered within an arc discharge and recognized as fullerene derivatives. Today metal-catalyzed carbon nanotubes are of great interest for many reasons. They can be used as supports for the metal catalysts like those found in catalytic converters. Open-ended nanotubes are highly desirable because they can be filled by other elements, metals or gases, for battery and fuel cell applications. Because of their highly crystalline structure, they are significantly stronger than the commercial carbon fibers that are currently available (10 times as strong as steel but possessing one-sixth of the weight). This property makes them highly desirable for strengthening polymer and ceramic composite materials. Current methods of synthesizing carbon nanotubes include thermal pyrolysis of organometallics, laser ablation of metal targets within hydrocarbon atmospheres at high temperatures, and arc discharges. Each of these methods is costly, and it is unclear if they can be scaled for the commercial synthesis of carbon nanotubes. In contrast, flame synthesis is an economical means of bulk synthesis of a variety of aerosol materials such as carbon black. Flame synthesis of carbon nanotubes could potentially realize an economy of scale that would enable their use in common structural materials such as car-body panels. The top figure is a transmission electron micrograph of a multiwalled carbon nanotube. The image shows a cross section of the atomic structure of the nanotube. The dark lines are individual atomic layer planes of

The improvement of SiO2 nanotubes electrochemical behavior by hydrogen atmosphere thermal treatment

NASA Astrophysics Data System (ADS)

Spataru, Nicolae; Anastasescu, Crina; Radu, Mihai Marian; Balint, Ioan; Negrila, Catalin; Spataru, Tanta; Fujishima, Akira

2018-06-01

Highly defected SiO2 nanotubes (SiO2-NT) were obtained by a simple sol-gel procedure followed by calcination. Boron-doped diamond (BDD) polycrystalline films coated with SiO2-NT were used as working electrodes and, unexpectedly, cyclic voltammetric experiments have shown that the concentration of both positive and negative defects at the surface is high enough to enable redox processes involving positively charged Ru(bpy)32+/3+ to occur. Conversely, no electrochemical activity was put into evidence for Fe(CN)63-/4- species, most likely as a result of the strong electrostatic repulsion exerted by the negatively charged SiO2 surface. The concentration of surface defects was further increased by a subsequent thermal treatment in a hydrogen atmosphere which, as EIS measurements have shown, significantly promotes Ru(bpy)32+ anodic oxidation. Digital simulation of the voltammetric responses demonstrated that this treatment does not lead to a similar increase of the number of electron-donor sites. It was also found that methanol anodic oxidation at hydrogenated SiO2-NT-supported platinum results in Tafel slopes of 116-220 mV decade-1, comparable to those reported for both conventional PtRu and Pt-oxide catalysts.

High surface area synthesis, electrochemical activity, and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Chhina, H.; Campbell, S.; Kesler, O.

The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 °C and compared to that of HiSpec 4000™ Pt/Vulcan XC-72R in 0.5 M H 2SO 4. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000™. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization.

A highly durable fuel cell electrocatalyst based on double-polymer-coated carbon nanotubes

PubMed Central

Berber, Mohamed R.; Hafez, Inas H.; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2015-01-01

Driven by the demand for the commercialization of fuel cell (FC) technology, we describe the design and fabrication of a highly durable FC electrocatalyst based on double-polymer-coated carbon nanotubes for use in polymer electrolyte membrane fuel cells. The fabricated electrocatalyst is composed of Pt-deposited polybenzimidazole-coated carbon nanotubes, which are further coated with Nafion. By using this electrocatalyst, a high FC performance with a power density of 375 mW/cm2 (at 70 ˚C, 50% relative humidity using air (cathode)/H2(anode)) was obtained, and a remarkable durability of 500,000 accelerated potential cycles was recorded with only a 5% loss of the initial FC potential and 20% loss of the maximum power density, which were far superior properties compared to those of the membrane electrode assembly prepared using carbon black in place of the carbon nanotubes. The present study indicates that the prepared highly durable fuel cell electrocatalyst is a promising material for the next generation of PEMFCs. PMID:26594045

Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2 O 4 spinel in oxidizing atmosphere

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

Li, Wei-Zhen; Nie, Lei; Cheng, Yingwen

With the capability of MgAl2O4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement in Pt exposure was achieved when themore » sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. A dynamic stabilization mechanism involving wetting\

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.

Patterned Growth of Carbon Nanotubes or Nanofibers

NASA Technical Reports Server (NTRS)

Delzeit, Lance D.

2004-01-01

A method and apparatus for the growth of carbon nanotubes or nanofibers in a desired pattern has been invented. The essence of the method is to grow the nanotubes or nanofibers by chemical vapor deposition (CVD) onto a patterned catalyst supported by a substrate. The figure schematically depicts salient aspects of the method and apparatus in a typical application. A substrate is placed in a chamber that contains both ion-beam sputtering and CVD equipment. The substrate can be made of any of a variety of materials that include several forms of silicon or carbon, and selected polymers, metals, ceramics, and even some natural minerals and similar materials. Optionally, the substrate is first coated with a noncatalytic metal layer (which could be a single layer or could comprise multiple different sublayers) by ion-beam sputtering. The choice of metal(s) and thickness(es) of the first layer (if any) and its sublayers (if any) depends on the chemical and electrical properties required for subsequent deposition of the catalyst and the subsequent CVD of the carbon nanotubes. A typical first-sublayer metal is Pt, Pd, Cr, Mo, Ti, W, or an alloy of two or more of these elements. A typical metal for the second sublayer or for an undivided first layer is Al at a thickness .1 nm or Ir at a thickness .5 nm. Proper choice of the metal for a second sublayer of a first layer makes it possible to use a catalyst that is chemically incompatible with the substrate. In the next step, a mask having holes in the desired pattern is placed over the coated substrate. The catalyst is then deposited on the coated substrate by ion-beam sputtering through the mask. Optionally, the catalyst could be deposited by a technique other than sputtering and/or patterned by use of photolithography, electron- beam lithography, or another suitable technique. The catalytic metal can be Fe, Co, Ni, or an alloy of two or more of these elements, deposited to a typical thickness in the range from 0.1 to 20 nm.

A polyacrylonitrile copolymer-silica template for three-dimensional hierarchical porous carbon as a Pt catalyst support for the oxygen reduction reaction.

PubMed

Liu, Minmin; Li, Jian; Cai, Chao; Zhou, Ziwei; Ling, Yun; Liu, Rui

2017-08-01

Herein, we report a novel route to construct a hierarchical three-dimensional porous carbon (3DC) through a copolymer-silica assembly. In the synthesis, silica acts as a hard template and leads to the formation of an interconnected 3D macropore, whereas styrene-co-acrylonitrile polymer has been used as both a carbon source and a soft template for micro- and meso-pores. The obtained 3DC materials possess a large surface area (∼550.5 m 2 g -1 ), which facilitates high dispersion of Pt nanoparticles on the carbon support. The 3DC-supported Pt electrocatalyst shows excellent performance in the oxygen reduction reaction (ORR). The easy processing ability along with the characteristics of hierarchical porosity offers a new strategy for the preparation of carbon nanomaterials for energy application.

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.

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.

Synthesis Methods of Carbon Nanotubes and Related Materials

PubMed Central

Szabó, Andrea; Perri, Caterina; Csató, Anita; Giordano, Girolamo; Vuono, Danilo; Nagy, János B.

2010-01-01

The challenge on carbon nanotubes is still the subject of many research groups. While in the first years the focus was on the new synthesis methods, new carbon sources and support materials, recently, the application possibilities are the principal arguments of the studies. The three main synthesis methods discussed in this review are the arc discharge, the laser ablation and the chemical vapour deposition (CVD) with a special regard to the latter one. In the early stage of the nanotube production the first two methods were utilized mainly for the production of SWNTs while the third one produced mainly MWNTs. The principle of CVD is the decomposition of various hydrocarbons over transition metal supported catalyst. Single-walled (SWNT), multi-walled (MWNT) and coiled carbon nanotubes are produced. In some case, interesting carbonaceous materials are formed during the synthesis process, such as bamboo-like tubes, onions, horn-like structures. In this paper, we refer to the progresses made in the field of the synthesis techniques of carbon nanotubes in the last decade.

Skeletal reactions of n-hexane over Pt-NaY, Pt/SiO{sub 2}, HY, and mixed Pt/SiO{sub 2} + HY catalysts

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

Paal, Z.; Zhan, Z.; Manninger, I.

The activity and selectivity of three samples of 8% Pt-NaY calcined at 633, 723, and 823 K, respectively, have been probed with n-hexane as the model reactant at 603 K and subatmospheric pressures in a glass closed-loop reactor. These catalysts were compared with 6.3% Pt/SiO{sub 2} (EUROPT-1), HY, and a physical mixture of the latter two. The activity of all Pt-NaY catalysts is superior to EUROPT-1 and they deactivate more slowly. The selectivity pattern of all Pt-NaY samples is closer to that characteristic of monofunctional Pt catalysts, as opposed to the pronounced acidic character of pure HY and the mechanicalmore » mixtures. The sample calcined at 633 K, which has the highest dispersion and probably contains Pt particles anchored to the support as [Pt{sub n} - H{sub x}]{sup x+} entities, shows the highest aromatization selectivity. The sample precalcined at 823 K with the lowest dispersion has a pronouncedly high skeletal isomerization selectivity. The isomerization pathway may be related to the C{sub 5} cyclic route on metal sites that are more abundant on the larger crystallites of this catalyst and are more easily accessible with its partially collapsed zeolite framework. Characteristic differences between samples in the response of their catalytic performance to changes in hydrogen and hydrocarbon pressure are discussed. 37 refs., 5 figs., 4 tabs.« less

High Electrocatalytic Activity of Vertically Aligned Single-Walled Carbon Nanotubes towards Sulfide Redox Shuttles.

PubMed

Hao, Feng; Dong, Pei; Zhang, Jing; Zhang, Yongchang; Loya, Phillip E; Hauge, Robert H; Li, Jianbao; Lou, Jun; Lin, Hong

2012-01-01

Vertically aligned single-walled carbon nanotubes (VASWCNTs) have been successfully transferred onto transparent conducting oxide glass and implemented as efficient low-cost, platinum-free counter electrode in sulfide -mediated dye-sensitized solar cells (DSCs), featuring notably improved electrocatalytic activity toward thiolate/disulfide redox shuttle over conventional Pt counter electrodes. Impressively, device with VASWCNTs counter electrode demonstrates a high fill factor of 0.68 and power conversion efficiency up to 5.25%, which is significantly higher than 0.56 and 3.49% for that with a conventional Pt electrode. Moreover, VASWCNTs counter electrode produces a charge transfer resistance of only 21.22 Ω towards aqueous polysulfide electrolyte commonly applied in quantum dots-sensitized solar cells (QDSCs), which is several orders of magnitude lower than that of a typical Pt electrode. Therefore, VASWCNTs counter electrodes are believed to be a versatile candidate for further improvement of the power conversion efficiency of other iodine-free redox couple based DSCs and polysulfide electrolyte based QDSCs.

Re-examination of the Pt Particle Size Effect on the Oxygen Reduction Reaction for Ultrathin Uniform Pt/C Catalyst Layers without Influence from Nafion

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

Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.

The platinum 'particle size effect' on the oxygen reduction reaction (ORR) has been re-evaluated using commercial Pt/C catalysts (2-10 nm Pt particle) and polycrystalline Pt (poly-Pt) in 0.1 M HClO4 with a rotating disk electrode method. Nafion-free catalyst layers were employed to obtain specific activities (SA) that were not perturbed (suppressed) by sulfonate anion adsorption/blocking. By using ultrathin uniform catalyst layers, O2 diffusion limitation was minimized as confirmed from the high SAs of our supported catalysts that were comparable to unsupported sputtered Pt having controlled sizes. The specific activity (SA) steeply increased for the particle sizes in the range -2-10more » nm (0.8-1.8 mA/cm2Pt at 0.9 V vs. RHE) and plateaued over -10 nm to 2.7 mA/cm2Pt for bulk poly-Pt. On the basis of the activity trend for the range of particle sizes studied, it appears that the effect of carbon support on activity is negligible. The experimental results and the concomitant profile of SA vs. particle size was found to be in an agreement to a truncated octahedral particle model that assumes active terrace sites.« less

Synthesis, crystal structure, theoretical calculations and antimicrobial properties of [Pt(tetramethylthiourea)4] [Pt(CN)4]·4H2O

NASA Astrophysics Data System (ADS)

Sadaf, Haseeba; Isab, Anvarhusein A.; Ahmad, Saeed; Espinosa, Arturo; Mas-Montoya, Míriam; Khan, Islam Ullah; Ejaz; Rehman, Seerat-ur; Ali, Muhammad Akhtar Javed; Saleem, Muhammad; Ruiz, José; Janiak, Christoph

2015-04-01

A new platinum(II) complex, [Pt(Tmtu)4][Pt(CN)4]·4H2O (1) was synthesized by reaction of K2[PtCl4], KCN and tetramethylthiourea (Tmtu). Its structure was determined by X-ray crystallography. The [Pt(CN)4]2- anion shows regular square planar geometry at platinum, while in the [Pt(Tmtu)4]2+ cation the geometry at platinum is somewhat distorted. Hydrogen bonding between water molecules and the cyanide nitrogen of [Pt(CN)4]2- ions stabilizes the structure and leads to a supramolecular 2D network. DFT calculations support the experimentally found dinuclear (homocoordinated) ion-pair structure 1 as the most stable in comparison to noncovalent dimer [Pt(CN)2(Tmtu)2]222 that could, in turn, be involved in the formation sequence of 1. Antimicrobial activities of the complex were evaluated by minimum inhibitory concentration and the results showed that the complex exhibited moderate activities against gram-negative bacteria (Escherichiacoli, Pseudomonas aeruginosa) and molds (Aspergillus niger,Penicilliumcitrinum).

Egg derived nitrogen-self-doped carbon/carbon nanotube hybrids as noble-metal-free catalysts for oxygen reduction

NASA Astrophysics Data System (ADS)

Zhang, Jian; Wu, Siyu; Chen, Xu; Pan, Mu; Mu, Shichun

2014-12-01

Currently, the development of nitrogen (N) doped carbon based non-precious metal ORR catalysts has become one of the most attractive topics in low temperature fuel cells. Here, we demonstrate a green synthesis route of N-self-doped carbon materials by using eggs as N sources combining with iron sources and multi-walled carbon nanotubes (CE-Fe-MWNT). After carbonized, such hybrid materials possess an outstanding electrocatalytic activity towards ORR comparable to the commercial Pt/C catalyst in alkaline media, and both superior stability and fuel (methanol and CO) tolerance than the commercial Pt/C catalyst, which provide a promising alternative to noble metal catalysts by using abundant natural biological resources.

Synthesis of Highly Active Sub-Nanometer Pt@Rh Core-Shell Nanocatalyst via a Photochemical Route: Porous Titania Nanoplates as a Superior Photoactive Support.

PubMed

Zhan, Wen-Wen; Zhu, Qi-Long; Dang, Song; Liu, Zheng; Kitta, Mitsunori; Suenaga, Kazutomo; Zheng, Lan-Sun; Xu, Qiang

2017-04-01

Sub-nanometer Pt@Rh nanoparticles highly dispersed on MIL-125-derived porous TiO 2 nanoplates are successfully prepared for the first time by a photochemical route, where the porous TiO 2 nanoplates with a relatively high specific surface area play a dual role as both effective photoreductant and catalyst support. The resulting Pt@Rh/p-TiO 2 can be utilized as a highly active catalyst. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Halloysite clay nanotubes and platinum nanoparticles dispersed in ionic liquid applied in the development of a catecholamine biosensor.

PubMed

Brondani, Daniela; Scheeren, Carla Weber; Dupont, Jairton; Vieira, Iolanda Cruz

2012-08-21

Halloysite clay nanotubes were used as a support for the immobilization of the enzyme peroxidase from clover sprouts (Trifolium), and employed together with platinum nanoparticles in 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid (Pt-BMI·PF(6)) in the development of a new biosensor for the determination of catecholamines by square-wave voltammetry. Under optimized conditions, the analytical curves showed detection limits of 0.05, 0.06, 0.07, 0.12 μM for dopamine, isoproterenol, dobutamine and epinephrine, respectively. The biosensor demonstrated high sensitivity, good repeatability and reproducibility, and long-term stability (18% decrease in response over 150 days). A recovery study of dopamine in pharmaceutical samples gave values from 97.5 to 101.4%. The proposed biosensor was successfully applied to the determination of dopamine in pharmaceutical samples, with a maximum relative error of ±1.0% in relation to the standard (spectrophotometric) method. The good analytical performance of the proposed method can be attributed to the efficient immobilization of the peroxidase in the nanoclay, and the facilitation of electron transfer between the protein and the electrode surface due to the presence of the Pt nanoparticles and ionic liquid.

Inorganic nanotubes.

PubMed

Tenne, Reshef; Rao, C N R

2004-10-15

Following the discovery of carbon fullerenes and carbon nanotubes, it was hypothesized that nanoparticles of inorganic compounds with layered (two-dimensional) structure, such as MoS(2), will not be stable against folding and form nanotubes and fullerene-like structures: IF. The synthesis of numerous other inorganic nanotubes has been reported in recent years. Various techniques for the synthesis of inorganic nanotubes, including high-temperature reactions and strategies based on 'chemie douce' (soft chemistry, i.e. low-temperature) processes, are described. First-principle, density functional theory based calculations are able to provide substantial information on the structure and properties of such nanotubes. Various properties of inorganic nanotubes, including mechanical, electronic and optical properties, are described in brief. Some potential applications of the nanotubes in tribology, protection against impact, (photo)catalysis, batteries, etc., are discussed.

Trends in Adsorption Energies of the Oxygenated Species on Single Platinum Atom Embedded in Carbon Nanotubes

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

Siahrostami, Samira; Li, Guo-Ling; Nørskov, Jens K.

Herein we study the effect of strain on the catalytic activity of different Pt-doped single wall metallic carbon nanotubes (SWCNT) towards the oxygen reduction reaction (ORR). We consider the possibility of the Pt-doped at single vacancy inside the SWCNT to investigate the effect of confinement on the reaction mechanism. Density functional theory calculations indicate that for the SWCNTs with tube diameters below 7 Å, the strain energy varies significantly influencing the adsorption energies of the key intermediates of the ORR reaction. For the SWCNTs with tube diameters above 7 Å, on the other hand, both the calculated strain and themore » adsorption energies are almost constant. We furthermore find that the adsorption energies are strongly affected by confinement effects as shown for Pt-doped systems that are located inside the SWCNT. We show that the Pt-doped at single vacancy of the SWCNT strongly binds the oxygenated species under ORR potentials and therefore the active species is covered by oxo- or hydroxo group. Because the presence of Pt atoms doped at the single and double vacancies of the SWCNT is equivalently probable we also studied the Pt-doped at double vacancy. We find that the most active motif is the Pt-doped at double vacancy of SWCNT with 0.24V overpotenital.« less

Trends in Adsorption Energies of the Oxygenated Species on Single Platinum Atom Embedded in Carbon Nanotubes

DOE PAGES

Siahrostami, Samira; Li, Guo-Ling; Nørskov, Jens K.; ...

2017-09-30

Herein we study the effect of strain on the catalytic activity of different Pt-doped single wall metallic carbon nanotubes (SWCNT) towards the oxygen reduction reaction (ORR). We consider the possibility of the Pt-doped at single vacancy inside the SWCNT to investigate the effect of confinement on the reaction mechanism. Density functional theory calculations indicate that for the SWCNTs with tube diameters below 7 Å, the strain energy varies significantly influencing the adsorption energies of the key intermediates of the ORR reaction. For the SWCNTs with tube diameters above 7 Å, on the other hand, both the calculated strain and themore » adsorption energies are almost constant. We furthermore find that the adsorption energies are strongly affected by confinement effects as shown for Pt-doped systems that are located inside the SWCNT. We show that the Pt-doped at single vacancy of the SWCNT strongly binds the oxygenated species under ORR potentials and therefore the active species is covered by oxo- or hydroxo group. Because the presence of Pt atoms doped at the single and double vacancies of the SWCNT is equivalently probable we also studied the Pt-doped at double vacancy. We find that the most active motif is the Pt-doped at double vacancy of SWCNT with 0.24V overpotenital.« 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.

Polyallylamine-Rh nanosheet nanoassemblies-carbon nanotubes organic-inorganic nanohybrids: A electrocatalyst superior to Pt for the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Bai, Juan; Xing, Shi-Hui; Zhu, Ying-Ying; Jiang, Jia-Xing; Zeng, Jing-Hui; Chen, Yu

2018-05-01

Rationally tailoring the surface/interface structures of noble metal nanostructures emerges as a highly efficient method for improving their electrocatalytic activity, selectivity, and long-term stability. Recently, hydrogen evolution reaction is attracting more and more attention due to the energy crisis and environment pollution. Herein, we successfully synthesize polyallylamine-functionalized rhodium nanosheet nanoassemblies-carbon nanotube nanohybrids via a facile one-pot hydrothermal method. Three-dimensionally branched rhodium nanosheet nanoassemblies are consisted of two dimensionally atomically thick ultrathin rhodium nanosheets. The as-prepared polyallylamine-functionalized rhodium nanosheet nanoassemblies-carbon nanotube nanohybrids show the excellent electrocatalytic activity for the hydrogen evolution reaction in acidic media, with a low onset reduction potential of -1 mV, a small overpotential of 5 mV at 10 mA cm-2, which is much superior to commercial platinum nanocrystals. Two dimensionally ultrathin morphology of rhodium nanosheet, particular rhodium-polyallylamine interface, and three-dimensionally networks induced by carbon nanotube are the key factors for the excellent hydrogen evolution reaction activity in acidic media.

Comparative study of n-hexane aromatization on Pt/KL, Pt/Mg(Al)O, and Pt/SiO{sub 2} catalysts: Clean and sulfur-containing feeds

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

Jacobs, G.; Padro, C.L.; Resasco, D.E.

The n-hexane aromatization has been studied on Pt/KL, Pt/Mg(Al)O, and Pt/SiO{sub 2} catalysts at 773 K using sulfur-free and 0.6 ppm sulfur containing feedstocks. Examination of the product distribution as a function of conversion suggests that the formation of benzene is preceded by the formation of hexenes. In contrast with previous reports, it has been found that the Pt/KL catalyst exhibits much higher aromatization activity than the Pt/Mg(Al)O catalyst. On Pt/KL the main product is benzene, with hexenes and lighter compounds as the principal by-products. By contrast, on the Pt/Mg(Al)O, the main products were hexenes. Since hexenes are primary productsmore » and benzene is a secondary product, the exceptional aromatization activity of Pt/KL is explained in terms of its ability to convert hexene into benzene. In the presence of sulfur, the Pt/KL exhibits a rapid loss in n-hexane conversion and benzene selectivity. Under these conditions, the sulfided Pt/KL catalyst presents a catalytic behavior typical of Pt/Mg(Al)O and Pt/SiO{sub 2}, generating larger amounts of hexenes. The observed results are consistent with the hypothesis that the most important role of the zeolite is to inhibit bimolecular interactions that lead to coke formation. The formation of coke has the net effect of selectively deactivating aromatization sites which require a large ensemble of atoms to constitute the active site but not affecting the dehydrogenation activity which is less ensemble-sensitive. Therefore, those particles that are not protected against coking inside the channels of the zeolite rapidly become unselective. In support of this hypothesis, the hydrogenolysis reaction which also requires a large ensemble of atoms, decreases in parallel with the aromatization reaction. The high sensitivity of Pt/KL to sulfur may be due to a combination of effects which may involve growth of metal particles outside the zeolite which would become unselective and partial poisoning of the

Carbon nanotubes as cancer therapeutic carriers and mediators

PubMed Central

Son, Kuk Hui; Hong, Jeong Hee; Lee, Jin Woo

2016-01-01

Carbon nanotubes (CNTs) have received increasing attention in biomedical fields because of their unique structures and properties, including high aspect ratios, large surface areas, rich surface chemical functionalities, and size stability on the nanoscale. Particularly, they are attractive as carriers and mediators for cancer therapy. Through appropriate functionalization, CNTs have been used as nanocarriers for anticancer drugs including doxorubicin, camptothecin, carboplatin, cisplatin, paclitaxel, Pt(II), and Pt(IV), and genes including plasmid DNA, small-interfering RNA, oligonucleotides, and RNA/DNA aptamers. CNTs can also deliver proteins and immunotherapy components. Using combinations of light energy, they have also been applied as mediators for photothermal therapy and photodynamic therapy to directly destroy cancer cells without severely damaging normal tissue. If limitations such as a long-term cytotoxicity in the body, lack of size uniformity during the synthetic process, loading deviations for drug–CNT complexes, and release controllability at the target point are overcome, CNTs will become one of the strongest tools that are available for various other biomedical fields as well as for cancer therapy. PMID:27785021

Platinum-doped titanate nanotubes/reduced graphene oxide: photocatalytic activity and flame retardancy

NASA Astrophysics Data System (ADS)

Liu, Guangya; Sang, Bin; Zhou, Zhiqi; Li, Zhiwei

2018-01-01

The ‘white pollution’ produced by wasted flexible polyvinyl chloride (PVC) with poor degradation ability and the potential fire hazard of PVC with high flammability not only restrict their application but also cause serious environmental problem. Thus platinum-doped titanate nanotubes/reduced graphene oxide (denoted as Pt-TNTs/rGO) nanocomposites were prepared by a facile method in order to improve the visible photodegradation and get rid of the ‘white pollution’ as well as flame retardancy of PVC. The photodegradation activity and flame retardancy effect of the as-prepared Pt-TNTs/rGO nanocomposites were investigated by ultraviolet and visible light irradiation as well as cone calorimetry. Results show that the Pt-TNTs/rGO-PVC nanocomposites exhibit enhanced visible light photodegradation performance (with mass loss being 6.5%) during 15 day exposure to solar irradiation, and good flame retardancy (providing a 44% reduction of total smoke release as compared with that of PVC matrix). Besides, Pt-TNTs/rGO-PVC nanocomposites show suppressed smoke and reduced CO production as compared with the PVC matrix. These results demonstrate that Pt-TNTs/rGO not only get rid of the ‘white pollution’ as the photocatalyst but also improve the fire safety of PVC as the flame retardant. This could be ascribed to the combination effect between Pt-TNTs and rGO. The present research, hopefully, is to pave a potential pathway to constructing polymer-matrix composites with desired photodegradation activity and flame retardancy, thereby shedding light on simultaneously dealing with the ‘white pollution’ and high flammability of polymer matrix like PVC.

Efficient Boron-Carbon-Nitrogen Nanotube Formation Via Combined Laser-Gas Flow Levitation

NASA Technical Reports Server (NTRS)

Whitney, R. Roy (Inventor); Smith, Michael W. (Inventor); Jordan, Kevin (Inventor)

2015-01-01

A process for producing boron nitride nanotubes and/or boron-carbon-nitrogen nanotubes of the general formula BxCyNz. The process utilizes a combination of laser light and nitrogen gas flow to support a boron ball target during heating of the boron ball target and production of a boron vapor plume which reacts with nitrogen or nitrogen and carbon to produce boron nitride nanotubes and/or boron-carbon-nitrogen nanotubes of the general formula BxCyNz.

Platinum decorated carbon nanotubes for highly sensitive amperometric glucose sensing

NASA Astrophysics Data System (ADS)

Xie, Jining; Wang, Shouyan; Aryasomayajula, L.; Varadan, V. K.

2007-02-01

Fine platinum nanoparticles (1-5 nm in diameter) were deposited on functionalized multi-walled carbon nanotubes (MWNTs) through a decoration technique. A novel type of enzymatic Pt/MWNTs paste-based mediated glucose sensor was fabricated. Electrochemical measurements revealed a significantly improved sensitivity (around 52.7 µA mM-1 cm-2) for glucose sensing without using any picoampere booster or Faraday cage. In addition, the calibration curve exhibited a good linearity in the range of 1-28 mM of glucose concentration. Transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS) were performed to investigate the nanoscale structure and the chemical bonding information of the Pt/MWNTs paste-based sensing material, respectively. The improved sensitivity of this novel glucose sensor could be ascribed to its higher electroactive surface area, enhanced electron transfer, efficient enzyme immobilization, unique interaction in nanoscale and a synergistic effect on the current signal from possible multi-redox reactions.

Nanotube junctions

DOEpatents

Crespi, Vincent Henry; Cohen, Marvin Lou; Louie, Steven Gwon; Zettl, Alexander Karlwalte

2004-12-28

The present invention comprises a new nanoscale metal-semiconductor, semiconductor-semiconductor, or metal-metal junction, designed by introducing topological or chemical defects in the atomic structure of the nanotube. Nanotubes comprising adjacent sections having differing electrical properties are described. These nanotubes can be constructed from combinations of carbon, boron, nitrogen and other elements. The nanotube can be designed having different indices on either side of a junction point in a continuous tube so that the electrical properties on either side of the junction vary in a useful fashion. For example, the inventive nanotube may be electrically conducting on one side of a junction and semiconducting on the other side. An example of a semiconductor-metal junction is a Schottky barrier. Alternatively, the nanotube may exhibit different semiconductor properties on either side of the junction. Nanotubes containing heterojunctions, Schottky barriers, and metal-metal junctions are useful for microcircuitry.

Nanotube junctions

DOEpatents

Crespi, Vincent Henry; Cohen, Marvin Lou; Louie, Steven Gwon Sheng; Zettl, Alexander Karlwalter

2003-01-01

The present invention comprises a new nanoscale metal-semiconductor, semiconductor-semiconductor, or metal-metal junction, designed by introducing topological or chemical defects in the atomic structure of the nanotube. Nanotubes comprising adjacent sections having differing electrical properties are described. These nanotubes can be constructed from combinations of carbon, boron, nitrogen and other elements. The nanotube can be designed having different indices on either side of a junction point in a continuous tube so that the electrical properties on either side of the junction vary in a useful fashion. For example, the inventive nanotube may be electrically conducting on one side of a junction and semiconducting on the other side. An example of a semiconductor-metal junction is a Schottky barrier. Alternatively, the nanotube may exhibit different semiconductor properties on either side of the junction. Nanotubes containing heterojunctions, Schottky barriers, and metal-metal junctions are useful for microcircuitry.

Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2O 4 spinel in oxidizing atmosphere

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

Li, Wei -Zhen; Nie, Lei; Cheng, Yingwen

With the capability of MgAl 2O 4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated in this paper, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2 nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement inmore » Pt exposure was achieved when the sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H 2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. Finally, a dynamic stabilization mechanism involving wetting/nucleation seems to be responsible for the evolution of surface compositions upon cyclic oxidizing and reducing thermal treatments.« less

Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2O 4 spinel in oxidizing atmosphere

DOE PAGES

Li, Wei -Zhen; Nie, Lei; Cheng, Yingwen; ...

2017-01-13

With the capability of MgAl 2O 4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated in this paper, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2 nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement inmore » Pt exposure was achieved when the sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H 2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. Finally, a dynamic stabilization mechanism involving wetting/nucleation seems to be responsible for the evolution of surface compositions upon cyclic oxidizing and reducing thermal treatments.« less

Carbon-Nanotube-Carpet Heat-Transfer Pads

NASA Technical Reports Server (NTRS)

Li, Jun; Cruden, Brett A.; Cassel, Alan M.

2006-01-01

Microscopic thermal-contact pads that include carpet-like arrays of carbon nanotubes have been invented for dissipating heat generated in integrated circuits and similarly sized single electronic components. The need for these or other innovative thermal-contact pads arises because the requisite high thermal conductances cannot be realized by scaling conventional macroscopic thermal-contact pads down to microscopic sizes. Overcoming limitations of conventional thermal-contact materials and components, the carbon-nanotube thermal-contact pads offer the high thermal conductivities needed to accommodate the high local thermal power densities of modern electronic circuits, without need for large clamping pressures, extreme smoothness of surfaces in contact, or gap-filling materials (e.g., thermally conductive greases) to ensure adequate thermal contact. Moreover, unlike some conventional thermal-contact components, these pads are reusable. The figure depicts a typical pad according to the invention, in contact with a rough surface on an electronic component that is to be cooled. Through reversible bending and buckling of carbon nanotubes at asperities on the rough surface, the pad yields sufficiently, under relatively low contact pressure, that thermal contact is distributed to many locations on the surface to be cooled, including valleys where contact would not ordinarily occur in conventional clamping of rigid surfaces. Hence, the effective thermal-contact area is greater than that achievable through scaling down of a macroscopic thermal-contact pad. The extremely high longitudinal thermal conductivities of the carbon nanotubes are utilized to conduct heat away from potential hot spots on the surface to be cooled. The fibers protrude from a layer of a filler material (Cu, Ag, Au, or metal-particle- filled gels), which provides both mechanical support to maintain the carbon nanotubes in alignment and thermal conductivity to enhance the diffusion of concentrated heat

Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

2016-02-01

High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

Efficient Boron Nitride Nanotube Formation via Combined Laser-Gas Flow Levitation

NASA Technical Reports Server (NTRS)

Whitney, R. Roy (Inventor); Jordan, Kevin (Inventor); Smith, Michael W. (Inventor)

2014-01-01

A process for producing boron nitride nanotubes and/or boron-carbon-nitrogen nanotubes of the general formula B(sub x)C(sub y)N(sub z) The process utilizes a combination of laser light and nitrogen gas flow to support a boron ball target during heating of the boron ball target and production of a boron vapor plume which reacts with nitrogen or nitrogen and carbon to produce boron nitride nanotubes and/or boron-carbon-nitrogen nanotubes of the general formula B(sub x)C(sub y)N(sub z).

Efficient boron nitride nanotube formation via combined laser-gas flow levitation

DOEpatents

Whitney, R. Roy; Jordan, Kevin; Smith, Michael

2014-03-18

A process for producing boron nitride nanotubes and/or boron-carbon-nitrogen nanotubes of the general formula B.sub.xC.sub.yN.sub.z. The process utilizes a combination of laser light and nitrogen gas flow to support a boron ball target during heating of the boron ball target and production of a boron vapor plume which reacts with nitrogen or nitrogen and carbon to produce boron nitride nanotubes and/or boron-carbon-nitrogen nanotubes of the general formula B.sub.xC.sub.yN.sub.z.

Electrocatalytic CO2 reduction near the theoretical potential in water using Ru complex supported on carbon nanotubes

NASA Astrophysics Data System (ADS)

Sato, Shunsuke; Arai, Takeo; Morikawa, Takeshi

2018-01-01

We successfully developed a highly efficient electrode for CO2 reduction using a Ru-complex catalyst ([Ru]) supported on carbon paper coated with multi-walled carbon nanotubes (CPCNT/[Ru]). The CPCNT/[Ru] electrode promoted the CO2 reduction reaction in aqueous solution near the theoretical potential, and produced formate linearly with a current density of greater than 0.9 mA cm-2 at -0.15 V (versus RHE) for at least 24 h. Due to the outstandingly low overpotential, a monolithic tablet-shaped photo-device was realized by coupling the CPCNT/[Ru] catalyst with amorphous SiGe-jn as a light absorber and IrO x as a water oxidation catalyst, and the device produced formate from CO2 and water in a single-compartment reactor. The nanotubes enhanced the rate for CO2 reduction at [Ru], and accordingly a solar-to-chemical conversion efficiency of 4.3% for formate production was achieved when the CO2 reduction and H2O oxidation sites had the same area.

Assembly of Modified Ferritin Proteins on Carbon Nanotubes and its Electrocatalytic Activity for Oxygen Reduction

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Lillehei, Peter T.; Park, Cheol

2012-01-01

Highly effective dispersions of carbon nanotubes (CNTs) can be made using a commercially available buffer solution. Buffer solutions of 3-(N-morpholino)-propanesulfonic acid (MOPS), which consists of a cyclic ring with nitrogen and oxygen heteroatoms, a charged group, and an alkyl chain greatly enhance the dispersibility and stability of CNTs in aqueous solutions. Additionally, the ability of biomolecules, especially cationized Pt-cored ferritins, to adhere onto the well-dispersed CNTs in the aqueous buffer solution is also improved. This was accomplished without the use of surfactant molecules, which are detrimental to the electrical, mechanical, and other physical properties of the resulting products. The assembled Pt-cored ferritin proteins on the CNTs were used as an electrocatalyst for oxygen reduction

Improved reaction kinetics and selectivity by the TiO2-embedded carbon nanofiber support for electro-oxidation of ethanol on PtRu nanoparticles

NASA Astrophysics Data System (ADS)

Nakagawa, Nobuyoshi; Ito, Yudai; Tsujiguchi, Takuya; Ishitobi, Hirokazu

2014-02-01

The electro-oxidation of ethanol by the catalyst of PtRu nanoparticles supported on a TiO2-embedded carbon nanofiber (PtRu/TECNF), which has recently been proposed by the authors as a highly active catalyst for methanol oxidation, is investigated by cyclic voltammetry using a glassy carbon electrode and by operating a direct ethanol fuel cell (DEFC) with the catalyst. The mass activity obtained from the cyclic voltammogram for the ethanol oxidation is compared to that for the methanol oxidation reported in our recent paper. The mass activity for the ethanol oxidation is comparable or slightly higher than that for the methanol oxidation, and the relationship between the TECNF composition, i.e., the Ti/C mass ratio, and the activity are also similar to that for the methanol oxidation. A DEFC fabricated with the PtRu/TECNF shows a higher power output compared to that with the commercial PtRu/C catalyst. An analysis of the reaction products by a simple two-step reaction model reveals that the PtRu/TECNF increases the rate constant for the reaction steps from ethanol to acetaldehyde and subsequently to CO2, but decreases that from acetaldehyde to acetic acid. This means that the PtRu/TECNF improves not only the kinetics, but also the selectivity to acetaldehyde.

Palladium-cobalt nanotube arrays supported on carbon fiber cloth as high-performance flexible electrocatalysts for ethanol oxidation.

PubMed

Wang, An-Liang; He, Xu-Jun; Lu, Xue-Feng; Xu, Han; Tong, Ye-Xiang; Li, Gao-Ren

2015-03-16

PdCo nanotube arrays (NTAs) supported on carbon fiber cloth (CFC) (PdCo NTAs/CFC) are presented as high-performance flexible electrocatalysts for ethanol oxidation. The fabricated flexible PdCo NTAs/CFC exhibits significantly improved electrocatalytic activity and durability compared with Pd NTAs/CFC and commercial Pd/C catalysts. Most importantly, the PdCo NTAs/CFC shows excellent flexibility and the high electrocatalytic performance remains almost constant under the different distorted states, such as normal, bending, and twisting states. This work shows the first example of Pd-based alloy NTAs supported on CFC as high-performance flexible electrocatalysts for ethanol oxidation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural resolution of inorganic nanotubes with complex stoichiometry.

PubMed

Monet, Geoffrey; Amara, Mohamed S; Rouzière, Stéphan; Paineau, Erwan; Chai, Ziwei; Elliott, Joshua D; Poli, Emiliano; Liu, Li-Min; Teobaldi, Gilberto; Launois, Pascale

2018-05-23

Determination of the atomic structure of inorganic single-walled nanotubes with complex stoichiometry remains elusive due to the too many atomic coordinates to be fitted with respect to X-ray diffractograms inherently exhibiting rather broad features. Here we introduce a methodology to reduce the number of fitted variables and enable resolution of the atomic structure for inorganic nanotubes with complex stoichiometry. We apply it to recently synthesized methylated aluminosilicate and aluminogermanate imogolite nanotubes of nominal composition (OH) 3 Al 2 O 3 Si(Ge)CH 3 . Fitting of X-ray scattering diagrams, supported by Density Functional Theory simulations, reveals an unexpected rolling mode for these systems. The transferability of the approach opens up for improved understanding of structure-property relationships of inorganic nanotubes to the benefit of fundamental and applicative research in these systems.

Fabrication of titanium dioxide nanotube arrays using organic electrolytes

NASA Astrophysics Data System (ADS)

Yoriya, Sorachon

to ~2 microm. In comparison to DMSO electrolyte, the electrochemical anodization rates are relatively slower in DEG electrolyte; as a result, the nanotube length is typically less than 10 microm. Pore size of nanotubes grown in DEG has been extended from 150 nm up to approximately 400 nm. The approach to pore widening could be achieved by using a specific condition of low HF concentration and prolonged anodization time. The study of evolution of nanotubes grown in DEG electrolytes showed that a fibrous layer was formed in the early growth stages and then was chemically and gradually removed after a long duration, leaving behind the nanotubes with large pore size. In DEG electrolyte, the closer spacing between Ti and Pt electrodes resulted in the larger nanotube morphological parameters due to the enhanced electrode kinetics facilitating the electrode reactions. Furthermore, this dissertation showed possibilities to crystallize the titania nanotube array films at room temperature via anodization in either DMSO or DEG electrolytes. The partially crystallized films could be achieved specifically in the optimum slow growth process conditions. Due to partial crystallization of the as-anodized samples, the high temperature annealing study revealed that the temperatures of phase transformation are 260 ºC and 430°C for respectively amorphous to anatase and anatase to rutile, which are accounted as the lowest phase transformation temperatures reported to date (2010). Finally, the photoelectrochemical properties of the DMSO fabricated nanotubes were investigated. The maximum photocurrent density of ~ 11 mA cm--2 was achieved by using the 46-microm long nanotube array sample with completely open pores, and photoconversion efficiencies of 5.425 % (+/- 0.087) (under UV light) and 0.197 % (+/- 0.001) (under solar spectrum AM 1.5) have been demonstrated. Biomedical applications of the DEG fabricated nanotube arrays films such as blood clotting, hemocompatibility, and drug

Ultralow charge-transfer resistance with ultralow Pt loading for hydrogen evolution and oxidation using Ru@Pt core-shell nanocatalysts

DOE PAGES

Wang, Jia X.; Zhang, Yu; Capuano, Christopher B.; ...

2015-07-15

We evaluated the activities of well-defined Ru@Pt core-shell nanocatalysts for hydrogen evolution and oxidation reactions (HER-HOR) using hanging strips of gas diffusion electrode (GDE) in solution cells. With gas transport limitation alleviated by micro-porous channels in the GDEs, the charge transfer resistances (CTRs) at the hydrogen reversible potential were conveniently determined from linear fit of ohmic-loss-corrected polarization curves. In 1M HClO₄ at 23°C, a CTR as low as 0.04 Ω cm² was obtained with only 20 μg cm⁻² Pt and 11 μg cm⁻² Ru using the carbon-supported Ru@Pt with 1:1 Ru:Pt atomic ratio. Derived from temperature-dependent CTRs, the activation barriermore » of the Ru@Pt catalyst for the HER-HOR in acids is 0.2 eV or 19 kJ mol⁻¹. Using the Ru@Pt catalyst with total metal loadings <50 μg cm⁻² for the HER in proton-exchange-membrane water electrolyzers, we recorded uncompromised activity and durability compared to the baseline established with 3 mg cm⁻² Pt black.« less

Strong metal support interaction of Pt on TiO2 grown by atomic layer deposition and physical vapor deposition for fuel cell applications

NASA Astrophysics Data System (ADS)

Hansen, Robin Paul

Several roadblocks prevent the large-scale commercialization of hydrogen fuel cells, including the stability of the Pt catalysts and their substrates, as well as the high cost of Pt. This is particularly true for the cathode, which requires a higher Pt loading because of the slow kinetics of the oxygen reduction reaction (ORR). The problem with the stability of the substrate can be solved by replacing the traditional carbon support with a conductive metal oxide such as reduced TiO2, which will not easily corrode and should result in longer lasting fuel cells. In this study, Pt was deposited either by atomic layer deposition (ALD) or physical vapor deposition (PVD). The typical size of the Pt islands that were grown using these deposition techniques was 3-8 nm. One factor that can inhibit the catalytic activity of a metal catalyst on a metal oxide is the strong metal support interaction (SMSI). This is where a metal on a reducible metal oxide can be encapsulated by a layer of the metal oxide support material at elevated temperatures. The processing of materials through atomic layer deposition can exceed this temperature. The TiO2 substrates used in this study were either grown by ALD, which results in a polycrystalline anatase film, or were single-crystal rutile TiO2(110) samples prepared in ultra-high vacuum (UHV). The Pt/TiO2 samples were tested electrochemically using cyclic voltammetry (CV) to determine the level of catalytic activity. To determine the effect of the SMSI interaction on the catalytic activity of the PVD grown samples, CV was performed on samples that were annealed in high vacuum after Pt deposition. Additional characterization was performed with scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectrometry (RBS), and four point probe analysis. Platinum that was deposited by PVD was used as a standard since it is not affected by the SMSI at the low temperature of the substrate during deposition

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

Functional materials based on carbon nanotubes: Carbon nanotube actuators and noncovalent carbon nanotube modification

NASA Astrophysics Data System (ADS)

Fifield, Leonard S.

Carbon nanotubes have attractive inherent properties that encourage the development of new functional materials and devices based on them. The use of single wall carbon nanotubes as electromechanical actuators takes advantage of the high mechanical strength, surface area and electrical conductivity intrinsic to these molecules. The work presented here investigates the mechanisms that have been discovered for actuation of carbon nanotube paper: electrostatic, quantum chemical charge injection, pneumatic and viscoelastic. A home-built apparatus for the measurement of actuation strain is developed and utilized in the investigation. An optical fiber switch, the first demonstrated macro-scale device based on the actuation of carbon nanotubes, is described and its performance evaluated. Also presented here is a new general process designed to modify the surface of carbon nanotubes in a non-covalent, non-destructive way. This method can be used to impart new functionalities to carbon nanotube samples for a variety of applications including sensing, solar energy conversion and chemical separation. The process described involves the achievement of large degrees of graphitic surface coverage with polycyclic aromatic hydrocarbons through the use of supercritical fluids. These molecules are bifunctional agents that anchor a desired chemical group to the aromatic surface of the carbon nanotubes without adversely disrupting the conjugated backbone that gives rise the attractive electronic and physical properties of the nanotubes. Both the nanotube functionalization work and the actuator work presented here emphasize how an understanding and control of nanoscale structure and phenomena can be of vital importance in achieving desired performance for active materials. Opportunities for new devices with improved function over current state-of-the-art can be envisioned and anticipated based on this understanding and control.

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.

Novel synthesis of core-shell Au-Pt dendritic nanoparticles supported on carbon black for enhanced methanol electro-oxidation

NASA Astrophysics Data System (ADS)

Cao, Ribing; Xia, Tiantian; Zhu, Ruizhi; Liu, Zhihua; Guo, Jinming; Chang, Gang; Zhang, Zaoli; Liu, Xiong; He, Yunbin

2018-03-01

Core-shell Au-Pt dendritic nanoparticles (Au-Pt NPs) has been synthesized via a facile seed-mediated growth method, in which dendritic Pt nanoparticles as shell grow on the surface of gold nanocores by using ascorbic acid (AA) as "green" reducing reagents. The morphologies and compositions of the as-prepared nanocomposites with core-shell structure are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Electrochemical experiments, including cyclic voltammetry (CV) and chronoamperometry (CA) are performed to investigate the electrocatalytic properties of the Au-Pt NPs loaded carbon black composites (Au-Pt NPs/V) towards methanol oxidation in an alkaline solution. It is found that the reduction time of AA could regulate the thickness and amount of Pt on the Au nanocores, which significantly affect catalytic activity of the Au-Pt NPs/V toward methanol oxidation. Au-Pt NPs/V with optimum reduction time 4 h exhibit 2.3-times higher electrocatalytic activity than that of a commercial catalyst (Pt/carbon black) and an excellent CO tolerance toward methanol oxidation. This behavior is attributed to large active electrochemical area of the bimetallic nanocomposites and the change in the electronic structure of Pt when Au surface modified with fewer Pt nanoparticles.

A study of the dispersity of iron oxide and iron oxide-noble metal (Me = Pd, Pt) supported systems

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Z. P.; Shopska, M. G.; Krstić, J. B.; Jovanović, D. M.; Mitov, I. G.; Kadinov, G. B.

2007-09-01

Samples of one-(Fe) and two-component (Fe-Pd and Fe-Pt) catalysts were prepared by incipient wetness impregnation of four different supports: TiO2 (anatase), γ-Al2O3, activated carbon, and diatomite. The chosen synthesis conditions resulted in the formation of nanosized supported phases—iron oxide (in the one-component samples), or iron oxide-noble metal (in the two-component ones). Different agglomeration degrees of these phases were obtained as a result of thermal treatment. Ultradisperse size of the supported phase was maintained in some samples, while a process of partial agglomeration occurred in others, giving rise to nearly bidisperse (ultra-and highdisperse) supported particles. The different texture of the used supports and their chemical composition are the reasons for the different stability of the nanosized supported phases. The samples were tested as heterogeneous catalysts in total benzene oxidation reaction.

Ecotoxicity of halloysite nanotube-supported palladium nanoparticles in Raphanus sativus L.

PubMed

Bellani, Lorenza; Giorgetti, Lucia; Riela, Serena; Lazzara, Giuseppe; Scialabba, Anna; Massaro, Marina

2016-10-01

Halloysite nanotubes (HNTs) are natural nanomaterials that are biocompatible and available in large amounts at low prices. They are emerging nanomaterials with appealing properties for applications like support for metal nanoparticles (NPs). The potential environmental impacts of NPs can be understood in terms of phytotoxicity. Current research has been focusing on HNT applications in cell or animal models, while their use in plants is limited so their ecotoxicological impact is poorly documented. To date there are no studies on the phytotoxic effects of functionalized halloysites (functionalized-HNTs). To develop a quantitative risk assessment model for predicting the potential impact of HNT-supported palladium nanoparticles (HNT-PdNPs) on plant life, an investigation was undertaken to explore their effects on seed germination, seedling development, and mitotic division in root tip cells of 2 lots of Raphanus sativus L. with different vigor. The results showed that exposure to 1500 mg/L of HNTs, functionalized-HNTs, and HNT-PdNPs had no significant influence on germination, seedling development, xylem differentiation, or mitotic index in both lots. Cytogenetic analyses revealed that treatments with functionalized-HNT significantly increased the number of aberrations in low-vigor seeds. These results suggest that low-vigor seeds represent a model for a stress test that would be useful to monitor the effects of NPs. Moreover the present study offers scientific evidence for the use of halloysite for environmental purposes, supporting the biological safety of HNT-PdNPs. Environ Toxicol Chem 2016;35:2503-2510. © 2016 SETAC. © 2016 SETAC.

Remote Joule heating by a carbon nanotube.

PubMed

Baloch, Kamal H; Voskanian, Norvik; Bronsgeest, Merijntje; Cumings, John

2012-04-08

Minimizing Joule heating remains an important goal in the design of electronic devices. The prevailing model of Joule heating relies on a simple semiclassical picture in which electrons collide with the atoms of a conductor, generating heat locally and only in regions of non-zero current density, and this model has been supported by most experiments. Recently, however, it has been predicted that electric currents in graphene and carbon nanotubes can couple to the vibrational modes of a neighbouring material, heating it remotely. Here, we use in situ electron thermal microscopy to detect the remote Joule heating of a silicon nitride substrate by a single multiwalled carbon nanotube. At least 84% of the electrical power supplied to the nanotube is dissipated directly into the substrate, rather than in the nanotube itself. Although it has different physical origins, this phenomenon is reminiscent of induction heating or microwave dielectric heating. Such an ability to dissipate waste energy remotely could lead to improved thermal management in electronic devices.

Remote Joule heating by a carbon nanotube

NASA Astrophysics Data System (ADS)

Baloch, Kamal H.; Voskanian, Norvik; Bronsgeest, Merijntje; Cumings, John

2012-05-01

Minimizing Joule heating remains an important goal in the design of electronic devices. The prevailing model of Joule heating relies on a simple semiclassical picture in which electrons collide with the atoms of a conductor, generating heat locally and only in regions of non-zero current density, and this model has been supported by most experiments. Recently, however, it has been predicted that electric currents in graphene and carbon nanotubes can couple to the vibrational modes of a neighbouring material, heating it remotely. Here, we use in situ electron thermal microscopy to detect the remote Joule heating of a silicon nitride substrate by a single multiwalled carbon nanotube. At least 84% of the electrical power supplied to the nanotube is dissipated directly into the substrate, rather than in the nanotube itself. Although it has different physical origins, this phenomenon is reminiscent of induction heating or microwave dielectric heating. Such an ability to dissipate waste energy remotely could lead to improved thermal management in electronic devices.

Electroluminescence from single-wall carbon nanotube network transistors.

PubMed

Adam, E; Aguirre, C M; Marty, L; St-Antoine, B C; Meunier, F; Desjardins, P; Ménard, D; Martel, R

2008-08-01

The electroluminescence (EL) properties from single-wall carbon nanotube network field-effect transistors (NNFETs) and small bundle carbon nanotube field effect transistors (CNFETs) are studied using spectroscopy and imaging in the near-infrared (NIR). At room temperature, NNFETs produce broad (approximately 180 meV) and structured NIR spectra, while they are narrower (approximately 80 meV) for CNFETs. EL emission from NNFETs is located in the vicinity of the minority carrier injecting contact (drain) and the spectrum of the emission is red shifted with respect to the corresponding absorption spectrum. A phenomenological model based on a Fermi-Dirac distribution of carriers in the nanotube network reproduces the spectral features observed. This work supports bipolar (electron-hole) current recombination as the main mechanism of emission and highlights the drastic influence of carrier distribution on the optoelectronic properties of carbon nanotube films.

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.

Efficient boron-carbon-nitrogen nanotube formation via combined laser-gas flow levitation

DOEpatents

Whitney, R Roy; Jordan, Kevin; Smith, Michael W

2015-03-24

A process for producing boron nitride nanotubes and/or boron-carbon-nitrogen nanotubes of the general formula B.sub.xC.sub.yN.sub.z. The process utilizes a combination of laser light and nitrogen gas flow to support a boron ball target during heating of the boron ball target and production of a boron vapor plume which reacts with nitrogen or nitrogen and carbon to produce boron nitride nanotubes and/or boron-carbon-nitrogen nanotubes of the general formula B.sub.xC.sub.yN.sub.z.

Switching and Rectification in Carbon-Nanotube Junctions

NASA Technical Reports Server (NTRS)

Srivastava, Deepak; Andriotis, Antonis N.; Menon, Madhu; Chernozatonskii, Leonid

2003-01-01

Multi-terminal carbon-nanotube junctions are under investigation as candidate components of nanoscale electronic devices and circuits. Three-terminal "Y" junctions of carbon nanotubes (see Figure 1) have proven to be especially interesting because (1) it is now possible to synthesize them in high yield in a controlled manner and (2) results of preliminary experimental and theoretical studies suggest that such junctions could exhibit switching and rectification properties. Following the preliminary studies, current-versus-voltage characteristics of a number of different "Y" junctions of single-wall carbon nanotubes connected to metal wires were computed. Both semiconducting and metallic nanotubes of various chiralities were considered. Most of the junctions considered were symmetric. These computations involved modeling of the quantum electrical conductivity of the carbon nanotubes and junctions, taking account of such complicating factors as the topological defects (pentagons, heptagons, and octagons) present in the hexagonal molecular structures at the junctions, and the effects of the nanotube/wire interfaces. A major component of the computational approach was the use of an efficient Green s function embedding scheme. The results of these computations showed that symmetric junctions could be expected to support both rectification and switching. The results also showed that rectification and switching properties of a junction could be expected to depend strongly on its symmetry and, to a lesser degree, on the chirality of the nanotubes. In particular, it was found that a zigzag nanotube branching at a symmetric "Y" junction could exhibit either perfect rectification or partial rectification (asymmetric current-versus-voltage characteristic, as in the example of Figure 2). It was also found that an asymmetric "Y" junction would not exhibit rectification.

Selective growth of palladium and titanium dioxide nanostructures inside carbon nanotube membranes.

PubMed

Hevia, Samuel; Homm, Pía; Cortes, Andrea; Núñez, Verónica; Contreras, Claudia; Vera, Jenniffer; Segura, Rodrigo

2012-06-25

Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors.

Selective growth of palladium and titanium dioxide nanostructures inside carbon nanotube membranes

PubMed Central

2012-01-01

Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors. PMID:22731888

Selective growth of palladium and titanium dioxide nanostructures inside carbon nanotube membranes

NASA Astrophysics Data System (ADS)

Hevia, Samuel; Homm, Pía; Cortes, Andrea; Núñez, Verónica; Contreras, Claudia; Vera, Jenniffer; Segura, Rodrigo

2012-06-01

Hybrid nanostructured arrays based on carbon nanotubes (CNT) and palladium or titanium dioxide materials have been synthesized using self-supported and silicon-supported anodized aluminum oxide (AAO) as nanoporous template. It is well demonstrated that carbon nanotubes can be grown using these membranes and hydrocarbon precursors that decompose at temperatures closer to 600°C without the use of a metal catalyst. In this process, carbonic fragments condensate to form stacked graphitic sheets, which adopt the shape of the pores, yielding from these moulds' multi-walled carbon nanotubes. After this process, the ends of the tubes remain open and accessible to other substances, whereas the outer walls are protected by the alumina. Taking advantage of this fact, we have performed the synthesis of palladium and titanium dioxide nanostructures selectively inside carbon nanotubes using these CNT-AAO membranes as nanoreactors.

Asymmetric resonance Raman excitation profiles and violation of the Condon approximation in single-wall carbon nanotubes

NASA Astrophysics Data System (ADS)

Doorn, Stephen; Duque, Juan; Telg, Hagen; Chen, Hang; Swan, Anna; Haroz, Erik; Kono, Junichiro; Tu, Xiaomin; Zheng, Ming

2012-02-01

DNA wrapping-based ion exchange chromatography and density gradient ultracentrifugation provide nanotube samples highly enriched in single chiralities. We present resonance Raman excitation profiles for the G-band of several single chirality semiconducting and metallic species. The expected incoming and outgoing resonance peaks are observed in the profiles, but contrary to long-held assumptions, the outgoing resonance is always significantly weaker than the ingoing resonance peak. This strong asymmetry in the profiles arises from a violation of the Condon approximation [1]. Results will be discussed in the context of theoretical models that suggest significant coordinate dependence in the transition dipole (non-Condon effects). The generality of the behavior across semiconducting and metallic types, nanotube family, phonon mode, and Eii will be demonstrated. [4pt] [1] J. Duque et. al., ACS Nano, 5, 5233 (2011).

Multi-walled carbon nanotubes decorated by platinum catalyst nanoparticles--examination and microanalysis using scanning and transmission electron microscopies.

PubMed

Guinel, M J-F; Brodusch, N; Verde-Gómez, Y; Escobar-Morales, B; Gauvin, R

2013-10-01

Carbon nanotubes (CNTs) decorated with platinum (Pt) nanoparticles (NPs) have been characterized using a cold field-emission scanning electron microscope (SEM) and a high resolution field-emission transmission electron microscope (TEM). With this particular composite material, the complementary nature of the two instruments was demonstrated. Although the long CNTs were found to be mostly bent and defective in some parts, the nucleation of Pt occurred randomly and uniformly covered the CNTs. The NPs displayed a large variation in size, were sometimes defective with twins and stacking faults, and were found to be faceted with the presence of surface steps. The shape and size of the NPs and the presence of defects may have significant consequences on the activity of the Pt catalyst material. Also, thin layers of platinum oxide were identified on the surface of some NPs. © 2013 The Authors Journal of Microscopy © 2013 Royal Microscopical Society.

Biopolymer protected silver nanoparticles on the support of carbon nanotube as interface for electrocatalytic applications

NASA Astrophysics Data System (ADS)

Satyanarayana, M.; Kumar, V. Sunil; Gobi, K. Vengatajalabathy

2016-04-01

In this research, silver nanoparticles (SNPs) are prepared on the surface of carbon nanotubes via chitosan, a biopolymer linkage. Here chitosan act as stabilizing agent for nanoparticles and forms a network on the surface of carbon nanotubes. Synthesized silver nanoparticles-MWCNT hybrid composite is characterized by UV-Visible spectroscopy, XRD analysis, and FESEM with EDS to evaluate the structural and chemical properties of the nanocomposite. The electrocatalytic activity of the fabricated SNP-MWCNT hybrid modified glassy carbon electrode has been evaluated by cyclic voltammetry and electrochemical impedance analysis. The silver nanoparticles are of size ˜35 nm and are well distributed on the surface of carbon nanotubes with chitosan linkage. The prepared nanocomposite shows efficient electrocatalytic properties with high active surface area and excellent electron transfer behaviour.

Carbon nanotubes: their potential and pitfalls for bone tissue regeneration and engineering.

PubMed

Newman, Peter; Minett, Andrew; Ellis-Behnke, Rutledge; Zreiqat, Hala

2013-11-01

The extracellular environment which supports cell life is composed of a hierarchy of maintenance, force and regulatory systems which integrate from the nano- through to macroscale. For this reason, strategies to recreate cell supporting environments have been investigating the use of nanocomposite biomaterials. Here, we review the use of carbon nanotubes as part of a bottom-up approach for use in bone tissue engineering. We evaluate the properties of carbon nanotubes in the context of synthetic tissue substrates and contrast them with the nanoscale features of the extracellular environment. Key studies are evaluated with an emphasis on understanding the mechanisms through which carbon nanotubes interact with biological systems. This includes an examination of how the different properties of carbon nanotubes affect tissue growth, how these properties and variation to them might be leveraged in regenerative tissue therapies and how impurities or contaminates affect their toxicity and biological interaction. In this comprehensive review, the authors describe the status and potential applications of carbon nanotubes in bone tissue engineering. © 2013.

System and method for controlling hydrogen elimination during carbon nanotube synthesis from hydrocarbons

DOEpatents

Reilly, Peter T. A.

2010-03-23

A system and method for producing carbon nanotubes by chemical vapor deposition includes a catalyst support having first and second surfaces. The catalyst support is capable of hydrogen transport from the first to the second surface. A catalyst is provided on the first surface of the catalyst support. The catalyst is selected to catalyze the chemical vapor deposition formation of carbon nanotubes. A fuel source is provided for supplying fuel to the catalyst.

Bolometric-Effect-Based Wavelength-Selective Photodetectors Using Sorted Single Chirality Carbon Nanotubes

PubMed Central

Zhang, Suoming; Cai, Le; Wang, Tongyu; Shi, Rongmei; Miao, Jinshui; Wei, Li; Chen, Yuan; Sepúlveda, Nelson; Wang, Chuan

2015-01-01

This paper exploits the chirality-dependent optical properties of single-wall carbon nanotubes for applications in wavelength-selective photodetectors. We demonstrate that thin-film transistors made with networks of carbon nanotubes work effectively as light sensors under laser illumination. Such photoresponse was attributed to photothermal effect instead of photogenerated carriers and the conclusion is further supported by temperature measurements. Additionally, by using different types of carbon nanotubes, including a single chirality (9,8) nanotube, the devices exhibit wavelength-selective response, which coincides well with the absorption spectra of the corresponding carbon nanotubes. This is one of the first reports of controllable and wavelength-selective bolometric photoresponse in macroscale assemblies of chirality-sorted carbon nanotubes. The results presented here provide a viable route for achieving bolometric-effect-based photodetectors with programmable response spanning from visible to near-infrared by using carbon nanotubes with pre-selected chiralities. PMID:26643777

Low content of Pt supported on Ni-MoCx/carbon black as a highly durable and active electrocatalyst for methanol oxidation, oxygen reduction and hydrogen evolution reactions in acidic condition

NASA Astrophysics Data System (ADS)

Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui

2017-08-01

Nickel and molybdenum carbide modified carbon black (Ni-MoCx/C) was synthesized by a two-step microwave-assisted deposition/carbonthermal reduction method and characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as-prepared Ni-MoCx/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoCx/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoCx/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoCx/C electrocatalyst had better electrocatalytic activity and stability performance than 20 wt% Pt/C (20Pt/C) electrocatalyst. Among them, the electrochemical surface area of 10Pt/Ni-MoCx/C reached 68.4 m2 g-1, which was higher than that of 20Pt/C (63.2 m2 g-1). The enhanced stability and activity of 10Pt/Ni-MoCx/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoCx formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoOx and MoCx. These findings indicated that 10Pt/Ni-MoCx/C was a promising electrocatalyst for direct methanol fuel cells.

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.

Constitutive Modeling of Nanotube/Polymer Composites with Various Nanotube Orientations

NASA Technical Reports Server (NTRS)

Odegard, Gregory M.; Gates, Thomas S.

2002-01-01

In this study, a technique has been proposed for developing constitutive models for polymer composite systems reinforced with single-walled carbon nanotubes (SWNT) with various orientations with respect to the bulk material coordinates. A nanotube, the local polymer adjacent to the nanotube, and the nanotube/polymer interface have been modeled as an equivalent-continuum fiber by using an equivalent-continuum modeling method. The equivalent-continuum fiber accounts for the local molecular structure and bonding information and serves as a means for incorporating micromechanical analyses for the prediction of bulk mechanical properties of SWNT/polymer composite. As an example, the proposed approach is used for the constitutive modeling of a SWNT/LaRC-SI (with a PmPV interface) composite system, with aligned nanotubes, three-dimensionally randomly oriented nanotubes, and nanotubes oriented with varying degrees of axisymmetry. It is shown that the Young s modulus is highly dependent on the SWNT orientation distribution.

Vertically aligned carbon nanotubes as anode and air-cathode in single chamber microbial fuel cells

NASA Astrophysics Data System (ADS)

Amade, R.; Moreno, H. A.; Hussain, S.; Vila-Costa, M.; Bertran, E.

2016-10-01

Electrode optimization in microbial fuel cells is a key issue to improve the power output and cell performance. Vertically aligned carbon nanotubes (VACNTs) grown on low cost stainless-steel mesh present an attractive approach to increase the cell performance while avoiding the use of expensive Pt-based materials. In comparison with non-aligned carbon nanotubes (NACNTs), VACNTs increase the oxygen reduction reaction taking place at the cathode by a factor of two. In addition, vertical alignment also increases the power density up to 2.5 times with respect to NACNTs. VACNTs grown at the anode can further improve the cell performance by increasing the electrode surface area and thus the electron transfer between bacteria and the electrode. The maximum power density obtained using VACNTs was 14 mW/m2 and 160 mV output voltage.

Nitrogen-Doped Ordered Mesoporous Carbon Supported Bimetallic PtCo Nanoparticles for Upgrading of Biophenolics.

PubMed

Wang, Guang-Hui; Cao, Zhengwen; Gu, Dong; Pfänder, Norbert; Swertz, Ann-Christin; Spliethoff, Bernd; Bongard, Hans-Josef; Weidenthaler, Claudia; Schmidt, Wolfgang; Rinaldi, Roberto; Schüth, Ferdi

2016-07-25

Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio-oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance. Herein we report a novel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen-doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im3‾ m) structure can be easily synthesized by simply adjusting the polymerization temperature. We also demonstrate that PtCo/NOMC (metal loading: Pt 9.90 wt %; Co 3.31 wt %) is a highly effective catalyst for HDO of phenolic compounds and "real-world" biomass-derived phenolic streams. In the presence of PtCo/NOMC, full deoxygenation of phenolic compounds and a biomass-derived phenolic stream is achieved under conditions of low severity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fe-Ni Nanoparticles supported on carbon nanotube-co-cyclodextrin polyurethanes for the removal of trichloroethylene in water

NASA Astrophysics Data System (ADS)

Krause, Rui W. M.; Mamba, Bhekie B.; Dlamini, Langelihle N.; Durbach, Shane H.

2010-02-01

Nanoscale bimetallic particles of nickel on iron were supported on carbon nanotubes and then co-polymerized with β-cyclodextrin (CNTs/CD) and the resulting polymers applied to the degradation of pollutants in water. The bimetallic nanoparticles (BMNPs) were first embedded on functionalized carbon nanotubes (f-CNTs) before being copolymerized with beta cyclodextrin (β-CD) and hexamethylene diisocyanate (HMDI) forming a water-insoluble polyurethane. The particle size and distribution of BMNPs were determined by Transmission Electron Microscopy (TEM), and the surface area was determined by using the Brunauer-Emmett-Teller (BET) method. Energy dispersive X-ray spectroscopy (EDXS) was used to confirm the formation of the BMNPs. Degradation of trichloroethylene (TCE) as a model pollutant was studied and more than 98% reduction in TCE was achieved by the polymers. Polymers with the BMNPs maintained their efficiency in degrading TCE after several cycles compared to metal-free polymers. The degradation was monitored by using gas chromatography-mass spectrometry (GC-MS), while the production of chlorides was verified by using ion chromatography (IC). Atomic absorption spectroscopy (AAS) was employed to determine the possible leaching of the BMNPs from the polymer, and confirmed to be extremely low.

A Forest of Sub-1.5-nm-wide Single-Walled Carbon Nanotubes over an Engineered Alumina Support

NASA Astrophysics Data System (ADS)

Yang, Ning; Li, Meng; Patscheider, Jörg; Youn, Seul Ki; Park, Hyung Gyu

2017-04-01

A precise control of the dimension of carbon nanotubes (CNTs) in their vertical array could enable many promising applications in various fields. Here, we demonstrate the growth of vertically aligned, single-walled CNTs (VA-SWCNTs) with diameters in the sub-1.5-nm range (0.98 ± 0.24 nm), by engineering a catalyst support layer of alumina via thermal annealing followed by ion beam treatment. We find out that the ion beam bombardment on the alumina allows the growth of ultra-narrow nanotubes, whereas the thermal annealing promotes the vertical alignment at the expense of enlarged diameters; in an optimal combination, these two effects can cooperate to produce the ultra-narrow VA-SWCNTs. According to micro- and spectroscopic characterizations, ion beam bombardment amorphizes the alumina surface to increase the porosity, defects, and oxygen-laden functional groups on it to inhibit Ostwald ripening of catalytic Fe nanoparticles effectively, while thermal annealing can densify bulk alumina to prevent subsurface diffusion of the catalyst particles. Our findings contribute to the current efforts of precise diameter control of VA-SWCNTs, essential for applications such as membranes and energy storage devices.

Oxidation of Half-Lantern Pt2(II,II) Compounds by Halocarbons. Evidence of Dioxygen Insertion into a Pt(III)-CH3 Bond.

PubMed

Sicilia, V; Baya, M; Borja, P; Martín, A

2015-08-03

The half-lantern compound [{Pt(bzq)(μ-N^S)}2] (1) [bzq = benzo[h]quinoline, HN^S = 2-mercaptopyrimidine (C4H3N2HS)] reacts with CH3I and haloforms CHX3 (X = Cl, Br, I) to give the corresponding oxidized diplatinum(III) derivatives [{Pt(bzq)(μ-N^S)X}2] (X = Cl 2a, Br 2b, I 2c). These compounds exhibit half-lantern structures with short intermetallic distances (∼2.6 Å) due to Pt-Pt bond formation. The halogen abstraction mechanisms from the halocarbon molecules by the Pt2(II,II) compound 1 were investigated. NMR spectroscopic evidence using labeled reagents support that in the case of (13)CH3I the reaction initiates with an oxidative addition through an SN2 mechanism giving rise to the intermediate species [I(bzq)Pt(μ-N^S)2Pt(bzq)((13)CH3)}]. However, with haloforms the reactions proceed through a radical-like mechanism, thermally (CHBr3, CHI3) or photochemically (CHCl3) activated, giving rise to mixtures of species [X(bzq)Pt(μ-N^S)2Pt(bzq)R] (3a-c) and [X(bzq)Pt(μ-N^S)2Pt(bzq)X] (2a-c). In these cases the presence of O2 favors the formation of species 2 over 3. Transformation of 3 into 2 was possible upon irradiation with UV light. In the case of [I(bzq)Pt(μ-N^S)2Pt(bzq)((13)CH3)}] (3d), in the presence of O2 the formation of the unusual methylperoxo derivative [I(bzq)Pt(μ-N^S)2Pt(bzq)(O-O(13)CH3)}] (4d) was detected, which in the presence of (13)CH3I rendered the final product [{Pt(bzq)(μ-N^S)I}2] (2c) and (13)CH3OH.

Photothermal optical coherence tomography for depth-resolved imaging of mesenchymal stem cells via single wall carbon nanotubes

NASA Astrophysics Data System (ADS)

Subhash, Hrebesh M.; Connolly, Emma; Murphy, Mary; Barron, Valerie; Leahy, Martin

2014-03-01

The progress in stem cell research over the past decade holds promise and potential to address many unmet clinical therapeutic needs. Tracking stem cell with modern imaging modalities are critically needed for optimizing stem cell therapy, which offers insight into various underlying biological processes such as cell migration, engraftment, homing, differentiation, and functions etc. In this study we report the feasibility of photothermal optical coherence tomography (PT-OCT) to image human mesenchymal stem cells (hMSCs) labeled with single-walled carbon nanotubes (SWNTs) for in vitro cell tracking in three dimensional scaffolds. PT-OCT is a functional extension of conventional OCT with extended capability of localized detection of absorbing targets from scattering background to provide depth-resolved molecular contrast imaging. A 91 kHz line rate, spectral domain PT-OCT system at 1310nm was developed to detect the photothermal signal generated by 800nm excitation laser. In general, MSCs do not have obvious optical absorption properties and cannot be directly visualized using PT-OCT imaging. However, the optical absorption properties of hMSCs can me modified by labeling with SWNTs. Using this approach, MSC were labeled with SWNT and the cell distribution imaged in a 3D polymer scaffold using PT-OCT.

Significant promotion effect of carbon nanotubes on the electrocatalytic activity of supported Pd NPs for ethanol oxidation reaction of fuel cells: the role of inner tubes.

PubMed

Zhang, Jin; Cheng, Yi; Lu, Shanfu; Jia, Lichao; Shen, Pei Kang; Jiang, San Ping

2014-11-18

The inner tubes of carbon nanotubes (CNTs) have a significant promotion effect on the electrocatalytic activity of Pd nanoparticles (NPs) for the ethanol oxidation of direct alcohol fuel cells (DAFCs) and Pd NPs supported on CNTs with 3-7 walls show a much higher activity as compared to that supported on typical single-walled and multi-walled CNTs.

Catalytic chemical vapor deposition synthesis and electron microscopy observation of coiled carbon nanotubes

NASA Astrophysics Data System (ADS)

Xie, Jining; Mukhopadyay, K.; Yadev, J.; Varadan, V. K.

2003-10-01

Coiled carbon nanotubes exhibit excellent mechanical and electrical properties because of the combination of coil morphology and properties of nanotubes. They could have potential novel applications in nanocomposites and nano-electronic devices as well as nano-electromechanical systems. In this work, synthesis of regularly coiled carbon nanotubes is presented. It involves pyrolysis of hydrocarbon gas over metal/support catalyst by both thermal filament and microwave catalytic chemical vapor deposition methods. Scanning electron microscopy and transmission electron microscopy were performed to observe the coil morphology and nanostructure of coiled nanotubes. The growth mechanism and structural and electrical properties of coiled carbon nanotubes are also discussed.

The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site

PubMed Central

Evans, Christopher D.; Smith, Paul J.; Manning, Troy D.; Miedziak, Peter J.; Brett, Gemma L.; Armstrong, Robert D.; Bartley, Jonathan K.; Taylor, Stuart H.; Rosseinsky, Matthew J.; Hutchings, Graham J.

2016-01-01

Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology. PMID:27074316

The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site.

PubMed

Evans, Christopher D; Kondrat, Simon A; Smith, Paul J; Manning, Troy D; Miedziak, Peter J; Brett, Gemma L; Armstrong, Robert D; Bartley, Jonathan K; Taylor, Stuart H; Rosseinsky, Matthew J; Hutchings, Graham J

2016-07-04

Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology.

Biopolymer protected silver nanoparticles on the support of carbon nanotube as interface for electrocatalytic applications

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

Satyanarayana, M.; Kumar, V. Sunil; Gobi, K. Vengatajalabathy, E-mail: drkvgobi@gmail.com, E-mail: satyam.nitw@gmail.com

In this research, silver nanoparticles (SNPs) are prepared on the surface of carbon nanotubes via chitosan, a biopolymer linkage. Here chitosan act as stabilizing agent for nanoparticles and forms a network on the surface of carbon nanotubes. Synthesized silver nanoparticles-MWCNT hybrid composite is characterized by UV-Visible spectroscopy, XRD analysis, and FESEM with EDS to evaluate the structural and chemical properties of the nanocomposite. The electrocatalytic activity of the fabricated SNP-MWCNT hybrid modified glassy carbon electrode has been evaluated by cyclic voltammetry and electrochemical impedance analysis. The silver nanoparticles are of size ∼35 nm and are well distributed on the surface ofmore » carbon nanotubes with chitosan linkage. The prepared nanocomposite shows efficient electrocatalytic properties with high active surface area and excellent electron transfer behaviour.« less

Statistical analysis of the electrocatalytic activity of Pt nanoparticles supported on novel functionalized reduced graphene oxide-chitosan for methanol electrooxidation

NASA Astrophysics Data System (ADS)

Ekrami-Kakhki, Mehri-Saddat; Abbasi, Sedigheh; Farzaneh, Nahid

2018-01-01

The purpose of this study is to statistically analyze the anodic current density and peak potential of methanol oxidation at Pt nanoparticles supported on functionalized reduced graphene oxide (RGO), using design of experiments methodology. RGO is functionalized with methyl viologen (MV) and chitosan (CH). The novel Pt/MV-RGO-CH catalyst is successfully prepared and characterized with transmission electron microscopy (TEM) image. The electrocatalytic activity of Pt/MV-RGOCH catalyst is experimentally evaluated for methanol oxidation. The effects of methanol concentration and scan rate factors are also investigated experimentally and statistically. The effects of these two main factors and their interactions are investigated, using analysis of variance test, Duncan's multiple range test and response surface method. The results of the analysis of variance show that all the main factors and their interactions have a significant effect on anodic current density and peak potential of methanol oxidation at α = 0.05. The suggested models which encompass significant factors can predict the variation of the anodic current density and peak potential of methanol oxidation. The results of Duncan's multiple range test confirmed that there is a significant difference between the studied levels of the main factors. [Figure not available: see fulltext.

Carbon nanotube macroelectronics

NASA Astrophysics Data System (ADS)

Zhang, Jialu

In this dissertation, I discuss the application of carbon nanotubes in macroelectronis. Due to the extraordinary electrical properties such as high intrinsic carrier mobility and current-carrying capacity, single wall carbon nanotubes are very desirable for thin-film transistor (TFT) applications such as flat panel display, transparent electronics, as well as flexible and stretchable electronics. Compared with other popular channel material for TFTs, namely amorphous silicon, polycrystalline silicon and organic materials, nanotube thin-films have the advantages of low-temperature processing compatibility, transparency, and flexibility, as well as high device performance. In order to demonstrate scalable, practical carbon nanotube macroelectroncis, I have developed a platform to fabricate high-density, uniform separated nanotube based thin-film transistors. In addition, many other essential analysis as well as technology components, such as nanotube film density control, purity and diameter dependent semiconducting nanotube electrical performance study, air-stable n-type transistor fabrication, and CMOS integration platform have also been demonstrated. On the basis of the above achievement, I have further demonstrated various kinds of applications including AMOLED display electronics, PMOS and CMOS logic circuits, flexible and transparent electronics. The dissertation is structured as follows. First, chapter 1 gives a brief introduction to the electronic properties of carbon nanotubes, which serves as the background knowledge for the following chapters. In chapter 2, I will present our approach of fabricating wafer-scale uniform semiconducting carbon nanotube thin-film transistors and demonstrate their application in display electronics and logic circuits. Following that, more detailed information about carbon nanotube thin-film transistor based active matrix organic light-emitting diode (AMOLED) displays is discussed in chapter 3. And in chapter 4, a technology to

Carbon nanotube modified probes for stable and high sensitivity conductive atomic force microscopy

NASA Astrophysics Data System (ADS)

Slattery, Ashley D.; Shearer, Cameron J.; Gibson, Christopher T.; Shapter, Joseph G.; Lewis, David A.; Stapleton, Andrew J.

2016-11-01

Conductive atomic force microscopy (C-AFM) is used to characterise the nanoscale electrical properties of many conducting and semiconducting materials. We investigate the effect of single walled carbon nanotube (SWCNT) modification of commercial Pt/Ir cantilevers on the sensitivity and image stability during C-AFM imaging. Pt/Ir cantilevers were modified with small bundles of SWCNTs via a manual attachment procedure and secured with a conductive platinum pad. AFM images of topography and current were collected from heterogeneous polymer and nanomaterial samples using both standard and SWCNT modified cantilevers. Typically, achieving a good current image comes at the cost of reduced feedback stability. In part, this is due to electrostatic interaction and increased tip wear upon applying a bias between the tip and the sample. The SWCNT modified tips displayed superior current sensitivity and feedback stability which, combined with superior wear resistance of SWCNTs, is a significant advancement for C-AFM.

Heteroporphyrin nanotubes and composites

DOEpatents

Shelnutt, John A.; Medforth, Craig J.; Wang, Zhongchun

2006-11-07

Heteroporphyrin nanotubes, metal nanostructures, and metal/porphyrin-nanotube composite nanostructures formed using the nanotubes as photocatalysts and structural templates, and the methods for forming the nanotubes and composites.

Heteroporphyrin nanotubes and composites

DOEpatents

Shelnutt, John A [Tijeras, NM; Medforth, Craig J [Winters, CA; Wang, Zhongchun [Albuquerque, NM

2007-05-29

Heteroporphyrin nanotubes, metal nanostructures, and metal/porphyrin-nanotube composite nanostructures formed using the nanotubes as photocatalysts and structural templates, and the methods for forming the nanotubes and composites.

Single photon generation through exciton-exciton annihilation in air-suspended carbon nanotubes

NASA Astrophysics Data System (ADS)

Ishii, Akihiro; Uda, Takushi; Kato, Yuichiro K.

Carbon nanotubes have great potential for single photon sources as they have stable exciton states even at room temperature and their emission wavelengths cover the telecommunication bands. In recent years, single photon emission from carbon nanotubes has been achieved by creating localized states of excitons. In contrast to such an approach, here we utilize mobile excitons and show that single photons can be generated in air-suspended carbon nanotubes, where exciton diffusion length is as long as several hundred nanometers and exciton-exciton annihilation is efficient. We perform photoluminescence microscopy on as-grown air-suspended carbon nanotubes in order to determine their chirality and suspended length. Photon correlation measurements are performed on nanotube emission at room temperature using a Hanbury-Brown-Twiss setup with InGaAs/InP single photon detectors. We observe antibunching with a clear excitation power dependence, where we obtain g (2) (0) value less than 0.5 at low excitation powers, indicating single photon generation. We show such g (2) (0) data with different chiralities and suspended lengths, and the effects of exciton diffusion on single photon generation processes are discussed. Work supported by KAKENHI (26610080, 16H05962), The Canon Foundation, and MEXT (Photon Frontier Network Program, Nanotechnology Platform). A.I. is supported by MERIT and JSPS Research Fellowship, and T.U. is supported by ALPS.

Accelerating oxygen reduction on Pt monolayer via substrate compression

NASA Astrophysics Data System (ADS)

Zhang, Xilin; Chen, Yue; Yang, Zongxian; Lu, Zhansheng

2017-11-01

Many methods have been proposed to accelerate the oxygen reduction and save the dosage of Pt. Here, we report a promising way in fulfilling these purposes by applying substrate strain on the supported Pt monolayer. The compressive strain would modify the geometric and electronic structures of tungsten carbide (WC) substrate, changing the interaction nature between substrate and Pt monolayer and resulting in a downward shift of the d-band center of surface Pt atoms. The activity of Pt monolayer on the compressed WC is further evaluated from the kinetics of the dissociation and protonation of O2. The dissociation barrier of O2 is increased and the hydrogenation barrier of O atom is decreased, indicating that the recovery of the catalytically active sites is accelerated and the deactivation by oxygen poison is alleviated. The present study provides an effective way in tuning the activity of Pt-based catalysts by applying the substrate strain.

Spectroscopic properties and STM images of carbon nanotubes

NASA Astrophysics Data System (ADS)

Rubio, A.

We present a theoretical study of the role of the local environment in the electronic properties of carbon nanotubes: isolated single- and multi-wall nanotubes, nanotube ropes, tubes supported on gold and cut to finite length. Interaction with the substrate or with other tubes does not alter the scanning tunneling microscopy patterns (STM) observed for isolated tubes. A finite-length nanotube shows standing-wave patterns that can be completely characterized by a set of four different three-dimensional shapes. These patterns are understood in terms of a simple π-electron tight-binding (TB) model. STM-topographic images of topological defects ani (pentagon/heptagon pair) and tube caps have also been studied. In both cases the image obtained depends on the sign of the applied voltage and can be described in terms of the previous catalog of STM images (interference between electronic waves scattered by the defect). We have also computed the electronic density of states for isolated tubes with different chiralities and radii, confirming a correlation between the peak structure in the DOS and nanotube diameter. However, the metallic plateau in the DOS also depends on the nanotube chirality. Furthermore the conduction an valence band structures are not fully symmetrical to one another. This anisotropy shows up in the DOS and indicates the limitations of the π-TB model in describing spectroscopic data. In contrast to STM images, here the interaction with the substrate does modify the energy levels of the nanotube. We observe opening of small pseudogaps around the Fermi level and broadening of the sharp van Hove singularities of the isolated single-walled nanotubes that can be used to extract useful information about the tube structure and bonding. The combination of STM and spectroscopic studies provides a new way to address the electronic and structural properties of carbon and composite nanotubes.

Preparation and UV-Vis photodegradation of gaseous benzene by TiO2 nanotube arrays supporting V2O5 nanoparticles

NASA Astrophysics Data System (ADS)

Zhao, Chunxia; Song, Yanbao; Yang, Yunxia; Chen, Wen; Li, Xiaoyu; Wang, Zongsheng

2015-07-01

TiO2-based catalysts effective in visible radiation for eliminating organic pollutants have attracted intense research activity as a future generation photocatalytic material. However, recombination of electron-hole pairs through trapping/de-trapping as well as the disadvantages of recycling and separation/filtration of powders lead to the limitation of powder TiO2 materials. TiO2 nanotube array films supporting vanadium pentoxide nanoparticles (VTNTs) were synthesized by electrophoresis deposition method with the prepared TiO2 nanotube arrays as the cathode and V2O5 sol as the electrolyte. The results indicate that the formation of Ti-O-V bonds and intimate interaction between host-guest interfaces help to enhance the hybrids’ photodegradation activity of gaseous benzene. Importantly, hybrid film catalysts prepared with 0.05 mol/L V2O5 sol for 10 min electrophoresis deposition perform a 98% conversion rate of benzene and 1028.8 mg/m3CO2 production in 80 min under UV-Vis irradiation.

Nanotube phonon waveguide

DOEpatents

Chang, Chih-Wei; Zettl, Alexander K.

2013-10-29

Disclosed are methods and devices in which certain types of nanotubes (e.g., carbon nanotubes and boron nitride nanotubes conduct heat with high efficiency and are therefore useful in electronic-type devices.

Production and Characterization of Carbon Nanotubes and Nanotube-Based Composites

NASA Technical Reports Server (NTRS)

Nikolaev, Pavel; Arepalli, Sivaram; Holmes, William; Gorelik, Olga; Files, Brad; Scott, Carl; Santos, Beatrice; Mayeaux, Brian; Victor, Joe

1999-01-01

The Nobel Prize winning discovery of the Buckuball (C60) in 1985 at Rice University by a group including Dr. Richard Smalley led to the whole new class of carbon allotropes including fullerenes and nanotubes. Especially interesting from many viewpoints are single-walled carbon nanotubes, which structurally are like a single graphitic sheet wrapped around a cylinder and capped at the ends. This cylinders have diameter as small as 0.5 - 2 nm (1/100,000th the diameter of a human hair) and are as long as 0.1 - 1 mm. Nanotubes are really individual molecules and believed to be defect-free, leading to high tensile strength despite their low density. Additionally, these fibers exhibit electrical conductivity as high as copper, thermal conductivity as high as diamond, strength 100 times higher than steel at one-sixth the weight, and high strain to failure. Thus it is believed that developments in the field of nanotechnology will lead to stronger and lighter composite materials for next generation spacecraft. Lack of a bulk method of production is the primary reason nanotubes are not used widely today. Toward this goal JSC nanotube team is exploring three distinct production techniques: laser ablation, arc discharge and chemical vapor deposition (CVD, in collaboration with Rice University). In laser ablation technique high-power laser impinges on the piece of carbon containing small amount of catalyst, and nanotubes self-assemble from the resulting carbon vapor. In arc generator similar vapor is created in arc discharge between carbon electrodes with catalyst. In CVD method nanotubes grow at much lower temperature on small catalyst particles from carbon-containing feedstock gas (methane or carbon monoxide). As of now, laser ablation produces cleanest material, but mass yield is rather small. Arc discharge produces grams of material, but purity is low. CVD technique is still in baby steps, but preliminary results look promising, as well as perspective of scaling the process

Reversibility of Pt-Skin and Pt-Skeleton Nanostructures in Acidic Media.

PubMed

Durst, Julien; Lopez-Haro, Miguel; Dubau, Laetitia; Chatenet, Marian; Soldo-Olivier, Yvonne; Guétaz, Laure; Bayle-Guillemaud, Pascale; Maillard, Frédéric

2014-02-06

Following a well-defined series of acid and heat treatments on a benchmark Pt3Co/C sample, three different nanostructures of interest for the electrocatalysis of the oxygen reduction reaction were tailored. These nanostructures could be sorted into the "Pt-skin" structure, made of one pure Pt overlayer, and the "Pt-skeleton" structure, made of 2-3 Pt overlayers surrounding the Pt-Co alloy core. Using a unique combination of high-resolution aberration-corrected STEM-EELS, XRD, EXAFS, and XANES measurements, we provide atomically resolved pictures of these different nanostructures, including measurement of the Pt-shell thickness forming in acidic media and the resulting changes of the bulk and core chemical composition. It is shown that the Pt-skin is reverted toward the Pt-skeleton upon contact with acid electrolyte. This change in structure causes strong variations of the chemical composition.