Applications of Nanoporous Materials in Agriculture

USDA-ARS?s Scientific Manuscript database

Nanoporous materials possess organized pore distributions and increased surface areas. Advances in the systematic design of nanoporous materials enable incorporation of functionality for better sensitivity in detection methods, increased capacity of sorbents, and improved selectivity and yield in ca...

Towards the Ultimate Membranes: Two-dimensional Nanoporous Materials and Films.

PubMed

Agrawal, Kumar Varoon

2018-05-30

The energy-efficient separation of molecules has been a popular topic in chemistry and chemical engineering as a consequence of the large energy-footprint of separation processes in the chemical industry. The Laboratory of Advanced Separations (LAS) at EPFL, led by Prof. Kumar Varoon Agrawal, is focused to develop next-generation, high-performance membranes that can improve the energy efficiency of hydrogen purification, carbon capture, hydrocarbon and water purification. For this, LAS is seeking to develop the ultimate nanoporous membranes, those with a thickness of 1 nm and possessing an array of size-selective nanopores. In this article, the research activities at LAS, especially in the bottom-up and top-down synthesis of chemically and thermally stable, nanoporous two-dimensional materials and membranes are discussed.

Computational materials chemistry for carbon capture using porous materials

NASA Astrophysics Data System (ADS)

Sharma, Abhishek; Huang, Runhong; Malani, Ateeque; Babarao, Ravichandar

2017-11-01

Control over carbon dioxide (CO2) release is extremely important to decrease its hazardous effects on the environment such as global warming, ocean acidification, etc. For CO2 capture and storage at industrial point sources, nanoporous materials offer an energetically viable and economically feasible approach compared to chemisorption in amines. There is a growing need to design and synthesize new nanoporous materials with enhanced capability for carbon capture. Computational materials chemistry offers tools to screen and design cost-effective materials for CO2 separation and storage, and it is less time consuming compared to trial and error experimental synthesis. It also provides a guide to synthesize new materials with better properties for real world applications. In this review, we briefly highlight the various carbon capture technologies and the need of computational materials design for carbon capture. This review discusses the commonly used computational chemistry-based simulation methods for structural characterization and prediction of thermodynamic properties of adsorbed gases in porous materials. Finally, simulation studies reported on various potential porous materials, such as zeolites, porous carbon, metal organic frameworks (MOFs) and covalent organic frameworks (COFs), for CO2 capture are discussed.

Lithium Titanate Confined in Carbon Nanopores for Asymmetric Supercapacitors.

PubMed

Zhao, Enbo; Qin, Chuanli; Jung, Hong-Ryun; Berdichevsky, Gene; Nese, Alper; Marder, Seth; Yushin, Gleb

2016-04-26

Porous carbons suffer from low specific capacitance, while intercalation-type active materials suffer from limited rate when used in asymmetric supercapacitors. We demonstrate that nanoconfinement of intercalation-type lithium titanate (Li4Ti5O12) nanoparticles in carbon nanopores yielded nanocomposite materials that offer both high ion storage density and rapid ion transport through open and interconnected pore channels. The use of titanate increased both the gravimetric and volumetric capacity of porous carbons by more than an order of magnitude. High electrical conductivity of carbon and the small size of titanate crystals allowed the composite electrodes to achieve characteristic charge and discharge times comparable to that of the electric double-layer capacitors. The proposed composite synthesis methodology is simple, scalable, and applicable for a broad range of active intercalation materials, while the produced composite powders are compatible with commercial electrode fabrication processes.

Characterization of Nanoporous Materials with Atom Probe Tomography.

PubMed

Pfeiffer, Björn; Erichsen, Torben; Epler, Eike; Volkert, Cynthia A; Trompenaars, Piet; Nowak, Carsten

2015-06-01

A method to characterize open-cell nanoporous materials with atom probe tomography (APT) has been developed. For this, open-cell nanoporous gold with pore diameters of around 50 nm was used as a model system, and filled by electron beam-induced deposition (EBID) to obtain a compact material. Two different EBID precursors were successfully tested-dicobalt octacarbonyl [Co2(CO)8] and diiron nonacarbonyl [Fe2(CO)9]. Penetration and filling depth are sufficient for focused ion beam-based APT sample preparation. With this approach, stable APT analysis of the nanoporous material can be performed. Reconstruction reveals the composition of the deposited precursor and the nanoporous material, as well as chemical information of the interfaces between them. Thus, it is shown that, using an appropriate EBID process, local chemical information in three dimensions with sub-nanometer resolution can be obtained from nanoporous materials using APT.

Optimized nanoporous materials.

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

Braun, Paul V.; Langham, Mary Elizabeth; Jacobs, Benjamin W.

2009-09-01

Nanoporous materials have maximum practical surface areas for electrical charge storage; every point in an electrode is within a few atoms of an interface at which charge can be stored. Metal-electrolyte interfaces make best use of surface area in porous materials. However, ion transport through long, narrow pores is slow. We seek to understand and optimize the tradeoff between capacity and transport. Modeling and measurements of nanoporous gold electrodes has allowed us to determine design principles, including the fact that these materials can deplete salt from the electrolyte, increasing resistance. We have developed fabrication techniques to demonstrate architectures inspired bymore » these principles that may overcome identified obstacles. A key concept is that electrodes should be as close together as possible; this is likely to involve an interpenetrating pore structure. However, this may prove extremely challenging to fabricate at the finest scales; a hierarchically porous structure can be a worthy compromise.« less

Nanoporous-carbon as a potential host material for reversible Mg ion intercalation

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

Siegal, Michael P.; Yelton, W. Graham; Perdue, Brian R.

Here, we study nanoporous-carbon (NPC) grown via pulsed laser deposition (PLD) as an electrically conductive anode host material for Mg 2+ intercalation. NPC has high surface area, and an open, accessible pore structure tunable via mass density that can improve diffusion. We fabricate 2032 coin cells using NPC coated stainless-steel disk anodes, metallic Mg cathodes, and a Grignard-based electrolyte. NPC mass density is controlled during growth, ranging from 0.06–1.3 g/cm 3. The specific surface area of NPC increases linearly from 1,000 to 1,700 m 2/g as mass density decreases from 1.3 to 0.26 g/cm 3, however, the surface area fallsmore » off dramatically at lower mass densities, implying a lack of mechanical integrity in such nanostructures. These structural characterizations correlate directly with coin cell electrochemical measurements. In particular, cyclic voltammetry (CV) scans for NPC with density ~0.5 g/cm 3 and BET surface area ~1500 m 2/g infer the possibility of reversible Mg-ion intercalation. Higher density NPC yields capacitive behavior, most likely resulting from the smaller interplanar spacings between graphene sheet fragments and tighter domain boundaries; lower density NPC results in asymmetrical CV scans, consistent with the likely structural degradation resulting from mass transport through soft, low-density carbon materials.« less

Nanoporous-carbon as a potential host material for reversible Mg ion intercalation

DOE PAGES

Siegal, Michael P.; Yelton, W. Graham; Perdue, Brian R.; ...

2016-03-25

Here, we study nanoporous-carbon (NPC) grown via pulsed laser deposition (PLD) as an electrically conductive anode host material for Mg 2+ intercalation. NPC has high surface area, and an open, accessible pore structure tunable via mass density that can improve diffusion. We fabricate 2032 coin cells using NPC coated stainless-steel disk anodes, metallic Mg cathodes, and a Grignard-based electrolyte. NPC mass density is controlled during growth, ranging from 0.06–1.3 g/cm 3. The specific surface area of NPC increases linearly from 1,000 to 1,700 m 2/g as mass density decreases from 1.3 to 0.26 g/cm 3, however, the surface area fallsmore » off dramatically at lower mass densities, implying a lack of mechanical integrity in such nanostructures. These structural characterizations correlate directly with coin cell electrochemical measurements. In particular, cyclic voltammetry (CV) scans for NPC with density ~0.5 g/cm 3 and BET surface area ~1500 m 2/g infer the possibility of reversible Mg-ion intercalation. Higher density NPC yields capacitive behavior, most likely resulting from the smaller interplanar spacings between graphene sheet fragments and tighter domain boundaries; lower density NPC results in asymmetrical CV scans, consistent with the likely structural degradation resulting from mass transport through soft, low-density carbon materials.« less

Top-down solid-phase fabrication of nanoporous cadmium oxide architectures.

PubMed

Yu, Haidong; Wang, Deshen; Han, Ming-Yong

2007-02-28

In this article, we have demonstrated one-step solid-phase transformation from high-quality cadmium carbonate microcrystals into highly nanoporous cadmium oxide. The high crystal quality of cadmium carbonate is critical for the successful fabrication of porous nanoarchitectures with predetermined morphology and well-controlled internal structure. This novel strategy has a good potential to prepare nanoporous materials at a large scale by using perfect monolithic carbonate crystals, and it is also useful to synthesize different nanoporous materials on metal-oxide-coated substrates. Meanwhile, this simple thermal transformation of cadmium carbonate into porous structures has further been extended to convert calcium carbonate into such porous structures.

Nanoporous thermosetting polymers.

PubMed

Raman, Vijay I; Palmese, Giuseppe R

2005-02-15

Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface.

High Density Methane Storage in Nanoporous Carbon

NASA Astrophysics Data System (ADS)

Rash, Tyler; Dohnke, Elmar; Soo, Yuchoong; Maland, Brett; Doynov, Plamen; Lin, Yuyi; Pfeifer, Peter; Mriglobal Collaboration; All-Craft Team

2014-03-01

Development of low-pressure, high-capacity adsorbent based storage technology for natural gas (NG) as fuel for advanced transportation (flat-panel tank for NG vehicles) is necessary in order to address the temperature, pressure, weight, and volume constraints present in conventional storage methods (CNG & LNG.) Subcritical nitrogen adsorption experiments show that our nanoporous carbon hosts extended narrow channels which generate a high surface area and strong Van der Waals forces capable of increasing the density of NG into a high-density fluid. This improvement in storage density over compressed natural gas without an adsorbent occurs at ambient temperature and pressures ranging from 0-260 bar (3600 psi.) The temperature, pressure, and storage capacity of a 40 L flat-panel adsorbed NG tank filled with 20 kg of nanoporous carbon will be featured.

A novel material screening platform for nanoporous gold-based neural electrodes

NASA Astrophysics Data System (ADS)

Chapman, Christopher Abbott Reece

Neural-electrical interfaces have emerged in the past decades as a promising modality to facilitate the understanding of the electropathophysiology of neurological disorders as well as the normal functioning of the central nervous system, and enable the treatment of neurological defects through electrical stimulation or electrically-controlled drug delivery. However, chronically implanted electrodes face a myriad of design challenges, including their coupling to neural tissue (biocompatibility), small form factor requirement, and their electrical properties (maintaining a low electrical impedance). Planar electrode materials such as planar platinum and gold experience a large increase in electrical impedance when electrode dimensions are reduced to increase spatial resolution of neural recordings. A decrease in electrode surface area reduces the total capacitance of the electrode double layer resulting in an increase in electrode impedance. This high impedance can reduce the signal amplitude and increase the thermal noise, resulting in degradation of signal-to-noise ratio. Conventionally, this increase in electrical impedance at small electrode dimensions has been mitigated by coatings with rough morphologies such as platinum black, conducting polymers, and titanium nitride. Porous surfaces have high effective surface area enabling low impedance at small electrode dimensions. However, achieving long-term stability of cellular coupling to the electrode surface has remained difficult. Designing electrodes that can physically couple with neurons successfully and maintain low impedance at small electrode dimensions necessitates consideration of novel electrode coatings, such as carbon nanotubes and gold nanopillars. Another promising material, and focus of this proposal, is thin film nanoporous gold (np-Au). Nanoporous gold is a promising material for addressing these limitations because of its inherently large effective surface area allows for lower impedances at

Electrical and galvanomagnetic properties of nanoporous carbon samples impregnated with bromine

NASA Astrophysics Data System (ADS)

Danishevskii, A. M.; Popov, V. V.; Kyutt, R. N.; Gordeev, S. K.

2013-07-01

Nanoporous carbon samples with a large specific surface area can be filled with heavier elements or their compounds, which makes it possible to investigate the interaction of their electronic subsystems with carbon. One of the elements convenient for filling pores of carbon materials is bromine. Impregnation of nanoporous carbon samples with bromine causes the occurrence of the processes of micropore filling, monolayer adsorption, and intercalation. It has been found that samples impregnated with bromine substantially change their electrical and galvanomagnetic properties, and these changes depend on the structure of the samples. It has been shown that, if in the skeleton of a porous carbon sample there is a fraction of graphite clusters, the impregnation of the sample with bromine increases the concentration of charged carriers (holes). But when the sample has a quasi-amorphous structure, the injection of bromine into the sample leads to the appearance of a certain concentration of electrons in addition to charged mobile holes of the initial sample; i.e., the electrical conductivity becomes bipolar. In the former case, bromine molecules intercalate graphite clusters and, since bromine is an acceptor during intercalation of graphite, the hole concentration in the carbon skeleton network increases. In the latter case, bromine molecules can only be adsorbed on pore walls. As a result, the adsorption interaction between the electron shells of bromine molecules and the carbon surface leads to the formation of a donor layer near the surface and to the generation of electrons in the carbon skeleton network.

Quantifying similarity of pore-geometry in nanoporous materials

DOE PAGES

Lee, Yongjin; Barthel, Senja D.; Dłotko, Paweł; ...

2017-05-23

In most applications of nanoporous materials the pore structure is as important as the chemical composition as a determinant of performance. For example, one can alter performance in applications like carbon capture or methane storage by orders of magnitude by only modifying the pore structure. For these applications it is therefore important to identify the optimal pore geometry and use this information to find similar materials. But, the mathematical language and tools to identify materials with similar pore structures, but different composition, has been lacking. We develop a pore recognition approach to quantify similarity of pore structures and classify themmore » using topological data analysis. This then allows us to identify materials with similar pore geometries, and to screen for materials that are similar to given top-performing structures. Using methane storage as a case study, we also show that materials can be divided into topologically distinct classes requiring different optimization strategies.« less

Facile synthesis of sewage sludge-derived in-situ multi-doped nanoporous carbon material for electrocatalytic oxygen reduction

NASA Astrophysics Data System (ADS)

Yuan, Shi-Jie; Dai, Xiao-Hu

2016-06-01

Developing efficient, low-cost, and stable carbon-based catalysts for oxygen reduction reaction (ORR) to replace the expensive platinum-based electrocatalysts remains a major challenge that hamper the practical application of fuel cells. Here, we report that N, Fe, and S co-doped nanoporous carbon material, derived via a facile one-step pyrolysis of sewage sludge, the major byproduct of wastewater treatment, can serve as an effective electrocatalyst for ORR. Except for the comparable catalytic activity with commercial 20% Pt/C via a nearly four-electron transfer pathway in both alkaline and acid medium, the as-synthesized co-doped electrocatalyst also exhibits excellent methanol crossover resistance and outstanding long-term operation stability. The organic compounds in sewage sludge act as the carbon source and the in-situ N and S dopant in the fabrication, while the inorganic compounds serve as the in-built template and the in-situ Fe dopant. Our protocol demonstrates a new approach in the economic and eco-friendly benign reuse of sewage sludge, and also provides a straightforward route for synthesizing excellent carbon-based electrocatalysts as promising candidates for ORR directly from a type of waste/pollution.

Recent advances in functionalized micro and mesoporous carbon materials: synthesis and applications.

PubMed

Benzigar, Mercy R; Talapaneni, Siddulu Naidu; Joseph, Stalin; Ramadass, Kavitha; Singh, Gurwinder; Scaranto, Jessica; Ravon, Ugo; Al-Bahily, Khalid; Vinu, Ajayan

2018-04-23

Functionalized nanoporous carbon materials have attracted the colossal interest of the materials science fraternity owing to their intriguing physical and chemical properties including a well-ordered porous structure, exemplary high specific surface areas, electronic and ionic conductivity, excellent accessibility to active sites, and enhanced mass transport and diffusion. These properties make them a special and unique choice for various applications in divergent fields such as energy storage batteries, supercapacitors, energy conversion fuel cells, adsorption/separation of bulky molecules, heterogeneous catalysts, catalyst supports, photocatalysis, carbon capture, gas storage, biomolecule detection, vapour sensing and drug delivery. Because of the anisotropic and synergistic effects arising from the heteroatom doping at the nanoscale, these novel materials show high potential especially in electrochemical applications such as batteries, supercapacitors and electrocatalysts for fuel cell applications and water electrolysis. In order to gain the optimal benefit, it is necessary to implement tailor made functionalities in the porous carbon surfaces as well as in the carbon skeleton through the comprehensive experimentation. These most appealing nanoporous carbon materials can be synthesized through the carbonization of high carbon containing molecular precursors by using soft or hard templating or non-templating pathways. This review encompasses the approaches and the wide range of methodologies that have been employed over the last five years in the preparation and functionalisation of nanoporous carbon materials via incorporation of metals, non-metal heteroatoms, multiple heteroatoms, and various surface functional groups that mostly dictate their place in a wide range of practical applications.

Water flow in carbon-based nanoporous membranes impacted by interactions between hydrated ions and aromatic rings.

PubMed

Liu, Jian; Shi, Guosheng; Fang, Haiping

2017-02-24

Carbon-based nanoporous membranes, such as carbon nanotubes (CNTs), graphene/graphene oxide and graphyne, have shown great potential in water desalination and purification, gas and ion separation, biosensors, and lithium-based batteries, etc. A deep understanding of the interaction between hydrated ions in an aqueous solution and the graphitic surface in systems composed of water, ions and a graphitic surface is essential for applications with carbon-based nanoporous membrane platforms. In this review, we describe the recent progress of the interaction between hydrated ions and aromatic ring structures on the carbon-based surface and its applications in the water flow in a carbon nanotube. We expect that these works can be extended to the understanding of water flow in other nanoporous membranes, such as nanoporous graphene, graphyne and stacked sheets of graphene oxide.

Nanoporous activated carbon derived from Lapsi (Choerospondias axillaris) seed stone for the removal of arsenic from water.

PubMed

Rajbhandari, Rinita; Shrestha, Lok Kumar; Pradhananga, Raja Ram

2012-09-01

Activated carbons were prepared from Lapsi (Choerospondias axillaris) seed stone by zinc chloride (ZnCl2) activation at three different Lapsi seed powder (LSP):ZnCl2 ratios: 1:0.5 (AC-0.5), 1:1 (AC-1), and 1:2 (AC-2). The properties of these activated carbons (ACs), including effective surface areas, pore volumes, and pore size distributions were characterized from N2 adsorption-desorption isotherms. The ACs obtained were essentially nanoporous (including both micro- and mesoporous) with effective surface area ranging from 1167 to 1328 m2/g. Fourier-transform infrared (FTIR) spectroscopy showed the presence of functional groups on the surface of ACs. Scanning electron microscopy (SEM) images showed a high pore development in the ACs. X-ray diffraction (XRD) patterns showed that, in addition to the amorphous structure, ACs contains crystalline ZnO formed during the carbonization. Presence of amorphous carbon is further confirmed by Raman scattering, where we observed only D and G bands. Iron impregnated nanoporous AC has been found to be very effective for arsenic removal from ground water; amount of arsenic is decreased from ca. 200 ppb to 10 ppb. These experimental results indicate the potential use of Lapsi seed as a precursor material for the preparation of high surface area nanoporous activated carbons.

Sulfur-doped nanoporous carbon spheres with ultrahigh specific surface area and high electrochemical activity for supercapacitor

NASA Astrophysics Data System (ADS)

Liu, Simin; Cai, Yijin; Zhao, Xiao; Liang, Yeru; Zheng, Mingtao; Hu, Hang; Dong, Hanwu; Jiang, Sanping; Liu, Yingliang; Xiao, Yong

2017-08-01

Development of facile and scalable synthesis process for the fabrication of nanoporous carbon materials with large specific surface areas, well-defined nanostructure, and high electrochemical activity is critical for the high performance energy storage applications. The key issue is the dedicated balance between the ultrahigh surface area and highly porous but interconnected nanostructure. Here, we demonstrate the fabrication of new sulfur doped nanoporous carbon sphere (S-NCS) with the ultrahigh surface area up to 3357 m2 g-1 via a high-temperature hydrothermal carbonization and subsequent KOH activation process. The as-prepared S-NCS which integrates the advantages of ultrahigh porous structure, well-defined nanospherical and modification of heteroatom displays excellent electrochemical performance. The best performance is obtained on S-NCS prepared by the hydrothermal carbonization of sublimed sulfur and glucose, S-NCS-4, reaching a high specific capacitance (405 F g-1 at a current density of 0.5 A g-1) and outstanding cycle stability. Moreover, the symmetric supercapacitor is assembled by S-NCS-4 displays a superior energy density of 53.5 Wh kg-1 at the power density of 74.2 W kg-1 in 1.0 M LiPF6 EC/DEC. The synthesis method is simple and scalable, providing a new route to prepare highly porous and heteroatom-doped nanoporous carbon spheres for high performance energy storage applications.

Hydroxyl-Exchanged Nanoporous Ionic Copolymer toward Low-Temperature Cycloaddition of Atmospheric Carbon Dioxide into Carbonates.

PubMed

Guo, Zengjing; Cai, Xiaochun; Xie, Jingyan; Wang, Xiaochen; Zhou, Yu; Wang, Jun

2016-05-25

An ionic copolymer catalyst with nanopores, large surface area, high ionic density, and superior basicity was prepared via the radical copolymerization of amino-functionalized ionic liquid bromide and divinylbenzene, followed with a hydroxyl exchange for removing bromonium. Evaluated in chemical fixation of CO2 with epoxides into cyclic carbonates in the absence of any solvent and basic additive, the nanoporous copolymer catalyst showed high and stable activity, superior to various control catalysts including the halogen-containing analogue. Further, high yields were obtained over a wide scope of substrates including aliphatic long carbon-chain alkyl epoxides and internal epoxide, even under atmospheric pressure and less than 100 °C for the majority of the substrates. On the basis of in situ Fourier transform infrared (FT-IR) investigation and density functional theory (DFT) calculation for the reaction intermediates, we proposed a possible reaction mechanism accounting for the superior catalytic activity of the ionic copolymer. The specifically prepared ionic copolymer material of this work features highly stable, noncorrosive, and sustainable catalysis and, thus, may be a new possibility for efficient chemical fixation of CO2 since it is an environmentally friendly, metal-free solid catalyst.

High capacity and stable all-solid-state Li ion battery using SnO2-embedded nanoporous carbon.

PubMed

Notohara, Hiroo; Urita, Koki; Yamamura, Hideyuki; Moriguchi, Isamu

2018-06-08

Extensive research efforts are devoted to development of high performance all-solid-state lithium ion batteries owing to their potential in not only improving safety but also achieving high stability and high capacity. However, conventional approaches based on a fabrication of highly dense electrode and solid electrolyte layers and their close contact interface is not always applicable to high capacity alloy- and/or conversion-based active materials such as SnO 2 accompanied with large volume change in charging-discharging. The present work demonstrates that SnO 2 -embedded nanoporous carbons without solid electrolyte inside the nanopores are a promising candidate for high capacity and stable anode material of all-solid-state battery, in which the volume change reactions are restricted in the nanopores to keep the constant electrode volume. A prototype all-solid-state full cell consisting of the SnO 2 -based anode and a LiNi 1/3 Co 1 / 3 Mn 1/3 O 2 -based cathode shows a good performance of 2040 Wh/kg at 268.6 W/kg based on the anode material weight.

Advanced structural analysis of nanoporous materials by thermal response measurements.

PubMed

Oschatz, Martin; Leistner, Matthias; Nickel, Winfried; Kaskel, Stefan

2015-04-07

Thermal response measurements based on optical adsorption calorimetry are presented as a versatile tool for the time-saving and profound characterization of the pore structure of porous carbon-based materials. This technique measures the time-resolved temperature change of an adsorbent during adsorption of a test gas. Six carbide and carbon materials with well-defined nanopore architecture including micro- and/or mesopores are characterized by thermal response measurements based on n-butane and carbon dioxide as the test gases. With this tool, the pore systems of the model materials can be clearly distinguished and accurately analyzed. The obtained calorimetric data are correlated with the adsorption/desorption isotherms of the materials. The pore structures can be estimated from a single experiment due to different adsorption enthalpies/temperature increases in micro- and mesopores. Adsorption/desorption cycling of n-butane at 298 K/1 bar with increasing desorption time allows to determine the pore structure of the materials in more detail due to different equilibration times. Adsorption of the organic test gas at selected relative pressures reveals specific contributions of particular pore systems to the increase of the temperature of the samples and different adsorption mechanisms. The use of carbon dioxide as the test gas at 298 K/1 bar provides detailed insights into the ultramicropore structure of the materials because under these conditions the adsorption of this test gas is very sensitive to the presence of pores smaller than 0.7 nm.

Citrus-Peel-Derived, Nanoporous Carbon Nanosheets Containing Redox-Active Heteroatoms for Sodium-Ion Storage.

PubMed

Kim, Na Rae; Yun, Young Soo; Song, Min Yeong; Hong, Sung Ju; Kang, Minjee; Leal, Cecilia; Park, Yung Woo; Jin, Hyoung-Joon

2016-02-10

Advanced design of nanostructured functional carbon materials for use in sustainable energy storage systems suffers from complex fabrication procedures and the use of special methods and/or expensive precursors, limiting their practical applications. In this study, nanoporous carbon nanosheets (NP-CNSs) containing numerous redox-active heteroatoms (C/O and C/N ratios of 5.5 and 34.3, respectively) were fabricated from citrus peels by simply heating the peels in the presence of potassium ions. The NP-CNSs had a 2D-like morphology with a high aspect ratio of >100, high specific surface area of 1167 m(2) g(-1), and a large amount of nanopores between 1 and 5 nm. The NP-CNSs also had an electrical conductivity of 2.6 × 10(1) s cm(-1), which is approximately 50 times higher than that of reduced graphene oxide. These unique material properties resulted in superior electrochemical performance with a high specific capacity of 140 mAh g(-1) in the cathodic potential range. In addition, symmetric full-cell devices based on the NP-CNSs showed excellent cyclic performance over 100,000 repetitive cycles.

Advanced Nanoporous Materials for Micro-Gravimetric Sensing to Trace-Level Bio/Chemical Molecules

PubMed Central

Xu, Pengcheng; Li, Xinxin; Yu, Haitao; Xu, Tiegang

2014-01-01

Functionalized nanoporous materials have been developed recently as bio/chemical sensing materials. Due to the huge specific surface of the nano-materials for molecular adsorption, high hopes have been placed on gravimetric detection with micro/nano resonant cantilevers for ultra-sensitive sensing of low-concentration bio/chemical substances. In order to enhance selectivity of the gravimetric resonant sensors to the target molecules, it is crucial to modify specific groups onto the pore-surface of the nano-materials. By loading the nanoporous sensing material onto the desired region of the mass-type transducers like resonant cantilevers, the micro-gravimetric bio/chemical sensors can be formed. Recently, such micro-gravimetric bio/chemical sensors have been successfully applied for rapid or on-the-spot detection of various bio/chemical molecules at the trace-concentration level. The applicable nanoporous sensing materials include mesoporous silica, zeolite, nanoporous graphene oxide (GO) and so on. This review article focuses on the recent achievements in design, preparation, functionalization and characterization of advanced nanoporous sensing materials for micro-gravimetric bio/chemical sensing. PMID:25313499

Molecular Insights into the Complex Relationship between Capacitance and Pore Morphology in Nanoporous Carbon-based Supercapacitors.

PubMed

Pak, Alexander J; Hwang, Gyeong S

2016-12-21

Electrochemical double layer capacitors, or supercapacitors, are high-power energy storage devices that consist of large surface area electrodes (filled with electrolyte) to accommodate ion packing in accordance with classical electric double layer (EDL) theory. Nanoporous carbons (NPCs) have recently emerged as a class of electrode materials with the potential to dramatically improve the capacitance of these devices by leveraging ion confinement. However, the molecular mechanisms underlying such enhancements are a clear departure from EDL theory and remain an open question. In this paper, we present the concept of ion reorganization kinetics during charge/discharge cycles, especially within highly confining subnanometer pores, which necessarily dictates the capacitance. Our molecular dynamics voltammetric simulations of ionic liquid immersed in NPC electrodes (of varying pore size distributions) demonstrate that the most efficient ion migration, and thereby largest capacitance, is facilitated by nonuniformity of shape (e.g., from cylindrical to slitlike) along nanopore channels. On the basis of this understanding, we propose that a new structural descriptor, coined as the pore shape factor, can provide a new avenue for materials optimization. These findings also present a framework to understand and evaluate ion migration kinetics within charged nanoporous materials.

Room-temperature Electrochemical Synthesis of Carbide-derived Carbons and Related Materials

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

Gogotsi, Yury

2015-02-28

This project addresses room-temperature electrochemical etching as an energy-efficient route to synthesis of 3D nanoporous carbon networks and layered 2D carbons and related structures, as well as provides fundamental understanding of structure and properties of materials produced by this method. Carbide-derived-carbons (CDCs) are a growing class of nanostructured carbon materials with properties that are desirable for many applications, such as electrical energy and gas storage. The structure of these functional materials is tunable by the choice of the starting carbide precursor, synthesis method, and process parameters. Moving from high-temperature synthesis of CDCs through vacuum decomposition above 1400°C and chlorination abovemore » 400°C, our studies under the previous DOE BES support led to identification of precursor materials and processing conditions for CDC synthesis at temperatures as low as 200°C, resulting in amorphous and highly reactive porous carbons. We also investigated synthesis of monolithic CDC films from carbide films at 250-1200°C. The results of our early studies provided new insights into CDC formation, led to development of materials for capacitive energy storage, and enabled fundamental understanding of the electrolyte ions confinement in nanoporous carbons.« less

Irradiation response and stability of nanoporous materials

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

Fu, Engang; Wang, Yongqiang; Serrano De Caro, Magdalena

2012-08-28

Nanoporous materials consist of a regular organic or inorganic framework supporting a regular, porous structure. Pores are by definition roughly in the nanometre range, that is between 0.2 nm and 100 nm. Nanoporous materials can be subdivided into 3 categories (IUPAC): (1) Microporous materials - 0.2-2 nm; (2) Mesoporous materials - 2-50 nm; and (3) Macroporous materials - 50-1000 nm. np-Au foams were successfully synthesized by de-alloying process. np-Au foams remain porous structure after Ne ion irradiation to 1 dpa. Stacking Fault Tetrahedra (SFTs) were observed in RT irradiated np-Au foams under the highest and intermediate fluxes, but not undermore » the lowest flux. SFTs were not observed in LNT irradiated np-Au foams under all fluxes. The vacancy diffusivity in Au at RT is high enough so that the vacancies have enough time to agglomerate and then collapse to form SFTs. The high ion flux creates more damage per unit time; vacancies don't have enough time to diffuse or recombine. As a result, SFTs were formed at high ion fluxes.« less

Engineering design and theoretical analysis of nanoporous carbon membranes for gas separation

NASA Astrophysics Data System (ADS)

Acharya, Madhav

1999-11-01

Gases are used in a direct or indirect manner in virtually every major industry, such as steel manufacturing, oil production, foodstuffs and electronics. Membranes are being investigated as an alternative to established methods of gas separation such as pressure swing adsorption and cryogenic distillation. Membranes can be used in continuous operation and work very well at ambient conditions, thus representing a tremendous energy and economic saving over the other technologies. In addition, the integration of reaction and separation into a single unit known as a membrane reactor has the potential to revolutionize the chemical industry by making selective reactions a reality. Nanoporous carbons are highly disordered materials obtained from organic polymers or natural sources. They have the ability to separate gas molecules by several different mechanisms, and hence there is a growing effort to form them into membranes. In this study, nanoporous carbon membranes were prepared on macroporous stainless steel supports of both tubular and disk geometries. The precursor used was poly(furfuryl alcohol) and different synthesis protocols were employed. A spray coating method also was developed which allowed reproducible synthesis of membranes with very few defects. High gas selectivities were obtained such as O2/N2 = 6, H2/C2H 4 = 70 and CO2/N2 = 20. Membranes also were characterized using SEM and AFM, which revealed thin layers of carbon that were quite uniform and homogeneous. The simulation of nanoporous carbon structures also was carried out using a simple algorithmic approach. 5,6 and 7-membered rings were introduced into the structure, thus resulting in considerable curvature. The density of the structures were calculated and found to compare favorably with experimental findings. Finally, a theoretical analysis of size selective transport was performed using transition state theory concepts. A definite correlation of gas permeance with molecular size was obtained after

Influence of Nanopore Shapes on Thermal Conductivity of Two-Dimensional Nanoporous Material.

PubMed

Huang, Cong-Liang; Huang, Zun; Lin, Zi-Zhen; Feng, Yan-Hui; Zhang, Xin-Xin; Wang, Ge

2016-12-01

The influence of nanopore shapes on the electronic thermal conductivity (ETC) was studied in this paper. It turns out that with same porosity, the ETC will be quite different for different nanopore shapes, caused by the different channel width for different nanopore shapes. With same channel width, the influence of different nanopore shapes can be approximately omitted if the nanopore is small enough (smaller than 0.5 times EMFP in this paper). The ETC anisotropy was discovered for triangle nanopores at a large porosity with a large nanopore size, while there is a similar ETC for small pore size. It confirmed that the structure difference for small pore size may not be seen by electrons in their moving.

Nanoporous Mo2C functionalized 3D carbon architecture anode for boosting flavins mediated interfacial bioelectrocatalysis in microbial fuel cells

NASA Astrophysics Data System (ADS)

Zou, Long; Lu, Zhisong; Huang, Yunhong; Long, Zhong-er; Qiao, Yan

2017-08-01

An efficient microbial electrocatalysis in microbial fuel cells (MFCs) needs both high loading of microbes (biocatalysts) and robust interfacial electron transfer from microbes to electrode. Herein a nanoporous molybdenum carbide (Mo2C) functionalized carbon felt electrode with rich 3D hierarchical porous architecture is applied as MFC anode to achieve superior electrocatalytic performance. The nanoporous Mo2C functionalized anode exhibits strikingly improved microbial electrocatalysis in MFCs with 5-fold higher power density and long-term stability of electricity production. The great enhancement is attributed to the introduction of rough Mo2C nanostructural interface into macroporous carbon architecture for promoting microbial growth with great excretion of endogenous electron shuttles (flavins) and rich available nanopores for enlarging electrochemically active surface area. Importantly, the nanoporous Mo2C functionalized anode is revealed for the first time to have unique electrocatalytic activity towards redox reaction of flavins with more negative redox potential, indicating a more favourable thermodynamic driving force for anodic electron transfer. This work not only provides a promising electrode for high performance MFCs but also brings up a new insight into the effect of nanostructured materials on interfacial bioelectrocatalysis.

Observation and analysis of the Coulter effect through carbon nanotube and graphene nanopores.

PubMed

Agrawal, Kumar Varoon; Drahushuk, Lee W; Strano, Michael S

2016-02-13

Carbon nanotubes (CNTs) and graphene are the rolled and flat analogues of graphitic carbon, respectively, with hexagonal crystalline lattices, and show exceptional molecular transport properties. The empirical study of a single isolated nanopore requires, as evidence, the observation of stochastic, telegraphic noise from a blocking molecule commensurate in size with the pore. This standard is used ubiquitously in patch clamp studies of single, isolated biological ion channels and a wide range of inorganic, synthetic nanopores. In this work, we show that observation and study of stochastic fluctuations for carbon nanopores, both CNTs and graphene-based, enable precision characterization of pore properties that is otherwise unattainable. In the case of voltage clamp measurements of long (0.5-1 mm) CNTs between 0.9 and 2.2 nm in diameter, Coulter blocking of cationic species reveals the complex structuring of the fluid phase for confined water in this diameter range. In the case of graphene, we have pioneered the study and the analysis of stochastic fluctuations in gas transport from a pressurized, graphene-covered micro-well compartment that reveal switching between different values of the membrane permeance attributed to chemical rearrangements of individual graphene pores. This analysis remains the only way to study such single isolated graphene nanopores under these realistic transport conditions of pore rearrangements, in keeping with the thesis of this work. In summary, observation and analysis of Coulter blocking or stochastic fluctuations of permeating flux is an invaluable tool to understand graphene and graphitic nanopores including CNTs. © 2015 The Author(s).

Synthesis of MOF-525 Derived Nanoporous Carbons with Different Particle Sizes for Supercapacitor Application.

PubMed

Chang, Ting-Hsiang; Young, Christine; Lee, Min-Han; Salunkhe, Rahul R; Alshehri, Saad M; Ahamad, Tansir; Islam, Md Tofazzal; Wu, Kevin C-W; Hossain, Md Shahriar A; Yamauchi, Yusuke; Ho, Kuo-Chuan

2017-11-02

Nanoporous carbon (NC) materials have attracted great research interest for supercapacitor applications, because of their excellent electrochemical and mechanical stability, good electrical conductivity, and high surface area. Although there are many reports on metal-organic framework (MOF)-derived carbon materials, previous synthetic studies have been hindered by imperfect control of particle sizes and shapes. Here, we show precise control of the particle sizes of MOF-525 from 100 nm to 750 nm. After conversion of MOF-525 to NC, the effects of variation of the particle size on the electrochemical performance have been carefully investigated. The results demonstrate that our NC is a potential candidate for practical supercapacitor applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

In-pore exchange and diffusion of carbonate solvent mixtures in nanoporous carbon

DOE PAGES

Alam, Todd M.; Osborn Popp, Thomas M.

2016-06-04

High resolution magic angle spinning (HRMAS) 1H NMR spectroscopy has been used to resolve different surface and in-pore solvent environments of ethylene carbonate (EC) and dimethyl carbonate (DMC) mixtures absorbed within nanoporous carbon (NPC). Two dimensional (2D) 1H HRMAS NMR exchange measurements revealed that the inhomogeneous broadened in-pore resonances have pore-to-pore exchange rates on the millisecond timescale. Pulsed-field gradient (PFG) NMR diffusometry revealed the in-pore self-diffusion constants for both EC and DMC were reduced by up to a factor of five with respect to the diffusion in the non-absorbed solvent mixtures.

Cost-efficient magnetic nanoporous carbon derived from citrus peel for the selective adsorption of seven insecticides.

PubMed

Zhou, Yuantao; Cao, Shurui; Xi, Cunxian; Chen, Jiuyan; Zhang, Lei; Li, Xianliang; Wang, Guomin; Chen, Zhiqiong

2018-05-18

A magnetic solid-phase extraction adsorbent that consisted of citrus peel-derived nanoporous carbon and silica-coated Fe 3 O 4 microspheres (C/SiO 2 @Fe 3 O 4 ) was successfully fabricated by co-precipitation. As a modifier for magnetic microspheres, citrus peel-derived nanoporous carbon was not only economical and renewable for its raw material, but exerted enormous nanosized pore structure, which could directly influence the type of adsorbed analytes. The C/SiO 2 @Fe 3 O 4 also possessed the advantages of Fe 3 O 4 microspheres like superparamagnetism, that could be easily separated magnetically after adsorption. Integrating the superior of biomass-derived nanoporous carbon and Fe 3 O 4 microspheres, the as-prepared C/SiO 2 @Fe 3 O 4 showed high extraction efficiency for target analytes. The obtained material was characterized by scanning electron microscopy, FTIR spectroscopy, X-ray photoelectron spectroscopy and the Brunauer-Emmett-Teller method, which demonstrated that C/SiO 2 @Fe 3 O 4 was successfully synthesized. Under the optimal conditions, the adsorbent was selected for the selective adsorption of seven insecticides before gas chromatography with mass spectrometry detection, good linearity was obtained in the concentration range of 2-200 μg/kg with the correlation coefficient ranging from 0.9952 to 0.9997. The limits of detection were in the range of 0.03-0.39 μg/kg. The proposed method has been successfully applied to the enrichment and detection of seven insecticides in real vegetable samples. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Nanoporous materials for reducing the over potential of creating hydrogen by water electrolysis

DOEpatents

Anderson, Marc A.; Leonard, Kevin C.

2016-06-14

Disclosed is an electrolyzer including an electrode including a nanoporous oxide-coated conducting material. Also disclosed is a method of producing a gas through electrolysis by contacting an aqueous solution with an electrode connected to an electrical power source, wherein the electrode includes a nanoporous oxide-coated conducting material.

Structure-dependent water transport across nanopores of carbon nanotubes: toward selective gating upon temperature regulation.

PubMed

Zhao, Kuiwen; Wu, Huiying

2015-04-28

Determining water structure in nanopores and its influence on water transport behaviour is of great importance for understanding and regulating the transport across nanopores. Here we report an ultrafast-slow flow transition phenomenon for water transport across nanopores of carbon nanotubes owing to the change in water structure in nanopores induced by temperature. By performing extensive molecular dynamics simulations, we show the dependence of water transport behaviours on water structures. Our results indicate that owing to the change in water structure in nanopores, water flux across nanopores with certain pore sizes decreases sharply (nearly 3 orders of magnitude) with the decreasing temperature. This phenomenon is very sensitive to the pore size. The threshold temperatures for the occurrence of the ultrafast-slow flow transition for water transport are also determined for various pore sizes. These findings suggest a novel protocol for selective gating of water and proton conduction across nanopores and temperature-controlled drug release.

Atomic Layer Deposition for the Conformal Coating of Nanoporous Materials

DOE PAGES

Elam, Jeffrey W.; Xiong, Guang; Han, Catherine Y.; ...

2006-01-01

Amore » tomic layer deposition ( LD ) is ideal for applying precise and conformal coatings over nanoporous materials. We have recently used LD to coat two nanoporous solids: anodic aluminum oxide ( O ) and silica aerogels. O possesses hexagonally ordered pores with diameters d ∼ 40 nm and pore length L ∼ 70 microns. The O membranes were coated by LD to fabricate catalytic membranes that demonstrate remarkable selectivity in the oxidative dehydrogenation of cyclohexane. dditional O membranes coated with LD Pd films show promise as hydrogen sensors. Silica aerogels have the lowest density and highest surface area of any solid material. Consequently, these materials serve as an excellent substrate to fabricate novel catalytic materials and gas sensors by LD .« less

Silver-halide photographic materials based on nanoporous glasses

NASA Astrophysics Data System (ADS)

Andreeva, O. V.; Obyknovennaya, I. E.; Gavrilyuk, E. R.; Paramonov, A. A.; Kushnarenko, A. P.

2005-12-01

This paper discusses the results of an investigation of the recording of composite nanoporous photographic materials with a photosensitive composite made from silver halide in gelatin, developed and created at S. I. Vavilov State Optical Institute.

Thermal conversion of an Fe₃O₄@metal-organic framework: a new method for an efficient Fe-Co/nanoporous carbon microwave absorbing material.

PubMed

Zhang, Xingmiao; Ji, Guangbin; Liu, Wei; Quan, Bin; Liang, Xiaohui; Shang, Chaomei; Cheng, Yan; Du, Youwei

2015-08-14

A novel FeCo nanoparticle embedded nanoporous carbon composite (Fe-Co/NPC) was synthesized via in situ carbonization of dehydro-ascorbic acid (DHAA) coated Fe3O4 nanoparticles encapsulated in a metal-organic framework (zeolitic imidazolate framework-67, ZIF-67). The molar ratio of Fe/Co significantly depends on the encapsulated content of Fe3O4 in ZIF-67. The composites filled with 50 wt% of the Fe-Co/NPC-2.0 samples in paraffin show a maximum reflection loss (RL) of -21.7 dB at a thickness of 1.2 mm; in addition, a broad absorption bandwidth for RL < -10 dB which covers from 12.2 to 18 GHz can be obtained, and its minimum reflection loss and bandwidth (RL values exceeding -10 dB) are far greater than those of commercial carbonyl iron powder under a very low thickness (1-1.5 mm). This study not only provides a good reference for future preparation of carbon-based lightweight microwave absorbing materials but also broadens the application of such kinds of metal-organic frameworks.

Microimaging of transient guest profiles to monitor mass transfer in nanoporous materials

NASA Astrophysics Data System (ADS)

Kärger, Jörg; Binder, Tomas; Chmelik, Christian; Hibbe, Florian; Krautscheid, Harald; Krishna, Rajamani; Weitkamp, Jens

2014-04-01

The intense interactions of guest molecules with the pore walls of nanoporous materials is the subject of continued fundamental research. Stimulated by their thermal energy, the guest molecules in these materials are subject to a continuous, irregular motion, referred to as diffusion. Diffusion, which is omnipresent in nature, influences the efficacy of nanoporous materials in reaction and separation processes. The recently introduced techniques of microimaging by interference and infrared microscopy provide us with a wealth of information on diffusion, hitherto inaccessible from commonly used techniques. Examples include the determination of surface barriers and the sticking coefficient's analogue, namely the probability that, on colliding with the particle surface, a molecule may continue its diffusion path into the interior. Microimaging is further seen to open new vistas in multicomponent guest diffusion (including the detection of a reversal in the preferred diffusion pathways), in guest-induced phase transitions in nanoporous materials and in matching the results of diffusion studies under equilibrium and non-equilibrium conditions.

Nanoporous SiC: a candidate semi-permeable material for biomedical applications.

PubMed

Rosenbloom, A J; Sipe, D M; Shishkin, Y; Ke, Y; Devaty, R P; Choyke, W J

2004-12-01

We have fabricated free-standing SiC nanoporous membranes in both p -type and n -type material. We showed that these membranes will permit the diffusion of proteins up to 29000 Daltons, while excluding larger proteins. By using radioactively labeled albumin, we also show that porous SiC has very low protein adsorption, comparable to the best commercially available polymer nanoporous membrane.

Modeling the self-assembly of ordered nanoporous materials

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

Monson, Peter; Auerbach, Scott

This report describes progress on a collaborative project on the multiscale modeling of the assembly processes in the synthesis of nanoporous materials. Such materials are of enormous importance in modern technology with application in the chemical process industries, biomedicine and biotechnology as well as microelectronics. The project focuses on two important classes of materials: i) microporous crystalline materials, such as zeolites, and ii) ordered mesoporous materials. In the first case the pores are part of the crystalline structure, while in the second the structures are amorphous on the atomistic length scale but where surfactant templating gives rise to order onmore » the length scale of 2 - 20 nm. We have developed a modeling framework that encompasses both these kinds of materials. Our models focus on the assembly of corner sharing silica tetrahedra in the presence of structure directing agents. We emphasize a balance between sufficient realism in the models and computational tractibility given the complex many-body phenomena. We use both on-lattice and off-lattice models and the primary computational tools are Monte Carlo simulations with sampling techniques and ensembles appropriate to specific situations. Our modeling approach is the first to capture silica polymerization, nanopore crystallization, and mesopore formation through computer-simulated self assembly.« less

A Nanopore-Structured Nitrogen-Doped Biocarbon Electrocatalyst for Oxygen Reduction from Two-Step Carbonization of Lemna minor Biomass

NASA Astrophysics Data System (ADS)

Guo, Chaozhong; Li, Zhongbin; Niu, Lidan; Liao, Wenli; Sun, Lingtao; Wen, Bixia; Nie, Yunqing; Cheng, Jing; Chen, Changguo

2016-05-01

So far, the development of highly active and stable carbon-based electrocatalysts for oxygen reduction reaction (ORR) to replace commercial Pt/C catalyst is a hot topic. In this study, a new nanoporous nitrogen-doped carbon material was facilely designed by two-step pyrolysis of the renewable Lemna minor enriched in crude protein under a nitrogen atmosphere. Electrochemical measurements show that the onset potential for ORR on this carbon material is around 0.93 V (versus reversible hydrogen electrode), slightly lower than that on the Pt/C catalyst, but its cycling stability is higher compared to the Pt/C catalyst in an alkaline medium. Besides, the ORR at this catalyst approaches to a four-electron transfer pathway. The obtained ORR performance can be basically attributed to the formation of high contents of pyridinic and graphitic nitrogen atoms inside this catalyst. Thus, this work opens up the path in the ORR catalysis for the design of nitrogen-doped carbon materials utilizing aquatic plants as starting precursors.

A Nanopore-Structured Nitrogen-Doped Biocarbon Electrocatalyst for Oxygen Reduction from Two-Step Carbonization of Lemna minor Biomass.

PubMed

Guo, Chaozhong; Li, Zhongbin; Niu, Lidan; Liao, Wenli; Sun, Lingtao; Wen, Bixia; Nie, Yunqing; Cheng, Jing; Chen, Changguo

2016-12-01

So far, the development of highly active and stable carbon-based electrocatalysts for oxygen reduction reaction (ORR) to replace commercial Pt/C catalyst is a hot topic. In this study, a new nanoporous nitrogen-doped carbon material was facilely designed by two-step pyrolysis of the renewable Lemna minor enriched in crude protein under a nitrogen atmosphere. Electrochemical measurements show that the onset potential for ORR on this carbon material is around 0.93 V (versus reversible hydrogen electrode), slightly lower than that on the Pt/C catalyst, but its cycling stability is higher compared to the Pt/C catalyst in an alkaline medium. Besides, the ORR at this catalyst approaches to a four-electron transfer pathway. The obtained ORR performance can be basically attributed to the formation of high contents of pyridinic and graphitic nitrogen atoms inside this catalyst. Thus, this work opens up the path in the ORR catalysis for the design of nitrogen-doped carbon materials utilizing aquatic plants as starting precursors.

Nanoarchitectures for Metal-Organic Framework-Derived Nanoporous Carbons toward Supercapacitor Applications.

PubMed

Salunkhe, Rahul R; Kaneti, Yusuf Valentino; Kim, Jeonghun; Kim, Jung Ho; Yamauchi, Yusuke

2016-12-20

The future advances of supercapacitors depend on the development of novel carbon materials with optimized porous structures, high surface area, high conductivity, and high electrochemical stability. Traditionally, nanoporous carbons (NPCs) have been prepared by a variety of methods, such as templated synthesis, carbonization of polymer precursors, physical and chemical activation, etc. Inorganic solid materials such as mesoporous silica and zeolites have been successfully utilized as templates to prepare NPCs. However, the hard-templating methods typically involve several synthetic steps, such as preparation of the original templates, formation of carbon frameworks, and removal of the original templates. Therefore, these methods are not favorable for large-scale production. Metal-organic frameworks (MOFs) with high surface areas and large pore volumes have been studied over the years, and recently, enormous efforts have been made to utilize MOFs for electrochemical applications. However, their low conductivity and poor stability still present major challenges toward their practical applications in supercapacitors. MOFs can be used as precursors for the preparation of NPCs with high porosity. Their parent MOFs can be prepared with endless combinations of organic and inorganic constituents by simple coordination chemistry, and it is possible to control their porous architectures, pore volumes, surface areas, etc. These unique properties of MOF-derived NPCs make them highly attractive for many technological applications. Compared with carbonaceous materials prepared using conventional precursors, MOF-derived carbons have significant advantages in terms of a simple synthesis with inherent diversity affording precise control over porous architectures, pore volumes, and surface areas. In this Account, we will summarize our recent research developments on the preparation of three-dimensional (3-D) MOF-derived carbons for supercapacitor applications. This Account will be

Nanoporous Ru as a carbon- and binder-free cathode for Li-O2 batteries.

PubMed

Liao, Kaiming; Zhang, Tao; Wang, Yongqing; Li, Fujun; Jian, Zelang; Yu, Haijun; Zhou, Haoshen

2015-04-24

Porous carbon-free cathodes are critical to achieve a high discharge capacity and efficient cycling for rechargeable Li-O2 battery. Herein, we present a very simple method to directly grow nanoporous Ru (composed of polycrystalline particles of ∼5 nm) on one side of a current collector of Ni foam via a galvanic replacement reaction. The resulting Ru@Ni can be employed as a carbon- and binder-free cathode for Li-O2 batteries and delivers a specific capacity of 3720 mAh gRu (-1) at a current density of 200 mA gRu (-1) . 100 cycles of continuous discharge and charge are obtained at a very narrow terminal voltage window of 2.75∼3.75 V with a limited capacity of 1000 mAh gRu (-1) . The good performance of the nanoporous Ru@Ni cathode can be mainly attributed to the effective suppression of the by-products related to carbon or binder, the good adhesion of the catalyst to the current collector, and the good permeation of O2 and electrolyte into the active sites of the nanoporous Ru with the open pore system. This new type electrode provides a snapshot toward developing high-performance carbon- and binder-free Li-O2 batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrasonic modification of carbon materials for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Rachiy, Bogdan I.; Nykoliuk, Marian O.; Budzulyak, Ivan M.; Kachmar, Andrii I.

2017-01-01

The paper is devoted to study the ultrasonic impact on the biomass of natural raw materials, which were used for the creation a nanoporous carbon material (NCM), which was used as electrode material for electrochemical capacitors (EC). The dry shells of apricot seeds were a feedstock, which were modified by the chemical treatment in the phosphoric acid and part of them were impacted by ultrasonic waves for 25 minutes. The NCM, which were obtained by carbonization at 550 °C, were modified by chemical treatment in the nitric acid. Thus, the different of modification NCM was obtained to compare their capacitance characteristics for EC. From experimental data we can do a conclusion, that ultrasonic modification and chemical treatment in nitric acidare improvecapacitance characteristics of NCM for EC.

Nanoporous Carbons: Looking Beyond Their Perception as Adsorbents, Catalyst Supports and Supercapacitors.

PubMed

Bandosz, Teresa J

2016-02-01

The discovery of carbon nanoforms, and especially graphene, has opened up new directions of science and technology. Many applications are based on the unique properties of graphene, such as its high electrical and thermal conductivity, strength, flexibility, photoactivity and transparency. Inspired by the emerging graphene science, we directed our efforts to the exploration of new applications of nanoporous (microporous) carbons. Their matrix is built of distorted graphene layers, between which pores with sizes ranging from a fraction of a nanometer to hundreds of nanometers exist. This is a very unique feature of nanoporous carbons resulting in their developed surface areas. Moreover, there are vast possibilities to modify the surface chemistry of carbons and thus their surface properties. Even though the traditional applications of porous carbons focus mainly on adsorption and separation, we decided to explore them as photocatalysts, oxygen reduction catalysts and sensors. Related to their visible-light activity, their possible application in solar energy harvesting is also indicated. This Personal Account presents our paths leading to the exploration of these directions, describing the results collected and difficulties encountered, along with the challenges remaining to be addressed. © 2015 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Constructing nanoporous carbon nanotubes/Bi2Te3 composite for synchronous regulation of the electrical and thermal performances

NASA Astrophysics Data System (ADS)

Zhang, Qihao; Xu, Leilei; Zhou, Zhenxing; Wang, Lianjun; Jiang, Wan; Chen, Lidong

2017-02-01

Porous nanograined thermoelectric materials exhibit low thermal conductivity due to scattering of phonons by pores, which are favorable for thermoelectric applications. However, the benefit is not large enough to overcome the deficiency in the electrical performance. Herein, an approach is presented to reduce the thermal conductivity and synchronously enhance the electrical conductivity through constructing a nanoporous thermoelectric composite. Carbon nanotubes (CNTs) are truncated and homogeneously dispersed within the Bi2Te3 matrix by a cryogenic grinding (CG) technique for the first time, which efficiently suppress the Bi2Te3 grain growth and create nanopores with the size ranging from dozens to hundreds of nanometers. The lattice thermal conductivity is substantially decreased by broad wavelength phonon scattering resulting from nanopores, increased grain boundaries, and newly formed interfaces. Meanwhile, the electrical conductivity is improved due to the enhanced carrier mobility, which may originate from the bridging effect between the Bi2Te3 grains and CNTs. The maximum ZT is improved by almost a factor of 2 due to the simultaneous optimization of electrical and thermal performances. Our study demonstrates the superiority of constructing a bulk thermoelectric composite with nanopores by the uniform dispersion of CNTs through a CG technique for enhanced thermoelectric properties, which provides a wider approach to thermoelectric nanostructure engineering.

Nanoporous separators for supercapacitor using activated carbon monolith electrode from oil palm empty fruit bunches

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

Nor, N. S. M., E-mail: madra@ukm.my; Deraman, M., E-mail: madra@ukm.my; Omar, R., E-mail: madra@ukm.my

Activated porous carbon electrode prepared from fibres of oil palm empty fruit bunches was used for preparing the carbon based supercapacitor cells. The symmetrical supercapacitor cells were fabricated using carbon electrodes, stainless steel current collector, H{sub 2}SO{sub 4} electrolyte, and three types of nanoporous separators. Cells A, B and C were fabricated using polypropylene, eggshell membrane, and filter paper, respectively. Electrochemical characterizations data from Electrochemical Impedance Spectroscopy, Cyclic Voltammetry, and Galvanic Charge Discharge techniques showed that specific capacitance, specific power and specific energy for cell A were 122 F g{sup −1}, 177 W kg{sup −1}, 3.42 Wh kg{sup −1}, cellmore » B; 125 F g{sup −1}, 179 W kg{sup −1}, and 3.64 Wh kg{sup −1}, and cell C; 180 F g{sup −1}, 178 W kg{sup −1}, 4.27 Wh kg{sup −1}. All the micrographs from Field Emission Scanning Electron Microscope showed that the different in nanoporous structure of the separators lead to a significant different in influencing the values of specific capacitance, power and energy of supercapacitors, which is associated with the mobility of ion into the pore network. These results indicated that the filter paper was superior than the eggshell membrane and polypropylene nanoporous separators. However, we found that in terms of acidic resistance, polypropylene was the best nanoporous separator for acidic medium.« less

A new family of fluidic precursors for the self-templated synthesis of hierarchical nanoporous carbons

DOE PAGES

Fulvio, Pasquale F.; Hillesheim, Patrick C.; Oyola, Yatsandra; ...

2016-06-24

Hierarchical nanoporous nitrogen-doped carbons were prepared from task specific ionic liquids having a bis-imidazolium motif linked with various organic groups. While ethyl chains linking the imidazolium ions afford microporous-mesoporous carbons, long or aromatic groups resulted in microporous samples.

Mechanisms of material removal and mass transport in focused ion beam nanopore formation

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

Das, Kallol, E-mail: das7@illinois.edu; Johnson, Harley T., E-mail: htj@illinois.edu; Freund, Jonathan B., E-mail: jbfreund@illinois.edu

2015-02-28

Despite the widespread use of focused ion beam (FIB) processing as a material removal method for applications ranging from electron microscope sample preparation to nanopore processing for DNA sequencing, the basic material removal mechanisms of FIB processing are not well understood. We present the first complete atomistic simulation of high-flux FIB using large-scale parallel molecular dynamics (MD) simulations of nanopore fabrication in freestanding thin films. We focus on the root mechanisms of material removal and rearrangement and describe the role of explosive boiling in forming nanopores. FIB nanopore fabrication is typically understood to occur via sputter erosion. This can bemore » shown to be the case in low flux systems, where individual ion impacts are sufficiently separated in time that they may be considered as independent events. But our detailed MD simulations show that in high flux FIB processing, above a threshold level at which thermal effects become significant, the primary mechanism of material removal changes to a significantly accelerated, thermally dominated process. Under these conditions, the target is heated by the ion beam faster than heat is conducted away by the material, leading quickly to melting, and then continued heating to nearly the material critical temperature. This leads to explosive boiling of the target material with spontaneous bubble formation and coalescence. Mass is rapidly rearranged at the atomistic scale, and material removal occurs orders of magnitude faster than would occur by simple sputtering. While the phenomenology is demonstrated computationally in silicon, it can be expected to occur at lower beam fluxes in other cases where thermal conduction is suppressed due to material properties, geometry, or ambient thermal conditions.« less

Nanoporous TiNb2O7/C Composite Microspheres with Three-Dimensional Conductive Network for Long-Cycle-Life and High-Rate-Capability Anode Materials for Lithium-Ion Batteries.

PubMed

Zhu, Guozhen; Li, Qing; Zhao, Yunhao; Che, Renchao

2017-11-29

On the basis of the advantages of ideal cycling stability, high discharge voltage (1.65 V), and excellent reversibility, more and more attention has been focused on TiNb 2 O 7 (marked as TNO) as an anode material candidate for lithium-ion batteries. However, the poor electronic conductivity and low ionic diffusion rate intrinsically restrict its practical use. Herein, we first synthesize the TNO/C composite microspheres with three-dimensionally (marked as 3D) electro-conductive carbon network and abundant nanoporous structure by a simple spray-drying method. The microspheres are constructed by irregularly primary cubic nanoparticle units with size of 100-200 nm. The nanopores throughout the microspheres range from 1 to 50 nm. As an anode material, the prepared TNO/C composite microspheres demonstrate a prominent charge/discharge capacity of 323.2/326 mA h g -1 after 300 cycles at 0.25 C (1 C = 388 mA g -1 ) and 259.9/262.5 mA h g -1 after 1000 long cycles at a high current density of 5 C, revealing the ideal reversible capacity and long cycling life. Meanwhile, the TNO/C composite microspheres present ideal rate performance, showing the discharge capacity of 120 mA h g -1 at 30 C after 10 cycles. The super electrochemical performance could be attributed to the 3D electro-conductive carbon network and nanoporous structure. The nanopores facilitate the permeation of electrolyte into the intercontacting regions of the anode materials. Carbon layers disperse uniformly throughout the 3D microspheres, effectively improving the electrical conductivity of the electrode. Hence, the prepared TNO/C composite microspheres have great potential to be used as an anode material for lithium-ion batteries.

Ultrasonic modification of carbon materials for electrochemical capacitors.

PubMed

Rachiy, Bogdan I; Nykoliuk, Marian O; Budzulyak, Ivan M; Kachmar, Andrii I

2017-12-01

The paper is devoted to study the ultrasonic impact on the biomass of natural raw materials, which were used for the creation a nanoporous carbon material (NCM), which was used as electrode material for electrochemical capacitors (EC). The dry shells of apricot seeds were a feedstock, which were modified by the chemical treatment in the phosphoric acid and part of them were impacted by ultrasonic waves for 25 minutes. The NCM, which were obtained by carbonization at 550 °C, were modified by chemical treatment in the nitric acid. Thus, the different of modification NCM was obtained to compare their capacitance characteristics for EC. From experimental data we can do a conclusion, that ultrasonic modification and chemical treatment in nitric acidare improvecapacitance characteristics of NCM for EC.

Solvent-Free Mechanochemical Synthesis of Nitrogen-Doped Nanoporous Carbon for Electrochemical Energy Storage.

PubMed

Schneidermann, Christina; Jäckel, Nicolas; Oswald, Steffen; Giebeler, Lars; Presser, Volker; Borchardt, Lars

2017-06-09

Nitrogen-doped nanoporous carbons were synthesized by a solvent-free mechanochemically induced one-pot synthesis. This facile approach involves the mechanochemical treatment and carbonization of three solid materials: potassium carbonate, urea, and lignin, which is a waste product from pulp industry. The resulting nitrogen-doped porous carbons offer a very high specific surface area up to 3000 m 2  g -1 and large pore volume up to 2 cm 3  g -1 . The mechanochemical reaction and the impact of activation and functionalization are investigated by nitrogen and water physisorption and high-resolution X-ray photoelectron spectroscopy (XPS). Our N-doped carbons are highly suitable for electrochemical energy storage as supercapacitor electrodes, showing high specific capacitances in aqueous 1 m Li 2 SO 4 electrolyte (177 F g -1 ), organic 1 m tetraethylammonium tetrafluoroborate in acetonitrile (147 F g -1 ), and an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate; 192 F g -1 ). This new mechanochemical pathway synergistically combines attractive energy-storage ratings with a scalable, time-efficient, cost-effective, and environmentally favorable synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

CNTs grown on nanoporous carbon from zeolitic imidazolate frameworks for supercapacitors.

PubMed

Kim, Jeonghun; Young, Christine; Lee, Jaewoo; Park, Min-Sik; Shahabuddin, Mohammed; Yamauchi, Yusuke; Kim, Jung Ho

2016-10-27

Carbon nanotubes (CNT) grown on nanoporous carbon (NPC), which yields coexisting amorphous and graphitic nanoarchitectures, have been prepared on a large scale from zeolitic imidazolate framework (ZIF) by introducing bimetallic ions (Co 2+ and Zn 2+ ). Interestingly, the hybrid Co/Zn-ZIF-derived NPC showed rich graphitic CNTs on the surface. This NPC was utilized for a coin-type supercapacitor cell with an aqueous electrolyte, which showed enhanced retention at high current density and good stability over 10 000 cycles.

The Upper Limit of Energy Density of Nanoporous Materials Functionalized Liquid

NASA Astrophysics Data System (ADS)

Han, Aijie; Punyamurtula, Venkata K.; Kim, Taewan; Qiao, Yu

2008-06-01

In this article, we report the experimental result of energy dissipation of a mobil crystalline material (MCM) 41 in mercury. The MCM41 contains a large volume fraction of nanometer-sized pores. As the applied pressure is relatively high, the nanopore surfaces are exposed to mercury. Due to the large nanopore surface area and the large solid-liquid interfacial tension, the energy dissipation effectiveness of this system is ultrahigh, representing the upper limit that can be achieved by the pressure-induced infiltration technique.

Synthesis of nanoporous TiO2 materials using a doubly surfactant system and applying them as useful adsorbents

NASA Astrophysics Data System (ADS)

Anbia, Mansoor; Khosravi, Faezeh

Hydrothermal and non-hydrothermal nanoporous TiO2 materials were synthesized via a doubly surfactant route by using cationic cetyltrimethylammonium bromide and anionic sodium dodecyl sulfate surfactants as the molecular template/structure directing agent. Hydrothermal treatment was performed for comparison. The bulk chemical and phase compositions, crystalline structures, particle morphologies, thermal stabilities and surface texturing were determined by means of X-ray powder analysis, SEM and N2 sorptiometry. The nanoporous TiO2 materials were found to have a spherical morphology with a diameter range of 50-200 nm and a high surface area (390 m2 g-1). Hydrothermal and non-hydrothermal nanoporous TiO2 materials were applied for adsorption of heavy metal cations and the toxic organic compound, copper phthalocyanine, from water for evaluation of their adsorption properties. Both nanoporous TiO2 materials were found to have similar adsorption capacities toward heavy metal cations and CuPc. Both hydrothermal and non-hydrothermal TiO2 nanoporous materials were found to have very good potential for application as a new adsorbent especially for adsorbing heavy metal cations from wastewaters.

Fabrication and characterization of a solid state nanopore with self-aligned carbon nanoelectrodes for molecular detection

NASA Astrophysics Data System (ADS)

Spinney, Patrick; Collins, Scott D.; Howitt, David G.; Smith, Rosemary L.

2012-06-01

Rapid and cost-effective DNA sequencing is a pivotal prerequisite for the genomics era. Many of the recent advances in forensics, medicine, agriculture, taxonomy, and drug discovery have paralleled critical advances in DNA sequencing technology. Nanopore modalities for DNA sequencing have recently surfaced including the electrical interrogation of protein ion channels and/or solid-state nanopores during translocation of DNA. However to date, most of this work has met with mixed success. In this work, we present a unique nanofabrication strategy that realizes an artificial nanopore articulated with carbon electrodes to sense the current modulations during the transport of DNA through the nanopore. This embodiment overcomes most of the technical difficulties inherent in other artificial nanopore embodiments and present a versatile platform for the testing of DNA single nucleotide detection. Characterization of the device using gold nanoparticles, silica nanoparticles, lambda dsDNA and 16-mer ssDNA are presented. Although single molecule DNA sequencing is still not demonstrated, the device shows a path towards this goal.

Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation

DOE PAGES

Personick, Michelle L.; Zugic, Branko; Biener, Monika M.; ...

2015-05-28

We report a new method for facile and reproducible activation of nanoporous gold (npAu) materials of different forms for the catalytic selective partial oxidation of alcohols under ambient pressure, steady flow conditions. This method, based on the surface cleaning of npAu ingots with ozone to remove carbon documented in ultrahigh vacuum conditions, produces active npAu catalysts from ingots, foils, and shells by flowing an ozone/dioxygen mixture over the catalyst at 150 °C, followed by a temperature ramp from 50 to 150 °C in a flowing stream of 10% methanol and 20% oxygen. With this treatment, all three materials (ingots, foils,more » and shells) can be reproducibly activated, despite potential carbonaceous poisons resulting from their synthesis, and are highly active for the selective oxidation of primary alcohols over prolonged periods of time. The npAu materials activated in this manner exhibit catalytic behavior substantially different from those activated under different conditions previously reported. Once activated in this manner, they can be stored and easily reactivated by flow of reactant gases at 150 °C for a few hours. They possess improved selectivity for the coupling of higher alcohols, such as 1-butanol, and are not active for carbon monoxide oxidation. As a result, this ozone-treated npAu is a functionally new catalytic material.« less

Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation

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

Personick, Michelle L.; Zugic, Branko; Biener, Monika M.

We report a new method for facile and reproducible activation of nanoporous gold (npAu) materials of different forms for the catalytic selective partial oxidation of alcohols under ambient pressure, steady flow conditions. This method, based on the surface cleaning of npAu ingots with ozone to remove carbon documented in ultrahigh vacuum conditions, produces active npAu catalysts from ingots, foils, and shells by flowing an ozone/dioxygen mixture over the catalyst at 150 °C, followed by a temperature ramp from 50 to 150 °C in a flowing stream of 10% methanol and 20% oxygen. With this treatment, all three materials (ingots, foils,more » and shells) can be reproducibly activated, despite potential carbonaceous poisons resulting from their synthesis, and are highly active for the selective oxidation of primary alcohols over prolonged periods of time. The npAu materials activated in this manner exhibit catalytic behavior substantially different from those activated under different conditions previously reported. Once activated in this manner, they can be stored and easily reactivated by flow of reactant gases at 150 °C for a few hours. They possess improved selectivity for the coupling of higher alcohols, such as 1-butanol, and are not active for carbon monoxide oxidation. As a result, this ozone-treated npAu is a functionally new catalytic material.« less

Confinement, Desolvation, And Electrosorption Effects on the Diffusion of Ions in Nanoporous Carbon Electrodes

PubMed Central

2015-01-01

Supercapacitors are electrochemical devices which store energy by ion adsorption on the surface of a porous carbon. They are characterized by high power delivery. The use of nanoporous carbon to increase their energy density should not hinder their fast charging. However, the mechanisms for ion transport inside electrified nanopores remain largely unknown. Here we show that the diffusion is characterized by a hierarchy of time scales arising from ion confinement, solvation, and electrosorption effects. By combining electrochemistry experiments with molecular dynamics simulations, we determine the in-pore conductivities and diffusion coefficients and their variations with the applied potential. We show that the diffusion of the ions is slower by 1 order of magnitude compared to the bulk electrolyte. The desolvation of the ions occurs on much faster time scales than electrosorption. PMID:26369420

Molecular simulations for energy, environmental and pharmaceutical applications of nanoporous materials: from zeolites, metal-organic frameworks to protein crystals.

PubMed

Jiang, Jianwen; Babarao, Ravichandar; Hu, Zhongqiao

2011-07-01

Nanoporous materials have widespread applications in chemical industry, but the pathway from laboratory synthesis and testing to practical utilization of nanoporous materials is substantially challenging and requires fundamental understanding from the bottom up. With ever-growing computational resources, molecular simulations have become an indispensable tool for material characterization, screening and design. This tutorial review summarizes the recent simulation studies in zeolites, metal-organic frameworks and protein crystals, and provides a molecular overview for energy, environmental and pharmaceutical applications of nanoporous materials with increasing degree of complexity in building blocks. It is demonstrated that molecular-level studies can bridge the gap between physical and engineering sciences, unravel microscopic insights that are otherwise experimentally inaccessible, and assist in the rational design of new materials. The review is concluded with major challenges in future simulation exploration of novel nanoporous materials for emerging applications.

Building membrane nanopores

NASA Astrophysics Data System (ADS)

Howorka, Stefan

2017-07-01

Membrane nanopores--hollow nanoscale barrels that puncture biological or synthetic membranes--have become powerful tools in chemical- and biosensing, and have achieved notable success in portable DNA sequencing. The pores can be self-assembled from a variety of materials, including proteins, peptides, synthetic organic compounds and, more recently, DNA. But which building material is best for which application, and what is the relationship between pore structure and function? In this Review, I critically compare the characteristics of the different building materials, and explore the influence of the building material on pore structure, dynamics and function. I also discuss the future challenges of developing nanopore technology, and consider what the next-generation of nanopore structures could be and where further practical applications might emerge.

Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores

PubMed Central

Futamura, Ryusuke; Iiyama, Taku; Takasaki, Yuma; Gogotsi, Yury; Biggs, Mark J.; Salanne, Mathieu; Ségalini, Julie; Simon, Patrice; Kaneko, Katsumi

2017-01-01

Ionic liquids are composed of equal quantities of positive and negative ions. In the bulk, electrical neutrality occurs in these liquids due to Coulombic ordering, in which ion shells of alternating charge form around a central ion. Their structure under confinement is far less well understood. This hinders the widespread application of ionic liquids in technological applications. Here we use scattering experiments to resolve the structure of the widely used ionic liquid (EMI-TFSI) when it is confined inside nanoporous carbons. We show that Coulombic ordering reduces when the pores can only accommodate a single layer of ions. Instead, equally-charged ion pairs are formed due to the induction of an electric potential of opposite sign in the carbon pore walls. This non-Coulombic ordering is further enhanced in the presence of an applied external electric potential. This finding opens the door for the design of better materials for electrochemical applications. PMID:28920938

Synthesis of Foam-Shaped Nanoporous Zeolite Material: A Simple Template-Based Method

ERIC Educational Resources Information Center

Saini, Vipin K.; Pires, Joao

2012-01-01

Nanoporous zeolite foam is an interesting crystalline material with an open-cell microcellular structure, similar to polyurethane foam (PUF). The aluminosilicate structure of this material has a large surface area, extended porosity, and mechanical strength. Owing to these properties, this material is suitable for industrial applications such as…

DNA translocation through graphene nanopores.

PubMed

Merchant, Christopher A; Healy, Ken; Wanunu, Meni; Ray, Vishva; Peterman, Neil; Bartel, John; Fischbein, Michael D; Venta, Kimberly; Luo, Zhengtang; Johnson, A T Charlie; Drndić, Marija

2010-08-11

We report on DNA translocations through nanopores created in graphene membranes. Devices consist of 1-5 nm thick graphene membranes with electron-beam sculpted nanopores from 5 to 10 nm in diameter. Due to the thin nature of the graphene membranes, we observe larger blocked currents than for traditional solid-state nanopores. However, ionic current noise levels are several orders of magnitude larger than those for silicon nitride nanopores. These fluctuations are reduced with the atomic-layer deposition of 5 nm of titanium dioxide over the device. Unlike traditional solid-state nanopore materials that are insulating, graphene is an excellent electrical conductor. Use of graphene as a membrane material opens the door to a new class of nanopore devices in which electronic sensing and control are performed directly at the pore.

Self-Sacrificial Salt Templating: Simple Auxiliary Control over the Nanoporous Structure of Porous Carbon Monoliths Prepared through the Solvothermal Route

PubMed Central

Feng, Junzong; Jiang, Yonggang; Liu, Ping; Zhang, Qiuhua; Wei, Ronghui; Chen, Xiang; Feng, Jian

2018-01-01

The conventional sol-gel method for preparing porous carbons is tedious and high-cost to prepare porous carbons and the control over the nanoporous architecture by solvents and carbonization is restricted. A simple and novel self-sacrificial salt templating method was first presented to adjust the microporous structure of porous carbon monoliths synthesized via the solvothermal method. Apart from good monolithic appearance, the solvothermal route allowed for ambient drying because it made sure that the polymerization reaction was completed quickly and thoroughly. The intact and crack-free porous carbon monoliths were investigated by scanning electron microscopy (SEM), thermogravimetric differential scanning calorimetry (TG-DSC), Fourier transform infrared (FT-IR), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and nitrogen sorption measurements. It was proven that the self-sacrificial salts NH4SCN had been removed during pyrolyzing and so, porous carbon monoliths could be directly obtained after carbonization without the need of washing removal of salts. Most importantly, the microporous specific surface area of the resultant porous carbon monoliths was dramatically increased up to 770 m2/g and the Brunauer–Emmett–Teller (BET) specific surface area was up to 1131 m2/g. That was because the salts NH4SCN as self-sacrificial templating helped to form more around 0.6 nm, 0.72 nm and 1.1 nm micropores. The self-sacrificial salt templating is also a suitable and feasible method for controlling the nanoporous structure of other porous materials. PMID:29671818

In situ heavy ion irradiation studies of nanopore shrinkage and enhanced radiation tolerance of nanoporous Au

DOE PAGES

Li, Jin; Fan, Cuncai; Ding, Jie; ...

2017-01-03

High energy particle radiations induce severe microstructural damage in metallic materials. Nanoporous materials with a giant surface-to-volume ratio may alleviate radiation damage in irradiated metallic materials as free surface are defect sinks. We show, by using in situ Kr ion irradiation in a transmission electron microscope at room temperature, that nanoporous Au indeed has significantly improved radiation tolerance comparing with coarse-grained, fully dense Au. In situ studies show that nanopores can absorb and eliminate a large number of radiation-induced defect clusters. Meanwhile, nanopores shrink (self-heal) during radiation, and their shrinkage rate is pore size dependent. Furthermore, the in situ studiesmore » show dose-rate-dependent diffusivity of defect clusters. Our study sheds light on the design of radiation-tolerant nanoporous metallic materials for advanced nuclear reactor applications.« less

Active pore space utilization in nanoporous carbon-based supercapacitors: Effects of conductivity and pore accessibility

NASA Astrophysics Data System (ADS)

Seredych, Mykola; Koscinski, Mikolaj; Sliwinska-Bartkowiak, Malgorzata; Bandosz, Teresa J.

2012-12-01

Composites of commercial graphene and nanoporous sodium-salt-polymer-derived carbons were prepared with 5 or 20 weight% graphene. The materials were characterized using the adsorption of nitrogen, SEM/EDX, thermal analysis, Raman spectroscopy and potentiometric titration. The samples' conductivity was also measured. The performance of the carbon composites in energy storage was linked to their porosity and electronic conductivity. The small pores (<0.7) were found as very active for double layer capacitance. It was demonstrated that when double layer capacitance is a predominant mechanism of charge storage, the degree of the pore space utilization for that storage can be increased by increasing the conductivity of the carbons. That active pore space utilization is defined as gravimetric capacitance per unit pore volume in pores smaller than 0.7 nm. Its magnitude is affected by conductivity of the carbon materials. The functional groups, besides pseudocapacitive contribution, increased the wettability and thus the degree of the pore space utilization. Graphene phase, owing to its conductivity, also took part in an insitu increase of the small pore accessibility and thus the capacitance of the composites via enhancing an electron transfer to small pores and thus imposing the reduction of groups blocking the pores for electrolyte ions.

In Operando Quantification of Three-Dimensional Water Distribution in Nanoporous Carbon-Based Layers in Polymer Electrolyte Membrane Fuel Cells.

PubMed

Alrwashdeh, Saad S; Manke, Ingo; Markötter, Henning; Klages, Merle; Göbel, Martin; Haußmann, Jan; Scholta, Joachim; Banhart, John

2017-06-27

Understanding the function of nanoporous materials employed in polymer electrolyte membrane fuel cells (PEMFCs) is crucial to improve their performance, durability, and cost efficiency. Up to now, the water distribution in the nm-sized pore structures was hardly accessible during operation of the cells. Here we demonstrate that phase contrast synchrotron X-ray tomography allows for an in operando quantification of the three-dimensional water distribution within the nm-sized pores of carbon-based microporous layers (MPLs). For this purpose, a fuel cell design optimized for tomographic phase contrast measurements was realized. Water in the pores of the entire MPL was detected and quantified. We found an inhomogeneous distribution of the local water saturation and a sharp boundary between mostly filled MPL and almost empty areas. We attribute the latter observation to the two-phase boundary created because condensation takes place predominantly on one side of the boundary. Furthermore, high water saturation in large areas hints at gas diffusion or transport along preferred three-dimensional paths through the material, therefore bypassing most of the MPL volume. Our approach may contribute significantly to future investigations of nanoporous fuel cell materials under realistic operating conditions.

Nanoporous frameworks exhibiting multiple stimuli responsiveness

NASA Astrophysics Data System (ADS)

Kundu, Pintu K.; Olsen, Gregory L.; Kiss, Vladimir; Klajn, Rafal

2014-04-01

Nanoporous frameworks are polymeric materials built from rigid molecules, which give rise to their nanoporous structures with applications in gas sorption and storage, catalysis and others. Conceptually new applications could emerge, should these beneficial properties be manipulated by external stimuli in a reversible manner. One approach to render nanoporous frameworks responsive to external signals would be to immobilize molecular switches within their nanopores. Although the majority of molecular switches require conformational freedom to isomerize, and switching in the solid state is prohibited, the nanopores may provide enough room for the switches to efficiently isomerize. Here we describe two families of nanoporous materials incorporating the spiropyran molecular switch. These materials exhibit a variety of interesting properties, including reversible photochromism and acidochromism under solvent-free conditions, light-controlled capture and release of metal ions, as well reversible chromism induced by solvation/desolvation.

Structure of nanoporous carbon materials for supercapacitors

NASA Astrophysics Data System (ADS)

Volperts, A.; Mironova-Ulmane, N.; Sildos, I.; Vervikishko, D.; Shkolnikov, E.; Dobele, G.

2012-08-01

Activated carbons with highly developed porous structure and nanosized pores (8 - 11 Å) were prepared from alder wood using thermochemical activation method with sodium hydroxide. Properties of the obtained activated carbons were examined by benzene and nitrogen sorption, X-Ray diffraction and Raman spectroscopy. Tests of activated carbons as electrodes in supercapacitors were performed as well. It was found that specific surface area of above mentioned activated carbons was 1800 m2/g (Dubinin - Radushkevich). Raman spectroscopy demonstrated the presence of ordered and disordered structures of graphite origin. The performance of activated carbons as electrodes in supercapacitors have shown superior results in comparison with electrodes made with commercial carbon tissues.

Nanoporous aerogel as a bacteria repelling hygienic material for healthcare environment

NASA Astrophysics Data System (ADS)

Oh, Jun Kyun; Kohli, Nandita; Zhang, Yuanzhong; Min, Younjin; Jayaraman, Arul; Cisneros-Zevallos, Luis; Akbulut, Mustafa

2016-02-01

Healthcare-associated infections (HAIs) caused by pathogenic bacteria are a worldwide problem and responsible for numerous cases of morbidity and mortality. Exogenous cross-contamination is one of the main mechanisms contributing to such infections. This work investigates the potential of hydrophobically modified nanoporous silica aerogel as an antiadhesive hygienic material that can inhibit exogenous bacterial contamination. Nanoporous silica aerogels were synthesized via sol-gel polymerization of tetraethyl orthosilicate and hydrophobized using trimethylsilyl chloride. Bacterial adhesion characteristics were evaluated via dip-inoculation in suspensions of Gram-negative Escherichia coli O157:H7 and Gram-positive Staphylococcus aureus. The attachment of E. coli O157:H7 and S. aureus to hydrophobic nanoporous silica aerogel (HNSA) was found to be significantly lower than that to hydrophilic and hydrophobic nonporous silica materials: 99.91% (E. coli O157:H7) and 99.93% (S. aureus) reduction in comparison to hydrophilic nonporous silica, and 82.95% (E. coli O157:H7) and 84.90% (S. aureus) reduction in comparison to hydrophobic nonporous silica. These results suggest that the use of HNSA as surfaces that come into contact with bacterial pathogens in the healthcare environment can improve bacterial hygiene, and therefore may reduce the rate of HAIs.

Nanoporous aerogel as a bacteria repelling hygienic material for healthcare environment.

PubMed

Oh, Jun Kyun; Kohli, Nandita; Zhang, Yuanzhong; Min, Younjin; Jayaraman, Arul; Cisneros-Zevallos, Luis; Akbulut, Mustafa

2016-02-26

Healthcare-associated infections (HAIs) caused by pathogenic bacteria are a worldwide problem and responsible for numerous cases of morbidity and mortality. Exogenous cross-contamination is one of the main mechanisms contributing to such infections. This work investigates the potential of hydrophobically modified nanoporous silica aerogel as an antiadhesive hygienic material that can inhibit exogenous bacterial contamination. Nanoporous silica aerogels were synthesized via sol-gel polymerization of tetraethyl orthosilicate and hydrophobized using trimethylsilyl chloride. Bacterial adhesion characteristics were evaluated via dip-inoculation in suspensions of Gram-negative Escherichia coli O157:H7 and Gram-positive Staphylococcus aureus. The attachment of E. coli O157:H7 and S. aureus to hydrophobic nanoporous silica aerogel (HNSA) was found to be significantly lower than that to hydrophilic and hydrophobic nonporous silica materials: 99.91% (E. coli O157:H7) and 99.93% (S. aureus) reduction in comparison to hydrophilic nonporous silica, and 82.95% (E. coli O157:H7) and 84.90% (S. aureus) reduction in comparison to hydrophobic nonporous silica. These results suggest that the use of HNSA as surfaces that come into contact with bacterial pathogens in the healthcare environment can improve bacterial hygiene, and therefore may reduce the rate of HAIs.

Role of heteroatoms in S, N-codoped nanoporous carbons in CO2 (photo)electrochemical reduction.

PubMed

Bandosz, Teresa; Li, Wanlu

2018-06-19

Thiourea-modified wood-based activated carbons were evaluated as catalysts for CO2 electrochemical reduction reaction (CO2ERR). The materials obtained at 950oC showed a long stability. The results indicated that thiophenic sulfur provides catalytic activity for CO formation. However, it was not as active for CH4 formation as was pyridinic-N. Tafel plots suggested that the nanoporous structure enhanced the kinetics for CO2 reduction. The electric conductivity limited the activity for CO2ERR in the materials modified at 600, 800 and 900oC. The effect of visible light on CO2ERR was also investigated in this study. Upon irradiation, photocurrent was generated, and a current density increased during CO2 reduction process. Combined with a band-gap alignment, the results indicate that thiophenic-S in the carbon matrix contributed to sample's photoactivity in visible light. These species enhance the overall reduction process promoting both hydrogen evolution reaction and CO2 reduction to CO. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design of Stratified Functional Nanoporous Materials for CO 2 Capture and Conversion

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

Johnson, J. Karl; Ye, Jingyun

The objective of this project is to develop novel nanoporous materials for CO 2 capture and conversion. The motivation of this work is that capture of CO 2 from flue gas or the atmosphere coupled with catalytic hydrogenation of CO 2 into valuable chemicals and fuels can reduce the net amount of CO 2 in the atmosphere while providing liquid transportation fuels and other commodity chemicals. One approach to increasing the economic viability of carbon capture and conversion is to design a single material that can be used for both the capture and catalytic conversion of CO 2, because suchmore » a material could increase efficiency through process intensification. We have used density functional theory (DFT) methods to design catalytic moieties that can be incorporated into various metal organic framework (MOF) materials. We chose to work with MOFs because they are highly tailorable, can be functionalized, and have been shown to selectively adsorb CO 2 over N 2, which is a requirement for CO 2 capture from flue gas. Moreover, the incorporation of molecular catalytic moieties into MOF, through covalent bonding, produces a heterogeneous catalytic material having activities and selectivities close to those of homogeneous catalysts, but without the draw-backs associated with homogeneous catalysis.« less

Surface chemistry driven actuation in nanoporous gold

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

Biener, J; Wittstock, A; Zepeda-Ruiz, L

Although actuation in biological systems is exclusively powered by chemical energy, this concept has not been realized in man-made actuator technologies, as these rely on generating heat or electricity first. Here, we demonstrate that surface-chemistry driven actuation can be realized in high surface area materials such as nanoporous gold. For example, we achieve reversible strain amplitudes in the order of a few tenths of a percent by alternating exposure of nanoporous Au to ozone and carbon monoxide. The effect can be explained by adsorbate-induced changes of the surface stress, and can be used to convert chemical energy directly into amore » mechanical response thus opening the door to surface-chemistry driven actuator and sensor technologies.« less

Davisson-Germer Prize Talk: Hydrogen storage in nanoporous materials

NASA Astrophysics Data System (ADS)

Chabal, Yves

2009-03-01

To develop a hydrogen-based energy technology, several classes of materials are being considered to achieve the DOE targets for gravimetric and volumetric hydrogen densities for hydrogen storage, including liquids (e.g. ammonium borohydrides), clathrate structures, complex metal hydrides, nanostructured (e.g. carbon) an nanoporous materials. Fundamental studies are necessary to determine the ultimate hydrogen capacity of each system. Nanoporous Metal-organic Framework (MOF) materials are promising candidates for hydrogen storage because the chemical nature and size of their unit cell can be tailored to weakly attract and incorporate H2 molecules, with good volumetric and mass density. In this talk, we consider the structure M2(BDC)2(TED), where M is a metal atom (Zn, Ni, Cu), BDC is benzenedicarboxylate and TED triethylenediamine, to determine the location and interaction of H2 molecules within the MOF. These compounds are isostructural and crystallize in the tetragonal phase (space group P4/ncc), they construct 3D porous structures with relatively large pore size (˜7-8 A ), pore volume (˜0.63-0.84 cc/g) and BET surface area (˜1500-1900 m^2/g). At high pressures (300-800 psi), the perturbation of the H-H stretching mode can be measured with IR absorption spectroscopy, showing a 35 cm-1 redshift from the unperturbed ortho (4155 cm-1 ) and para (4161 cm-1 ) frequencies. Using a newly developed non empirical van der Waals DFT method vdW-DFT),ootnotetextJ.Y. Lee, D.H. Olson, L. Pan, T.J. Emge, J. Li, Adv. Func. Mater. 17, 1255 (2007) it can be shown that the locus of the deepest H2 binding positions lies within to types of narrow channels. The energies of the most stable binding sites, as well as the number of such binding sites, are consistent with the values obtained from experimental adsorption isotherms, and heat of adsorption) data.ootnotetextM. Dion, H. Ryberg, E. Schroder, D. C. Langreth, B.I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004). Importantly, the

Phonon bottleneck identification in disordered nanoporous materials

NASA Astrophysics Data System (ADS)

Romano, Giuseppe; Grossman, Jeffrey C.

2017-09-01

Nanoporous materials are a promising platform for thermoelectrics in that they offer high thermal conductivity tunability while preserving good electrical properties, a crucial requirement for high-efficiency thermal energy conversion. Understanding the impact of the pore arrangement on thermal transport is pivotal to engineering realistic materials, where pore disorder is unavoidable. Although there has been considerable progress in modeling thermal size effects in nanostructures, it has remained a challenge to screen such materials over a large phase space due to the slow simulation time required for accurate results. We use density functional theory in connection with the Boltzmann transport equation to perform calculations of thermal conductivity in disordered porous materials. By leveraging graph theory and regressive analysis, we identify the set of pores representing the phonon bottleneck and obtain a descriptor for thermal transport, based on the sum of the pore-pore distances between such pores. This approach provide a simple tool to estimate phonon suppression in realistic porous materials for thermoelectric applications and enhance our understanding of heat transport in disordered materials.

Mechanisms for sodium insertion in carbon materials

NASA Astrophysics Data System (ADS)

Stevens, David Andrew

2000-12-01

This thesis details the mechanisms for sodium insertion into different carbons using both electrochemical and vapour techniques. Room temperature electrochemical measurements were completed to examine the insertion and removal of sodium from soft (graphitizable) and nanoporous hard (non-graphitizable) carbons prepared by the heat treatment of organic precursors to a range of temperatures. The mechanisms identified from these studies were further investigated through a series of in situ x-ray scattering studies on operating electrochemical cells. The results obtained were then compared with x-ray scattering measurements on carbons after exposure to sodium vapour at 890C. This work is primarily driven by the aluminium industry's need to understand how sodium insertion causes carbon cathode blocks in aluminium reduction cells to swell. The results obtained are also of relevance to the lithium-ion battery field as they help to verify mechanisms proposed in the literature for lithium insertion into carbon hosts. Some carbons were also identified that could accommodate large amounts of sodium, making them attractive candidates for anodes in rechargeable sodium ion batteries. For soft carbons, the results showed that both sodium and lithium insert between approximately parallel carbon layers along the sloping voltage region of the electrochemical curves, increasing the average interlayer spacing. The sodium and lithium capacities decreased with increasing carbon heat treatment temperature. For the soft carbons studied, the sodium capacity was found to be consistently lower than the lithium capacity, implying that some lithium-accessible sites were unavailable for sodium insertion. The electrochemical profiles for the hard carbons also contained capacity along a sloping voltage region and, as with the soft carbons, this was shown to result from the insertion of sodium and lithium between approximately parallel carbon layers. In contrast to the soft carbons, however, the

WS2 nanopores for molecule analysis

NASA Astrophysics Data System (ADS)

Danda, Gopinath; Masih Das, Paul; Chou, Yung-Chien; Mlack, Jerome; Naylor, Carl; Perea-Lopez, Nestor; Lin, Zhong; Fulton, Laura Beth; Terrones, Mauricio; Johnson, A. T. Charlie; Drndic, Marija

Atomically thin 2D materials like graphene and transition metal dichalcogenides (TMDs) are interesting as membranes in solid state nanopore sensors for DNA analysis as they may facilitate single base resolution sequencing. These materials also exhibit unique optical and electronic properties which may be exploited to enhance the functionality of nanopore sensors. Here, we report WS2 nanopores, fabricated using a focused TEM beam. We also report their controlled laser-induced expansion in ionic solution. This study demonstrates the possibility of dynamic control of nanopore characteristics optically. NIH Grant R21HG007856, NSF EFRI-1542707.

Eco-friendly synthesis for MCM-41 nanoporous materials using the non-reacted reagents in mother liquor.

PubMed

Ng, Eng-Poh; Goh, Jia-Yi; Ling, Tau Chuan; Mukti, Rino R

2013-03-04

Nanoporous materials such as Mobil composite material number 41 (MCM-41) are attractive for applications such as catalysis, adsorption, supports, and carriers. Green synthesis of MCM-41 is particularly appealing because the chemical reagents are useful and valuable. We report on the eco-friendly synthesis of MCM-41 nanoporous materials via multi-cycle approach by re-using the non-reacted reagents in supernatant as mother liquor after separating the solid product. This approach was achieved via minimal requirement of chemical compensation where additional fresh reactants were added into the mother liquor followed by pH adjustment after each cycle of synthesis. The solid product of each successive batch was collected and characterized while the non-reacted reagents in supernatant can be recovered and re-used to produce subsequent cycle of MCM-41. The multi-cycle synthesis is demonstrated up to three times in this research. This approach suggests a low cost and eco-friendly synthesis of nanoporous material since less waste is discarded after the product has been collected, and in addition, product yield can be maintained at the high level.

Eco-friendly synthesis for MCM-41 nanoporous materials using the non-reacted reagents in mother liquor

PubMed Central

2013-01-01

Nanoporous materials such as Mobil composite material number 41 (MCM-41) are attractive for applications such as catalysis, adsorption, supports, and carriers. Green synthesis of MCM-41 is particularly appealing because the chemical reagents are useful and valuable. We report on the eco-friendly synthesis of MCM-41 nanoporous materials via multi-cycle approach by re-using the non-reacted reagents in supernatant as mother liquor after separating the solid product. This approach was achieved via minimal requirement of chemical compensation where additional fresh reactants were added into the mother liquor followed by pH adjustment after each cycle of synthesis. The solid product of each successive batch was collected and characterized while the non-reacted reagents in supernatant can be recovered and re-used to produce subsequent cycle of MCM-41. The multi-cycle synthesis is demonstrated up to three times in this research. This approach suggests a low cost and eco-friendly synthesis of nanoporous material since less waste is discarded after the product has been collected, and in addition, product yield can be maintained at the high level. PMID:23497184

Eco-friendly synthesis for MCM-41 nanoporous materials using the non-reacted reagents in mother liquor

NASA Astrophysics Data System (ADS)

Ng, Eng-Poh; Goh, Jia-Yi; Ling, Tau Chuan; Mukti, Rino R.

2013-03-01

Nanoporous materials such as Mobil composite material number 41 (MCM-41) are attractive for applications such as catalysis, adsorption, supports, and carriers. Green synthesis of MCM-41 is particularly appealing because the chemical reagents are useful and valuable. We report on the eco-friendly synthesis of MCM-41 nanoporous materials via multi-cycle approach by re-using the non-reacted reagents in supernatant as mother liquor after separating the solid product. This approach was achieved via minimal requirement of chemical compensation where additional fresh reactants were added into the mother liquor followed by pH adjustment after each cycle of synthesis. The solid product of each successive batch was collected and characterized while the non-reacted reagents in supernatant can be recovered and re-used to produce subsequent cycle of MCM-41. The multi-cycle synthesis is demonstrated up to three times in this research. This approach suggests a low cost and eco-friendly synthesis of nanoporous material since less waste is discarded after the product has been collected, and in addition, product yield can be maintained at the high level.

Nanoporous carbon materials with enhanced supercapacitance performance and non-aromatic chemical sensing with C1/C2 alcohol discrimination

NASA Astrophysics Data System (ADS)

Shrestha, Lok Kumar; Adhikari, Laxmi; Shrestha, Rekha Goswami; Adhikari, Mandira Pradhananga; Adhikari, Rina; Hill, Jonathan P.; Pradhananga, Raja Ram; Ariga, Katsuhiko

2016-01-01

We have investigated the textural properties, electrochemical supercapacitances and vapor sensing performances of bamboo-derived nanoporous carbon materials (NCM). Bamboo, an abundant natural biomaterial, was chemically activated with phosphoric acid at 400 °C and the effect of impregnation ratio of phosphoric acid on the textural properties and electrochemical performances was systematically investigated. Fourier transform-infrared (FTIR) spectroscopy confirmed the presence of various oxygen-containing surface functional groups (i.e. carboxyl, carboxylate, carbonyl and phenolic groups) in NCM. The prepared NCM are amorphous in nature and contain hierarchical micropores and mesopores. Surface areas and pore volumes were found in the range 218-1431 m2 g-1 and 0.26-1.26 cm3 g-1, respectively, and could be controlled by adjusting the impregnation ratio of phosphoric acid and bamboo cane powder. NCM exhibited electrical double-layer supercapacitor behavior giving a high specific capacitance of c.256 F g-1 at a scan rate of 5 mV s-1 together with high cyclic stability with capacitance retention of about 92.6% after 1000 cycles. Furthermore, NCM exhibited excellent vapor sensing performance with high sensitivity for non-aromatic chemicals such as acetic acid. The system would be useful to discriminate C1 and C2 alcohol (methanol and ethanol).

Multiply Surface-Functionalized Nanoporous Carbon for Vehicular Hydrogen Storage

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

Pfeifer, Peter; Gillespie, Andrew; Stalla, David

The purpose of the project “Multiply Surface-Functionalized Nanoporous Carbon for Vehicular Hydrogen Storage” is the development of materials that store hydrogen (H 2) by adsorption in quantities and at conditions that outperform current compressed-gas H 2 storage systems for electric power generation from hydrogen fuel cells (HFCs). Prominent areas of interest for HFCs are light-duty vehicles (“hydrogen cars”) and replacement of batteries with HFC systems in a wide spectrum of applications, ranging from forklifts to unmanned areal vehicles to portable power sources. State-of-the-art compressed H 2 tanks operate at pressures between 350 and 700 bar at ambient temperature and storemore » 3-4 percent of H 2 by weight (wt%) and less than 25 grams of H 2 per liter (g/L) of tank volume. Thus, the purpose of the project is to engineer adsorbents that achieve storage capacities better than compressed H 2 at pressures less than 350 bar. Adsorption holds H 2 molecules as a high-density film on the surface of a solid at low pressure, by virtue of attractive surface-gas interactions. At a given pressure, the density of the adsorbed film is the higher the stronger the binding of the molecules to the surface is (high binding energies). Thus, critical for high storage capacities are high surface areas, high binding energies, and low void fractions (high void fractions, such as in interstitial space between adsorbent particles, “waste” storage volume by holding hydrogen as non-adsorbed gas). Coexistence of high surface area and low void fraction makes the ideal adsorbent a nanoporous monolith, with pores wide enough to hold high-density hydrogen films, narrow enough to minimize storage as non-adsorbed gas, and thin walls between pores to minimize the volume occupied by solid instead of hydrogen. A monolith can be machined to fit into a rectangular tank (low pressure, conformable tank), cylindrical tank (high pressure), or other tank shape without any waste of volume.« less

Metal-Free Carbon Materials for CO2 Electrochemical Reduction.

PubMed

Duan, Xiaochuan; Xu, Jiantie; Wei, Zengxi; Ma, Jianmin; Guo, Shaojun; Wang, Shuangyin; Liu, Huakun; Dou, Shixue

2017-11-01

The rapid increase of the CO 2 concentration in the Earth's atmosphere has resulted in numerous environmental issues, such as global warming, ocean acidification, melting of the polar ice, rising sea level, and extinction of species. To search for suitable and capable catalytic systems for CO 2 conversion, electrochemical reduction of CO 2 (CO 2 RR) holds great promise. Emerging heterogeneous carbon materials have been considered as promising metal-free electrocatalysts for the CO 2 RR, owing to their abundant natural resources, tailorable porous structures, resistance to acids and bases, high-temperature stability, and environmental friendliness. They exhibit remarkable CO 2 RR properties, including catalytic activity, long durability, and high selectivity. Here, various carbon materials (e.g., carbon fibers, carbon nanotubes, graphene, diamond, nanoporous carbon, and graphene dots) with heteroatom doping (e.g., N, S, and B) that can be used as metal-free catalysts for the CO 2 RR are highlighted. Recent advances regarding the identification of active sites for the CO 2 RR and the pathway of reduction of CO 2 to the final product are comprehensively reviewed. Additionally, the emerging challenges and some perspectives on the development of heteroatom-doped carbon materials as metal-free electrocatalysts for the CO 2 RR are included. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design of Zeolitic Imidazolate Framework Derived Nitrogen-Doped Nanoporous Carbons Containing Metal Species for Carbon Dioxide Fixation Reactions.

PubMed

Toyao, Takashi; Fujiwaki, Mika; Miyahara, Kenta; Kim, Tae-Ho; Horiuchi, Yu; Matsuoka, Masaya

2015-11-01

Various N-doped nanoporous carbons containing metal species were prepared by direct thermal conversion of zeolitic imidazolate frameworks (ZIFs; ZIF-7, -8, -9, and -67) at different temperatures (600, 800, and 1000 °C). These materials were utilized as bifunctional acid-base catalysts to promote the reaction of CO2 with epoxides to form cyclic carbonates under 0.6 MPa of CO2 at 80 °C. The catalyst generated by thermal conversion of ZIF-9 at 600 °C (C600-ZIF-9) was found to exhibit a higher catalytic activity than the other ZIFs, other conventional catalysts, and other metal-organic framework catalysts. The results of various characterization techniques including elemental analysis, X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and transmission electron microscopy show that C600-ZIF-9 contains partly oxidized Co nanoparticles and N species. Temperature-programmed desorption measurements by using CO2 and NH3 as probe molecules revealed that C600-ZIF-9 has both Lewis acid and Lewis base catalytic sites. Finally, the substrate scope was extended to seven other kinds of epoxides. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single molecule detection with graphene and other two-dimensional materials: nanopores and beyond

PubMed Central

Arjmandi-Tash, Hadi; Belyaeva, Liubov A.

2016-01-01

Graphene and other two dimensional (2D) materials are currently integrated into nanoscaled devices that may – one day – sequence genomes. The challenge to solve is conceptually straightforward: cut a sheet out of a 2D material and use the edge of the sheet to scan an unfolded biomolecule from head to tail. As the scan proceeds – and because 2D materials are atomically thin – the information provided by the edge might be used to identify different segments – ideally single nucleotides – in the biomolecular strand. So far, the most efficient approach was to drill a nano-sized pore in the sheet and use this pore as a channel to guide and detect individual molecules by measuring the electrochemical ionic current. Nanoscaled gaps between two electrodes in 2D materials recently emerged as powerful alternatives to nanopores. This article reviews the current status and prospects of integrating 2D materials in nanopores, nanogaps and similar devices for single molecule biosensing applications. We discuss the pros and cons, the challenges, and the latest achievements in the field. To achieve high-throughput sequencing with 2D materials, interdisciplinary research is essential. PMID:26612268

Synthesis of single-crystal-like nanoporous carbon membranes and their application in overall water splitting

PubMed Central

Wang, Hong; Min, Shixiong; Ma, Chun; Liu, Zhixiong; Zhang, Weiyi; Wang, Qiang; Li, Debao; Li, Yangyang; Turner, Stuart; Han, Yu; Zhu, Haibo; Abou-hamad, Edy; Hedhili, Mohamed Nejib; Pan, Jun; Yu, Weili; Huang, Kuo-Wei; Li, Lain-Jong; Yuan, Jiayin; Antonietti, Markus; Wu, Tom

2017-01-01

Nanoporous graphitic carbon membranes with defined chemical composition and pore architecture are novel nanomaterials that are actively pursued. Compared with easy-to-make porous carbon powders that dominate the porous carbon research and applications in energy generation/conversion and environmental remediation, porous carbon membranes are synthetically more challenging though rather appealing from an application perspective due to their structural integrity, interconnectivity and purity. Here we report a simple bottom–up approach to fabricate large-size, freestanding and porous carbon membranes that feature an unusual single-crystal-like graphitic order and hierarchical pore architecture plus favourable nitrogen doping. When loaded with cobalt nanoparticles, such carbon membranes serve as high-performance carbon-based non-noble metal electrocatalyst for overall water splitting. PMID:28051082

Recent Advances in Nanoporous Membranes for Water Purification

PubMed Central

Wang, Zhuqing; Colombi Ciacchi, Lucio

2018-01-01

Nanoporous materials exhibit wide applications in the fields of electrocatalysis, nanodevice fabrication, energy, and environmental science, as well as analytical science. In this review, we present a summary of recent studies on nanoporous membranes for water purification application. The types and fabrication strategies of various nanoporous membranes are first introduced, and then the fabricated nanoporous membranes for removing various water pollutants, such as salt, metallic ions, anions, nanoparticles, organic chemicals, and biological substrates, are demonstrated and discussed. This work will be valuable for readers to understand the design and fabrication of various nanoporous membranes, and their potential purification mechanisms towards different water pollutants. In addition, it will be helpful for developing new nanoporous materials for quick, economic, and high-performance water purification. PMID:29370128

Sinus Floor Elevation and Augmentation Using Synthetic Nanocrystalline and Nanoporous Hydroxyapatite Bone Substitute Materials: Preliminary Histologic Results.

PubMed

Belouka, Sofia-Maria; Strietzel, Frank Peter

To compare the tissue composition of augmented sites after using two different synthetic bone substitute materials, nanocrystalline and nanoporous hydroxyapatite (HA), for sinus floor elevation and augmentation. Forty-four patients received 88 titanium screw implants (Camlog Promote plus) of 4.3-mm diameter and 11- or 13-mm length, placed simultaneously during sinus floor elevation and augmentation. Nanocrystalline (Ostim) or nanoporous (NanoBone) HA were used exclusively. Bone substitute materials and implant lengths were allocated by randomization. Bone biopsy specimens were obtained from the former area of the lateral access window at implant exposure during healing abutment placement after 6 months. Biopsy specimens were prepared and examined histologically and histomorphometrically. All implants were osseointegrated at the time of exposure. Clinically and histologically, no signs of inflammation in the augmented sites were present. The histomorphometric analysis of 44 biopsy specimens revealed 31.8% ± 11.6% newly formed bone for sites augmented with nanocrystalline HA and 34.6% ± 9.2% for nanoporous HA (P = .467). The proportion of remaining bone substitute material was 28.4% ± 18.6% and 30% ± 13%, respectively (P = .453). The proportion of soft tissue within the biopsy specimens was 39.9% ± 11.1% and 35.4% ± 6.8%, respectively (P = .064). No significant differences were found between the area fractions of bone, bone substitute material, and soft tissue concerning the bone substitute material utilized. Within the present study, both synthetic bone substitute materials, nanocrystalline and nanoporous HA, were found to support bone formation in sinus floor elevation and augmentation procedures by osteoconductivity. They were not completely resorbed after 6 months. The amounts of newly formed bone, soft tissue, and bone substitute material remnants were found to be similar, indicating that both materials are likewise suitable for sinus floor elevation and

Building Nanoporous Metal-Organic Frameworks "Armor" on Fibers for High-Performance Composite Materials.

PubMed

Yang, Xiaobin; Jiang, Xu; Huang, Yudong; Guo, Zhanhu; Shao, Lu

2017-02-15

The nanoporous metal-organic frameworks (MOFs) "armor" is in situ intergrown onto the surfaces of carbon fibers (CFs) by nitric acid oxidization to supply nucleation sites and serves as a novel interfacial linker between the fiber and polymer matrix and a smart cushion to release interior and exterior applied forces. Simultaneous enhancements of the interfacial and interlaminar shear strength as well as the tensile strength of CFs were achieved. With the aid of an ultrasonic "cleaning" process, the optimized surface energy and tensile strength of CFs with a MOF "armor" are 83.79 mN m -1 and 5.09 GPa, for an increase of 102% and 11.6%, respectively. Our work finds that the template-induced nucleation of 3D MOF onto 1D fibers is a general and promising approach toward advanced composite materials for diverse applications to meet scientific and technical demands.

Functional Carbon Materials for Electrochemical Energy Storage

NASA Astrophysics Data System (ADS)

Zhou, Huihui

The ability to harvest and convert solar energy has been associated with the evolution of human civilization. The increasing consumption of fossil fuels since the industrial revolution, however, has brought to concerns in ecological deterioration and depletion of the fossil fuels. Facing these challenges, humankind is forced to seek for clean, sustainable and renewable energy resources, such as biofuels, hydraulic power, wind power, geothermal energy and other kinds of alternative energies. However, most alternative energy sources, generally in the form of electrical energy, could not be made available on a continuous basis. It is, therefore, essential to store such energy into chemical energy, which are portable and various applications. In this context, electrochemical energy-storage devices hold great promises towards this goal. The most common electrochemical energy-storage devices are electrochemical capacitors (ECs, also called supercapacitors) and batteries. In comparison to batteries, ECs posses high power density, high efficiency, long cycling life and low cost. ECs commonly utilize carbon as both (symmetric) or one of the electrodes (asymmetric), of which their performance is generally limited by the capacitance of the carbon electrodes. Therefore, developing better carbon materials with high energy density has been emerging as one the most essential challenges in the field. The primary objective of this dissertation is to design and synthesize functional carbon materials with high energy density at both aqueous and organic electrolyte systems. The energy density (E) of ECs are governed by E = CV 2/2, where C is the total capacitance and V is the voltage of the devices. Carbon electrodes with high capacitance and high working voltage should lead to high energy density. In the first part of this thesis, a new class of nanoporous carbons were synthesized for symmetric supercapacitors using aqueous Li2SO4 as the electrolyte. A unique precursor was adopted to

Preparation of resveratrol-loaded nanoporous silica materials with different structures

NASA Astrophysics Data System (ADS)

Popova, Margarita; Szegedi, Agnes; Mavrodinova, Vesselina; Novak Tušar, Natasa; Mihály, Judith; Klébert, Szilvia; Benbassat, Niko; Yoncheva, Krassimira

2014-11-01

Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound.

Solid-State Explosive Reaction for Nanoporous Bulk Thermoelectric Materials.

PubMed

Zhao, Kunpeng; Duan, Haozhi; Raghavendra, Nunna; Qiu, Pengfei; Zeng, Yi; Zhang, Wenqing; Yang, Jihui; Shi, Xun; Chen, Lidong

2017-11-01

High-performance thermoelectric materials require ultralow lattice thermal conductivity typically through either shortening the phonon mean free path or reducing the specific heat. Beyond these two approaches, a new unique, simple, yet ultrafast solid-state explosive reaction is proposed to fabricate nanoporous bulk thermoelectric materials with well-controlled pore sizes and distributions to suppress thermal conductivity. By investigating a wide variety of functional materials, general criteria for solid-state explosive reactions are built upon both thermodynamics and kinetics, and then successfully used to tailor material's microstructures and porosity. A drastic decrease in lattice thermal conductivity down below the minimum value of the fully densified materials and enhancement in thermoelectric figure of merit are achieved in porous bulk materials. This work demonstrates that controlling materials' porosity is a very effective strategy and is easy to be combined with other approaches for optimizing thermoelectric performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

3D architecture constructed via the confined growth of MoS2 nanosheets in nanoporous carbon derived from metal-organic frameworks for efficient hydrogen production.

PubMed

Liu, Yun; Zhou, Xiaoli; Ding, Tao; Wang, Chunde; Yang, Qing

2015-11-21

The design and synthesis of robust, high-performance and low-cost three-dimensional (3D) hierarchical structured materials for the electrochemical reduction of water to generate hydrogen is of great significance for practical water splitting applications. In this study, we develop an in situ space-confined method to synthesize an MoS2-based 3D hierarchical structure, in which the MoS2 nanosheets grow in the confined nanopores of metal-organic frameworks (MOFs)-derived 3D carbons as electrocatalysts for efficient hydrogen production. Benefiting from its unique structure, which has more exposed active sites and enhanced conductivity, the as-prepared MoS2/3D nanoporous carbon (3D-NPC) composite exhibits remarkable electrocatalytic activity for the hydrogen evolution reaction (HER) with a small onset overpotential of ∼0.16 V, large cathodic currents, small Tafel slope of 51 mV per decade and good durability. We anticipate that this in situ confined growth provides new insights into the construction of high performance catalysts for energy storage and conversion.

The Influence of Pore Size on the Indentation Behavior of Metallic Nanoporous Materials: A Molecular Dynamics Study

PubMed Central

Esqué-de los Ojos, Daniel; Pellicer, Eva; Sort, Jordi

2016-01-01

In general, the influence of pore size is not considered when determining the Young’s modulus of nanoporous materials. Here, we demonstrate that the pore size needs to be taken into account to properly assess the mechanical properties of these materials. Molecular dynamics simulations of spherical indentation experiments on single crystalline nanoporous Cu have been undertaken in systems with: (i) a constant degree of porosity and variable pore diameter; and (ii) a constant pore diameter and variable porosity degree. The classical Gibson and Ashby expression relating Young’s modulus with the relative density of the nanoporous metal is modified to include the influence of the pore size. The simulations reveal that, for a fixed porosity degree, the mechanical behavior of materials with smaller pores differs more significantly from the behavior of the bulk, fully dense counterpart. This effect is ascribed to the increase of the overall surface area as the pore size is reduced, together with the reduced coordination number of the atoms located at the pores edges. PMID:28773476

Outlook and Challenges for Hydrogen Storage in Nanoporous Materials

DOE PAGES

Broom, D. P.; Webb, C. J.; Hurst, Katherine E.; ...

2016-02-16

Considerable progress has been made recently in the use of nanoporous materials for hydrogen storage. In our article, the current status of the field and future challenges are discussed, ranging from important open fundamental questions, such as the density and volume of the adsorbed phase and its relationship to overall storage capacity, to the development of new functional materials and complete storage system design. With regard to fundamentals, the use of neutron scattering to study adsorbed H 2, suitable adsorption isotherm equations, and the accurate computational modelling and simulation of H 2 adsorption are discussed. We cover new materials andmore » they include flexible metal–organic frameworks, core–shell materials, and porous organic cage compounds. The article concludes with a discussion of the experimental investigation of real adsorptive hydrogen storage tanks, the improvement in the thermal conductivity of storage beds, and new storage system concepts and designs.« less

Methane storage in nanoporous material at supercritical temperature over a wide range of pressures

PubMed Central

Wu, Keliu; Chen, Zhangxin; Li, Xiangfang; Dong, Xiaohu

2016-01-01

The methane storage behavior in nanoporous material is significantly different from that of a bulk phase, and has a fundamental role in methane extraction from shale and its storage for vehicular applications. Here we show that the behavior and mechanisms of the methane storage are mainly dominated by the ratio of the interaction between methane molecules and nanopores walls to the methane intermolecular interaction, and a geometric constraint. By linking the macroscopic properties of the methane storage to the microscopic properties of a system of methane molecules-nanopores walls, we develop an equation of state for methane at supercritical temperature over a wide range of pressures. Molecular dynamic simulation data demonstrates that this equation is able to relate very well the methane storage behavior with each of the key physical parameters, including a pore size and shape and wall chemistry and roughness. Moreover, this equation only requires one fitted parameter, and is simple, reliable and powerful in application. PMID:27628747

Heteroatom-doped nanoporous carbon derived from MOF-5 for CO2 capture

NASA Astrophysics Data System (ADS)

Ma, Xiancheng; Li, Liqing; Chen, Ruofei; Wang, Chunhao; Li, Hailong; Wang, Shaobin

2018-03-01

Four nanoporous carbons (MUCT) were prepared from metal-organic framework (MOF-5) template and additional carbon source (i.e. urea) by carbonization at different temperatures (600-900 °C). The results showed that specific surface area of four samples was obtained in the range from 1030 to 2307 m2 g-1. By changing the carbonization temperature it can finely tune the pore volume of the MUCT, which having a uniform pore size of around 4.0 nm. With an increasing carbonization temperature, the micropore surface area of MUCT samples varied slightly, but mesopore surface area increased obviously, which had little influence on carbon dioxide (CO2) adsorption capacity. The as-obtained sample MUC900 exhibited the superior CO2 capture capacity of 3.7 mmol g-1 at 0 °C (1 atm). First principle calculations were conducted on carbon models with various functional groups to distinguish heterogeneity and understand carbon surface chemistry for CO2 adsorption. The interaction between CO2 and N-containing functional groups is mainly weak Lewis acid-base interaction. On the other hand, the pyrrole and amine groups show exceptional hydrogen-bonding interaction. The hydroxyls promote the interaction between carbon dioxide and functional groups through hydrogen-bonding interactions and electrostatic potentials, thereby increasing CO2 capture of MUCT.

Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media

NASA Astrophysics Data System (ADS)

Huber, Patrick

2015-03-01

Spatial confinement in nanoporous media affects the structure, thermodynamics and mobility of molecular soft matter often markedly. This article reviews thermodynamic equilibrium phenomena, such as physisorption, capillary condensation, crystallisation, self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equilibrium physics, i.e. the rheology of liquids, capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined molecular species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcohols to liquid crystals, polymers, ionic liquids, proteins and water. Mostly, experiments with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diameters ranging from a few up to 50 nm are presented. The observed peculiarities of nanopore-confined condensed matter are also discussed with regard to applications. A particular emphasis is put on texture formation upon crystallisation in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnological importance, e.g. for the synthesis of organic/inorganic hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochemical deposition of nano structures.

Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media.

PubMed

Huber, Patrick

2015-03-18

Spatial confinement in nanoporous media affects the structure, thermodynamics and mobility of molecular soft matter often markedly. This article reviews thermodynamic equilibrium phenomena, such as physisorption, capillary condensation, crystallisation, self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equilibrium physics, i.e. the rheology of liquids, capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined molecular species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcohols to liquid crystals, polymers, ionic liquids, proteins and water. Mostly, experiments with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diameters ranging from a few up to 50 nm are presented. The observed peculiarities of nanopore-confined condensed matter are also discussed with regard to applications. A particular emphasis is put on texture formation upon crystallisation in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnological importance, e.g. for the synthesis of organic/inorganic hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochemical deposition of nano structures.

Preparation of resveratrol-loaded nanoporous silica materials with different structures

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

Popova, Margarita, E-mail: mpopova@orgchem.bas.bg; Szegedi, Agnes; Mavrodinova, Vesselina

2014-11-15

Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated.more » Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound. - Graphical abstract: trans-Resveratrol was stabilized in the pores of BEA zeolite, MCM-41and KIL2 mesoporous silicas. - Highlights: • BEA, KIL-2 and MCM-41 materials were used as carriers for resveratrol loading. • Resveratrol encapsulation in ethanol solution and solid state procedure were applied. • The solid-state preparation appears very effective for stabilization of trans-resveratrol.« less

Nanopore fabrication and characterization by helium ion microscopy

NASA Astrophysics Data System (ADS)

Emmrich, D.; Beyer, A.; Nadzeyka, A.; Bauerdick, S.; Meyer, J. C.; Kotakoski, J.; Gölzhäuser, A.

2016-04-01

The Helium Ion Microscope (HIM) has the capability to image small features with a resolution down to 0.35 nm due to its highly focused gas field ionization source and its small beam-sample interaction volume. In this work, the focused helium ion beam of a HIM is utilized to create nanopores with diameters down to 1.3 nm. It will be demonstrated that nanopores can be milled into silicon nitride, carbon nanomembranes, and graphene with well-defined aspect ratio. To image and characterize the produced nanopores, helium ion microscopy and high resolution scanning transmission electron microscopy were used. The analysis of the nanopores' growth behavior allows inferring on the profile of the helium ion beam.

High-performance supercapacitors using a nanoporous current collector made from super-aligned carbon nanotubes.

PubMed

Zhou, Ruifeng; Meng, Chuizhou; Zhu, Feng; Li, Qunqing; Liu, Changhong; Fan, Shoushan; Jiang, Kaili

2010-08-27

Nanoporous current collectors for supercapacitors have been fabricated by cross-stacking super-aligned carbon nanotube (SACNT) films as a replacement for heavy conventional metallic current collectors. The CNT-film current collectors have good conductivity, extremely low density (27 microg cm(-2)), high specific surface area, excellent flexibility and good electrochemical stability. Nanosized active materials such as NiO, Co(3)O(4) or Mn(2)O(3) nanoparticles can be directly synthesized on the SACNT films by a straightforward one-step, in situ decomposition strategy that is both efficient and environmentally friendly. These composite films can be integrated into a pseudo-capacitor that does not use metallic current collectors, but nevertheless shows very good performance, including high specific capacitance (approximately 500 F g(-1), including the current collector mass), reliable electrochemical stability (<4.5% degradation in 2500 cycles) and a very high rate capability (245 F g(-1) at 155 A g(-1)).

High-performance supercapacitors using a nanoporous current collector made from super-aligned carbon nanotubes

NASA Astrophysics Data System (ADS)

Zhou, Ruifeng; Meng, Chuizhou; Zhu, Feng; Li, Qunqing; Liu, Changhong; Fan, Shoushan; Jiang, Kaili

2010-08-01

Nanoporous current collectors for supercapacitors have been fabricated by cross-stacking super-aligned carbon nanotube (SACNT) films as a replacement for heavy conventional metallic current collectors. The CNT-film current collectors have good conductivity, extremely low density (27 µg cm - 2), high specific surface area, excellent flexibility and good electrochemical stability. Nanosized active materials such as NiO, Co3O4 or Mn2O3 nanoparticles can be directly synthesized on the SACNT films by a straightforward one-step, in situ decomposition strategy that is both efficient and environmentally friendly. These composite films can be integrated into a pseudo-capacitor that does not use metallic current collectors, but nevertheless shows very good performance, including high specific capacitance (~500 F g - 1, including the current collector mass), reliable electrochemical stability (<4.5% degradation in 2500 cycles) and a very high rate capability (245 F g - 1 at 155 A g - 1).

Threading DNA through nanopores for biosensing applications

NASA Astrophysics Data System (ADS)

Fyta, Maria

2015-07-01

This review outlines the recent achievements in the field of nanopore research. Nanopores are typically used in single-molecule experiments and are believed to have a high potential to realize an ultra-fast and very cheap genome sequencer. Here, the various types of nanopore materials, ranging from biological to 2D nanopores are discussed together with their advantages and disadvantages. These nanopores can utilize different protocols to read out the DNA nucleobases. Although, the first nanopore devices have reached the market, many still have issues which do not allow a full realization of a nanopore sequencer able to sequence the human genome in about a day. Ways to control the DNA, its dynamics and speed as the biomolecule translocates the nanopore in order to increase the signal-to-noise ratio in the reading-out process are examined in this review. Finally, the advantages, as well as the drawbacks in distinguishing the DNA nucleotides, i.e., the genetic information, are presented in view of their importance in the field of nanopore sequencing.

Adsorptive separation of CO 2 in sulfur-doped nanoporous carbons: Selectivity and breakthrough simulation

DOE PAGES

Saha, Dipendu; Orkoulas, Gerassimos; Chen, Jihua; ...

2017-03-01

In this research, we have synthesized two sulfur functionalized nanoporous carbons by post-synthesis modifications with sulfur bearing activating agents that simultaneously enhanced the surface area and introduced sulfur functionalities on the carbon surface. The Brunauer–Emmett–Teller (BET) surface areas of these materials were 2865 and 837 m 2/g with total sulfur contents of 8.2 and 12.9 %, respectively. The sulfur-functionalized carbons were characterized with pore textural properties, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and electron microscopy (SEM and TEM). In both the carbons, CO 2 adsorption isotherms and kinetics were measured in three different temperatures of 298, 288 and 278more » K and pressures up to 760 torr. The gravimetric CO 2 uptake followed the trend with BET surface area but the surface area-based uptake was reversed and it followed the trend of sulfur content. The heat of adsorption of CO 2 in low uptake was 60-65 kJ/mol, which is the highest for CO 2 adsorption in porous carbons. In order to investigate the adsorptive separation of CO 2, N 2 and CH 4 adsorption isotherms were also measured at 298 K and 760 torr. The selectivity of separation for CO 2/N 2 and CO 2/CH 4 was calculated based on the Ideal Adsorbed Solution Theory (IAST) and all the results demonstrated the high CO 2 selectivity for the carbon with higher sulfur content. The adsorption isotherms were combined with mass balances to calculate the breakthrough behavior of the binary mixtures of CO 2/N 2 and CO 2/CH 4. The simulation results demonstrated that the dimensionless breakthrough time is a decreasing function of the mole fraction of CO 2 in the feed stream. The overall results suggest that the sulfurfunctionalized carbons can be employed as potential adsorbents for CO 2 separation.« less

Graphene nanopore devices for DNA sensing.

PubMed

Merchant, Chris A; Drndić, Marija

2012-01-01

We describe here a method for detecting the translocation of individual DNA molecules through nanopores created in graphene membranes. The devices consist of 1-5-nm thick graphene membranes with electron-beam sculpted nanopores from 5 to 10 nm in diameter. Due to the thin nature of the graphene membranes, and the reduced electrical resistance, we observe larger blocked currents than for traditional solid-state nanopores. We also show how ionic current noise levels can be reduced with the atomic-layer deposition of a few nanometers of titanium dioxide over the graphene surface. Unlike traditional solid-state nanopore materials that are insulating, graphene is an excellent electrical conductor, and its use opens the door to a new future class of nanopore devices in which electronic sensing and control is performed directly at the pore.

Direct fabrication of 3D graphene on nanoporous anodic alumina by plasma-enhanced chemical vapor deposition

PubMed Central

Zhan, Hualin; Garrett, David J.; Apollo, Nicholas V.; Ganesan, Kumaravelu; Lau, Desmond; Prawer, Steven; Cervenka, Jiri

2016-01-01

High surface area electrode materials are of interest for a wide range of potential applications such as super-capacitors and electrochemical cells. This paper describes a fabrication method of three-dimensional (3D) graphene conformally coated on nanoporous insulating substrate with uniform nanopore size. 3D graphene films were formed by controlled graphitization of diamond-like amorphous carbon precursor films, deposited by plasma-enhanced chemical vapour deposition (PECVD). Plasma-assisted graphitization was found to produce better quality graphene than a simple thermal graphitization process. The resulting 3D graphene/amorphous carbon/alumina structure has a very high surface area, good electrical conductivity and exhibits excellent chemically stability, providing a good material platform for electrochemical applications. Consequently very large electrochemical capacitance values, as high as 2.1 mF for a sample of 10 mm3, were achieved. The electrochemical capacitance of the material exhibits a dependence on bias voltage, a phenomenon observed by other groups when studying graphene quantum capacitance. The plasma-assisted graphitization, which dominates the graphitization process, is analyzed and discussed in detail. PMID:26805546

Direct fabrication of 3D graphene on nanoporous anodic alumina by plasma-enhanced chemical vapor deposition.

PubMed

Zhan, Hualin; Garrett, David J; Apollo, Nicholas V; Ganesan, Kumaravelu; Lau, Desmond; Prawer, Steven; Cervenka, Jiri

2016-01-25

High surface area electrode materials are of interest for a wide range of potential applications such as super-capacitors and electrochemical cells. This paper describes a fabrication method of three-dimensional (3D) graphene conformally coated on nanoporous insulating substrate with uniform nanopore size. 3D graphene films were formed by controlled graphitization of diamond-like amorphous carbon precursor films, deposited by plasma-enhanced chemical vapour deposition (PECVD). Plasma-assisted graphitization was found to produce better quality graphene than a simple thermal graphitization process. The resulting 3D graphene/amorphous carbon/alumina structure has a very high surface area, good electrical conductivity and exhibits excellent chemically stability, providing a good material platform for electrochemical applications. Consequently very large electrochemical capacitance values, as high as 2.1 mF for a sample of 10 mm(3), were achieved. The electrochemical capacitance of the material exhibits a dependence on bias voltage, a phenomenon observed by other groups when studying graphene quantum capacitance. The plasma-assisted graphitization, which dominates the graphitization process, is analyzed and discussed in detail.

High-flux water desalination with interfacial salt sieving effect in nanoporous carbon composite membranes

NASA Astrophysics Data System (ADS)

Chen, Wei; Chen, Shuyu; Liang, Tengfei; Zhang, Qiang; Fan, Zhongli; Yin, Hang; Huang, Kuo-Wei; Zhang, Xixiang; Lai, Zhiping; Sheng, Ping

2018-04-01

Freshwater flux and energy consumption are two important benchmarks for the membrane desalination process. Here, we show that nanoporous carbon composite membranes, which comprise a layer of porous carbon fibre structures grown on a porous ceramic substrate, can exhibit 100% desalination and a freshwater flux that is 3-20 times higher than existing polymeric membranes. Thermal accounting experiments demonstrated that the carbon composite membrane saved over 80% of the latent heat consumption. Theoretical calculations combined with molecular dynamics simulations revealed the unique microscopic process occurring in the membrane. When the salt solution is stopped at the openings to the nanoscale porous channels and forms a meniscus, the vapour can rapidly transport across the nanoscale gap to condense on the permeate side. This process is driven by the chemical potential gradient and aided by the unique smoothness of the carbon surface. The high thermal conductivity of the carbon composite membrane ensures that most of the latent heat is recovered.

A New Approach to the Computer Modeling of Amorphous Nanoporous Structures of Semiconducting and Metallic Materials: A Review

PubMed Central

Romero, Cristina; Noyola, Juan C.; Santiago, Ulises; Valladares, Renela M.; Valladares, Alexander; Valladares, Ariel A.

2010-01-01

We review our approach to the generation of nanoporous materials, both semiconducting and metallic, which leads to the existence of nanopores within the bulk structure. This method, which we have named as the expanding lattice method, is a novel transferable approach which consists first of constructing crystalline supercells with a large number of atoms and a density close to the real value and then lowering the density by increasing the volume. The resulting supercells are subjected to either ab initio or parameterized—Tersoff-based—molecular dynamics processes at various temperatures, all below the corresponding bulk melting points, followed by geometry relaxations. The resulting samples are essentially amorphous and display pores along some of the “crystallographic” directions without the need of incorporating ad hoc semiconducting atomic structural elements such as graphene-like sheets and/or chain-like patterns (reconstructive simulations) or of reproducing the experimental processes (mimetic simulations). We report radial (pair) distribution functions, nanoporous structures of C and Si, and some computational predictions for their vibrational density of states. We present numerical estimates and discuss possible applications of semiconducting materials for hydrogen storage in potential fuel tanks. Nanopore structures for metallic elements like Al and Au also obtained through the expanding lattice method are reported.

The formation of nanopores in metal materials after irradiation by beams of Ar+ with energy of 30 keV

NASA Astrophysics Data System (ADS)

Ivchenko, V. A.

2017-01-01

In this paper are the results of direction observations of nanopores in the subsurface volume of metals materials Pt and Pd(CuAg) using field-ion microscopy (FIM). Radiation of tip specimens was carried out with ions having an energy ˜ 25-30 keV in the fluency range of 1016 - 1018 ions/cm2, the current density lying within 150- 340 µA/cm2. Nanopores have been observed immediately after removal of the first atomic layers from the irradiated surface. It was established that, the threshold for ion-implanted platinum corresponds to fluence F = 1017 ions/cm2. For Pd(CuAg) it was revealed that nanopores have been down to 80 nm deep with current density 340 µA/cm2. Their dimensions and volume fractions were determined. The obtained results can be used for prediction of radiation stability of materials based on fcc metals.

Atomic layer deposition of nanoporous biomaterials.

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

Narayan, R. J.; Adiga, S. P.; Pellin, M. J.

2010-03-01

Due to its chemical stability, uniform pore size, and high pore density, nanoporous alumina is being investigated for use in biosensing, drug delivery, hemodialysis, and other medical applications. In recent work, we have examined the use of atomic layer deposition for coating the surfaces of nanoporous alumina membranes. Zinc oxide coatings were deposited on nanoporous alumina membranes using atomic layer deposition. The zinc oxide-coated nanoporous alumina membranes demonstrated antimicrobial activity against Escherichia coli and Staphylococcus aureus bacteria. These results suggest that atomic layer deposition is an attractive technique for modifying the surfaces of nanoporous alumina membranes and other nanostructured biomaterials.more » Nanoporous alumina, also known as anodic aluminum oxide (AAO), is a nanomaterial that exhibits several unusual properties, including high pore densities, straight pores, small pore sizes, and uniform pore sizes. In 1953, Keller et al. showed that anodizing aluminum in acid electrolytes results in a thick layer of nearly cylindrical pores, which are arranged in a close-packed hexagonal cell structure. More recently, Matsuda & Fukuda demonstrated preparation of highly ordered platinum and gold nanohole arrays using a replication process. In this study, a negative structure of nanoporous alumina was initially fabricated and a positive structure of a nanoporous metal was subsequently fabricated. Over the past fifteen years, nanoporous alumina membranes have been used as templates for growth of a variety of nanostructured materials, including nanotubes, nanowires, nanorods, and nanoporous membranes.« less

Adiabatic burst evaporation from bicontinuous nanoporous membranes

PubMed Central

Ichilmann, Sachar; Rücker, Kerstin; Haase, Markus; Enke, Dirk

2015-01-01

Evaporation of volatile liquids from nanoporous media with bicontinuous morphology and pore diameters of a few 10 nm is an ubiquitous process. For example, such drying processes occur during syntheses of nanoporous materials by sol–gel chemistry or by spinodal decomposition in the presence of solvents as well as during solution impregnation of nanoporous hosts with functional guests. It is commonly assumed that drying is endothermic and driven by non-equilibrium partial pressures of the evaporating species in the gas phase. We show that nearly half of the liquid evaporates in an adiabatic mode involving burst-like liquid-to-gas conversions. During single adiabatic burst evaporation events liquid volumes of up to 107 μm3 are converted to gas. The adiabatic liquid-to-gas conversions occur if air invasion fronts get unstable because of the built-up of high capillary pressures. Adiabatic evaporation bursts propagate avalanche-like through the nanopore systems until the air invasion fronts have reached new stable configurations. Adiabatic cavitation bursts thus compete with Haines jumps involving air invasion front relaxation by local liquid flow without enhanced mass transport out of the nanoporous medium and prevail if the mean pore diameter is in the range of a few 10 nm. The results reported here may help optimize membrane preparation via solvent-based approaches, solution-loading of nanopore systems with guest materials as well as routine use of nanoporous membranes with bicontinuous morphology and may contribute to better understanding of adsorption/desorption processes in nanoporous media. PMID:25926406

Sulfur containing nanoporous materials, nanoparticles, methods and applications

DOEpatents

Archer, Lynden A.; Navaneedhakrishnan, Jayaprakash

2018-01-30

Sulfur containing nanoparticles that may be used within cathode electrodes within lithium ion batteries include in a first instance porous carbon shape materials (i.e., either nanoparticle shapes or "bulk" shapes that are subsequently ground to nanoparticle shapes) that are infused with a sulfur material. A synthetic route to these carbon and sulfur containing nanoparticles may use a template nanoparticle to form a hollow carbon shape shell, and subsequent dissolution of the template nanoparticle prior to infusion of the hollow carbon shape shell with a sulfur material. Sulfur infusion into other porous carbon shapes that are not hollow is also contemplated. A second type of sulfur containing nanoparticle includes a metal oxide material core upon which is located a shell layer that includes a vulcanized polymultiene polymer material and ion conducting polymer material. The foregoing sulfur containing nanoparticle materials provide the electrodes and lithium ion batteries with enhanced performance.

Nanopores formed by DNA origami: a review.

PubMed

Bell, Nicholas A W; Keyser, Ulrich F

2014-10-01

Nanopores have emerged over the past two decades to become an important technique in single molecule experimental physics and biomolecule sensing. Recently DNA nanotechnology, in particular DNA origami, has been used for the formation of nanopores in insulating materials. DNA origami is a very attractive technique for the formation of nanopores since it enables the construction of 3D shapes with precise control over geometry and surface functionality. DNA origami has been applied to nanopore research by forming hybrid architectures with solid state nanopores and by direct insertion into lipid bilayers. This review discusses recent experimental work in this area and provides an outlook for future avenues and challenges. Copyright © 2014 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Using X-ray Microscopy To Understand How Nanoporous Materials Can Be Used To Reduce the Large Volume Change in Alloy Anodes

DOE PAGES

Cook, John B.; Lin, Terri C.; Detsi, Eric; ...

2017-01-05

Tin metal is an attractive negative electrode material to replace graphite in Li-ion batteries due to its high energy density. However, tin undergoes a large volume change upon alloying with Li, which pulverizes the particles, and ultimately leads to short cycling lifetimes. Nevertheless, nanoporous materials have been shown to extend battery life well past what is observed in nonporous material. Despite the exciting potential of porous alloying anodes to significantly increase the energy density in Li-ion batteries, the fundamental physics of how nanoscale architectures accommodate the electrochemically induced volume changes are poorly understood. Here, operando transmission X-ray microscopy has beenmore » used to develop an understanding of the mechanisms that govern the enhanced cycling stability in nanoporous tin. We found that in comparison to dense tin, nanoporous tin undergoes a 6-fold smaller areal expansion after lithiation, as a result of the internal porosity and unique nanoscale architecture. The expansion is also more gradual in nanoporous tin compared to the dense material. The nanoscale resolution of the microscope used in this study is ~30 nm, which allowed us to directly observe the pore structure during lithiation and delithiation. We found that nanoporous tin remains porous during the first insertion and desinsertion cycle. This observation is key, as fully closed pores could lead to mechanical instability, electrolyte inaccessibility, and short lifetimes. Here, while tin was chosen for this study because of its high X-ray contrast, the results of this work should be general to other alloy-type systems, such as Si, that also suffer from volume change based cycling degradation.« less

Using X-ray Microscopy To Understand How Nanoporous Materials Can Be Used To Reduce the Large Volume Change in Alloy Anodes

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

Cook, John B.; Lin, Terri C.; Detsi, Eric

Tin metal is an attractive negative electrode material to replace graphite in Li-ion batteries due to its high energy density. However, tin undergoes a large volume change upon alloying with Li, which pulverizes the particles, and ultimately leads to short cycling lifetimes. Nevertheless, nanoporous materials have been shown to extend battery life well past what is observed in nonporous material. Despite the exciting potential of porous alloying anodes to significantly increase the energy density in Li-ion batteries, the fundamental physics of how nanoscale architectures accommodate the electrochemically induced volume changes are poorly understood. Here, operando transmission X-ray microscopy has beenmore » used to develop an understanding of the mechanisms that govern the enhanced cycling stability in nanoporous tin. We found that in comparison to dense tin, nanoporous tin undergoes a 6-fold smaller areal expansion after lithiation, as a result of the internal porosity and unique nanoscale architecture. The expansion is also more gradual in nanoporous tin compared to the dense material. The nanoscale resolution of the microscope used in this study is ~30 nm, which allowed us to directly observe the pore structure during lithiation and delithiation. We found that nanoporous tin remains porous during the first insertion and desinsertion cycle. This observation is key, as fully closed pores could lead to mechanical instability, electrolyte inaccessibility, and short lifetimes. Here, while tin was chosen for this study because of its high X-ray contrast, the results of this work should be general to other alloy-type systems, such as Si, that also suffer from volume change based cycling degradation.« less

Predicting the structure of screw dislocations in nanoporous materials

NASA Astrophysics Data System (ADS)

Walker, Andrew M.; Slater, Ben; Gale, Julian D.; Wright, Kate

2004-10-01

Extended microscale crystal defects, including dislocations and stacking faults, can radically alter the properties of technologically important materials. Determining the atomic structure and the influence of defects on properties remains a major experimental and computational challenge. Using a newly developed simulation technique, the structure of the 1/2a <100> screw dislocation in nanoporous zeolite A has been modelled. The predicted channel structure has a spiral form that resembles a nanoscale corkscrew. Our findings suggest that the dislocation will enhance the transport of molecules from the surface to the interior of the crystal while retarding transport parallel to the surface. Crucially, the dislocation creates an activated, locally chiral environment that may have enantioselective applications. These predictions highlight the influence that microscale defects have on the properties of structurally complex materials, in addition to their pivotal role in crystal growth.

Thermoelectric studies of nanoporous thin films with adjusted pore-edge charges

NASA Astrophysics Data System (ADS)

Hao, Qing; Zhao, Hongbo; Xu, Dongchao

2017-03-01

In recent years, nanoporous thin films have been widely studied for thermoelectric applications. High thermoelectric performance is reported for nanoporous Si films, which is attributed to the dramatically reduced lattice thermal conductivity and bulk-like electrical properties. Porous materials can also be used in gas sensing applications by engineering the surface-trapped charges on pore edges. In this work, an analytical model is developed to explore the relationship between the thermoelectric properties and pore-edge charges in a periodic two-dimensional nanoporous material. The presented model can be widely used to analyze the measured electrical properties of general nanoporous thin films and two-dimensional materials.

Electric double-layer capacitors based on highly graphitized nanoporous carbons derived from ZIF-67.

PubMed

Torad, Nagy L; Salunkhe, Rahul R; Li, Yunqi; Hamoudi, Hicham; Imura, Masataka; Sakka, Yoshio; Hu, Chi-Chang; Yamauchi, Yusuke

2014-06-23

Nanoporous carbons (NPCs) have large specific surface areas, good electrical and thermal conductivity, and both chemical and mechanical stability, which facilitate their use in energy storage device applications. In the present study, highly graphitized NPCs are synthesized by one-step direct carbonization of cobalt-containing zeolitic imidazolate framework-67 (ZIF-67). After chemical etching, the deposited Co content can be completely removed to prepare pure NPCs with high specific surface area, large pore volume, and intrinsic electrical conductivity (high content of sp(2) -bonded carbons). A detailed electrochemical study is performed using cyclic voltammetry and galvanostatic charge-discharge measurements. Our NPC is very promising for efficient electrodes for high-performance supercapacitor applications. A maximum specific capacitance of 238 F g(-1) is observed at a scan rate of 20 mV s(-1) . This value is very high compared to previous works on carbon-based electric double layer capacitors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoporous Tin with a Granular Hierarchical Ligament Morphology as a Highly Stable Li-Ion Battery Anode

DOE PAGES

Cook, John B.; Detsi, Eric; Liu, Yijin; ...

2016-12-07

Next generation Li-ion batteries will require negative electrode materials with energy densities many-fold higher than that found in the graphitic carbon currently used in commercial Li-ion batteries. While various nanostructured alloying-type anode materials may satisfy that requirement, such materials do not always exhibit long cycle lifetimes and/or their processing routes are not always suitable for large-scale synthesis. Here, we report on a high-performance anode material for next generation Li-ion batteries made of nanoporous Sn powders with hierarchical ligament morphology. This material system combines both long cycle lifetimes (more than 72% capacity retention after 350 cycles), high capacity (693 mAh/g, nearlymore » twice that of commercial graphitic carbon), good charging/discharging capabilities (545 mAh/g at 1 A/g, 1.5C), and a scalable processing route that involves selective alloy corrosion. The good cycling performance of this system is attributed to its nanoporous architecture and its unique hierarchical ligament morphology, which accommodates the large volume changes taking place during lithiation, as confirmed by synchrotron-based ex-situ X-ray 3D tomography analysis. In conclusion, our findings are an important step for the development of high-performance Li-ion batteries.« less

Room-temperature synthesis of nanoporous 1D microrods of graphitic carbon nitride (g-C3N4) with highly enhanced photocatalytic activity and stability.

PubMed

Pawar, Rajendra C; Kang, Suhee; Park, Jung Hyun; Kim, Jong-Ho; Ahn, Sunghoon; Lee, Caroline S

2016-08-08

A one-dimensional (1D) nanostructure having a porous network is an exceptional photocatalytic material to generate hydrogen (H2) and decontaminate wastewater using solar energy. In this report, we synthesized nanoporous 1D microrods of graphitic carbon nitride (g-C3N4) via a facile and template-free chemical approach at room temperature. The use of concentrated acids induced etching and lift-off because of strong oxidation and protonation. Compared with the bulk g-C3N4, the porous 1D microrod structure showed five times higher photocatalytic degradation performance toward methylene blue dye (MB) under visible light irradiation. The photocatalytic H2 evolution of the 1D nanostructure (34 μmol g(-1)) was almost 26 times higher than that of the bulk g-C3N4 structure (1.26 μmol g(-1)). Additionally, the photocurrent stability of this nanoporous 1D morphology over 24 h indicated remarkable photocorrosion resistance. The improved photocatalytic activities were attributed to prolonged carrier lifetime because of its quantum confinement effect, effective separation and transport of charge carriers, and increased number of active sites from interconnected nanopores throughout the microrods. The present 1D nanostructure would be highly suited for photocatalytic water purification as well as water splitting devices. Finally, this facile and room temperature strategy to fabricate the nanostructures is very cost-effective.

Room-temperature synthesis of nanoporous 1D microrods of graphitic carbon nitride (g-C3N4) with highly enhanced photocatalytic activity and stability

NASA Astrophysics Data System (ADS)

Pawar, Rajendra C.; Kang, Suhee; Park, Jung Hyun; Kim, Jong-Ho; Ahn, Sunghoon; Lee, Caroline S.

2016-08-01

A one-dimensional (1D) nanostructure having a porous network is an exceptional photocatalytic material to generate hydrogen (H2) and decontaminate wastewater using solar energy. In this report, we synthesized nanoporous 1D microrods of graphitic carbon nitride (g-C3N4) via a facile and template-free chemical approach at room temperature. The use of concentrated acids induced etching and lift-off because of strong oxidation and protonation. Compared with the bulk g-C3N4, the porous 1D microrod structure showed five times higher photocatalytic degradation performance toward methylene blue dye (MB) under visible light irradiation. The photocatalytic H2 evolution of the 1D nanostructure (34 μmol g-1) was almost 26 times higher than that of the bulk g-C3N4 structure (1.26 μmol g-1). Additionally, the photocurrent stability of this nanoporous 1D morphology over 24 h indicated remarkable photocorrosion resistance. The improved photocatalytic activities were attributed to prolonged carrier lifetime because of its quantum confinement effect, effective separation and transport of charge carriers, and increased number of active sites from interconnected nanopores throughout the microrods. The present 1D nanostructure would be highly suited for photocatalytic water purification as well as water splitting devices. Finally, this facile and room temperature strategy to fabricate the nanostructures is very cost-effective.

Room-temperature synthesis of nanoporous 1D microrods of graphitic carbon nitride (g-C3N4) with highly enhanced photocatalytic activity and stability

PubMed Central

Pawar, Rajendra C.; Kang, Suhee; Park, Jung Hyun; Kim, Jong-ho; Ahn, Sunghoon; Lee, Caroline S.

2016-01-01

A one-dimensional (1D) nanostructure having a porous network is an exceptional photocatalytic material to generate hydrogen (H2) and decontaminate wastewater using solar energy. In this report, we synthesized nanoporous 1D microrods of graphitic carbon nitride (g-C3N4) via a facile and template-free chemical approach at room temperature. The use of concentrated acids induced etching and lift-off because of strong oxidation and protonation. Compared with the bulk g-C3N4, the porous 1D microrod structure showed five times higher photocatalytic degradation performance toward methylene blue dye (MB) under visible light irradiation. The photocatalytic H2 evolution of the 1D nanostructure (34 μmol g−1) was almost 26 times higher than that of the bulk g-C3N4 structure (1.26 μmol g−1). Additionally, the photocurrent stability of this nanoporous 1D morphology over 24 h indicated remarkable photocorrosion resistance. The improved photocatalytic activities were attributed to prolonged carrier lifetime because of its quantum confinement effect, effective separation and transport of charge carriers, and increased number of active sites from interconnected nanopores throughout the microrods. The present 1D nanostructure would be highly suited for photocatalytic water purification as well as water splitting devices. Finally, this facile and room temperature strategy to fabricate the nanostructures is very cost-effective. PMID:27498979

Thermal Conductivity in Nanoporous Gold Films during Electron-Phonon Nonequilibrium

DOE PAGES

Hopkins, Patrick E.; Norris, Pamela M.; Phinney, Leslie M.; ...

2008-01-01

The reduction of nanodevices has given recent attention to nanoporous materials due to their structure and geometry. However, the thermophysical properties of these materials are relatively unknown. In this article, an expression for thermal conductivity of nanoporous structures is derived based on the assumption that the finite size of the ligaments leads to electron-ligament wall scattering. This expression is then used to analyze the thermal conductivity of nanoporous structures in the event of electron-phonon nonequilibrium.

Single Molecule Sensing by Nanopores and Nanopore Devices

PubMed Central

Gu, Li-Qun; Shim, Ji Wook

2010-01-01

Molecular-scale pore structures, called nanopores, can be assembled by protein ion channels through genetic engineering or be artificially fabricated on solid substrates using fashion nanotechnology. When target molecules interact with the functionalized lumen of a nanopore, they characteristically block the ion pathway. The resulting conductance changes allow for identification of single molecules and quantification of target species in the mixture. In this review, we first overview nanopore-based sensory techniques that have been created for the detection of myriad biomedical targets, from metal ions, drug compounds, and cellular second messengers to proteins and DNA. Then we introduce our recent discoveries in nanopore single molecule detection: (1) using the protein nanopore to study folding/unfolding of the G-quadruplex aptamer; (2) creating a portable and durable biochip that is integrated with a single-protein pore sensor (this chip is compared with recently developed protein pore sensors based on stabilized bilayers on glass nanopore membranes and droplet interface bilayer); and (3) creating a glass nanopore-terminated probe for single-molecule DNA detection, chiral enantiomer discrimination, and identification of the bioterrorist agent ricin with an aptamer-encoded nanopore. PMID:20174694

Hierarchical nanoporous metals as a path toward the ultimate three-dimensional functionality.

PubMed

Fujita, Takeshi

2017-01-01

Nanoporous metals prepared via dealloying or selective leaching of solid solution alloys and compounds represent an emerging class of materials. They possess a three-dimensional (3D) structure of randomly interpenetrating ligaments/nanopores with sizes between 5 nm and several tens of micrometers, which can be tuned by varying their preparation conditions (such as dealloying time and temperature) or additional thermal coarsening. As compared to other nanostructured materials, nanoporous metals have many advantages, including their bicontinuous structure, tunable pore sizes, bulk form, good electrical conductivity, and high structural stability. Therefore, nanoporous metals represent ideal 3D materials with versatile functionality, which can be utilized in various fields. In this review, we describe the recent applications of nanoporous metals in molecular detection, catalysis, 3D graphene synthesis, hierarchical pore formation, and additive manufacturing (3D printing) together with our own achievements in these areas. Finally, we discuss possible ways of realizing the ultimate 3D functionality beyond the scope of nanoporous metals.

Hierarchical nanoporous metals as a path toward the ultimate three-dimensional functionality

PubMed Central

Fujita, Takeshi

2017-01-01

Abstract Nanoporous metals prepared via dealloying or selective leaching of solid solution alloys and compounds represent an emerging class of materials. They possess a three-dimensional (3D) structure of randomly interpenetrating ligaments/nanopores with sizes between 5 nm and several tens of micrometers, which can be tuned by varying their preparation conditions (such as dealloying time and temperature) or additional thermal coarsening. As compared to other nanostructured materials, nanoporous metals have many advantages, including their bicontinuous structure, tunable pore sizes, bulk form, good electrical conductivity, and high structural stability. Therefore, nanoporous metals represent ideal 3D materials with versatile functionality, which can be utilized in various fields. In this review, we describe the recent applications of nanoporous metals in molecular detection, catalysis, 3D graphene synthesis, hierarchical pore formation, and additive manufacturing (3D printing) together with our own achievements in these areas. Finally, we discuss possible ways of realizing the ultimate 3D functionality beyond the scope of nanoporous metals. PMID:29057026

Hierarchical nanoporous metals as a path toward the ultimate three-dimensional functionality

NASA Astrophysics Data System (ADS)

Fujita, Takeshi

2017-12-01

Nanoporous metals prepared via dealloying or selective leaching of solid solution alloys and compounds represent an emerging class of materials. They possess a three-dimensional (3D) structure of randomly interpenetrating ligaments/nanopores with sizes between 5 nm and several tens of micrometers, which can be tuned by varying their preparation conditions (such as dealloying time and temperature) or additional thermal coarsening. As compared to other nanostructured materials, nanoporous metals have many advantages, including their bicontinuous structure, tunable pore sizes, bulk form, good electrical conductivity, and high structural stability. Therefore, nanoporous metals represent ideal 3D materials with versatile functionality, which can be utilized in various fields. In this review, we describe the recent applications of nanoporous metals in molecular detection, catalysis, 3D graphene synthesis, hierarchical pore formation, and additive manufacturing (3D printing) together with our own achievements in these areas. Finally, we discuss possible ways of realizing the ultimate 3D functionality beyond the scope of nanoporous metals.

Self-assembling synthesis of free-standing nanoporous graphene-transition-metal oxide flexible electrodes for high-performance lithium-ion batteries and supercapacitors.

PubMed

Huang, Xiaodan; Sun, Bing; Chen, Shuangqiang; Wang, Guoxiu

2014-01-01

The synthesis of nanoporous graphene by a convenient carbon nanofiber assisted self-assembly approach is reported. Porous structures with large pore volumes, high surface areas, and well-controlled pore sizes were achieved by employing spherical silica as hard templates with different diameters. Through a general wet-immersion method, transition-metal oxide (Fe3O4, Co3O4, NiO) nanocrystals can be easily loaded into nanoporous graphene papers to form three-dimensional flexible nanoarchitectures. When directly applied as electrodes in lithium-ion batteries and supercapacitors, the materials exhibited superior electrochemical performances, including an ultra-high specific capacity, an extended long cycle life, and a high rate capability. In particular, nanoporous Fe3O4-graphene composites can deliver a reversible specific capacity of 1427.5 mAh g(-1) at a high current density of 1000 mA g(-1) as anode materials in lithium-ion batteries. Furthermore, nanoporous Co3O4-graphene composites achieved a high supercapacitance of 424.2 F g(-1) . This work demonstrated that the as-developed freestanding nanoporous graphene papers could have significant potential for energy storage and conversion applications. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An overview on the characterization and mechanical behavior of nanoporous Gold

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

Hodge, A M; Hayes, J R; Caro, J A

2005-09-13

In this paper we present what we believe are the most pressing issues in understanding the mechanical behavior of nanoporous foams. We have postulated that a gold foam presents the best candidate for a systematic study of nanoporous foams since it can be synthesized with a wide range of ligaments sizes and densities. We have also conducted preliminary tests that demonstrate (a) Au foams have a fracture behavior dictated by the ligament size, and (b) nanoporous Au is a high yield strength material. Thus, we have demonstrated the potential in developing nanoporous foams as a new class of high yieldmore » strength/low density materials.« less

Nanoporous sorbent material as an oral phosphate binder and for aqueous phosphate, chromate, and arsenate removal

PubMed Central

Sangvanich, Thanapon; Ngamcherdtrakul, Worapol; Lee, Richard; Morry, Jingga; Castro, David; Fryxell, Glen E.; Yantasee, Wassana

2014-01-01

Phosphate removal is both biologically and environmentally important. Biologically, hyperphosphatemia is a critical condition in end-stage chronic kidney disease patients. Patients with hyperphosphatemia are treated long-term with oral phosphate binders to prevent phosphate absorption to the body by capturing phosphate in the gastrointestinal (GI) tract followed by fecal excretion. Environmentally, phosphate levels in natural water resources must be regulated according to limits set forth by the US Environmental Protection Agency. By utilizing nanotechnology and ligand design, we developed a new material to overcome limitations of traditional sorbent materials such as low phosphate binding capacity, slow binding kinetics, and negative interference by other anions. A phosphate binder based on iron-ethylenediamine on nanoporous silica (Fe-EDA-SAMMS) has been optimized for substrates and Fe(III) deposition methods. The Fe-EDA-SAMMS material had a 4-fold increase in phosphate binding capacity and a broader operating pH window compared to other reports. The material had a faster phosphate binding rate and was significantly less affected by other anions than Sevelamer HCl, the gold standard oral phosphate binder, and AG® 1-X8, a commercially available anion exchanger. It had less cytotoxicity to Caco-2 cells than lanthanum carbonate, another prescribed oral phosphate binder. The Fe-EDA-SAMMS also had high capacity for arsenate and chromate, two of the most toxic anions in natural water. PMID:25554735

Nanoporous biomaterials for uremic toxin adsorption in artificial kidney systems: A review.

PubMed

Cheah, Wee-Keat; Ishikawa, Kunio; Othman, Radzali; Yeoh, Fei-Yee

2017-07-01

Hemodialysis, one of the earliest artificial kidney systems, removes uremic toxins via diffusion through a semipermeable porous membrane into the dialysate fluid. Miniaturization of the present hemodialysis system into a portable and wearable device to maintain continuous removal of uremic toxins would require that the amount of dialysate used within a closed-system is greatly reduced. Diffused uremic toxins within a closed-system dialysate need to be removed to maintain the optimum concentration gradient for continuous uremic toxin removal by the dialyzer. In this dialysate regenerative system, adsorption of uremic toxins by nanoporous biomaterials is essential. Throughout the years of artificial kidney development, activated carbon has been identified as a potential adsorbent for uremic toxins. Adsorption of uremic toxins necessitates nanoporous biomaterials, especially activated carbon. Nanoporous biomaterials are also utilized in hemoperfusion for uremic toxin removal. Further miniaturization of artificial kidney system and improvements on uremic toxin adsorption capacity would require high performance nanoporous biomaterials which possess not only higher surface area, controlled pore size, but also designed architecture or structure and surface functional groups. This article reviews on various nanoporous biomaterials used in current artificial kidney systems and several emerging nanoporous biomaterials. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1232-1240, 2017. © 2016 Wiley Periodicals, Inc.

Sn Nanoparticles Encapsulated in 3D Nanoporous Carbon Derived from a Metal-Organic Framework for Anode Material in Lithium-Ion Batteries.

PubMed

Guo, Yuanyuan; Zeng, Xiaoqiao; Zhang, Yu; Dai, Zhengfei; Fan, Haosen; Huang, Ying; Zhang, Weina; Zhang, Hua; Lu, Jun; Huo, Fengwei; Yan, Qingyu

2017-05-24

Three-dimensional nanoporous carbon frameworks encapsulated Sn nanoparticles (Sn@3D-NPC) are developed by a facile method as an improved lithium ion battery anode. The Sn@3D-NPC delivers a reversible capacity of 740 mAh g -1 after 200 cycles at a current density of 200 mA g -1 , corresponding to a capacity retention of 85% (against the second capacity) and high rate capability (300 mAh g -1 at 5 A g -1 ). Compared to the Sn nanoparticles (SnNPs), such improvements are attributed to the 3D porous and conductive framework. The whole structure can provide not only the high electrical conductivity that facilities the electron transfer but also the elasticity that will suppress the volume expansion and aggregation of SnNPs during the charge and discharge process. This work opens a new application of metal-organic frameworks in energy storage.

Mechanochemical synthesis of carbon-based nanocomposites for supercapacitors

NASA Astrophysics Data System (ADS)

Mateyshina, Yuliya G.; Ulihin, Artem S.; Uvarov, Nikolai F.

2014-12-01

New nanoporous carbon-SiO2 composite materials were synthesized from organic raw materials (rice shells) and their electrochemical properties were investigated by cyclic voltammetry in liquid electrolytes (6 M KOH or 1 M H2SO4). A correlation between specific capacitance and specific surface area was observed. Due to high specific capacitance of 90 F/g the carbon materials under study may be regarded as promising electrode materials for electrochemical supercapacitors.

Reaching the Ionic Current Detection Limit in Silicon-Based Nanopores

NASA Astrophysics Data System (ADS)

Puster, Matthew; Rodriguez-Manzo, Julio Alejandro; Nicolai, Adrien; Meunier, Vincent; Drndic, Marija

2015-03-01

Solid-state nanopores act as single-molecule sensors whereby passage of an individual molecule in aqueous electrolyte through a nanopore is registered as a change in ionic conductance (ΔG). Future nanopore applications such as DNA sequencing at high bandwidth require high ΔG for optimal signal-to-noise ratio. Reducing the nanopore diameter and thickness increase ΔG. Molecule size limits the diameter, thus efforts concentrate on minimizing the thickness by thinning oxide/nitride films or using 2D materials. Weighted by electrolyte conductivity the highest ΔG reported to date for DNA translocations were obtained with nanopores made in oxide/nitride films. We present a controlled electron irradiation technique to thin such films to the limit of their stability, producing nanopores tailored to molecule size in amorphous Si with thicknesses less than 2 nm. We compare ΔG values with results found in the literature for DNA translocation through these nanopores, where access resistance becomes comparable to the resistance through the nanopore itself.

Catalytic nanoporous membranes

DOEpatents

Pellin, Michael J [Naperville, IL; Hryn, John N [Naperville, IL; Elam, Jeffrey W [Elmhurst, IL

2009-12-01

A nanoporous catalytic membrane which displays several unique features including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity.

Substrate Dependent Ad-Atom Migration on Graphene and the Impact on Electron-Beam Sculpting Functional Nanopores.

PubMed

Freedman, Kevin J; Goyal, Gaurav; Ahn, Chi Won; Kim, Min Jun

2017-05-10

The use of atomically thin graphene for molecular sensing has attracted tremendous attention over the years and, in some instances, could displace the use of classical thin films. For nanopore sensing, graphene must be suspended over an aperture so that a single pore can be formed in the free-standing region. Nanopores are typically drilled using an electron beam (e-beam) which is tightly focused until a desired pore size is obtained. E-beam sculpting of graphene however is not just dependent on the ability to displace atoms but also the ability to hinder the migration of ad-atoms on the surface of graphene. Using relatively lower e-beam fluxes from a thermionic electron source, the C-atom knockout rate seems to be comparable to the rate of carbon ad-atom attraction and accumulation at the e-beam/graphene interface (i.e., R knockout ≈ R accumulation ). Working at this unique regime has allowed the study of carbon ad-atom migration as well as the influence of various substrate materials on e-beam sculpting of graphene. We also show that this information was pivotal to fabricating functional graphene nanopores for studying DNA with increased spatial resolution which is attributed to atomically thin membranes.

Wall-collision line broadening of molecular oxygen within nanoporous materials

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

Xu, Can T.; Lewander, Maerta; Andersson-Engels, Stefan

2011-10-15

Wall-collision broadening of near-infrared absorption lines of molecular oxygen confined in nanoporous zirconia is studied by employing high-resolution diode-laser spectroscopy. The broadening is studied for pores of different sizes under a range of pressures, providing new insights on how wall collisions and intermolecular collisions influence the total spectroscopic line profile. The pressure series show that wall-collision broadening is relatively more prominent under reduced pressures, enabling sensitive means to probe pore sizes of porous materials. In addition, we show that the total wall-collision-broadened profile strongly deviates from a Voigt profile and that wall-collision broadening exhibits an additive-like behavior to the pressuremore » and Doppler broadening.« less

Molecular Sensing by Nanoporous Crystalline Polymers

PubMed Central

Pilla, Pierluigi; Cusano, Andrea; Cutolo, Antonello; Giordano, Michele; Mensitieri, Giuseppe; Rizzo, Paola; Sanguigno, Luigi; Venditto, Vincenzo; Guerra, Gaetano

2009-01-01

Chemical sensors are generally based on the integration of suitable sensitive layers and transducing mechanisms. Although inorganic porous materials can be effective, there is significant interest in the use of polymeric materials because of their easy fabrication process, lower costs and mechanical flexibility. However, porous polymeric absorbents are generally amorphous and hence present poor molecular selectivity and undesired changes of mechanical properties as a consequence of large analyte uptake. In this contribution the structure, properties and some possible applications of sensing polymeric films based on nanoporous crystalline phases, which exhibit all identical nanopores, will be reviewed. The main advantages of crystalline nanoporous polymeric materials with respect to their amorphous counterparts are, besides a higher selectivity, the ability to maintain their physical state as well as geometry, even after large guest uptake (up to 10–15 wt%), and the possibility to control guest diffusivity by controlling the orientation of the host polymeric crystalline phase. The final section of the review also describes the ability of suitable polymeric films to act as chirality sensors, i.e., to sense and memorize the presence of non-racemic volatile organic compounds. PMID:22303150

Atomic layer deposition of TIO{sub 2} thin films on nanoporous alumina templates : medical applications.

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

Narayan, R. J.; Monteiro-Riviere, N. A.; Brigmon, R. L.

2009-06-01

Nanostructured materials may play a significant role in controlled release of pharmacologic agents for treatment of cancer. Many nanoporous polymer materials are inadequate for use in drug delivery. Nanoporous alumina provides several advantages over other materials for use in controlled drug delivery and other medical applications. Atomic layer deposition was used to coat all the surfaces of a nanoporous alumina membrane in order to reduce the pore size in a controlled manner. Neither the 20 nm nor the 100 nm TiO{sub 2}-coated nanoporous alumina membranes exhibited statistically lower viability compared to the uncoated nanoporous alumina membrane control materials. Nanostructured materialsmore » prepared using atomic layer deposition may be useful for delivering a pharmacologic agent at a precise rate to a specific location in the body. These materials may serve as the basis for 'smart' drug delivery devices, orthopedic implants, or self-sterilizing medical devices.« less

Sn Nanoparticles Encapsulated in 3D Nanoporous Carbon Derived from a Metal–Organic Framework for Anode Material in Lithium-Ion Batteries

DOE PAGES

Guo, Yuanyuan; Zeng, Xiaoqiao; Zhang, Yu; ...

2017-05-04

Three-dimensional nanoporous carbon frameworks encapsulated Sn nanoparticles (Sn@3D-NPC) are developed by a facile method as an improved lithium ion battery anode. The Sn@3D-NPC delivers a reversible capacity of 740 mAh g –1 after 200 cycles at a current density of 200 mA g –1, corresponding to a capacity retention of 85% (against the second capacity) and high rate capability (300 mAh g –1 at 5 A g –1). Compared to the Sn nanoparticles (SnNPs), such improvements are attributed to the 3D porous and conductive framework. The whole structure can provide not only the high electrical conductivity that facilities the electronmore » transfer but also the elasticity that will suppress the volume expansion and aggregation of SnNPs during the charge and discharge process. Lastly, this work opens a new application of metal–organic frameworks in energy storage.« less

Electrosorption capacitance of nanostructured carbon-based materials.

PubMed

Hou, Chia-Hung; Liang, Chengdu; Yiacoumi, Sotira; Dai, Sheng; Tsouris, Costas

2006-10-01

The fundamental mechanism of electrosorption of ions developing a double layer inside nanopores was studied via a combination of experimental and theoretical studies. A novel graphitized-carbon monolithic material has proven to be a good electrical double-layer capacitor that can be applied in the separation of ions from aqueous solutions. An extended electrical double-layer model indicated that the pore size distribution plays a key role in determining the double-layer capacitance in an electrosorption process. Because of the occurrence of double-layer overlapping in narrow pores, mesopores and micropores make significantly different contributions to the double-layer capacitance. Mesopores show good electrochemical accessibility. Micropores present a slow mass transfer of ions and a considerable loss of double-layer capacitance, associated with a shallow potential distribution inside pores. The formation of the diffuse layer inside the micropores determines the magnitude of the double-layer capacitance at low electrolyte concentrations and at conditions close to the point of zero charge of the material. The effect of the double-layer overlapping on the electrosorption capacitance can be reduced by increasing the pore size, electrolyte concentration, and applied potential. The results are relevant to water deionization.

Preparation and characterization of pitch-based nanoporous carbons for improving CO{sub 2} capture

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

Lee, Seul-Yi; Yoo, Hye-Min; Park, Sang Wook

2014-07-01

Pitch is considered a promising low-cost carbon precursor. However, when pitch is pyrolyzed, it forms polycrystalline graphite, which is non-porous, and therefore, not useful for CO{sub 2} adsorption. In this work, pitch was chemically activated to obtain a large specific surface area and micropore volume. Varying weight ratios of KOH (i.e., 0, 1, 2, and 3) were used as the activating agent. The characteristics of the samples were investigated using scanning electron microscopy (SEM), N{sub 2}/77 K adsorption isotherms, and X-ray diffraction (XRD). The CO{sub 2} adsorption performance was studied by isothermal adsorption/desorption measurements. The results showed that an increasemore » in specific surface areas and total pore volumes of pitch-based nanoporous carbons, resulted in an enhancement of CO{sub 2} adsorption capacity. - Graphical abstract: This is the surface morphologies of pitch precursor and pitch-derived activated carbon (AC-2). - Highlights: • Pitch is considered a promising low-cost carbon precursor. • Specific surface area: 1442 m{sup 2}/g and micropore volume: 0.504 cm{sup 3}/g. • CO{sub 2} adsorption capacity showed 203 mg/g (@ RT/1 bar)« less

Confining metal-halide perovskites in nanoporous thin films

PubMed Central

Demchyshyn, Stepan; Roemer, Janina Melanie; Groiß, Heiko; Heilbrunner, Herwig; Ulbricht, Christoph; Apaydin, Dogukan; Böhm, Anton; Rütt, Uta; Bertram, Florian; Hesser, Günter; Scharber, Markus Clark; Sariciftci, Niyazi Serdar; Nickel, Bert; Bauer, Siegfried; Głowacki, Eric Daniel; Kaltenbrunner, Martin

2017-01-01

Controlling the size and shape of semiconducting nanocrystals advances nanoelectronics and photonics. Quantum-confined, inexpensive, solution-derived metal halide perovskites offer narrowband, color-pure emitters as integral parts of next-generation displays and optoelectronic devices. We use nanoporous silicon and alumina thin films as templates for the growth of perovskite nanocrystallites directly within device-relevant architectures without the use of colloidal stabilization. We find significantly blue-shifted photoluminescence emission by reducing the pore size; normally infrared-emitting materials become visibly red, and green-emitting materials become cyan and blue. Confining perovskite nanocrystals within porous oxide thin films drastically increases photoluminescence stability because the templates auspiciously serve as encapsulation. We quantify the template-induced size of the perovskite crystals in nanoporous silicon with microfocus high-energy x-ray depth profiling in transmission geometry, verifying the growth of perovskite nanocrystals throughout the entire thickness of the nanoporous films. Low-voltage electroluminescent diodes with narrow, blue-shifted emission fabricated from nanocrystalline perovskites grown in embedded nanoporous alumina thin films substantiate our general concept for next-generation photonic devices. PMID:28798959

Ion-sculpting of nanopores in amorphous metals, semiconductors, and insulators

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

George, H. Bola; Madi, Charbel S.; Aziz, Michael J.

2010-06-28

We report the closure of nanopores to single-digit nanometer dimensions by ion sculpting in a range of amorphous materials including insulators (SiO{sub 2} and SiN), semiconductors (a-Si), and metallic glasses (Pd{sub 80}Si{sub 20})--the building blocks of a single-digit nanometer electronic device. Ion irradiation of nanopores in crystalline materials (Pt and Ag) does not cause nanopore closure. Ion irradiation of c-Si pores below 100 deg. C and above 600 deg. C, straddling the amorphous-crystalline dynamic transition temperature, yields closure at the lower temperature but no mass transport at the higher temperature. Ion beam nanosculpting appears to be restricted to materials thatmore » either are or become amorphous during ion irradiation.« less

Systematic screening of carbon-based anode materials for microbial fuel cells with Shewanella oneidensis MR-1.

PubMed

Kipf, Elena; Koch, Julia; Geiger, Bettina; Erben, Johannes; Richter, Katrin; Gescher, Johannes; Zengerle, Roland; Kerzenmacher, Sven

2013-10-01

We present a systematic screening of carbon-based anode materials for microbial fuel cells with Shewanella oneidensis MR-1. Under anoxic conditions nanoporous activated carbon cloth is a superior anode material in terms of current density normalized to the projected anode area and anode volume (24.0±0.3 μA cm(-2) and 482±7 μA cm(-3) at -0.2 vs. SCE, respectively). The good performance can be attributed to the high specific surface area of the material, which is available for mediated electron transfer through self-secreted flavins. Under aerated conditions no influence of the specific surface area is observed, which we attribute to a shift from primary indirect electron transfer by mediators to direct electron transfer via adherent cells. Furthermore, we show that an aerated initial growth phase enhances the current density under subsequent anoxic conditions fivefold when compared to a similar experiment that was conducted under permanently anoxic conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Lithography-based fabrication of nanopore arrays in freestanding SiN and graphene membranes

NASA Astrophysics Data System (ADS)

Verschueren, Daniel V.; Yang, Wayne; Dekker, Cees

2018-04-01

We report a simple and scalable technique for the fabrication of nanopore arrays on freestanding SiN and graphene membranes based on electron-beam lithography and reactive ion etching. By controlling the dose of the single-shot electron-beam exposure, circular nanopores of any size down to 16 nm in diameter can be fabricated in both materials at high accuracy and precision. We demonstrate the sensing capabilities of these nanopores by translocating dsDNA through pores fabricated using this method, and find signal-to-noise characteristics on par with transmission-electron-microscope-drilled nanopores. This versatile lithography-based approach allows for the high-throughput manufacturing of nanopores and can in principle be used on any substrate, in particular membranes made out of transferable two-dimensional materials.

Materials property definition and generation for carbon-carbon and carbon phenolic materials

NASA Technical Reports Server (NTRS)

Canfield, A. R.; Mathis, J. R.; Starrett, H. S.; Koenig, J. R.

1987-01-01

A data base program to generate statistically significant material-property data for carbon-carbon and carbon phenolic materials to be used in designs of Space Shuttle is described. The program, which will provide data necessary for thermal and stress modeling of Shuttle nozzle and exit cone structures, includes evaluation of tension, compression, shear strength, shear modulus, thermal expansion, thermal conductivity, permeability, and emittance for both materials; the testing of carbon phenolic materials also includes CTE, off-gassing, pyrolysis, and RTG. Materials to be tested will be excised from Space Shuttle inlet, throat, and exit cone billets and modified involute carbon-carbon exit cones; coprocessed blocks, panels, and cylinders will also be tested.

Sodium Hydroxide Activated Nanoporous Carbons Based on Lapsi Seed Stone.

PubMed

Joshi, Sahira; Shrestha, Lok Kumar; Kamachi, Yuichiro; Yamauchi, Yusuke; Pradhananga, Mandira Adhikari; Pokhrel, Bhadra Prasad; Ariga, Katsuhiko; Pradhananga, Raja Ram

2015-02-01

Nanoporous activated carbons (ACs) were prepared from Lapsi (Choerospondias axillaris) seed powder by chemical activation with sodium hydroxide (NaOH) at different NaOH impregnation ratios. The prepared ACs were characterized by Fourier transform-infrared (FTIR) spectroscopy, Raman scattering, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Semi-quantitative information on the surface properties was obtained by estimating iodine number. FTIR spectra showed the presence of oxygenated functional groups such as hydroxyl, carbonyl, and carboxyl in the prepared ACs. Raman scattering showed clear D and G bands in the spectra. The intensity ratio of G and D band peak intensity was ca. 1.39 at lowest NaOH and Lapsi seed powder ratio 0.25:1 showing high graphitic degree. This ratio decreased with increase in the NaOH impregnation ratio and reached minimum ca. 0.94 (comparable with commercial AC) at NaOH and Lapsi seed powder ratio 1:1 demonstrating that higher NaOH impregnation reduces the graphitic structure of the carbon. XRD patterns showed two broad peaks at diffraction angles of approximately 25 and 43 degrees indicating the amorphous structure. Surface properties of the ACs (BET surface area, pore volume, and pore size distributions) were evaluated by nitrogen adsorption-desorption isotherm. Our ACs showed strong methylene blue adsorption property (maximum methylene blue is ca. 200 mg/g). Judging from the iodine number and methylene blue values, structure, and surface areas, it can be concluded that NaOH impregnation ratio is one of the key parameters to tune the surface properties of Lapsi seed stone-based activated carbons.

Ionic polymer metal composites with nanoporous carbon electrodes

NASA Astrophysics Data System (ADS)

Palmre, Viljar; Brandell, Daniel; Mäeorg, Uno; Torop, Janno; Volobujeva, Olga; Punning, Andres; Johanson, Urmas; Aabloo, Alvo

2010-04-01

Ionic Polymer Metal Composites (IPMCs) are soft electroactive polymer materials that bend in response to the voltage stimulus (1 - 4 V). They can be used as actuators or sensors. In this paper, we introduce two new highly-porous carbon materials for assembling high specific area electrodes for IPMC actuators and compare their electromechanical performance with recently reported IPMCs based on RuO2 electrodes. We synthesize ionic liquid (Emi-Tf) actuators with either Carbide-Derived Carbon (CDC) (derived from TiC) or coconut shell based activated carbon electrodes. The carbon electrodes are applied onto ionic liquid-swollen Nafion membranes using the direct assembly process. Our results show that actuators assembled with CDC electrodes have the greatest peak-to-peak strain output, reaching up to 20.4 mɛ (equivalent to >2%) at a 2 V actuation signal, exceeding that of the RuO2 electrodes by more than 100%. The electrodes synthesized from TiC-derived carbon also revealed significantly higher maximum strain rate. The differences between the materials are discussed in terms of molecular interactions and mechanisms upon actuation in the different electrodes.

A novel adenine-based metal organic framework derived nitrogen-doped nanoporous carbon for flexible solid-state supercapacitor.

PubMed

Li, Haowen; Fu, Dongying; Zhang, Xian-Ming

2018-01-01

In this article, we have synthesized a series of nitrogen-doped nanoporous carbon (NPC) from metal organic framework of UiO-66 with different ratios of adenine and 1,4-benzendicarboxylate (H 2 BDC) coated on carbon nanotube film (CNTF) to obtain a flexible porous electrode (NPC/CNTF). It is worth noting that the introduction of adenine at different ratios did not change the structure of UiO-66. We also investigated the effect of carbonization temperature from 800 to 1000°C on the electrochemical properties of the NPC. The ratio (H 2 BDC:adenine) 9 : 1 and the NPC carbonized at 900°C (denoted as NPC-1-900) exhibits better electrochemical properties. The results show that NPC-1-900/CNTF electrode exhibits an exceptional areal capacitance of 121.5 mF cm -2 compared to that of PC-900/CNTF electrode (22.8 mF cm -2 ) at 5 mV s -1 in a three-electrode system, indicating that the incorporation of nitrogen is beneficial to the electrochemical properties of nanoporous carbon. A symmetric flexible solid-state supercapacitor of NPC-1-900/CNTF has also been assembled and tested. Electrochemical data show that the device exhibited superior areal capacitance (43.2 mF cm -2 ) at the scan rate of 5 mV s -1 ; the volumetric energy density is 57.3 µWh cm -3 and the volumetric power density is 2.4 mW cm -3 at the current density of 0.5 mA cm -2 based on poly(vinyl alcohol)/H 3 PO 4 gel electrolyte. For practical application, we have also studied the bending tests of the device, which show that the device exhibits outstanding mechanical stability under different bending angles. Furthermore, the flexible device shows excellent cyclic stability, which can retain 91.5% of the initial capacitance after 2000 cycles.

A novel adenine-based metal organic framework derived nitrogen-doped nanoporous carbon for flexible solid-state supercapacitor

PubMed Central

Li, Haowen; Zhang, Xian-Ming

2018-01-01

In this article, we have synthesized a series of nitrogen-doped nanoporous carbon (NPC) from metal organic framework of UiO-66 with different ratios of adenine and 1,4-benzendicarboxylate (H2BDC) coated on carbon nanotube film (CNTF) to obtain a flexible porous electrode (NPC/CNTF). It is worth noting that the introduction of adenine at different ratios did not change the structure of UiO-66. We also investigated the effect of carbonization temperature from 800 to 1000°C on the electrochemical properties of the NPC. The ratio (H2BDC:adenine) 9 : 1 and the NPC carbonized at 900°C (denoted as NPC-1-900) exhibits better electrochemical properties. The results show that NPC-1-900/CNTF electrode exhibits an exceptional areal capacitance of 121.5 mF cm−2 compared to that of PC-900/CNTF electrode (22.8 mF cm−2) at 5 mV s−1 in a three-electrode system, indicating that the incorporation of nitrogen is beneficial to the electrochemical properties of nanoporous carbon. A symmetric flexible solid-state supercapacitor of NPC-1-900/CNTF has also been assembled and tested. Electrochemical data show that the device exhibited superior areal capacitance (43.2 mF cm−2) at the scan rate of 5 mV s−1; the volumetric energy density is 57.3 µWh cm−3 and the volumetric power density is 2.4 mW cm−3 at the current density of 0.5 mA cm−2 based on poly(vinyl alcohol)/H3PO4 gel electrolyte. For practical application, we have also studied the bending tests of the device, which show that the device exhibits outstanding mechanical stability under different bending angles. Furthermore, the flexible device shows excellent cyclic stability, which can retain 91.5% of the initial capacitance after 2000 cycles. PMID:29410815

Understanding Energy Absorption Behaviors of Nanoporous Materials

DTIC Science & Technology

2008-05-23

induced liquid infiltration in nanopores. J. Appl. Phys. 100, 014308.1-3 (2006). 26. Surani, F. B. and Qiao, Y. Energy absorption of a polyacrylic ...that the infiltration pressure decreases as the cation size increases (Fig.K-2). The ionic radii of cesium, potassium , sodium and lithium are...REPORT DOCUMENTATION PAGE Form Approved OMB NO. 0704-0188 Public Reporting burden for this collection of information is estimated to average 1 hour

Nanostructural Engineering of Nanoporous Anodic Alumina for Biosensing Applications

PubMed Central

Ferré-Borrull, Josep; Pallarès, Josep; Macías, Gerard; Marsal, Lluis F.

2014-01-01

Modifying the diameter of the pores in nanoporous anodic alumina opens new possibilities in the application of this material. In this work, we review the different nanoengineering methods by classifying them into two kinds: in situ and ex situ. Ex situ methods imply the interruption of the anodization process and the addition of intermediate steps, while in situ methods aim at realizing the in-depth pore modulation by continuous changes in the anodization conditions. Ex situ methods permit a greater versatility in the pore geometry, while in situ methods are simpler and adequate for repeated cycles. As an example of ex situ methods, we analyze the effect of changing drastically one of the anodization parameters (anodization voltage, electrolyte composition or concentration). We also introduce in situ methods to obtain distributed Bragg reflectors or rugate filters in nanoporous anodic alumina with cyclic anodization voltage or current. This nanopore engineering permits us to propose new applications in the field of biosensing: using the unique reflectance or photoluminescence properties of the material to obtain photonic barcodes, applying a gold-coated double-layer nanoporous alumina to design a self-referencing protein sensor or giving a proof-of-concept of the refractive index sensing capabilities of nanoporous rugate filters. PMID:28788127

Differential retention and release of CO 2 and CH 4 in kerogen nanopores: Implications for gas extraction and carbon sequestration

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

Ho, Tuan Anh; Wang, Yifeng; Xiong, Yongliang

Methane (CH 4) and carbon dioxide (CO 2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H 2O). In addition, supercritical CO 2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH 4-CO 2-H 2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO 2 over CH 4 andmore » that the majority of CO 2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO 2 may be released only if the reservoir pressure drops below the supercritical CO 2 pressure. When water is present in the kerogen matrix, it may block CH 4 release. Furthermore, the addition of CO 2 may enhance CH 4 release because CO 2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.« less

Differential retention and release of CO 2 and CH 4 in kerogen nanopores: Implications for gas extraction and carbon sequestration

DOE PAGES

Ho, Tuan Anh; Wang, Yifeng; Xiong, Yongliang; ...

2018-02-06

Methane (CH 4) and carbon dioxide (CO 2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H 2O). In addition, supercritical CO 2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH 4-CO 2-H 2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO 2 over CH 4 andmore » that the majority of CO 2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO 2 may be released only if the reservoir pressure drops below the supercritical CO 2 pressure. When water is present in the kerogen matrix, it may block CH 4 release. Furthermore, the addition of CO 2 may enhance CH 4 release because CO 2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.« less

Improved Analysis of Nanopore Sequence Data and Scanning Nanopore Techniques

NASA Astrophysics Data System (ADS)

Szalay, Tamas

The field of nanopore research has been driven by the need to inexpensively and rapidly sequence DNA. In order to help realize this goal, this thesis describes the PoreSeq algorithm that identifies and corrects errors in real-world nanopore sequencing data and improves the accuracy of de novo genome assembly with increasing coverage depth. The approach relies on modeling the possible sources of uncertainty that occur as DNA advances through the nanopore and then using this model to find the sequence that best explains multiple reads of the same region of DNA. PoreSeq increases nanopore sequencing read accuracy of M13 bacteriophage DNA from 85% to 99% at 100X coverage. We also use the algorithm to assemble E. coli with 30X coverage and the lambda genome at a range of coverages from 3X to 50X. Additionally, we classify sequence variants at an order of magnitude lower coverage than is possible with existing methods. This thesis also reports preliminary progress towards controlling the motion of DNA using two nanopores instead of one. The speed at which the DNA travels through the nanopore needs to be carefully controlled to facilitate the detection of individual bases. A second nanopore in close proximity to the first could be used to slow or stop the motion of the DNA in order to enable a more accurate readout. The fabrication process for a new pyramidal nanopore geometry was developed in order to facilitate the positioning of the nanopores. This thesis demonstrates that two of them can be placed close enough to interact with a single molecule of DNA, which is a prerequisite for being able to use the driving force of the pores to exert fine control over the motion of the DNA. Another strategy for reading the DNA is to trap it completely with one pore and to move the second nanopore instead. To that end, this thesis also shows that a single strand of immobilized DNA can be captured in a scanning nanopore and examined for a full hour, with data from many scans at many

Polyhedral Boranes: A Versatile Building Block for Nanoporous Materials

NASA Astrophysics Data System (ADS)

Clingerman, Daniel Jon

The studies described in this dissertation examine several new concepts related to polyhedral boranes and their applications towards the synthesis of novel nanoporous materials. The unique thermal and chemical robustness, rigidity, quasi-spherical geometry, and high boron content of polyhedral boranes are explored to generate materials not possible with typical organic synthons. Aside from the fundamental synthetic work, this work was also aimed at solving larger global issues such as energy storage and new routes to therapeutics. Chapter 2 highlights the discovery of the first highly porous carborane-based metal-organic framework, where the spherical nature of the carborane increases volumetric surface area without reducing pore volume. Chapter 3 examines the first tritopic carborane-based ligand and the stabilizing effect the rigid, sterically bulky carboranyl groups have on highly porous topologies not stable with typical organic ligands. Chapters 4 and 5 describe the use of polyhedral borane-based ligands as a means to influence and generate unexpected topologies. Lastly, chapter 6 explores using a simple carborane-based ligand that harnesses the power of coordination-driven assembly to rapidly generate a high boron-containing supramolecular cuboctahedron.

Electrospinning and electrospraying of silicon oxycarbide-derived nanoporous carbon for supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Tolosa, Aura; Krüner, Benjamin; Jäckel, Nicolas; Aslan, Mesut; Vakifahmetoglu, Cekdar; Presser, Volker

2016-05-01

In this study, carbide-derived carbon fibers from silicon oxycarbide precursor were synthesized by electrospinning of a commercially available silicone resin without adding a carrier polymer for the electrospinning process. The electrospun fibers were pyrolyzed yielding SiOC. Modifying the synthesis procedure, we were also able to obtain electrosprayed SiOC beads instead of fibers. After chlorine treatment, nanoporous carbon with a specific surface area of up to 2394 m2 g-1 was obtained (3089 m2 g-1 BET). Electrochemical characterization of the SiOC-CDC either as free-standing fiber mat electrodes or polymer-bound bead films was performed in 1 M tetraethylammonium tetrafluoroborate in acetonitrile (TEA-BF4 in ACN). The electrospun fibers presented a high gravimetric capacitance of 135 F g-1 at 10 mV s-1 and a very high power handling, maintaining 63% of the capacitance at 100 A g-1. Comparative data of SiOC-CDC beads and fibers show enhanced power handling for fiber mats only when the fiber network is intact, that is, a lowered performance was observed when using crushed mats that employ polymer binder.

Propagation of elastic wave in nanoporous material with distributed cylindrical nanoholes

NASA Astrophysics Data System (ADS)

Qiang, FangWei; Wei, PeiJun; Liu, XiQiang

2013-08-01

The effective propagation constants of plane longitudinal and shear waves in nanoporous material with random distributed parallel cylindrical nanoholes are studied. The surface elastic theory is used to consider the surface stress effects and to derive the nontraditional boundary condition on the surface of nanoholes. The plane wave expansion method is used to obtain the scattering waves from the single nanohole. The multiple scattering effects are taken into consideration by summing the scattered waves from all scatterers and performing the configuration averaging of random distributed scatterers. The effective propagation constants of coherent waves along with the associated dynamic effective elastic modulus are numerically evaluated. The influences of surface stress are discussed based on the numerical results.

Single-molecule nanopore enzymology

PubMed Central

Wloka, Carsten; Maglia, Giovanni

2017-01-01

Biological nanopores are a class of membrane proteins that open nanoscale water-conduits in biological membranes. When they are reconstituted in artificial membranes and a bias voltage is applied across the membrane, the ionic current passing through individual nanopores can be used to monitor chemical reactions, to recognize individual molecules and, of most interest, to sequence DNA. More recently, proteins and enzymes have started being analysed with nanopores. Monitoring enzymatic reactions with nanopores, i.e. nanopore enzymology, has the unique advantage that it allows long-timescale observations of native proteins at the single-molecule level. Here we describe the approaches and challenges in nanopore enzymology. PMID:28630164

Gassmann Theory Applies to Nanoporous Media

NASA Astrophysics Data System (ADS)

Gor, Gennady Y.; Gurevich, Boris

2018-01-01

Recent progress in extraction of unconventional hydrocarbon resources has ignited the interest in the studies of nanoporous media. Since many thermodynamic and mechanical properties of nanoscale solids and fluids differ from the analogous bulk materials, it is not obvious whether wave propagation in nanoporous media can be described using the same framework as in macroporous media. Here we test the validity of Gassmann equation using two published sets of ultrasonic measurements for a model nanoporous medium, Vycor glass, saturated with two different fluids, argon, and n-hexane. Predictions of the Gassmann theory depend on the bulk and shear moduli of the dry samples, which are known from ultrasonic measurements and the bulk moduli of the solid and fluid constituents. The solid bulk modulus can be estimated from adsorption-induced deformation or from elastic effective medium theory. The fluid modulus can be calculated according to the Tait-Murnaghan equation at the solvation pressure in the pore. Substitution of these parameters into the Gassmann equation provides predictions consistent with measured data. Our findings set up a theoretical framework for investigation of fluid-saturated nanoporous media using ultrasonic elastic wave propagation.

Crystal shape controlled H2 storage rate in nanoporous carbon composite with ultra-fine Pt nanoparticle

NASA Astrophysics Data System (ADS)

Chen, Tsan-Yao; Zhang, Yanhui; Hsu, Liang-Ching; Hu, Alice; Zhuang, Yu; Fan, Chia-Ming; Wang, Cheng-Yu; Chung, Tsui-Yun; Tsao, Cheng-Si; Chuang, Haw-Yeu

2017-02-01

This study demonstrates that the hydrogen storage rate (HSR) of nanoporous carbon supported platinum nanocatalysts (NC) is determined by their heterojunction and geometric configurations. The present NC is synthesized in an average particle size of ~1.5 nm by incipient wetness impregnation of Pt4+ at carbon support followed by annealing in H2 ambient at 102-105 °C. Among the steps in hydrogen storage, decomposition of H2 molecule into 2 H atoms on Pt NC surface is the deciding factor in HSR that is controlled by the thickness of Pt NC. For the best condition, HSR of Pt NC in 1~2 atomic layers thick (4.7 μg/g min) is 2.6 times faster than that (1.3 μg/g min) of Pt NC with higher than 3 atomic layers thick.

Pharmacokinetic properties of new antitumor radiopharmaceutical on the basis of diamond nanoporous composites labeled with rhenium-188

NASA Astrophysics Data System (ADS)

Petriev, V. M.; Tishchenko, V. K.; Kuril'chik, A. A.; Skvortsov, V. G.

2017-01-01

Today the development of address therapeutic radionuclide delivery systems directly to tumor tissue is of current interest. It can be achieved by the design of drug containers of specific sizes and shapes from carbon-based composite materials. It will be allowed to enhance the efficacy of anticancer therapy and avoid serious side effects. In this work we studied the pharmacokinetic properties of nanodiamond nanoporous composite labeled with rhenium-188 in rats with hepatocholangioma PC-1 after intratumoral injection. It was established that substantial part of injected radioactivity remained in tumor tissue. Within three hours after 188Re-nanoporous composites injection activity in tumor constituted 79.1-91.3% of injected dose (ID). Then activity level declined to 45.9% ID at 120 hours. No more than 1.34% ID entered the bloodstream. In soft organs and tissues, except thyroid gland, the content of compound didn’t exceed 0.3% ID/g. The highest activity in thyroid gland was 6.95% ID/g. In conclusion, received results suggest 188Re-nanoporous composites can be promising radionuclide delivery systems for cancer treatment.

Catalytic nanoporous membranes

DOEpatents

Pellin, Michael J; Hryn, John N; Elam, Jeffrey W

2013-08-27

A nanoporous catalytic membrane which displays several unique features Including pores which can go through the entire thickness of the membrane. The membrane has a higher catalytic and product selectivity than conventional catalysts. Anodic aluminum oxide (AAO) membranes serve as the catalyst substrate. This substrate is then subjected to Atomic Layer Deposition (ALD), which allows the controlled narrowing of the pores from 40 nm to 10 nm in the substrate by deposition of a preparatory material. Subsequent deposition of a catalytic layer on the inner surfaces of the pores reduces pore sizes to less than 10 nm and allows for a higher degree of reaction selectivity. The small pore sizes allow control over which molecules enter the pores, and the flow-through feature can allow for partial oxidation of reactant species as opposed to complete oxidation. A nanoporous separation membrane, produced by ALD is also provided for use in gaseous and liquid separations. The membrane has a high flow rate of material with 100% selectivity. Also provided is a method for producing a catalytic membrane having flow-through pores and discreet catalytic clusters adhering to the inside surfaces of the pores.

Method for making nanoporous hydrophobic coatings

DOEpatents

Fan, Hongyou; Sun, Zaicheng

2013-04-23

A simple coating method is used to form nanoporous hydrophobic films that can be used as optical coatings. The method uses evaporation-induced self-assembly of materials. The coating method starts with a homogeneous solution comprising a hydrophobic polymer and a surfactant polymer in a selective solvent. The solution is coated onto a substrate. The surfactant polymer forms micelles with the hydrophobic polymer residing in the particle core when the coating is dried. The surfactant polymer can be dissolved and selectively removed from the separated phases by washing with a polar solvent to form the nanoporous hydrophobic film.

Hydrogen storage in engineered carbon nanospaces.

PubMed

Burress, Jacob; Kraus, Michael; Beckner, Matt; Cepel, Raina; Suppes, Galen; Wexler, Carlos; Pfeifer, Peter

2009-05-20

It is shown how appropriately engineered nanoporous carbons provide materials for reversible hydrogen storage, based on physisorption, with exceptional storage capacities (approximately 80 g H2/kg carbon, approximately 50 g H2/liter carbon, at 50 bar and 77 K). Nanopores generate high storage capacities (a) by having high surface area to volume ratios, and (b) by hosting deep potential wells through overlapping substrate potentials from opposite pore walls, giving rise to a binding energy nearly twice the binding energy in wide pores. Experimental case studies are presented with surface areas as high as 3100 m(2) g(-1), in which 40% of all surface sites reside in pores of width approximately 0.7 nm and binding energy approximately 9 kJ mol(-1), and 60% of sites in pores of width>1.0 nm and binding energy approximately 5 kJ mol(-1). The findings, including the prevalence of just two distinct binding energies, are in excellent agreement with results from molecular dynamics simulations. It is also shown, from statistical mechanical models, that one can experimentally distinguish between the situation in which molecules do (mobile adsorption) and do not (localized adsorption) move parallel to the surface, how such lateral dynamics affects the hydrogen storage capacity, and how the two situations are controlled by the vibrational frequencies of adsorbed hydrogen molecules parallel and perpendicular to the surface: in the samples presented, adsorption is mobile at 293 K, and localized at 77 K. These findings make a strong case for it being possible to significantly increase hydrogen storage capacities in nanoporous carbons by suitable engineering of the nanopore space.

Three-dimensionally arrayed and mutually connected 1.2-nm nanopores for high-performance electric double layer capacitor.

PubMed

Itoi, Hiroyuki; Nishihara, Hirotomo; Kogure, Taichi; Kyotani, Takashi

2011-02-09

Zeolite-templated carbon is a promising candidate as an electrode material for constructing an electric double layer capacitor with both high-power and high-energy densities, due to its three-dimensionally arrayed and mutually connected 1.2-nm nanopores. This carbon exhibits both very high gravimetric (140-190 F g(-1)) and volumetric (75-83 F cm(-3)) capacitances in an organic electrolyte solution. Moreover, such a high capacitance can be well retained even at a very high current up to 20 A g(-1). This extraordinary high performance is attributed to the unique pore structure.

Optical Sensors for Biomolecules Using Nanoporous Sol-Gel Materials

NASA Technical Reports Server (NTRS)

Fang, Jonathan; Zhou, Jing C.; Lan, Esther H.; Dunn, Bruce; Gillman, Patricia L.; Smith, Scott M.

2004-01-01

An important consideration for space missions to Mars is the ability to detect biosignatures. Solid-state sensing elements for optical detection of biological entities are possible using sol-gel based biologically active materials. We have used these materials as optical sensing elements in a variety of bioassays, including immunoassays and enzyme assays. By immobilizing an appropriate biomolecule in the sol-gel sensing element, we have successfully detected analytes such as amino acids and hormones. In the case of the amino acid glutamate, the enzyme glutamate dehydrogenase was the immobilized molecule, whereas in the case of the hormone cortisol, an anti-cortisol antibody was immobilized in the sensing element. In this previous work with immobilized enzymes and antibodies, excellent sensitivity and specificity were demonstrated in a variety of formats including bulk materials, thin films and fibers. We believe that the sol-gel approach is an attractive platform for bioastronautics sensing applications because of the ability to detect a wide range of entities such as amino acids, fatty acids, hopanes, porphyrins, etc. The sol-gel approach produces an optically transparent 3D silica matrix that forms around the biomolecule of interest, thus stabilizing its structure and functionality while allowing for optical detection. This encapsulation process protects the biomolecule and leads to a more "rugged" sensor. The nanoporous structure of the sol-gel matrix allows diffusion of small target molecules but keeps larger, biomolecules immobilized in the pores. We are currently developing these biologically active sol-gel materials into small portable devices for on-orbit cortisol detection

Dependence of cell adhesion on extracellular matrix materials formed on pore bridge boundaries by nanopore opening and closing geometry.

PubMed

Kim, Sueon; Han, Dong Yeol; Chen, Zhenzhong; Lee, Won Gu

2018-04-30

In this study, we report experimental results for characterization of the growth and formation of pore bridge materials that modified the adhesion structures of cells cultured on nanomembranes with opening and closing geometry. To perform the proof-of-concept experiments, we fabricated two types of anodized alumina oxide substrates with single-sided opening (i.e., one side open, but closed at the other side) and double-sided opening (i.e., both sides open). In our experiment, we compared the densities of pores formed and of bridge materials which differently act as connective proteins depending on the size of pores. The results show that the pore opening geometry can be used to promote the net contact force between pores, resulting in the growth and formation of pore bridge materials before and after cell culture. The results also imply that the bridge materials can be used to attract the structural protrusion of filopodia that can promote the adhesion of cell-to-cell and cell-to-pore bridge. It is observed that the shape and size of cellular structures of filopodia depend on the presence of pore bridge materials. Overall, this observation brought us a significant clue that cells cultured on nanopore substrates would change the adhesion property depending on not only the formation of nanopores formed on the surface of topological substrates, but also that of pore bridge materials by its morphological growth.

Pt-Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores.

PubMed

Pardon, Gaspard; Gatty, Hithesh K; Stemme, Göran; van der Wijngaart, Wouter; Roxhed, Niclas

2013-01-11

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al(2)O(3)) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al(2)O(3) layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al(2)O(3) using ALD.

Pt-Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores

NASA Astrophysics Data System (ADS)

Pardon, Gaspard; Gatty, Hithesh K.; Stemme, Göran; van der Wijngaart, Wouter; Roxhed, Niclas

2013-01-01

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al2O3) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al2O3 layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al2O3 using ALD.

Heterobimetallic Metal–Organic Framework as a Precursor to Prepare a Nickel/Nanoporous Carbon Composite Catalyst for 4-Nitrophenol Reduction

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

Yang, Ying; Zhang, Ying; Sun, Cheng Jun

2014-11-01

Nickel/nanoporous carbon (Ni/NPC) composites are facilely prepared by direct pyrolysis of nonporous heterobimetallic zinc-nickel-terephthalate frameworks (Zn1-xNixMOF, x approximate to 0-1, MOF= metal-organic framework) at 1223 K in situ. Tailoring the Ni/Zn ratio creates densely populated and small Ni nanocrystals (Ni NCs) while maintaining sufficient porosity and surface area in the final product, which exhibits the largest activity factor (9.2 s(-1)g(-1)) and excellent stability toward 4-nitrophenol reduction.

Nanoporous carbon-based electrodes for high strain ionomeric bending actuators

NASA Astrophysics Data System (ADS)

Palmre, Viljar; Brandell, Daniel; Mäeorg, Uno; Torop, Janno; Volobujeva, Olga; Punning, Andres; Johanson, Urmas; Kruusmaa, Maarja; Aabloo, Alvo

2009-09-01

Ionic polymer metal composites (IPMCs) are electroactive material devices that bend at low applied voltage (1-4 V). Inversely, a voltage is generated when the materials are deformed, which makes them useful both as sensors and actuators. In this paper, we propose two new highly porous carbon materials as electrodes for IPMC actuators, generating a high specific area, and compare their electromechanical performance with recently reported RuO2 electrodes and conventional IPMCs. Using a direct assembly process (DAP), we synthesize ionic liquid (Emi-Tf) actuators with either carbide-derived carbon (CDC) or coconut-shell-based activated carbon-based electrodes. The carbon electrodes were applied onto ionic liquid-swollen Nafion membranes using a direct assembly process. The study demonstrates that actuators based on carbon electrodes derived from TiC have the greatest peak-to-peak strain output, reaching up to 20.4 mɛ (equivalent to>2%) at a 2 V actuation signal, exceeding that of the RuO2 electrodes by more than 100%. The electrodes synthesized from TiC-derived carbon also exhibit significantly higher maximum strain rate. The differences between the materials are discussed in terms of molecular interactions and mechanisms upon actuation in the different electrodes.

Crystal shape controlled H2 storage rate in nanoporous carbon composite with ultra-fine Pt nanoparticle

PubMed Central

Chen, Tsan-Yao; Zhang, Yanhui; Hsu, Liang-Ching; Hu, Alice; Zhuang, Yu; Fan, Chia-Ming; Wang, Cheng-Yu; Chung, Tsui-Yun; Tsao, Cheng-Si; Chuang, Haw-Yeu

2017-01-01

This study demonstrates that the hydrogen storage rate (HSR) of nanoporous carbon supported platinum nanocatalysts (NC) is determined by their heterojunction and geometric configurations. The present NC is synthesized in an average particle size of ~1.5 nm by incipient wetness impregnation of Pt4+ at carbon support followed by annealing in H2 ambient at 102–105 °C. Among the steps in hydrogen storage, decomposition of H2 molecule into 2 H atoms on Pt NC surface is the deciding factor in HSR that is controlled by the thickness of Pt NC. For the best condition, HSR of Pt NC in 1~2 atomic layers thick (4.7 μg/g min) is 2.6 times faster than that (1.3 μg/g min) of Pt NC with higher than 3 atomic layers thick. PMID:28195224

Mesoporous carbon materials

DOEpatents

Dai, Sheng [Knoxville, TN; Wang, Xiqing [Oak Ridge, TN

2012-02-14

The invention is directed to a method for fabricating a mesoporous carbon material, the method comprising subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition comprising: (i) a templating component comprised of a block copolymer, (ii) a phenolic compound or material, (iii) a crosslinkable aldehyde component, and (iv) at least 0.5 M concentration of a strong acid having a pKa of or less than -2, wherein said carbonization step comprises heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a mesoporous carbon material. The invention is also directed to a mesoporous carbon material having an improved thermal stability, preferably produced according to the above method.

Mesoporous carbon materials

DOEpatents

Dai, Sheng; Wang, Xiqing

2013-08-20

The invention is directed to a method for fabricating a mesoporous carbon material, the method comprising subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition comprising: (i) a templating component comprised of a block copolymer, (ii) a phenolic compound or material, (iii) a crosslinkable aldehyde component, and (iv) at least 0.5 M concentration of a strong acid having a pKa of or less than -2, wherein said carbonization step comprises heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a mesoporous carbon material. The invention is also directed to a mesoporous carbon material having an improved thermal stability, preferably produced according to the above method.

Hydrothermally formed three-dimensional nanoporous Ni(OH)2 thin-film supercapacitors.

PubMed

Yang, Yang; Li, Lei; Ruan, Gedeng; Fei, Huilong; Xiang, Changsheng; Fan, Xiujun; Tour, James M

2014-09-23

A three-dimensional nanoporous Ni(OH)2 thin-film was hydrothermally converted from an anodically formed porous layer of nickel fluoride/oxide. The nanoporous Ni(OH)2 thin-films can be used as additive-free electrodes for energy storage. The nanoporous layer delivers a high capacitance of 1765 F g(-1) under three electrode testing. After assembly with porous activated carbon in asymmetric supercapacitor configurations, the devices deliver superior supercapacitive performances with capacitance of 192 F g(-1), energy density of 68 Wh kg(-1), and power density of 44 kW kg(-1). The wide working potential window (up to 1.6 V in 6 M aq KOH) and stable cyclability (∼90% capacitance retention over 10,000 cycles) make the thin-film ideal for practical supercapacitor devices.

Synthesis of Three-Dimensional Nanoporous Li-Rich Layered Cathode Oxides for High Volumetric and Power Energy Density Lithium-Ion Batteries.

PubMed

Qiu, Bao; Yin, Chong; Xia, Yonggao; Liu, Zhaoping

2017-02-01

As rechargeable Li-ion batteries have expanded their applications into on-board energy storage for electric vehicles, the energy and power must be increased to meet the new demands. Li-rich layered oxides are one of the most promising candidate materials; however, it is very difficult to make them compatible with high volumetric energy density and power density. Here, we develop an innovative approach to synthesize three-dimensional (3D) nanoporous Li-rich layered oxides Li[Li 0.144 Ni 0.136 Co 0.136 Mn 0.544 ]O 2 , directly occurring at deep chemical delithiation with carbon dioxide. It is found that the as-prepared material presents a micrometer-sized spherical structure that is typically composed of interconnected nanosized subunits with narrow distributed pores at 3.6 nm. As a result, this unique 3D micro-/nanostructure not only has a high tap density over 2.20 g cm -3 but also exhibits excellent rate capability (197.6 mA h g -1 at 1250 mA g -1 ) as an electrode. The excellent electrochemical performance is ascribed to the unique nanoporous micro-nanostructures, which facilitates the Li + diffusion and enhances the structural stability of the Li-rich layered cathode materials. Our work offers a comprehensive designing strategy to construct 3D nanoporous Li-rich layered oxides for both high volumetric energy density and power density in Li-ion batteries.

Nanocontainers made of Various Materials with Tunable Shape and Size

NASA Astrophysics Data System (ADS)

Zhao, Xianglong; Meng, Guowen; Han, Fangming; Li, Xiangdong; Chen, Bensong; Xu, Qiaoling; Zhu, Xiaoguang; Chu, Zhaoqin; Kong, Mingguang; Huang, Qing

2013-07-01

Nanocontainers have great potentials in targeted drug delivery and nanospace-confined reactions. However, the previous synthetic approaches exhibited limited control over the morphology, size and materials of the nanocontainers, which are crucial in practical applications. Here, we present a synthetic approach to multi-segment linear-shaped nanopores with pre-designed morphologies inside anodic aluminium oxide (AAO), by tailoring the anodizing duration after a rational increase of the applied anodizing voltage and the number of voltage increase during Al foil anodization. Then, we achieve nanocontainers with designed morphologies, such as nanofunnels, nanobottles, nano-separating-funnels and nanodroppers, with tunable sizes and diverse materials of carbon, silicon, germanium, hafnium oxide, silica and nickel/carbon magnetic composite, by depositing a thin layer of materials on the inner walls of the pre-designed AAO nanopores. The strategy has far-reaching implications in the designing and large-scale fabrication of nanocontainers, opening up new opportunities in nanotechnology applications.

Nanocontainers made of Various Materials with Tunable Shape and Size

PubMed Central

Zhao, Xianglong; Meng, Guowen; Han, Fangming; Li, Xiangdong; Chen, Bensong; Xu, Qiaoling; Zhu, Xiaoguang; Chu, Zhaoqin; Kong, Mingguang; Huang, Qing

2013-01-01

Nanocontainers have great potentials in targeted drug delivery and nanospace-confined reactions. However, the previous synthetic approaches exhibited limited control over the morphology, size and materials of the nanocontainers, which are crucial in practical applications. Here, we present a synthetic approach to multi-segment linear-shaped nanopores with pre-designed morphologies inside anodic aluminium oxide (AAO), by tailoring the anodizing duration after a rational increase of the applied anodizing voltage and the number of voltage increase during Al foil anodization. Then, we achieve nanocontainers with designed morphologies, such as nanofunnels, nanobottles, nano-separating-funnels and nanodroppers, with tunable sizes and diverse materials of carbon, silicon, germanium, hafnium oxide, silica and nickel/carbon magnetic composite, by depositing a thin layer of materials on the inner walls of the pre-designed AAO nanopores. The strategy has far-reaching implications in the designing and large-scale fabrication of nanocontainers, opening up new opportunities in nanotechnology applications. PMID:23867836

Nanoporous Gold: Fabrication, Characterization, and Applications

PubMed Central

Seker, Erkin; Reed, Michael L.; Begley, Matthew R.

2009-01-01

Nanoporous gold (np-Au) has intriguing material properties that offer potential benefits for many applications due to its high specific surface area, well-characterized thiol-gold surface chemistry, high electrical conductivity, and reduced stiffness. The research on np-Au has taken place on various fronts, including advanced microfabrication and characterization techniques to probe unusual nanoscale properties and applications spanning from fuel cells to electrochemical sensors. Here, we provide a review of the recent advances in np-Au research, with special emphasis on microfabrication and characterization techniques. We conclude the paper with a brief outline of challenges to overcome in the study of nanoporous metals.

PALS and SPM/EFM investigation of charged nanoporous electret films

NASA Astrophysics Data System (ADS)

Chiang, Dar-Ming; Liu, Wen-Liang; Chen, Jen-Luan; Susuki, Ryoichi

2005-08-01

The electret properties of nanoporous Teflon-FEP films, fabricated by the super-critical fluids method and charged by the corona method at room temperature, are investigated. PALS and SAXS are applied first to examine the charge characteristics of a free volume of electret materials. The topography and surface charges of electret materials are determined by scanning probe microscopy and electric field microscopy, respectively. The experimental results reveal that the interior surface areas of the pores of the electret materials influence the retention and stability of charge. Initial and aged surface charge was increased by factors of two and ten, with and without nanoporous Teflon-FEP films, respectively.

MOF-derived Cu-Pd/nanoporous carbon composite as an efficient catalyst for hydrogen evolution reaction: A comparison between hydrothermal and electrochemical synthesis

NASA Astrophysics Data System (ADS)

Mandegarzad, Sakineh; Raoof, Jahan Bakhsh; Hosseini, Sayed Reza; Ojani, Reza

2018-04-01

In this study, a novel catalyst based on Cu-Pd bimetallic nanoparticles supported on nanoporous carbon composite (NPCC) is successfully fabricated through three-step process and used as an electrocatalyst towards hydrogen evolution reaction (HER). At the first step, MOF-199 is synthesized via two distinct strategies; (1) hydrothermal (HT) and (2) electrochemical (EC). Next, the synthesized MOF-199 is used as a template in order to prepare Cu/NPCC by direct carbonization under N2 atmosphere followed by galvanic replacement reaction of Cu metals by PdII ions. All the prepared materials are characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), and nitrogen adsorption/desorption measurements. The effect of synthesis method of MOF-199 on the electrocatalytic activity of the final product towards HER is investigated. The electrochemical measurements indicate that Cu-Pd/NPCC derived from the MOF prepared by EC method (Cu-Pd/NPCC/EC) exhibits an enhanced catalytic activity towards HER in H2SO4 solution than the Cu-Pd/NPCC/HT. This improvement may be attributed to using of supporting electrolyte in the preparation of Cu-Pd/NPCC/EC.

PREFACE New developments in nanopore research—from fundamentals to applications New developments in nanopore research—from fundamentals to applications

NASA Astrophysics Data System (ADS)

Albrecht, Tim; Edel, Joshua B.; Winterhalter, Mathias

2010-11-01

refereeing process, and Ms Natalia Goehring for the beautiful cover artwork. Finally, to the readers, we hope you find this special issue a valuable source of information and insight into the field of nanopores. New developments in nanopore research—from fundamentals to applications contents Mathematical modeling and simulation of nanopore blocking by precipitation M-T Wolfram, M Burger and Z S Siwy Protein conducting nanopores Anke Harsman, Vivien Krüger, Philipp Bartsch, Alf Honigmann, Oliver Schmidt, Sanjana Rao, Christof Meisinger and Richard Wagner Electrically sensing protease activity with nanopores Mikiembo Kukwikila and Stefan Howorka Electrical characterization of DNA-functionalized solid state nanopores for bio-sensing V Mussi, P Fanzio, L Repetto, G Firpo, P Scaruffi, S Stigliani, M Menotta, M Magnani, G P Tonini and U Valbusa Automatable lipid bilayer formation and ion channel measurement using sessile droplets J L Poulos, S A Portonovo, H Bang and J J Schmidt Critical assessment of OmpF channel selectivity: merging information from different experimental protocols M L López, E García-Giménez, V M Aguilella and A Alcaraz Chemically modified solid state nanopores for high throughput nanoparticle separation Anmiv S Prabhu, Talukder Zaki N Jubery, Kevin J Freedman, Rafael Mulero, Prashanta Dutta and Min Jun Kim Changes in ion channel geometry resolved to sub-ångström precision via single molecule mass spectrometry Joseph W F Robertson, John J Kasianowicz and Joseph E Reiner Entropic transport of finite size particles W Riefler, G Schmid, P S Burada and P Hänggi Osmotic stress regulates the strength and kinetics of sugar binding to the maltoporin channel Philip A Gurnev, Daniel Harries, V Adrian Parsegian and Sergey M Bezrukov Detection of urea-induced internal denaturation of dsDNA using solid-state nanoporesn Alon Singer, Heiko Kuhn, Maxim Frank-Kamenetskii and Amit Meller Translocation events in a single-walled carbon nanotube Jin He, Hao Liu, Pei Pang

Nanoporous PbSe-SiO2 Thermoelectric Composites.

PubMed

Wu, Chao-Feng; Wei, Tian-Ran; Sun, Fu-Hua; Li, Jing-Feng

2017-11-01

Nanoporous architecture has long been predicted theoretically for its proficiency in suppressing thermal conduction, but less concerned as a practical approach for better thermoelectric materials hitherto probably due to its technical challenges. This article demonstrates a study on nanoporous PbSe-SiO 2 composites fabricated by a facile method of mechanical alloying assisted by subsequent wet-milling and then spark plasma sintering. Owing to the formation of random nanopores and additional interface scattering, the lattice thermal conductivity is limited to a value as low as 0.56 W m -1 K -1 at above 600 K, almost the same low level achieved by introducing nanoscale precipitates. Besides, the room-temperature electrical transport is found to be dominated by the grain-boundary potential barrier scattering, whose effect fades away with increasing temperatures. Consequently, a maximum ZT of 1.15 at 823 K is achieved in the PbSe + 0.7 vol% SiO 2 composition with >20% increase in average ZT , indicating the great potential of nanoporous structuring toward high thermoelectric conversion efficiency.

Electroactive Nanoporous Metal Oxides and Chalcogenides by Chemical Design

PubMed Central

2017-01-01

The archetypal silica- and aluminosilicate-based zeolite-type materials are renowned for wide-ranging applications in heterogeneous catalysis, gas-separation and ion-exchange. Their compositional space can be expanded to include nanoporous metal chalcogenides, exemplified by germanium and tin sulfides and selenides. By comparison with the properties of bulk metal dichalcogenides and their 2D derivatives, these open-framework analogues may be viewed as three-dimensional semiconductors filled with nanometer voids. Applications exist in a range of molecule size and shape discriminating devices. However, what is the electronic structure of nanoporous metal chalcogenides? Herein, materials modeling is used to describe the properties of a homologous series of nanoporous metal chalcogenides denoted np-MX2, where M = Si, Ge, Sn, Pb, and X = O, S, Se, Te, with Sodalite, LTA and aluminum chromium phosphate-1 structure types. Depending on the choice of metal and anion their properties can be tuned from insulators to semiconductors to metals with additional modification achieved through doping, solid solutions, and inclusion (with fullerene, quantum dots, and hole transport materials). These systems form the basis of a new branch of semiconductor nanochemistry in three dimensions. PMID:28572706

Membranes with functionalized carbon nanotube pores for selective transport

DOEpatents

Bakajin, Olgica; Noy, Aleksandr; Fornasiero, Francesco; Park, Hyung Gyu; Holt, Jason K; Kim, Sangil

2015-01-27

Provided herein composition and methods for nanoporous membranes comprising single walled, double walled, or multi-walled carbon nanotubes embedded in a matrix material. Average pore size of the carbon nanotube can be 6 nm or less. These membranes are a robust platform for the study of confined molecular transport, with applications in liquid and gas separations and chemical sensing including desalination, dialysis, and fabric formation.

The Molecular Design of Active Sites in Nanoporous Materials for Sustainable Catalysis.

PubMed

Chapman, Stephanie; Potter, Matthew E; Raja, Robert

2017-12-02

At the forefront of global development, the chemical industry is being confronted by a growing demand for products and services, but also the need to provide these in a manner that is sustainable in the long-term. In facing this challenge, the industry is being revolutionised by advances in catalysis that allow chemical transformations to be performed in a more efficient and economical manner. To this end, molecular design, facilitated by detailed theoretical and empirical studies, has played a pivotal role in creating highly-active and selective heterogeneous catalysts. In this review, the industrially-relevant Beckmann rearrangement is presented as an exemplar of how judicious characterisation and ab initio experiments can be used to understand and optimise nanoporous materials for sustainable catalysis.

Laser Hybrid Fabrication of Nanoporous Structures on Metallic Material Surface

DTIC Science & Technology

2009-06-01

Research Center, Department of Mechanical Engineering,Beijing, 100084&# 65292 ;China, 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING...rials, 2005, 15: 989-994. [9]Jia F, Yu C, Ai Z, et al. Fabrication of nanoporous gold film electrodes with ultrahigh surface area and electro

Nanoporous Ca3Co4O9 Thin Films for Transferable Thermoelectrics

PubMed Central

2018-01-01

The development of high-performance and transferable thin-film thermoelectric materials is important for low-power applications, e.g., to power wearable electronics, and for on-chip cooling. Nanoporous films offer an opportunity to improve thermoelectric performance by selectively scattering phonons without affecting electronic transport. Here, we report the growth of nanoporous Ca3Co4O9 thin films by a sequential sputtering-annealing method. Ca3Co4O9 is promising for its high Seebeck coefficient and good electrical conductivity and important for its nontoxicity, low cost, and abundance of its constituent raw materials. To grow nanoporous films, multilayered CaO/CoO films were deposited on sapphire and mica substrates by rf-magnetron reactive sputtering from elemental Ca and Co targets, followed by annealing at 700 °C to form the final phase of Ca3Co4O9. This phase transformation is accompanied by a volume contraction causing formation of nanopores in the film. The thermoelectric propoperties of the nanoporous Ca3Co4O9 films can be altered by controlling the porosity. The lowest electrical resistivity is ∼7 mΩ cm, yielding a power factor of 2.32 × 10–4 Wm–1K–2 near room temperature. Furthermore, the films are transferable from the primary mica substrates to other arbitrary polymer platforms by simple dry transfer, which opens an opportunity of low-temperature use these materials. PMID:29905306

Microfluidic multiplexing of solid-state nanopores

NASA Astrophysics Data System (ADS)

Jain, Tarun; Rasera, Benjamin C.; Guerrero, Ricardo Jose S.; Lim, Jong-Min; Karnik, Rohit

2017-12-01

Although solid-state nanopores enable electronic analysis of many clinically and biologically relevant molecular structures, there are few existing device architectures that enable high-throughput measurement of solid-state nanopores. Herein, we report a method for microfluidic integration of multiple solid-state nanopores at a high density of one nanopore per (35 µm2). By configuring microfluidic devices with microfluidic valves, the nanopores can be rinsed from a single fluid input while retaining compatibility for multichannel electrical measurements. The microfluidic valves serve the dual purpose of fluidic switching and electric switching, enabling serial multiplexing of the eight nanopores with a single pair of electrodes. Furthermore, the device architecture exhibits low noise and is compatible with electroporation-based in situ nanopore fabrication, providing a scalable platform for automated electronic measurement of a large number of integrated solid-state nanopores.

Nanotechnology Based Materials and Devices for Health Care

NASA Technical Reports Server (NTRS)

Srivastava, Deepaka; Cho, K.; Brenner, Don; Menon, Madhu; Andriotis, Antonis; Sagman, Uri; Biegel, Bryan A. (Technical Monitor)

2002-01-01

This viewgraph presentation provides information on trends in NASA nanotechnology research and development, and future biotechnological applications for that nanotechnology. The presentation covers nanoelectronics, nanosensors, and nanomaterials, biomimetics, devices and materials for health care, carbon nanotubes, biosensors for astrobiology, solid-state nanopores for DNA sequencing, and protein nanotubes.

Characterization of Noble Gas Ion Beam Fabricated Single Molecule Nanopore Detectors

NASA Astrophysics Data System (ADS)

Rollings, Ryan; Ledden, Bradley; Shultz, John; Fologea, Daniel; Li, Jiali; Chervinsky, John; Golovchenko, Jene

2006-03-01

Nanopores fabricated with low energy noble gas ion beams in a silicon nitride membrane can be employed as the fundamental element of single biomolecule detection and characterization devices [1,2]. With the help of X-ray Photoelectron Spectroscopy (XPS) and Rutherford Backscattering (RBS), we demonstrate that the electrical noise properties, and hence ultimate sensitivity of nanopore single molecule detectors depends on ion beam species and nanopore annealing conditions. .1. Li, J., D. Stein, C. McMullan, D. Branton, M.J. Aziz, and J.A. Golovchenko, Ion-beam sculpting at nanometre length scales. Nature, 2001. 412(12 July): p. 166-169. 2. Li, J., M. Gershow, D. Stein, E. Brandin, and J.A. Golovchenko, DNA Molecules and Configurations in a Solid-state Nanopore Microscope. Nature Materials, 2003. 2: p. 611-615.

Nanoporous metal-carbon composite

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

Worsley, Marcus A.; Satcher, Joe; Kucheyev, Sergei

Described here is a metal-carbon composite, comprising (a) a porous three-dimensional scaffold comprising one or more of carbon nanotubes, graphene and graphene oxide, and (b) metal nanoparticles disposed on said porous scaffold, wherein the metal-carbon composite has a density of 1 g/cm.sup.3 or less, and wherein the metal nanoparticles account for 1 wt. % or more of the metal-carbon composite. Also described are methods for making the metal-carbon composite.

Nanoporous polymer electrolyte

DOEpatents

Elliott, Brian [Wheat Ridge, CO; Nguyen, Vinh [Wheat Ridge, CO

2012-04-24

A nanoporous polymer electrolyte and methods for making the polymer electrolyte are disclosed. The polymer electrolyte comprises a crosslinked self-assembly of a polymerizable salt surfactant, wherein the crosslinked self-assembly includes nanopores and wherein the crosslinked self-assembly has a conductivity of at least 1.0.times.10.sup.-6 S/cm at 25.degree. C. The method of making a polymer electrolyte comprises providing a polymerizable salt surfactant. The method further comprises crosslinking the polymerizable salt surfactant to form a nanoporous polymer electrolyte.

Nanoporous membranes enable concentration and transport in fully wet paper-based assays.

PubMed

Gong, Max M; Zhang, Pei; MacDonald, Brendan D; Sinton, David

2014-08-19

Low-cost paper-based assays are emerging as the platform for diagnostics worldwide. Paper does not, however, readily enable advanced functionality required for complex diagnostics, such as analyte concentration and controlled analyte transport. That is, after the initial wetting, no further analyte manipulation is possible. Here, we demonstrate active concentration and transport of analytes in fully wet paper-based assays by leveraging nanoporous material (mean pore diameter ≈ 4 nm) and ion concentration polarization. Two classes of devices are developed, an external stamp-like device with the nanoporous material separate from the paper-based assay, and an in-paper device patterned with the nanoporous material. Experimental results demonstrate up to 40-fold concentration of a fluorescent tracer in fully wet paper, and directional transport of the tracer over centimeters with efficiencies up to 96%. In-paper devices are applied to concentrate protein and colored dye, extending their limits of detection from ∼10 to ∼2 pmol/mL and from ∼40 to ∼10 μM, respectively. This approach is demonstrated in nitrocellulose membrane as well as paper, and the added cost of the nanoporous material is very low at ∼0.015 USD per device. The result is a major advance in analyte concentration and manipulation for the growing field of low-cost paper-based assays.

Magnetic solid-phase extraction using nanoporous three dimensional graphene hybrid materials for high-capacity enrichment and simultaneous detection of nine bisphenol analogs from water sample.

PubMed

Wang, Lingling; Zhang, Zhenzhen; Zhang, Jing; Zhang, Lei

2016-09-09

The synthesis of a magnetic nanoporous three dimensional graphene (3DG)/ZnFe2O4 composite has been achieved. Through formation of graphene hydrogel, ZnFe2O4 magnetic particles was successfully introduced into the nanoporous 3DG, resulting in a magnetic porous carbon material. The morphology, structure, and magnetic behavior of the as-prepared 3DG/ZnFe2O4 were characterized by using the techniques of SEM, XRD, BET, VSM, FTIR, Raman and TGA. The 3DG/ZnFe2O4 has a high specific surface area and super paramagnetism. Its performance was evaluated by the magnetic solid-phase extraction of nine bisphenol analogs (BPs) from water samples followed by HPLC analysis, and showed excellent adsorption capability for the nine target compounds. Under optimized condition, the lower method detection limits (0.05-0.18ngmL(-1)), the higher enrichment factors (800 fold) and good recoveries (95.1-103.8%) with relative standard deviation (RSD) values less than 6.2% were achieved. The results indicated that the developed method based on the use of 3DG/ZnFe2O4 as the magnetic adsorbent has the advantages of convenience and high efficiency, and can be successfully applied to detect the nine BPs in real water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Detecting trihalomethanes using nanoporous-carbon coated surface-acoustic-wave sensors

DOE PAGES

Siegal, Michael P.; Mowry, Curtis D.; Pfeifer, Kent B.; ...

2015-03-07

We study nanoporous-carbon (NPC) grown via pulsed laser deposition (PLD) as a sorbent coating on 96.5-MHz surface-acoustic-wave (SAW) devices to detect trihalomethanes (THMs), regulated byproducts from the chemical treatment of drinking water. Using both insertion-loss and isothermal-response measurements from known quantities of chloroform, the highest vapor pressure THM, we optimize the NPC mass-density at 1.05 ± 0.08 g/cm3 by controlling the background argon pressure during PLD. Precise THM quantities in a chlorobenzene solvent are directly injected into a separation column and detected as the phase-angle shift of the SAW device output compared to the drive signal. Using optimized NPC-coated SAWs,more » we study the chloroform response as a function of operating temperatures ranging from 10–50°C. Finally, we demonstrate individual responses from complex mixtures of all four THMs, with masses ranging from 10–2000 ng, after gas chromatography separation. As a result, estimates for each THM detection limit using a simple peak-height response evaluation are 4.4 ng for chloroform and 1 ng for bromoform; using an integrated-peak area response analysis improves the detection limits to 0.73 ng for chloroform and 0.003 ng bromoform.« less

Probing Interactions at the Nanoscale by Ion Current through Nanopores and Nanovoids

NASA Astrophysics Data System (ADS)

Gamble, Trevor Patrick

Polymer nanopores offer themselves as excellent test beds for study of phenomena that occur on the nano-scale, such as Debye layer formation, surface charge modulation, current saturation, and rectification. Studying ions interactions within the Debye layer, for example, is not possible on the micro-scale, where the pore diameter can be 100 times the size of the zone where interactions of interest occur. However, in our nanopores with an opening diameter less than 10 nm, a slight change of the Debye length can lead to drastic changes of the recorded ion current. Here we present our nanopores' use as a tool to study geometrical and electrochemical properties of porous manganese oxide. There is great value in studying nano-scale properties of this material because of its importance in lithium ion batteries and newly developed nano-architectures within supercapacitors. We electrodeposited manganese oxide wires into our cylindrical nanopores, filling them completely. In this use, nanopores became a template to probe properties of the embedded material such as surface charge, ion selectivity, and porosity. This information was then reported to the Energy Frontier Research Center (EFRC) collaboration, so that other groups can incorporate these recently discovered characteristics into future their nano-architecture design. Additionally, we constructed conical nanopores to study interactions between the surface charges found on the walls and alkali metal ions. In particular we looked at lithium, as it is the electrochemically active ion during charge cycling in EFRC energy storage devices. We attempted to reveal lithium ion's affinity to bind to surface charges. We found this binding led to lowering of the effective surface charge of the pore walls, while also decreasing lithium's ability to move through channels or voids that have charged walls. In connection to manganese oxide, a porous, charged material with voids, information on lithium's interaction with these charges

Asymmetric nanopore membranes: Single molecule detection and unique transport properties

NASA Astrophysics Data System (ADS)

Bishop, Gregory William

Biological systems rely on the transport properties of transmembrane channels. Such pores can display selective transport by allowing the passage of certain ions or molecules while rejecting others. Recent advances in nanoscale fabrication have allowed the production of synthetic analogs of such channels. Synthetic nanopores (pores with a limiting dimension of 1--100 nm) can be produced in a variety of materials by several different methods. In the Martin group, we have been exploring the track-etch method to produce asymmetric nanopores in thin films of polymeric or crystalline materials. Asymmetric nanopores are of particular interest due to their ability to serve as ion-current rectifiers. This means that when a membrane that contains such a pore or collection of pores is used to separate identical portions of electrolyte solution, the magnitude of the ionic current will depend not only on the magnitude of the applied potential (as expected) but also the polarity. Ion-current rectification is characterized by an asymmetric current--potential response. Here, the interesting transport properties of asymmetric nanopores (ion-current rectification and the related phenomenon of electroosmotic flow rectification) are explored. The effects of pore shape and pore density on these phenomena are investigated. Membranes that contain a single nanopore can serve as platforms for the single-molecule sensing technique known as resistive pulse sensing. The resistive-pulse sensing method is based on the Coulter principle. Thus, the selectivity of the technique is based largely upon size, making the analysis of mixtures by this method difficult in many cases. Here, the surface of a single nanopore membrane is modified with a molecular recognition agent in an attempt to obtain a more selective resistive-pulse sensor for a specific analyte.

Ultrathin Hierarchical Porous Carbon Nanosheets for High-Performance Supercapacitors and Redox Electrolyte Energy Storage.

PubMed

Jayaramulu, Kolleboyina; Dubal, Deepak P; Nagar, Bhawna; Ranc, Vaclav; Tomanec, Ondrej; Petr, Martin; Datta, Kasibhatta Kumara Ramanatha; Zboril, Radek; Gómez-Romero, Pedro; Fischer, Roland A

2018-04-01

The design of advanced high-energy-density supercapacitors requires the design of unique materials that combine hierarchical nanoporous structures with high surface area to facilitate ion transport and excellent electrolyte permeability. Here, shape-controlled 2D nanoporous carbon sheets (NPSs) with graphitic wall structure through the pyrolysis of metal-organic frameworks (MOFs) are developed. As a proof-of-concept application, the obtained NPSs are used as the electrode material for a supercapacitor. The carbon-sheet-based symmetric cell shows an ultrahigh Brunauer-Emmett-Teller (BET)-area-normalized capacitance of 21.4 µF cm -2 (233 F g -1 ), exceeding other carbon-based supercapacitors. The addition of potassium iodide as redox-active species in a sulfuric acid (supporting electrolyte) leads to the ground-breaking enhancement in the energy density up to 90 Wh kg -1 , which is higher than commercial aqueous rechargeable batteries, maintaining its superior power density. Thus, the new material provides a double profits strategy such as battery-level energy and capacitor-level power density. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoporous Gold as a Platform for a Building Block Catalyst

DOE PAGES

Wittstock, Arne; Wichmann, Andre; Baeumer, Marcus

2012-09-25

The porous bulk materials are of great interest in catalysis because they can be employed in heterogeneous gas and liquid phase catalysis, electrocatalysis, and in electrocatalytic sensing. Nanoporous gold gained considerable attraction in this context because it is the prime example of a corrosion-derived nanoporous bulk metal. Moreover, the material was shown to be a very active and selective Au type catalyst for a variety of oxidation reactions. In leveraging the functionalization of the surface of the material with various additives, its catalytic applications can be extended and tuned. In this review, we will summarize recent developments in using nanoporousmore » gold as the platform for the development of high performance catalytic materials by adding metals, metal oxides, and molecular functionalities as building blocks.« less

Selective Separation of Metal Ions via Monolayer Nanoporous Graphene with Carboxyl Groups.

PubMed

Li, Zhan; Liu, Yanqi; Zhao, Yang; Zhang, Xin; Qian, Lijuan; Tian, Longlong; Bai, Jing; Qi, Wei; Yao, Huijun; Gao, Bin; Liu, Jie; Wu, Wangsuo; Qiu, Hongdeng

2016-10-18

Graphene-coated plastic substrates, such as polyethylene terephthalate (PET), are regularly used in flexible electronic devices. Here we demonstrate a new application of the graphene-coated nanoporous PET membrane for the selective separation of metal ions in an ion exchange manner. Irradiation with swift heavy ions is used to perforate graphene and PET substrate. This process could create graphene nanopores with carboxyl groups, thus forming conical holes in the PET after chemical etching to support graphene nanopores. Therefore, a monolayer nanoporous graphene membrane with a PET substrate is constructed successfully to investigate its ionic selective separation. We find that the permeation ratio of ions strongly depends on the temperature and H + concentration in the driving solution. An electric field can increase the permeation ratio of ions through the graphene nanopores, but it inhibits the ion selective separation. Moreover, the structure of the graphene nanopore with carboxyl groups is resolved at the density functional theory level. The results show the asymmetric structure of the nanopore with carboxyl groups, and the analysis indicates that the ionic permeation can be attributed to the ion exchange between metal ions and protons on the two sides of graphene nanopores. These results would be beneficial to the design of membrane separation materials made from graphene with efficient online and offline bulk separation.

Supercapacitive transport of pharmacologic agents using nanoporous gold electrodes.

PubMed

Gittard, Shaun D; Pierson, Bonnie E; Ha, Cindy M; Wu, Chung-An Max; Narayan, Roger J; Robinson, David B

2010-02-01

In this study, nanoporous gold supercapacitors were produced by electrochemical dealloying of gold-silver alloy. Scanning electron microscopy and energy dispersive X-ray spectroscopy confirmed completion of the dealloying process and generation of a porous gold material with approximately 10 nm diameter pores. Cyclic voltammetry and chronoamperometry of the nanoporous gold electrodes indicated that these materials exhibited supercapacitor behavior. The storage capacity of the electrodes measured by chronoamperometry was approximately 3 mC at 200 mV. Electrochemical storage and voltage-controlled delivery of two model pharmacologic agents, benzylammonium and salicylic acid, was demonstrated. These results suggest that capacitance-based storage and delivery of pharmacologic agents may serve as an alternative to conventional drug delivery methods.

Competitive adsorption of a binary CO2-CH4 mixture in nanoporous carbons: effects of edge-functionalization.

PubMed

Lu, Xiaoqing; Jin, Dongliang; Wei, Shuxian; Zhang, Mingmin; Zhu, Qing; Shi, Xiaofan; Deng, Zhigang; Guo, Wenyue; Shen, Wenzhong

2015-01-21

The effect of edge-functionalization on the competitive adsorption of a binary CO2-CH4 mixture in nanoporous carbons (NPCs) has been investigated for the first time by combining density functional theory (DFT) and grand canonical Monte Carlo (GCMC) simulation. Our results show that edge-functionalization has a more positive effect on the single-component adsorption of CO2 than CH4, therefore significantly enhancing the selectivity of CO2 over CH4, in the order of NH2-NPC > COOH-NPC > OH-NPC > H-NPC > NPC at low pressure. The enhanced adsorption originates essentially from the effects of (1) the conducive environment with a large pore size and an effective accessible surface area, (2) the high electronegativity/electropositivity, (3) the strong adsorption energy, and (4) the large electrostatic contribution, due to the inductive effect/direct interaction of the embedded edge-functionalized groups. The larger difference from these effects results in the higher competitive adsorption advantage of CO2 in the binary CO2-CH4 mixture. Temperature has a negative effect on the gas adsorption, but no obvious influence on the electrostatic contribution on selectivity. With the increase of pressure, the selectivity of CO2 over CH4 first decreases sharply and subsequently flattens out to a constant value. This work highlights the potential of edge-functionalized NPCs in competitive adsorption, capture, and separation for the binary CO2-CH4 mixture, and provides an effective and superior alternative strategy in the design and screening of adsorbent materials for carbon capture and storage.

Computational modeling and analysis of thermoelectric properties of nanoporous silicon

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

Li, H.; Yu, Y.; Li, G., E-mail: gli@clemson.edu

2014-03-28

In this paper, thermoelectric properties of nanoporous silicon are modeled and studied by using a computational approach. The computational approach combines a quantum non-equilibrium Green's function (NEGF) coupled with the Poisson equation for electrical transport analysis, a phonon Boltzmann transport equation (BTE) for phonon thermal transport analysis and the Wiedemann-Franz law for calculating the electronic thermal conductivity. By solving the NEGF/Poisson equations self-consistently using a finite difference method, the electrical conductivity σ and Seebeck coefficient S of the material are numerically computed. The BTE is solved by using a finite volume method to obtain the phonon thermal conductivity k{sub p}more » and the Wiedemann-Franz law is used to obtain the electronic thermal conductivity k{sub e}. The figure of merit of nanoporous silicon is calculated by ZT=S{sup 2}σT/(k{sub p}+k{sub e}). The effects of doping density, porosity, temperature, and nanopore size on thermoelectric properties of nanoporous silicon are investigated. It is confirmed that nanoporous silicon has significantly higher thermoelectric energy conversion efficiency than its nonporous counterpart. Specifically, this study shows that, with a n-type doping density of 10{sup 20} cm{sup –3}, a porosity of 36% and nanopore size of 3 nm × 3 nm, the figure of merit ZT can reach 0.32 at 600 K. The results also show that the degradation of electrical conductivity of nanoporous Si due to the inclusion of nanopores is compensated by the large reduction in the phonon thermal conductivity and increase of absolute value of the Seebeck coefficient, resulting in a significantly improved ZT.« less

Electrochemical detection of single molecules using abiotic nanopores having electrically tunable dimensions

DOEpatents

Sansinena, Jose-Maria [Los Alamos, NM; Redondo, Antonio [Los Alamos, NM; Olazabal, Virginia [Los Alamos, NM; Hoffbauer, Mark A [Los Alamos, NM; Akhadov, Elshan A [Los Alamos, NM

2009-12-29

A barrier structure for use in an electrochemical stochastic membrane sensor for single molecule detection. The sensor is based upon inorganic nanopores having electrically tunable dimensions. The inorganic nanopores are formed from inorganic materials and an electrically conductive polymer. Methods of making the barrier structure and sensing single molecules using the barrier structure are also described.

Electrochemical detection of single molecules using abiotic nanopores having electrically tunable dimensions

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

Sansinena, Jose-Maria; Redondo, Antonio; Olazabal, Virginia

2017-09-12

A barrier structure for use in an electrochemical stochastic membrane sensor for single molecule detection. The sensor is based upon inorganic nanopores having electrically tunable dimensions. The inorganic nanopores are formed from inorganic materials and an electrically conductive polymer. Methods of making the barrier structure and sensing single molecules using the barrier structure are also described.

Electrochemical detection of single molecules using abiotic nanopores having electrically tunable dimensions

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

Sansinena, Jose-Maria; Redondo, Antonio; Olazabal, Virginia

2017-07-18

A barrier structure for use in an electrochemical stochastic membrane sensor for single molecule detection. The sensor is based upon inorganic nanopores having electrically tunable dimensions. The inorganic nanopores are formed from inorganic materials and an electrically conductive polymer. Methods of making the barrier structure and sensing single molecules using the barrier structure are also described.

Electrochemical detection of single molecules using abiotic nanopores having electrically tunable dimensions

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

Sansinena, Jose-Maria; Redondo, Antonio; Olazabal, Virginia

A barrier structure for use in an electrochemical stochastic membrane sensor for single molecule detection. The sensor is based upon inorganic nanopores having electrically tunable dimensions. The inorganic nanopores are formed from inorganic materials and an electrically conductive polymer. Methods of making the barrier structure and sensing single molecules using the barrier structure are also described.

Self-grown oxy-hydroxide@ nanoporous metal electrode for high-performance supercapacitors.

PubMed

Kang, JianLi; Hirata, Akihiko; Qiu, H-J; Chen, LuYang; Ge, XingBo; Fujita, Takeshi; Chen, MingWei

2014-01-15

A binder-free self-grown oxy-hydroxide@nanoporous Ni-Mn hybrid electrode with high capacitance and cyclic stability is fabricated by electrochemical polarization of a dealloyed nanoporous Ni-Mn alloy. Combined with the low material costs, high electrochemical stability, and environmentally friendly nature, this novel electrode holds great promise for applications in high-capacity commercial supercapacitors. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gate modulation of proton transport in a nanopore.

PubMed

Mei, Lanju; Yeh, Li-Hsien; Qian, Shizhi

2016-03-14

Proton transport in confined spaces plays a crucial role in many biological processes as well as in modern technological applications, such as fuel cells. To achieve active control of proton conductance, we investigate for the first time the gate modulation of proton transport in a pH-regulated nanopore by a multi-ion model. The model takes into account surface protonation/deprotonation reactions, surface curvature, electroosmotic flow, Stern layer, and electric double layer overlap. The proposed model is validated by good agreement with the existing experimental data on nanopore conductance with and without a gate voltage. The results show that the modulation of proton transport in a nanopore depends on the concentration of the background salt and solution pH. Without background salt, the gated nanopore exhibits an interesting ambipolar conductance behavior when pH is close to the isoelectric point of the dielectric pore material, and the net ionic and proton conductance can be actively regulated with a gate voltage as low as 1 V. The higher the background salt concentration, the lower is the performance of the gate control on the proton transport.

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers

PubMed Central

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-01-01

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO2/nanoporous-Si and the TiO2/nanoporous-Si by I–V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO2/nanoporous Si are lower than that of the HfO2/nanoporous Si, the former is more stable than the later. PMID:28252106

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers

NASA Astrophysics Data System (ADS)

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-03-01

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO2/nanoporous-Si and the TiO2/nanoporous-Si by I-V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO2/nanoporous Si are lower than that of the HfO2/nanoporous Si, the former is more stable than the later.

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers.

PubMed

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-03-02

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO 2 /nanoporous-Si and the TiO 2 /nanoporous-Si by I-V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO 2 /nanoporous Si are lower than that of the HfO 2 /nanoporous Si, the former is more stable than the later.

Nanofluidic Device with Embedded Nanopore

NASA Astrophysics Data System (ADS)

Zhang, Yuning; Reisner, Walter

2014-03-01

Nanofluidic based devices are robust methods for biomolecular sensing and single DNA manipulation. Nanopore-based DNA sensing has attractive features that make it a leading candidate as a single-molecule DNA sequencing technology. Nanochannel based extension of DNA, combined with enzymatic or denaturation-based barcoding schemes, is already a powerful approach for genome analysis. We believe that there is revolutionary potential in devices that combine nanochannels with nanpore detectors. In particular, due to the fast translocation of a DNA molecule through a standard nanopore configuration, there is an unfavorable trade-off between signal and sequence resolution. With a combined nanochannel-nanopore device, based on embedding a nanopore inside a nanochannel, we can in principle gain independent control over both DNA translocation speed and sensing signal, solving the key draw-back of the standard nanopore configuration. We demonstrate that we can detect - using fluorescent microscopy - successful translocation of DNA from the nanochannel out through the nanopore, a possible method to 'select' a given barcode for further analysis. We also show that in equilibrium DNA will not escape through an embedded sub-persistence length nanopore until a certain voltage bias is added.

Engineering on-chip nanoporous gold material libraries via precision photothermal treatment

NASA Astrophysics Data System (ADS)

Chapman, Christopher A. R.; Wang, Ling; Biener, Juergen; Seker, Erkin; Biener, Monika M.; Matthews, Manyalibo J.

2015-12-01

Libraries of nanostructured materials on a single chip are a promising platform for high throughput and combinatorial studies of structure-property relationships in the fields of physics and biology. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a nanostructured material specifically suited for such studies because of its self-similar thermally induced coarsening behavior. However, traditional heat application techniques for the modification of np-Au are bulk processes that cannot be used to generate a library of different pore sizes on a single chip. Here, laser micro-processing offers an attractive solution to this problem by providing a means to apply energy with high spatial and temporal resolution. In the present study we use finite element multiphysics simulations to predict the effects of laser mode (continuous-wave vs. pulsed) and thermal conductivity of the supporting substrate on the local np-Au film temperatures during photothermal annealing. Based on these results we discuss the mechanisms by which the np-Au network is coarsened. Thermal transport simulations predict that continuous-wave mode laser irradiation of np-Au thin films on a silicon substrate supports the widest range of morphologies that can be created through photothermal annealing of np-Au. Using the guidance provided by simulations, we successfully fabricate an on-chip material library consisting of 81 np-Au samples of 9 different morphologies for use in the parallel study of structure-property relationships.Libraries of nanostructured materials on a single chip are a promising platform for high throughput and combinatorial studies of structure-property relationships in the fields of physics and biology. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a nanostructured material specifically suited for such studies because of its self-similar thermally induced coarsening behavior. However, traditional heat application techniques for the modification

Voltage-Rectified Current and Fluid Flow in Conical Nanopores.

PubMed

Lan, Wen-Jie; Edwards, Martin A; Luo, Long; Perera, Rukshan T; Wu, Xiaojian; Martin, Charles R; White, Henry S

2016-11-15

Ion current rectification (ICR) refers to the asymmetric potential-dependent rate of the passage of solution ions through a nanopore, giving rise to electrical current-voltage characteristics that mimic those of a solid-state electrical diode. Since the discovery of ICR in quartz nanopipettes two decades ago, synthetic nanopores and nanochannels of various geometries, fabricated in membranes and on wafers, have been extensively investigated to understand fundamental aspects of ion transport in highly confined geometries. It is now generally accepted that ICR requires an asymmetric electrical double layer within the nanopore, producing an accumulation or depletion of charge-carrying ions at opposite voltage polarities. Our research groups have recently explored how the voltage-dependent ion distributions and ICR within nanopores can induce novel nanoscale flow phenomena that have applications in understanding ionics in porous materials used in energy storage devices, chemical sensing, and low-cost electrical pumping of fluids. In this Account, we review our most recent investigations on this topic, based on experiments using conical nanopores (10-300 nm tip opening) fabricated in thin glass, mica, and polymer membranes. Measurable fluid flow in nanopores can be induced either using external pressure forces, electrically via electroosmotic forces, or by a combination of these two forces. We demonstrate that pressure-driven flow can greatly alter the electrical properties of nanopores and, vice versa, that the nonlinear electrical properties of conical nanopores can impart novel and useful flow phenomena. Electroosmotic flow (EOF), which depends on the magnitude of the ion fluxes within the double layer of the nanopore, is strongly coupled to the accumulation/depletion of ions. Thus, the same underlying cause of ICR also leads to EOF rectification, i.e., unequal flows occurring for the same voltage but opposite polarities. EOF rectification can be used to electrically

Controlling porosity in lignin-derived nanoporous carbon for supercapacitor applications

DOE PAGES

Jeon, Ju-Won; Zhang, Libing; Lutkenhaus, Jodie L.; ...

2015-02-01

Low-cost renewable lignin has been used as a precursor to produce porous carbons. However, to date, it has not been easy to obtain high surface area porous carbon without activation processes or templating agents. Here, we demonstrate that low molecular weight lignin yields highly porous carbon (1092 m² g⁻¹) with more graphitization through direct carbonization without additional activation processes or templating agents. We found that molecular weight and oxygen consumption during carbonization are critical factors to obtain high surface area, graphitized porous carbons. This highly porous carbon from low-cost renewable lignin sources is a good candidate for supercapacitor electrode materials.

Controlling porosity in lignin-derived nanoporous carbon for supercapacitor applications

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

Jeon, Ju-Won; Zhang, Libing; Lutkenhaus, Jodie L.

Low-cost renewable lignin has been used as a precursor to produce porous carbons. However, to date, it has not been easy to obtain high surface area porous carbon without activation processes or templating agents. Here, we demonstrate that low molecular weight lignin yields highly porous carbon (1092 m² g⁻¹) with more graphitization through direct carbonization without additional activation processes or templating agents. We found that molecular weight and oxygen consumption during carbonization are critical factors to obtain high surface area, graphitized porous carbons. This highly porous carbon from low-cost renewable lignin sources is a good candidate for supercapacitor electrode materials.

Engineering on-chip nanoporous gold material libraries via precision photothermal treatment [Precision Photothermal Annealing of Nanoporous Gold Thin Films for the Microfabrication of a Single-ship Material Libraries

DOE PAGES

Chapman, Christopher A. R.; Wang, Ling; Biener, Juergen; ...

2016-01-01

Single-chip material libraries of thin films of nanostructured materials are a promising approach for high throughput studies of structure-property relationship in the fields of physics and biology. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a nanostructured material of specific interest in both these fields. One attractive property of np-Au is its self-similar coarsening behavior by thermally induced surface diffusion. However, traditional heat application techniques for the modification of np-Au are bulk processes that cannot be used to generate a library of different pore sizes on a single chip. Laser micromachining offers an attractive solution to this problemmore » by providing a means to apply energy with high spatial and temporal resolution. In our present study we use finite element multiphysics simulations to predict the effects of laser mode (continuous-wave vs. pulsed) and supporting substrate thermal conductivity on the local np-Au film temperatures during photothermal annealing and subsequently investigate the mechanisms by which the np-Au network is coarsening. Our simulations predict that continuous-wave mode laser irradiation on a silicon supporting substrate supports the widest range of morphologies that can be created through the photothermal annealing of thin film np-Au. Using this result we successfully fabricate a single-chip material library consisting of 81 np-Au samples of 9 different morphologies for use in increased throughput material interaction studies.« less

Engineering on-chip nanoporous gold material libraries via precision photothermal treatment [Precision Photothermal Annealing of Nanoporous Gold Thin Films for the Microfabrication of a Single-ship Material Libraries

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

Chapman, Christopher A. R.; Wang, Ling; Biener, Juergen

Single-chip material libraries of thin films of nanostructured materials are a promising approach for high throughput studies of structure-property relationship in the fields of physics and biology. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a nanostructured material of specific interest in both these fields. One attractive property of np-Au is its self-similar coarsening behavior by thermally induced surface diffusion. However, traditional heat application techniques for the modification of np-Au are bulk processes that cannot be used to generate a library of different pore sizes on a single chip. Laser micromachining offers an attractive solution to this problemmore » by providing a means to apply energy with high spatial and temporal resolution. In our present study we use finite element multiphysics simulations to predict the effects of laser mode (continuous-wave vs. pulsed) and supporting substrate thermal conductivity on the local np-Au film temperatures during photothermal annealing and subsequently investigate the mechanisms by which the np-Au network is coarsening. Our simulations predict that continuous-wave mode laser irradiation on a silicon supporting substrate supports the widest range of morphologies that can be created through the photothermal annealing of thin film np-Au. Using this result we successfully fabricate a single-chip material library consisting of 81 np-Au samples of 9 different morphologies for use in increased throughput material interaction studies.« less

SEM-induced shrinkage and site-selective modification of single-crystal silicon nanopores

NASA Astrophysics Data System (ADS)

Chen, Qi; Wang, Yifan; Deng, Tao; Liu, Zewen

2017-07-01

Solid-state nanopores with feature sizes around 5 nm play a critical role in bio-sensing fields, especially in single molecule detection and sequencing of DNA, RNA and proteins. In this paper we present a systematic study on shrinkage and site-selective modification of single-crystal silicon nanopores with a conventional scanning electron microscope (SEM). Square nanopores with measurable sizes as small as 8 nm × 8 nm and rectangle nanopores with feature sizes (the smaller one between length and width) down to 5 nm have been obtained, using the SEM-induced shrinkage technique. The analysis of energy dispersive x-ray spectroscopy and the recovery of the pore size and morphology reveal that the grown material along with the edge of the nanopore is the result of deposition of hydrocarbon compounds, without structural damage during the shrinking process. A simplified model for pore shrinkage has been developed based on observation of the cross-sectional morphology of the shrunk nanopore. The main factors impacting on the task of controllably shrinking the nanopores, such as the accelerating voltage, spot size, scanned area of e-beam, and the initial pore size have been discussed. It is found that single-crystal silicon nanopores shrink linearly with time under localized irradiation by SEM e-beam in all cases, and the pore shrinkage rate is inversely proportional to the initial equivalent diameter of the pore under the same e-beam conditions.

Stimuli-Responsive Polymer Brushes for Flow Control through Nanopores

PubMed Central

Adiga, Shashishekar P.; Brenner, Donald W.

2012-01-01

Responsive polymers attached to the inside of nano/micro-pores have attracted great interest owing to the prospect of designing flow-control devices and signal responsive delivery systems. An intriguing possibility involves functionalizing nanoporous materials with smart polymers to modulate biomolecular transport in response to pH, temperature, ionic concentration, light or electric field. These efforts open up avenues to develop smart medical devices that respond to specific physiological conditions. In this work, an overview of nanoporous materials functionalized with responsive polymers is given. Various examples of pH, temperature and solvent responsive polymers are discussed. A theoretical treatment that accounts for polymer conformational change in response to a stimulus and the associated flow-control effect is presented. PMID:24955529

Optical characterization of nanoporous AAO sensor substrate

NASA Astrophysics Data System (ADS)

Kassu, Aschalew; Farley, Carlton W.; Sharma, Anup

2014-05-01

Nanoporous anodic aluminum oxide (AAO) has been investigated as an ideal and cost-effective chemical and biosensing platform. In this paper, we report the optical properties of periodic 100 micron thick nanoporous anodic alumina membranes with uniform and high density cylindrical pores penetrating the entire thickness of the substrate, ranging in size from 18 nm to 150 nm in diameter and pore periods from 44 nm to 243 nm. The surface geometry of the top and bottom surface of each membrane is studied using atomic force microscopy. The optical properties including transmittance, reflectance, and absorbance spectra on both sides of each substrate are studied and found to be symmetrical. It is observed that, as the pore size increases, the peak resonance intensity in transmittance decreases and in absorbance increases. The effects of the pore sizes on the optical properties of the bare nanoporous membranes and the benefit of using arrays of nanohole arrays with varying hole size and periodicity as a chemical sensing platform is also discussed. To characterize the optical sensing technique, transmittance and reflectance measurements of various concentrations of a standard chemical adsorbed on the bare nanoporous substrates are investigated. The preliminary results presented here show variation in transmittance and reflectance spectra with the concentration of the chemical used or the amount of the material adsorbed on the surface of the substrate.

In vitro extracellular recording and stimulation performance of nanoporous gold-modified multi-electrode arrays.

PubMed

Kim, Yong Hee; Kim, Gook Hwa; Kim, Ah Young; Han, Young Hwan; Chung, Myung-Ae; Jung, Sang-Don

2015-12-01

Nanoporous gold (Au) structures can reduce the impedance and enhance the charge injection capability of multi-electrode arrays (MEAs) used for interfacing neuronal networks. Even though there are various nanoporous Au preparation techniques, fabrication of MEA based on low-cost electro-codeposition of Ag:Au has not been performed. In this work, we have modified a Au MEA via the electro-codeposition of Ag:Au alloy, followed by the chemical etching of Ag, and report on the in vitro extracellular recording and stimulation performance of the nanoporous Au-modified MEA. Ag:Au alloy was electro-codeposited on a bilayer lift-off resist sputter-deposition passivated Au MEA followed by chemical etching of Ag to form a porous Au structure. The porous Au structure was analyzed by scanning electron microscopy and tunneling electron microscopy and found to have an interconnected nanoporous Au structure. The impedance value of the nanoporous Au-modified MEA is 15.4 ± 0.55 kΩ at 1 kHz, accompanied by the base noise V rms of 2.4 ± 0.3 μV. The charge injection limit of the nanoporous Au-modified electrode estimated from voltage transient measurement is approximately 1 mC cm(-2), which is comparable to roughened platinum and carbon nanotube electrodes. The charge injection capability of the nanoporous Au-modified MEA was confirmed by observing stimulus-induced spikes at above 0.2 V. The nanoporous Au-modified MEA showed mechanical durability upon ultrasonic treatment for up to an hour. Electro-codeposition of Ag:Au alloy combined with chemical etching Ag is a low-cost process for fabricating nanoporous Au-modified MEA suitable for establishing the stimulus-response relationship of cultured neuronal networks.

In vitro extracellular recording and stimulation performance of nanoporous gold-modified multi-electrode arrays

NASA Astrophysics Data System (ADS)

Kim, Yong Hee; Kim, Gook Hwa; Kim, Ah Young; Han, Young Hwan; Chung, Myung-Ae; Jung, Sang-Don

2015-12-01

Objective. Nanoporous gold (Au) structures can reduce the impedance and enhance the charge injection capability of multi-electrode arrays (MEAs) used for interfacing neuronal networks. Even though there are various nanoporous Au preparation techniques, fabrication of MEA based on low-cost electro-codeposition of Ag:Au has not been performed. In this work, we have modified a Au MEA via the electro-codeposition of Ag:Au alloy, followed by the chemical etching of Ag, and report on the in vitro extracellular recording and stimulation performance of the nanoporous Au-modified MEA. Approach. Ag:Au alloy was electro-codeposited on a bilayer lift-off resist sputter-deposition passivated Au MEA followed by chemical etching of Ag to form a porous Au structure. Main results. The porous Au structure was analyzed by scanning electron microscopy and tunneling electron microscopy and found to have an interconnected nanoporous Au structure. The impedance value of the nanoporous Au-modified MEA is 15.4 ± 0.55 kΩ at 1 kHz, accompanied by the base noise V rms of 2.4 ± 0.3 μV. The charge injection limit of the nanoporous Au-modified electrode estimated from voltage transient measurement is approximately 1 mC cm-2, which is comparable to roughened platinum and carbon nanotube electrodes. The charge injection capability of the nanoporous Au-modified MEA was confirmed by observing stimulus-induced spikes at above 0.2 V. The nanoporous Au-modified MEA showed mechanical durability upon ultrasonic treatment for up to an hour. Significance. Electro-codeposition of Ag:Au alloy combined with chemical etching Ag is a low-cost process for fabricating nanoporous Au-modified MEA suitable for establishing the stimulus-response relationship of cultured neuronal networks.

Solid-State Ionic Diodes Demonstrated in Conical Nanopores

DOE PAGES

Plett, Timothy S.; Cai, Wenjia; Le Thai, Mya; ...

2017-02-27

Ionic transport at the nanoscale features phenomena that are not observed in larger systems. Nonlinear current–voltage curves characteristic of ionic diodes as well as ion selectivity are examples of effects observed at the nanoscale. Many man-made nanopore systems are inspired by biological channels in a cell membrane, thus measurements are often performed in aqueous solutions. Consequently, much less is known about ionic transport in nonaqueous systems, especially in solid-state electrolytes. Here we show ionic transport through single pores filled with gel electrolyte of poly(methyl methacrylate) (PMMA) doped with LiClO 4 in propylene carbonate. The system has no liquid interface andmore » the ionic transport occurs through the porous gel structure. We demonstrate that a conically shaped nanopore filled with the gel rectifies the current and works as a solid-state ionic diode.« less

A nanoporous MXene film enables flexible supercapacitors with high energy storage.

PubMed

Fan, Zhimin; Wang, Youshan; Xie, Zhimin; Xu, Xueqing; Yuan, Yin; Cheng, Zhongjun; Liu, Yuyan

2018-05-14

MXene films are attractive for use in advanced supercapacitor electrodes on account of their ultrahigh density and pseudocapacitive charge storage mechanism in sulfuric acid. However, the self-restacking of MXene nanosheets severely affects their rate capability and mass loading. Herein, a free-standing and flexible modified nanoporous MXene film is fabricated by incorporating Fe(OH)3 nanoparticles with diameters of 3-5 nm into MXene films and then dissolving the Fe(OH)3 nanoparticles, followed by low calcination at 200 °C, resulting in highly interconnected nanopore channels that promote efficient ion transport without compromising ultrahigh density. As a result, the modified nanoporous MXene film presents an attractive volumetric capacitance (1142 F cm-3 at 0.5 A g-1) and good rate capability (828 F cm-3 at 20 A g-1). Furthermore, it still displays a high volumetric capacitance of 749 F cm-3 and good flexibility even at a high mass loading of 11.2 mg cm-2. Therefore, this flexible and free-standing nanoporous MXene film is a promising electrode material for flexible, portable and compact storage devices. This study provides an efficient material design for flexible energy storage devices possessing high volumetric capacitance and good rate capability even at a high mass loading.

Noise Properties of Rectifying Nanopores

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

Powell, M R; Sa, N; Davenport, M

2011-02-18

Ion currents through three types of rectifying nanoporous structures are studied and compared for the first time: conically shaped polymer nanopores, glass nanopipettes, and silicon nitride nanopores. Time signals of ion currents are analyzed by power spectrum. We focus on the low-frequency range where the power spectrum magnitude scales with frequency, f, as 1/f. Glass nanopipettes and polymer nanopores exhibit non-equilibrium 1/f noise, thus the normalized power spectrum depends on the voltage polarity and magnitude. In contrast, 1/f noise in rectifying silicon nitride nanopores is of equilibrium character. Various mechanisms underlying the voltage-dependent 1/f noise are explored and discussed, includingmore » intrinsic pore wall dynamics, and formation of vortices and non-linear flow patterns in the pore. Experimental data are supported by modeling of ion currents based on the coupled Poisson-Nernst-Planck and Navier Stokes equations. We conclude that the voltage-dependent 1/f noise observed in polymer and glass asymmetric nanopores might result from high and asymmetric electric fields inducing secondary effects in the pore such as enhanced water dissociation.« less

Noise Properties of Rectifying Nanopore

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

Vlassiouk, Ivan V

2011-01-01

Ion currents through three types of rectifying nanoporous structures are studied and compared: conically shaped polymer nanopores, glass nanopipettes, and silicon nitride nanopores. Time signals of ion currents are analyzed by the power spectrum. We focus on the low-frequency range where the power spectrum magnitude scales with frequency, f, as 1/f. Glass nanopipettes and polymer nanopores exhibit nonequilibrium 1/f noise; thus, the normalized power spectrum depends on the voltage polarity and magnitude. In contrast, 1/f noise in rectifying silicon nitride nanopores is of equilibrium character. Various mechanisms underlying the voltage-dependent 1/f noise are explored and discussed, including intrinsic pore wallmore » dynamics and formation of vortices and nonlinear flow patterns in the pore. Experimental data are supported by modeling of ion currents based on the coupled Poisson-Nernst-Planck and Navier-Stokes equations. We conclude that the voltage-dependent 1/f noise observed in polymer and glass asymmetric nanopores might result from high and asymmetric electric fields, inducing secondary effects in the pore, such as enhanced water dissociation.« less

Expanding the functionality and applications of nanopore sensors

NASA Astrophysics Data System (ADS)

Venta, Kimberly E.

Nanopore sensors have developed into powerful tools for single-molecule studies since their inception two decades ago. Nanopore sensors function as nanoscale Coulter counters, by monitoring ionic current modulations as particles pass through a nanopore. While nanopore sensors can be used to study any nanoscale particle, their most notable application is as a low cost, fast alternative to current DNA sequencing technologies. In recent years, signifcant progress has been made toward the goal of nanopore-based DNA sequencing, which requires an ambitious combination of a low-noise and high-bandwidth nanopore measurement system and spatial resolution. In this dissertation, nanopore sensors in thin membranes are developed to improve dimensional resolution, and these membranes are used in parallel with a high-bandwidth amplfier. Using this nanopore sensor system, the signals of three DNA homopolymers are differentiated for the first time in solid-state nanopores. The nanopore noise is also reduced through the addition of a layer of SU8, a spin-on polymer, to the supporting chip structure. By increasing the temporal and spatial resolution of nanopore sensors, studies of shorter molecules are now possible. Nanopore sensors are beginning to be used for the study and characterization of nanoparticles. Nanoparticles have found many uses from biomedical imaging to next-generation solar cells. However, further insights into the formation and characterization of nanoparticles would aid in developing improved synthesis methods leading to more effective and customizable nanoparticles. This dissertation presents two methods of employing nanopore sensors to benet nanoparticle characterization and fabrication. Nanopores were used to study the formation of individual nanoparticles and serve as nanoparticle growth templates that could be exploited to create custom nanoparticle arrays. Additionally, nanopore sensors were used to characterize the surface charge density of anisotropic

Carbon membranes for efficient water-ethanol separation.

PubMed

Gravelle, Simon; Yoshida, Hiroaki; Joly, Laurent; Ybert, Christophe; Bocquet, Lydéric

2016-09-28

We demonstrate, on the basis of molecular dynamics simulations, the possibility of an efficient water-ethanol separation using nanoporous carbon membranes, namely, carbon nanotube membranes, nanoporous graphene sheets, and multilayer graphene membranes. While these carbon membranes are in general permeable to both pure liquids, they exhibit a counter-intuitive "self-semi-permeability" to water in the presence of water-ethanol mixtures. This originates in a preferred ethanol adsorption in nanoconfinement that prevents water molecules from entering the carbon nanopores. An osmotic pressure is accordingly expressed across the carbon membranes for the water-ethanol mixture, which agrees with the classic van't Hoff type expression. This suggests a robust and versatile membrane-based separation, built on a pressure-driven reverse-osmosis process across these carbon-based membranes. In particular, the recent development of large-scale "graphene-oxide" like membranes then opens an avenue for a versatile and efficient ethanol dehydration using this separation process, with possible application for bio-ethanol fabrication.

Carbon membranes for efficient water-ethanol separation

NASA Astrophysics Data System (ADS)

Gravelle, Simon; Yoshida, Hiroaki; Joly, Laurent; Ybert, Christophe; Bocquet, Lydéric

2016-09-01

We demonstrate, on the basis of molecular dynamics simulations, the possibility of an efficient water-ethanol separation using nanoporous carbon membranes, namely, carbon nanotube membranes, nanoporous graphene sheets, and multilayer graphene membranes. While these carbon membranes are in general permeable to both pure liquids, they exhibit a counter-intuitive "self-semi-permeability" to water in the presence of water-ethanol mixtures. This originates in a preferred ethanol adsorption in nanoconfinement that prevents water molecules from entering the carbon nanopores. An osmotic pressure is accordingly expressed across the carbon membranes for the water-ethanol mixture, which agrees with the classic van't Hoff type expression. This suggests a robust and versatile membrane-based separation, built on a pressure-driven reverse-osmosis process across these carbon-based membranes. In particular, the recent development of large-scale "graphene-oxide" like membranes then opens an avenue for a versatile and efficient ethanol dehydration using this separation process, with possible application for bio-ethanol fabrication.

Responsive nanoporous metals: recoverable modulations on strength and shape by watering

NASA Astrophysics Data System (ADS)

Ye, Xing-Long; Liu, Ling-Zhi; Jin, Hai-Jun

2016-08-01

Many biological materials can readily modulate their mechanical properties and shape by interacting with water in the surrounding environment, which is essential to their high performance in application. In contrast, typical inorganic materials (such as the metals) cannot change their strength and shape without involving thermal/mechanical treatments. By introducing nano-scale porous structure and exploiting a simple physical concept—the water-capillarity in nanopores, here we report that a ‘dead’ metal can be transformed into a ‘smart’ material with water-responsive properties. We demonstrate that the apparent strength, volume and shape of nanoporous Au and Au(Pt) can be modulated in situ, dramatically and recoverably, in response to water-dipping and partial-drying. The amplitude of strength-modulation reaches 20 MPa, which is nearly 50% of the yield strength at initial state. This approach also leads to reversible length change up to 1.3% in nanoporous Au and a large reversible bending motion of a bi-layer strip with tip displacement of ˜20 mm, which may be used for actuation. This method is simple and effective, occurring in situ under ambient conditions and requiring no external power, analogous to biological materials. The findings may open up novel applications in many areas such as micro-robotics and bio-medical devices.

Structural evolution of nanoporous ultra-low k dielectrics under voltage stress

NASA Astrophysics Data System (ADS)

Raja, Archana; Shaw, Thomas; Grill, Alfred; Laibowitz, Robert; Heinz, Tony

2013-03-01

High speed interconnects in advanced integrated circuits require ultra-low-k dielectrics. Reduction of the dielectric constant is achieved via incorporation of nanopores in structures containing silicon, carbon, oxygen and hydrogen (SiCOH). We study nanoporous SiCOH films of k=2.5 and thicknesses of 40 - 400 nm. Leakage currents develop in the films under long-term voltage stress, eventually leading to breakdown and chip failure. Previous work* has shown the build-up of trap states as dielectric breakdown progresses. Using FTIR spectroscopy we have tracked the reorganization of the bonds in the SiCOH networks induced by voltage stress. Our results indicate that the cleavage of the Si-C and SiC-O bonds contribute toward increase in the density of bulk trapping states as breakdown is approached. AC conductance and capacitance measurements have also been carried out to describe interfacial and bulk traps and mechanisms. Comparison of breakdown properties of films with differing carbon content will also be presented to further delineate the role of carbon. *Atkin, J.M.; Shaw, T.M.; Liniger, E.; Laibowitz, R.B.; Heinz, T.F. Reliability Physics Symposium (IRPS), 2012 IEEE International Supported by the Semiconductor Research Corporation

Fabrication of complete titania nanoporous structures via electrochemical anodization of Ti

PubMed Central

2011-01-01

We present a novel method to fabricate complete and highly oriented anodic titanium oxide (ATO) nano-porous structures with uniform and parallel nanochannels. ATO nano-porous structures are fabricated by anodizing a Ti-foil in two different organic viscous electrolytes at room temperature using a two-step anodizing method. TiO2 nanotubes covered with a few nanometer thin nano-porous layer is produced when the first and the second anodization are carried out in the same electrolyte. However, a complete titania nano-porous (TNP) structures are obtained when the second anodization is conducted in a viscous electrolyte when compared to the first one. TNP structure was attributed to the suppression of F-rich layer dissolution between the cell boundaries in the viscous electrolyte. The structural morphologies were examined by field emission scanning electron microscope. The average pore diameter is approximately 70 nm, while the average inter-pore distance is approximately 130 nm. These TNP structures are useful to fabricate other nanostructure materials and nanodevices. PMID:21711844

Nanopore-CMOS Interfaces for DNA Sequencing

PubMed Central

Magierowski, Sebastian; Huang, Yiyun; Wang, Chengjie; Ghafar-Zadeh, Ebrahim

2016-01-01

DNA sequencers based on nanopore sensors present an opportunity for a significant break from the template-based incumbents of the last forty years. Key advantages ushered by nanopore technology include a simplified chemistry and the ability to interface to CMOS technology. The latter opportunity offers substantial promise for improvement in sequencing speed, size and cost. This paper reviews existing and emerging means of interfacing nanopores to CMOS technology with an emphasis on massively-arrayed structures. It presents this in the context of incumbent DNA sequencing techniques, reviews and quantifies nanopore characteristics and models and presents CMOS circuit methods for the amplification of low-current nanopore signals in such interfaces. PMID:27509529

Nanopore-CMOS Interfaces for DNA Sequencing.

PubMed

Magierowski, Sebastian; Huang, Yiyun; Wang, Chengjie; Ghafar-Zadeh, Ebrahim

2016-08-06

DNA sequencers based on nanopore sensors present an opportunity for a significant break from the template-based incumbents of the last forty years. Key advantages ushered by nanopore technology include a simplified chemistry and the ability to interface to CMOS technology. The latter opportunity offers substantial promise for improvement in sequencing speed, size and cost. This paper reviews existing and emerging means of interfacing nanopores to CMOS technology with an emphasis on massively-arrayed structures. It presents this in the context of incumbent DNA sequencing techniques, reviews and quantifies nanopore characteristics and models and presents CMOS circuit methods for the amplification of low-current nanopore signals in such interfaces.

Computational predictions of the new Gallium nitride nanoporous structures

NASA Astrophysics Data System (ADS)

Lien, Le Thi Hong; Tuoc, Vu Ngoc; Duong, Do Thi; Thu Huyen, Nguyen

2018-05-01

Nanoporous structural prediction is emerging area of research because of their advantages for a wide range of materials science and technology applications in opto-electronics, environment, sensors, shape-selective and bio-catalysis, to name just a few. We propose a computationally and technically feasible approach for predicting Gallium nitride nanoporous structures with hollows at the nano scale. The designed porous structures are studied with computations using the density functional tight binding (DFTB) and conventional density functional theory methods, revealing a variety of promising mechanical and electronic properties, which can potentially find future realistic applications. Their stability is discussed by means of the free energy computed within the lattice-dynamics approach. Our calculations also indicate that all the reported hollow structures are wide band gap semiconductors in the same fashion with their parent’s bulk stable phase. The electronic band structures of these nanoporous structures are finally examined in detail.

Nanoporous Cyanate Ester Resins: Structure-Gas Transport Property Relationships

NASA Astrophysics Data System (ADS)

Gusakova, Kristina; Fainleib, Alexander; Espuche, Eliane; Grigoryeva, Olga; Starostenko, Olga; Gouanve, Fabrice; Boiteux, Gisèle; Saiter, Jean-Marc; Grande, Daniel

2017-04-01

This contribution addresses the relationships between the structure and gas transport properties of nanoporous thermostable cyanate ester resins (CERs) derived from polycyclotrimerization of 1,1'-bis(4-cyanatophenyl)ethane in the presence of 30 or 50 wt% of inert high-boiling temperature porogens (i.e., dimethyl- or dibutyl phthalates), followed by their quantitative removal. The nanopores in the films obtained were generated via a chemically induced phase separation route with further porogen extraction from the densely crosslinked CERs. To ensure a total desorption of the porogen moieties from the networks, an additional short-term thermal annealing at 250 °C was performed. The structure and morphology of such nanoporous CER-based films were investigated by FTIR and SEM techniques, respectively. Further, the gas transport properties of CER films were analyzed after the different processing steps, and relationships between the material structure and the main gas transport parameters were established.

Transport of Proteins through Nanopores

NASA Astrophysics Data System (ADS)

Luan, Binquan

In biological cells, a malfunctioned protein (such as misfolded or damaged) is degraded by a protease in which an unfoldase actively drags the protein into a nanopore-like structure and then a peptidase cuts the linearized protein into small fragments (i.e. a recycling process). Mimicking this biological process, many experimental studies have focused on the transport of proteins through a biological protein pore or a synthetic solid-state nanopore. Potentially, the nanopore-based sensors can provide a platform for interrogating proteins that might be disease-related or be targeted by a new drug molecule. The single-profile of a protein chain inside an extremely small nanopore might even permit the sequencing of the protein. Here, through all-atom molecular dynamics simulations, I will show various types of protein transport through a nanopore and reveal the nanoscale mechanics/energetics that plays an important role governing the protein transport.

Blue Energy and Desalination with Nanoporous Carbon Electrodes: Capacitance from Molecular Simulations to Continuous Models

NASA Astrophysics Data System (ADS)

Simoncelli, Michele; Ganfoud, Nidhal; Sene, Assane; Haefele, Matthieu; Daffos, Barbara; Taberna, Pierre-Louis; Salanne, Mathieu; Simon, Patrice; Rotenberg, Benjamin

2018-04-01

Capacitive mixing (CapMix) and capacitive deionization (CDI) are currently developed as alternatives to membrane-based processes to harvest blue energy—from salinity gradients between river and sea water—and to desalinate water—using charge-discharge cycles of capacitors. Nanoporous electrodes increase the contact area with the electrolyte and hence, in principle, also the performance of the process. However, models to design and optimize devices should be used with caution when the size of the pores becomes comparable to that of ions and water molecules. Here, we address this issue by simulating realistic capacitors based on aqueous electrolytes and nanoporous carbide-derived carbon (CDC) electrodes, accounting for both their complex structure and their polarization by the electrolyte under applied voltage. We compute the capacitance for two salt concentrations and validate our simulations by comparison with cyclic voltammetry experiments. We discuss the predictions of Debye-Hückel and Poisson-Boltzmann theories, as well as modified Donnan models, and we show that the latter can be parametrized using the molecular simulation results at high concentration. This then allows us to extrapolate the capacitance and salt adsorption capacity at lower concentrations, which cannot be simulated, finding a reasonable agreement with the experimental capacitance. We analyze the solvation of ions and their confinement within the electrodes—microscopic properties that are much more difficult to obtain experimentally than the electrochemical response but very important to understand the mechanisms at play. We finally discuss the implications of our findings for CapMix and CDI, both from the modeling point of view and from the use of CDCs in these contexts.

A nanoporous gold membrane for sensing applications

PubMed Central

Oo, Swe Zin; Silva, Gloria; Carpignano, Francesca; Noual, Adnane; Pechstedt, Katrin; Mateos, Luis; Grant-Jacob, James A.; Brocklesby, Bill; Horak, Peter; Charlton, Martin; Boden, Stuart A.; Melvin, Tracy

2016-01-01

Design and fabrication of three-dimensionally structured, gold membranes containing hexagonally close-packed microcavities with nanopores in the base, are described. Our aim is to create a nanoporous structure with localized enhancement of the fluorescence or Raman scattering at, and in the nanopore when excited with light of approximately 600 nm, with a view to provide sensitive detection of biomolecules. A range of geometries of the nanopore integrated into hexagonally close-packed assemblies of gold micro-cavities was first evaluated theoretically. The optimal size and shape of the nanopore in a single microcavity were then considered to provide the highest localized plasmon enhancement (of fluorescence or Raman scattering) at the very center of the nanopore for a bioanalyte traversing through. The optimized design was established to be a 1200 nm diameter cavity of 600 nm depth with a 50 nm square nanopore with rounded corners in the base. A gold 3D-structured membrane containing these sized microcavities with the integrated nanopore was successfully fabricated and ‘proof of concept’ Raman scattering experiments are described. PMID:26973809

Developments in carbon materials

NASA Technical Reports Server (NTRS)

Burchell, Timothy D.

1994-01-01

The following carbon-based materials are reviewed and their applications discussed: fullerenes; graphite (synthetic and manufactured); activated carbon fibers; and carbon-carbon composites. Carbon R&D activities at ORNL are emphasized.

Spontaneous Transport of Single-Stranded DNA through Graphene-MoS2 Heterostructure Nanopores.

PubMed

Luan, Binquan; Zhou, Ruhong

2018-04-24

The effective transport of a single-stranded DNA (ssDNA) molecule through a solid-state nanopore is essential to the future success of high-throughput and low-cost DNA sequencing. Compatible with current electric sensing technologies, here, we propose and demonstrate by molecular dynamics simulations the ssDNA transport through a quasi-two-dimensional nanopore in a heterostructure stacked together with different 2D materials, such as graphene and molybdenum disulfide (MoS 2 ). Due to different chemical potentials, U, of DNA bases on different 2D materials, it is energetically favorable for a ssDNA molecule to move from the low- U MoS 2 surface to the high- U graphene surface through a nanopore. With the proper attraction between the negatively charged phosphate group in each nucleotide and the positively charged Mo atoms exposed on the pore surface, the ssDNA molecule can be temporarily seized and released thereafter through a thermal activation, that is, a slow and possible nucleotide-by-nucleotide transport. A theoretical formulation is then developed for the free energy of the ssDNA transiting a heterostructure nanopore to properly characterize the non-equilibrium stick-slip-like motion of a ssDNA molecule.

The kinetic enhancement of hydrogen cycling in NaAlH(4) by melt infusion into nanoporous carbon aerogel.

PubMed

Stephens, Robert D; Gross, Adam F; Van Atta, Sky L; Vajo, John J; Pinkerton, Frederick E

2009-05-20

Enhanced kinetic performance and reversibility have been achieved with uncatalyzed NaAlH4 by incorporation into nanoporous carbon aerogel. Aerogel with a pore size distribution peaked at 13 nm and a pore volume of 0.8 cm(3) g(-1) was filled with NaAlH4 to 94% capacity by melt infusion at 189 degrees C under 183 bar H(2) gas overpressure. Dehydrogenation to NaH + Al with reasonable kinetics was accomplished at 150 degrees C, well below the NaAlH4 melting temperature (183 degrees C), compared to hydrogen release above 230 degrees C for bulk uncatalyzed NaAlH4. Uncatalyzed bulk samples did not rehydrogenate under laboratory conditions, whereas NaAlH4 in a carbon aerogel host was readily rehydrogenated at approximately 160 degrees C and 100 bar H(2) to approximately 85% of its initial capacity. Ball-milled NaAlH4 catalyzed with 4 mol% TiCl3 showed somewhat better kinetics compared to the infused aerogel; nevertheless, the large kinetic enhancement obtained by incorporation into carbon aerogel, even in the absence of a catalyst, demonstrates the substantial benefit of confining the NaAlH4 to nanoscale dimensions.

Boosting infrared energy transfer in 3D nanoporous gold antennas.

PubMed

Garoli, D; Calandrini, E; Bozzola, A; Ortolani, M; Cattarin, S; Barison, S; Toma, A; De Angelis, F

2017-01-05

The applications of plasmonics to energy transfer from free-space radiation to molecules are currently limited to the visible region of the electromagnetic spectrum due to the intrinsic optical properties of bulk noble metals that support strong electromagnetic field confinement only close to their plasma frequency in the visible/ultraviolet range. In this work, we show that nanoporous gold can be exploited as a plasmonic material for the mid-infrared region to obtain strong electromagnetic field confinement, co-localized with target molecules into the nanopores and resonant with their vibrational frequency. The effective optical response of the nanoporous metal enables the penetration of optical fields deep into the nanopores, where molecules can be loaded thus achieving a more efficient light-matter coupling if compared to bulk gold. In order to realize plasmonic resonators made of nanoporous gold, we develop a nanofabrication method based on polymeric templates for metal deposition and we obtain antenna arrays resonating at mid-infrared wavelengths selected by design. We then coat the antennas with a thin (3 nm) silica layer acting as the target dielectric layer for optical energy transfer. We study the strength of the light-matter coupling at the vibrational absorption frequency of silica at 1240 cm -1 through the analysis of the experimental Fano lineshape that is benchmarked against identical structures made of bulk gold. The boost in the optical energy transfer from free-space mid-infrared radiation to molecular vibrations in nanoporous 3D nanoantenna arrays can open new application routes for plasmon-enhanced physical-chemical reactions.

Lignin-Derived Advanced Carbon Materials

DOE PAGES

Chatterjee, Sabornie; Saito, Tomonori

2015-11-16

Lignin is a highly abundant source of renewable carbon that can be considered as a valuable sustainable source of biobased materials. By applying specific pretreatments and manufacturing methods, it has been found that lignin can be converted into a variety of value-added carbon materials. However, the physical and chemical heterogeneities of lignin complicate its use as a feedstock. Herein, we discuss the lignin manufacturing process, the effects of pretreatments and manufacturing methods on the properties of product lignin, and structure–property relationships in various applications of lignin-derived carbon materials, such as carbon fibers, carbon mats, activated carbons, carbon films, and templatedmore » carbon.« less

Lignin-Derived Advanced Carbon Materials

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

Chatterjee, Sabornie; Saito, Tomonori

Lignin is a highly abundant source of renewable carbon that can be considered as a valuable sustainable source of biobased materials. By applying specific pretreatments and manufacturing methods, it has been found that lignin can be converted into a variety of value-added carbon materials. However, the physical and chemical heterogeneities of lignin complicate its use as a feedstock. Herein, we discuss the lignin manufacturing process, the effects of pretreatments and manufacturing methods on the properties of product lignin, and structure–property relationships in various applications of lignin-derived carbon materials, such as carbon fibers, carbon mats, activated carbons, carbon films, and templatedmore » carbon.« less

Sodium-ion supercapacitors based on nanoporous pyroproteins containing redox-active heteroatoms

NASA Astrophysics Data System (ADS)

Cho, Se Youn; Yoon, Hyeon Ji; Kim, Na Rae; Yun, Young Soo; Jin, Hyoung-Joon

2016-10-01

Nanostructured carbon-based materials fabricated via simple methods from renewable bio-resources have great potential in rechargeable energy storage systems. In this study, nanoporous pyroproteins containing a large amount of redox-active heteroatoms (H-NPs) were fabricated from silk fibroin by an in situ carbonization/activation method. The H-NPs have a large surface area of ∼3050 m2 g-1, which is mainly comprised of nanometer-scale pores. Also, these H-NPs have oxygen and nitrogen heteroatoms of 17.4 wt% and 2.9 wt%, respectively. Synergistic sodium ion storage behaviors originate from electrochemical double layer capacitance and pseudocapacitance, leading to very high electrochemical performances of H-NPs in aqueous and non-aqueous electrolyte systems. Sodium-ion supercapacitors (NISs) based on commercial graphite//H-NPs show a high specific power of ∼1900 W kg-1 at ∼77 Wh kg-1. Also, NISs based on commercial hard carbon//H-NPs exhibit a high specific energy of ∼217 Wh kg-1 at ∼42 W kg-1. In addition, outstanding cycling performances over 30,000 cycles are achieved for symmetric NISs.

Resizing metal-coated nanopores using a scanning electron microscope.

PubMed

Chansin, Guillaume A T; Hong, Jongin; Dusting, Jonathan; deMello, Andrew J; Albrecht, Tim; Edel, Joshua B

2011-10-04

Electron beam-induced shrinkage provides a convenient way of resizing solid-state nanopores in Si(3) N(4) membranes. Here, a scanning electron microscope (SEM) has been used to resize a range of different focussed ion beam-milled nanopores in Al-coated Si(3) N(4) membranes. Energy-dispersive X-ray spectra and SEM images acquired during resizing highlight that a time-variant carbon deposition process is the dominant mechanism of pore shrinkage, although granular structures on the membrane surface in the vicinity of the pores suggest that competing processes may occur. Shrinkage is observed on the Al side of the pore as well as on the Si(3) N(4) side, while the shrinkage rate is observed to be dependent on a variety of factors. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon Nanotube-Enhanced Carbon-Phenenolic Ablator Material

NASA Technical Reports Server (NTRS)

Kikolaev, P.; Stackpoole, M.; Fan, W.; Cruden, B. A.; Waid, M.; Moloney, P.; Arepalli, S.; Arnold, J.; Partridge, H.; Yowell, L.

2006-01-01

This viewgraph presentation reviews the use of PICA (phenolic impregnated carbon ablator) as the selected material for heat shielding for future earth return vehicles. It briefly reviews the manufacturing of PICA and the advantages for the use of heat shielding, and then explains the reason for using Carbon Nanotubes to improve strength of phenolic resin that binds carbon fibers together. It reviews the work being done to create a carbon nanotube enhanced PICA. Also shown are various micrographic images of the various PICA materials.

Evolution of dealloying induced strain in nanoporous gold crystals

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

Chen-Wiegart, Yu-chen Karen; Harder, Ross; Dunand, David C.

For this paper, we studied the evolution of dealloying-induced strain along the {111} in a Ag-Au nano-crystal in situ, during formation of nanoporous gold at the initial stage of dealloying using Bragg coherent x-ray diffractive imaging. The maximum strain magnitude in the crystal doubled in 10 s of dealloying. Although formation of nano-pores just began at the surface, the greatest strain is located 60-80 nm deep within the crystal. Dealloying induced a compressive strain in this region, indicating volume shrinkage occurred during pore formation. The crystal interior showed a small tensile strain, which can be explained by 'pulling' of themore » dealloyed region by the non-dealloyed region during volume reduction. A surface strain relaxation developed, attributed to atomic rearrangement during dealloying. This clearer understanding of the role of strain in the initial stages of formation of nanoporous gold by dealloying can be exploited for development of new sensors, battery electrodes, and materials for catalysis.« less

Evolution of dealloying induced strain in nanoporous gold crystals

DOE PAGES

Chen-Wiegart, Yu-chen Karen; Harder, Ross; Dunand, David C.; ...

2017-04-10

For this paper, we studied the evolution of dealloying-induced strain along the {111} in a Ag-Au nano-crystal in situ, during formation of nanoporous gold at the initial stage of dealloying using Bragg coherent x-ray diffractive imaging. The maximum strain magnitude in the crystal doubled in 10 s of dealloying. Although formation of nano-pores just began at the surface, the greatest strain is located 60-80 nm deep within the crystal. Dealloying induced a compressive strain in this region, indicating volume shrinkage occurred during pore formation. The crystal interior showed a small tensile strain, which can be explained by 'pulling' of themore » dealloyed region by the non-dealloyed region during volume reduction. A surface strain relaxation developed, attributed to atomic rearrangement during dealloying. This clearer understanding of the role of strain in the initial stages of formation of nanoporous gold by dealloying can be exploited for development of new sensors, battery electrodes, and materials for catalysis.« less

Synthesis of organically templated nanoporous tin (II/IV) phosphate for radionuclide and metal sequestration

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

Wellman, Dawn M.; Mattigod, Shas V.; Parker, Kent E.

2006-03-20

Nanoporous tin (II/IV) phosphate materials, with spherical morphology, have been synthesized using cetyltrimethylammonium chloride (CH3(CH2)15N(CH3)3Cl) as the surfactant. The structure of the material is stable at 500°C; however, partial oxidation of the material occurs with redox conversion of Sn2+ to Sn4+, resulting in a mixed Sn(II)/ Sn(IV) material. Preliminary batch contact studies were conducted to assess the effectiveness of nanoporous tin phosphate, NP-SnPO, in sequestering redox sensitive metals and radionuclides, technetium(VII), neptunium(V), thorium(IV), and a toxic metal, chromium(VI), from aqueous matrices. Results indicate tin (II) phosphate removed > 95% of all contaminants investigated from solution.

Ion transport in a pH-regulated nanopore.

PubMed

Yeh, Li-Hsien; Zhang, Mingkan; Qian, Shizhi

2013-08-06

Fundamental understanding of ion transport phenomena in nanopores is crucial for designing the next-generation nanofluidic devices. Due to surface reactions of dissociable functional groups on the nanopore wall, the surface charge density highly depends upon the proton concentration on the nanopore wall, which in turn affects the electrokinetic transport of ions, fluid, and particles within the nanopore. Electrokinetic ion transport in a pH-regulated nanopore, taking into account both multiple ionic species and charge regulation on the nanopore wall, is theoretically investigated for the first time. The model is verified by the experimental data of nanopore conductance available in the literature. The results demonstrate that the spatial distribution of the surface charge density at the nanopore wall and the resulting ion transport phenomena, such as ion concentration polarization (ICP), ion selectivity, and conductance, are significantly affected by the background solution properties, such as the pH and salt concentration.

Effect of Graphene with Nanopores on Metal Clusters

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

Zhou, Hu; Chen, Xianlang; Wang, Lei

Porous graphene, which is a novel type of defective graphene, shows excellent potential as a support material for metal clusters. In this work, the stability and electronic structures of metal clusters (Pd, Ir, Rh) supported on pristine graphene and graphene with different sizes of nanopore were investigated by first-principle density functional theory (DFT) calculations. Thereafter, CO adsorption and oxidation reaction on the Pd-graphene system were chosen to evaluate its catalytic performance. Graphene with nanopore can strongly stabilize the metal clusters and cause a substantial downshift of the d-band center of the metal clusters, thus decreasing CO adsorption. All binding energies,more » d-band centers, and adsorption energies show a linear change with the size of the nanopore: a bigger size of nanopore corresponds to a stronger metal clusters bond to the graphene, lower downshift of the d-band center, and weaker CO adsorption. By using a suitable size nanopore, supported Pd clusters on the graphene will have similar CO and O2 adsorption ability, thus leading to superior CO tolerance. The DFT calculated reaction energy barriers show that graphene with nanopore is a superior catalyst for CO oxidation reaction. These properties can play an important role in instructing graphene-supported metal catalyst preparation to prevent the diffusion or agglomeration of metal clusters and enhance catalytic performance. This work was supported by National Basic Research Program of China (973Program) (2013CB733501), the National Natural Science Foundation of China (NSFC-21176221, 21136001, 21101137, 21306169, and 91334013). D. Mei acknowledges the support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational

Nano-assembly and Controlled Release Kinetics of Nanoelements from Nanoporous Templates

NASA Astrophysics Data System (ADS)

Gultepe, E.; Nagesha, D.; McNulty, J.; Sridhar, S.

2008-03-01

Nanotemplates and nanoparticles have potential for use in the area of nanomanufacturing and biomedical applications. We are using highly ordered nanoporous alumina as a template for drug delivery and to assemble nanoelements such as latex beads and single wall carbon nanotubes (SWNT) by the means of electrophoresis and/or dielectrophoresis. The results of 100% assembly of latex beads and controlled elution of drugs from nanoporous templates will be discussed. Vertically assembled SWNT and with the I-V characteristic as 3D interconnects, will also be presented. We have developed a variety of platforms incorporating superparamagnetic iron oxide nanoparticles for targeted delivery, magnetic hyperthermia and as a contrast agent for magnetic resonance imaging. The results of cell studies on these platforms will be discussed.

Polymer-modified opal nanopores.

PubMed

Schepelina, Olga; Zharov, Ilya

2006-12-05

The surface of nanopores in opal films, assembled from 205 nm silica spheres, was modified with poly(acrylamide) brushes using surface-initiated atom transfer radical polymerization. The colloidal crystal lattice remained unperturbed by the polymerization. The polymer brush thickness was controlled by polymerization time and was monitored by measuring the flux of redox species across the opal film using cyclic voltammetry. The nanopore size and polymer brush thickness were calculated on the basis of the limiting current change. Polymer brush thickness increased over the course of 26 h of polymerization in a logarithmic manner from 1.3 to 8.5 nm, leading to nanopores as small as 7.5 nm.

Characterization of nanoporous shales with gas sorption

NASA Astrophysics Data System (ADS)

Joewondo, N.; Prasad, M.

2017-12-01

The understanding of the fluid flow in porous media requires the knowledge of the pore system involved. Fluid flow in fine grained shales falls under different regime than transport regime in conventional reservoir due to the different average pore sizes in the two materials; the average pore diameter of conventional sandstones is on the micrometer scale, while of shales can be as small as several nanometers. Mercury intrusion porosimetry is normally used to characterize the pores of conventional reservoir, however with increasingly small pores, the injection pressure required to imbibe the pores becomes infinitely large due to surface tension. Characterization of pores can be expressed by a pore size distribution (PSD) plot, which reflects distribution of pore volume or surface area with respect to pore size. For the case of nanoporous materials, the surface area, which serves as the interface between the rock matrix and fluid, becomes increasingly large and important. Physisorption of gas has been extensively studied as a method of nanoporous solid characterization (particularly for the application of catalysis, metal organic frameworks, etc). The PSD is obtained by matching the experimental result to the calculated theoretical result (using Density Functional Theory (DFT), a quantum mechanics based modelling method for molecular scale interactions). We present the challenges and experimental result of Nitrogen and CO2 gas sorption on shales with various mineralogy and the interpreted PSD obtained by DFT method. Our result shows significant surface area contributed by the nanopores of shales, hence the importance of surface area measurements for the characterization of shales.

Controlling reactivity of nanoporous catalyst materials by tuning reaction product-pore interior interactions: Statistical mechanical modeling

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

Wang, Jing; Ackerman, David M.; Lin, Victor S.-Y.

2013-04-02

Statistical mechanical modeling is performed of a catalytic conversion reaction within a functionalized nanoporous material to assess the effect of varying the reaction product-pore interior interaction from attractive to repulsive. A strong enhancement in reactivity is observed not just due to the shift in reaction equilibrium towards completion but also due to enhanced transport within the pore resulting from reduced loading. The latter effect is strongest for highly restricted transport (single-file diffusion), and applies even for irreversible reactions. The analysis is performed utilizing a generalized hydrodynamic formulation of the reaction-diffusion equations which can reliably capture the complex interplay between reactionmore » and restricted transport.« less

Pistons and Cylinders Made of Carbon-Carbon Composite Materials

NASA Technical Reports Server (NTRS)

Rivers, H. Kevin (Inventor); Ransone, Philip O. (Inventor); Northam, G. Burton (Inventor); Schwind, Francis A. (Inventor)

2000-01-01

An improved reciprocating internal combustion engine has a plurality of engine pistons, which are fabricated from carbon-carbon composite materials, in operative association with an engine cylinder block, or an engine cylinder tube, or an engine cylinder jug, all of which are also fabricated from carbon-carbon composite materials.

Optofluidic devices with integrated solid-state nanopores

PubMed Central

Hawkins, Aaron R.; Schmidt, Holger

2016-01-01

This review (with 90 refs.) covers the state of the art in optofluidic devices with integrated solid-state nanopores for use in detection and sensing. Following an introduction into principles of optofluidics and solid-state nanopore technology, we discuss features of solid-state nanopore based assays using optofluidics. This includes the incorporation of solid-state nanopores into optofluidic platforms based on liquid-core anti-resonant reflecting optical waveguides (ARROWs), methods for their fabrication, aspects of single particle detection and particle manipulation. We then describe the new functionalities provided by solid-state nanopores integrated into optofluidic chips, in particular acting as smart gates for correlated electro-optical detection and discrimination of nanoparticles. This enables the identification of viruses and λ-DNA, particle trajectory simulations, enhancing sensitivity by tuning the shape of nanopores. The review concludes with a summary and an outlook. PMID:27046940

Controlled formation of closed-edge nanopores in graphene

NASA Astrophysics Data System (ADS)

He, Kuang; Robertson, Alex W.; Gong, Chuncheng; Allen, Christopher S.; Xu, Qiang; Zandbergen, Henny; Grossman, Jeffrey C.; Kirkland, Angus I.; Warner, Jamie H.

2015-07-01

Dangling bonds at the edge of a nanopore in monolayer graphene make it susceptible to back-filling at low temperatures from atmospheric hydrocarbons, leading to potential instability for nanopore applications, such as DNA sequencing. We show that closed edge nanopores in bilayer graphene are robust to back-filling under atmospheric conditions for days. A controlled method for closed edge nanopore formation starting from monolayer graphene is reported using an in situ heating holder and electron beam irradiation within an aberration-corrected transmission electron microscopy. Tailoring of closed-edge nanopore sizes is demonstrated from 1.4-7.4 nm. These results should provide mechanisms for improving the stability of nanopores in graphene for a wide range of applications involving mass transport.Dangling bonds at the edge of a nanopore in monolayer graphene make it susceptible to back-filling at low temperatures from atmospheric hydrocarbons, leading to potential instability for nanopore applications, such as DNA sequencing. We show that closed edge nanopores in bilayer graphene are robust to back-filling under atmospheric conditions for days. A controlled method for closed edge nanopore formation starting from monolayer graphene is reported using an in situ heating holder and electron beam irradiation within an aberration-corrected transmission electron microscopy. Tailoring of closed-edge nanopore sizes is demonstrated from 1.4-7.4 nm. These results should provide mechanisms for improving the stability of nanopores in graphene for a wide range of applications involving mass transport. Electronic supplementary information (ESI) available: Low magnification images, image processing techniques employed, modelling and simulation of closed edge nanoribbon, comprehensive AC-TEM dataset, and supporting analysis. See DOI: 10.1039/c5nr02277k

Experimental Evidence of Accelerated Seismic Release without Critical Failure in Acoustic Emissions of Compressed Nanoporous Materials

NASA Astrophysics Data System (ADS)

Baró, Jordi; Dahmen, Karin A.; Davidsen, Jörn; Planes, Antoni; Castillo, Pedro O.; Nataf, Guillaume F.; Salje, Ekhard K. H.; Vives, Eduard

2018-06-01

The total energy of acoustic emission (AE) events in externally stressed materials diverges when approaching macroscopic failure. Numerical and conceptual models explain this accelerated seismic release (ASR) as the approach to a critical point that coincides with ultimate failure. Here, we report ASR during soft uniaxial compression of three silica-based (SiO2 ) nanoporous materials. Instead of a singular critical point, the distribution of AE energies is stationary, and variations in the activity rate are sufficient to explain the presence of multiple periods of ASR leading to distinct brittle failure events. We propose that critical failure is suppressed in the AE statistics by mechanisms of transient hardening. Some of the critical exponents estimated from the experiments are compatible with mean field models, while others are still open to interpretation in terms of the solution of frictional and fracture avalanche models.

The Influence of Nanopore Dimensions on the Electrochemical Properties of Nanopore Arrays Studied by Impedance Spectroscopy

PubMed Central

Kant, Krishna; Priest, Craig; Shapter, Joe G.; Losic, Dusan

2014-01-01

The understanding of the electrochemical properties of nanopores is the key factor for better understanding their performance and applications for nanopore-based sensing devices. In this study, the influence of pore dimensions of nanoporous alumina (NPA) membranes prepared by an anodization process and their electrochemical properties as a sensing platform using impedance spectroscopy was explored. NPA with four different pore diameters (25 nm, 45 nm and 65 nm) and lengths (5 μm to 20 μm) was used and their electrochemical properties were explored using different concentration of electrolyte solution (NaCl) ranging from 1 to 100 μM. Our results show that the impedance and resistance of nanopores are influenced by the concentration and ion species of electrolytes, while the capacitance is independent of them. It was found that nanopore diameters also have a significant influence on impedance due to changes in the thickness of the double layer inside the pores. PMID:25393785

Functionalized nanoporous silicas for the immobilization of penicillin acylase

NASA Astrophysics Data System (ADS)

Maria Chong, A. S.; Zhao, X. S.

2004-10-01

Nanoporous silica materials with uniform pore size and ordered structure have drawn growing interest of researchers since 1990s. A large-pore nanoporous material, SBA-15, was functionalized with organosilanes by co-condensation method in the presence of nonionic triblock copolymer P123 as a template under acidic conditions. The functionalization was demonstrated by using five organosilanes, namely 3-aminopropyltriethoxysilane (APTES), 3-mercaptopropyltrimethoxysilane (MPTMS), phenyltrimethoxysilane (PTMS), vinyltriethoxysilane (VTES), and 4-(triethoxysilyl)butyronitrile (TSBN), which modified the surface properties of the silica materials, enabling the materials to be a promising support for immobilization of biological molecules. The functionalized SBA-15 materials exhibited long-range ordering of two-dimensional hexagonal pore arrays of size ranging from 66 to 90 Å as demonstrated by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and physical adsorption techniques. A variety of organosilane density in the range of 0.5-2.6 mmol/g was achieved as revealed by elemental analysis and solid-state nuclear magnetic resonance (NMR) techniques. The functionalized materials displayed improved properties for immobilization of penicillin acylase (PA) in comparison with pure-silica SBA-15. Such improvement is believed to be due to the enhanced surface hydrophobicity and electrostatic interactions of the functional groups with the enzyme.

Super flame-retardant lightweight rime-like carbon-phenolic nanofoam

NASA Astrophysics Data System (ADS)

Cheng, Haiming; Hong, Changqing; Zhang, Xinghong; Xue, Huafei; Meng, Songhe; Han, Jiecai

2016-09-01

The desire for lightweight nanoporous materials with high-performance thermal insulation and efficient anti-ablation resistance for energy conservation and thermal protection/insulation has greatly motivated research and development recently. The main challenge to synthesize such lightweight materials is how to balance the relationship of low thermal conductivity and flame retardancy. Herein, we propose a new concept of lightweight “rime-like” structured carbon-phenolic nanocomposites to solve this problem, where the 3D chopped network-structured carbon fiber (NCF) monoliths are incorporated with nanoporous phenolic aerogel to retain structural and functional integrity. The nanometer-scaled porous phenolic (NP) was synthesized through polymerization-induced phase separation and ambient pressure drying using phenolic resin (PR) solution as reaction source, ethylene glycol (EG) as solvent and hexamethylenetetramine (HMTA) as catalyst. We demonstrate that the as-prepared NCF-NP nanocomposite exhibits with a low density of 0.25-0.35 g/cm3, low thermal conductivity of 0.125 Wm-1K-1 and outstanding flame retardancy exceeding 2000 °C under arc-jet wind tunnel simulation environment. Our results show that the synthesis strategy is a promising approach for producing nanocomposites with excellent high-temperature heat blocking property.

Improved electrochemical performance of polyindole/carbon nanotubes composite as electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

Cai, Zhi-Jiang; Zhang, Qin; Song, Xian-You

2016-09-01

Polyindole/carbon nanotubes (PIN/CNTs) composite was prepared by an in-situ chemical oxidative polymerization of indole monomer with CNTs using ammonium persulfate as oxidant. The obtained composite material was characterized by SEM, TEM, FT-IR, Raman spectroscopy, XPS, XRD and BET surface areas measurements. It was found that the CNTs were incorporated into the PIN matrix and nanoporous structure was formed. Spectroscopy results showed that interfacial interaction bonds might be formed between the polyindole chains and CNTs during the in-situ polymerization. PIN/CNTs composite was evaluated by electrochemical impedance spectroscopy, cyclic voltammetry and charge/discharge tests to determine electrode performances in relation to supercapacitors properties in both aqueous and non-aqueous system. A maximum specific capacitance and specific volumetric capacitance of 555.6 F/g and 222.2 F/cm3 can be achieved at 0.5 A/g in non-aqueous system. It also displayed good rate performance and cycling stability. The specific capacitance retention is over 60% at 10 A/g and 91.3% after 5000 cycles at 2 A/g, respectively. These characteristics point to its promising applications in the electrode material for supercapacitors.

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.

Excitation of luminescence of the nanoporous bioactive nanocrystalline carbonate-substituted hydroxyapatite for early tooth disease detection

NASA Astrophysics Data System (ADS)

Goloshchapov, D. L.; Minakov, D. A.; Domashevskaya, E. P.; Seredin, P. V.

This paper deals with the luminescence characteristics of an analogue of the mineral component of dental enamel of the nanocrystalline B-type carbonate-substituted hydroxyapatite (CHAP) with 3D defects (i.e. nanopores of ∼2-5 nm) on the nanocrystalline surface. The laser-induced luminescence (LIL) of the synthesized CHAP samples was in the range of ∼515 nm (∼2.4 eV) and is due to CO3 groups replacing the PO4 group. It was found that the intensity of the luminescence of the CHAP is caused by structurally incorporated CO3 groups in the HAP structure. Furthermore, the intensity of the luminescence also decreases as the number of the above intracentre defects (CO3) in the apatite structure declines. These results are potentially promising for developing the foundations for precise methods for the early detection of caries in human solid dental tissue.

Hybrid aerogel-derived Sn-Ni alloy immobilized within porous carbon/graphene dual matrices for high-performance lithium storage.

PubMed

Zhang, Hao; Zhang, Mengru; Zhang, Meiling; Zhang, Lin; Zhang, Anping; Zhou, Yiming; Wu, Ping; Tang, Yawen

2017-09-01

Nanoporous networks of tin-based alloys immobilized within carbon matrices possess unique structural and compositional superiorities toward lithium-storage, and are expected to manifest improved strain-accommodation and charge-transport capabilities and thus desirable anodic performance for advanced lithium-ion batteries (LIBs). Herein, a facile and scalable hybrid aerogel-derived thermal-autoreduction route has been developed for the construction of nanoporous network of SnNi alloy immobilized within carbon/graphene dual matrices (SnNi@C/G network). When applied as an anode material for LIBs, the SnNi@C/G network manifests desirable lithium-storage performances in terms of specific capacities, cycle life, and rate capability. The facile aerogel-derived route and desirable Li-storage performance of the SnNi@C/G network facilitate its practical application as a high-capacity, long-life, and high-rate anode material for advanced LIBs. Copyright © 2017 Elsevier Inc. All rights reserved.

Ultra-Thin Solid-State Nanopores: Fabrication and Applications

NASA Astrophysics Data System (ADS)

Kuan, Aaron Tzeyang

Solid-state nanopores are a nanofluidic platform with unique advantages for single-molecule analysis and filtration applications. However, significant improvements in device performance and scalable fabrication methods are needed to make nanopore devices competitive with existing technologies. This dissertation investigates the potential advantages of ultra-thin nanopores in which the thickness of the membrane is significantly smaller than the nanopore diameter. Novel, scalable fabrication methods were first developed and then utilized to examine device performance for water filtration and single molecule sensing applications. Fabrication of nanometer-thin pores in silicon nitride membranes was achieved using a feedback-controlled ion beam method in which ion sputtering is arrested upon detection of the first few ions that drill through the membrane. Performing fabrication at liquid nitrogen temperatures prevents surface atom rearrangements that have previously complicated similar processes. A novel cross-sectional imaging method was also developed to allow careful examination of the full nanopore geometry. Atomically-thin graphene nanopores were fabricated via an electrical pulse method in which sub-microsecond electrical pulses applied across a graphene membrane in electrolyte solution are used to create a defect in the membrane and controllably enlarge it into a nanopore. This method dramatically increases the accuracy and reliability of graphene nanopore production, allowing consistent production of single nanopores down to subnanometer sizes. In filtration applications in which nanopores are used to selectively restrict the passage of dissolved contaminants, ultra-thin nanopores minimize the flow resistance, increasing throughput and energy-efficiency. The ability of graphene nanopores to separate different ions was characterized via ionic conductance and reversal potential measurements. Graphene nanopores were observed to conduct cations preferentially over

Metallic carbon materials

DOEpatents

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

1999-01-01

Novel metallic forms of planar carbon are described, as well as methods of designing and making them. Nonhexagonal arrangements of carbon are introduced into a graphite carbon network essentially without destroying the planar structure. Specifically a form of carbon comprising primarily pentagons and heptagons, and having a large density of states at the Fermi level is described. Other arrangements of pentagons and heptagons that include some hexagons, and structures incorporating squares and octagons are additionally disclosed. Reducing the bond angle symmetry associated with a hexagonal arrangement of carbons increases the likelihood that the carbon material will have a metallic electron structure.

Pre-Combustion Carbon Capture by a Nanoporous, Superhydrophobic Membrane Contactor Process

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

Meyer, Howard; Zhou, S James; Ding, Yong

2012-03-31

This report summarizes progress made during Phase I and Phase II of the project: "Pre-Combustion Carbon Capture by a Nanoporous, Superhydrophobic Membrane Contactor Process," under contract DE-FE-0000646. The objective of this project is to develop a practical and cost effective technology for CO{sub 2} separation and capture for pre-combustion coal-based gasification plants using a membrane contactor/solvent absorption process. The goals of this technology development project are to separate and capture at least 90% of the CO{sub 2} from Integrated Gasification Combined Cycle (IGCC) power plants with less than 10% increase in the cost of energy services. Unlike conventional gas separationmore » membranes, the membrane contactor is a novel gas separation process based on the gas/liquid membrane concept. The membrane contactor is an advanced mass transfer device that operates with liquid on one side of the membrane and gas on the other. The membrane contactor can operate with pressures that are almost the same on both sides of the membrane, whereas the gas separation membranes use the differential pressure across the membrane as driving force for separation. The driving force for separation for the membrane contactor process is the chemical potential difference of CO{sub 2} in the gas phase and in the absorption liquid. This process is thus easily tailored to suit the needs for pre-combustion separation and capture of CO{sub 2}. Gas Technology Institute (GTI) and PoroGen Corporation (PGC) have developed a novel hollow fiber membrane technology that is based on chemically and thermally resistant commercial engineered polymer poly(ether ether ketone) or PEEK. The PEEK membrane material used in the membrane contactor during this technology development program is a high temperature engineered plastic that is virtually non-destructible under the operating conditions encountered in typical gas absorption applications. It can withstand contact with most of the common

Solid-State Nanopore.

PubMed

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-20

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

Solid-State Nanopore

NASA Astrophysics Data System (ADS)

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-01

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

Fabricatable nanopore sensors with an atomic thickness

NASA Astrophysics Data System (ADS)

Luan, Binquan; Bai, Jingwei; Stolovitzky, Gustavo

2013-10-01

When analyzing biological molecules (such as DNA and proteins) transported through a nanopore sensor, the pore length limits both the sensitivity and the spatial resolution. Atomically thin as a graphene nanopore is, it is difficult to make graphene pores and the scalable-fabrication of those pores has not yet been possible. We theoretically studied a type of atomically thin nanopores that are formed by intersection of two perpendicular nano-slits. Based on theoretical analyses, we demonstrate that slit nanopores behave similarly to graphene pores and can be manufactured at a wafer scale.

Thermal conductivity model for nanoporous thin films

NASA Astrophysics Data System (ADS)

Huang, Congliang; Zhao, Xinpeng; Regner, Keith; Yang, Ronggui

2018-03-01

Nanoporous thin films have attracted great interest because of their extremely low thermal conductivity and potential applications in thin thermal insulators and thermoelectrics. Although there are some numerical and experimental studies about the thermal conductivity of nanoporous thin films, a simplified model is still needed to provide a straightforward prediction. In this paper, by including the phonon scattering lifetimes due to film thickness boundary scattering, nanopore scattering and the frequency-dependent intrinsic phonon-phonon scattering, a fitting-parameter-free model based on the kinetic theory of phonon transport is developed to predict both the in-plane and the cross-plane thermal conductivities of nanoporous thin films. With input parameters such as the lattice constants, thermal conductivity, and the group velocity of acoustic phonons of bulk silicon, our model shows a good agreement with available experimental and numerical results of nanoporous silicon thin films. It illustrates that the size effect of film thickness boundary scattering not only depends on the film thickness but also on the size of nanopores, and a larger nanopore leads to a stronger size effect of the film thickness. Our model also reveals that there are different optimal structures for getting the lowest in-plane and cross-plane thermal conductivities.

Acoustics of multiscale sorptive porous materials

NASA Astrophysics Data System (ADS)

Venegas, R.; Boutin, C.; Umnova, O.

2017-08-01

This paper investigates sound propagation in multiscale rigid-frame porous materials that support mass transfer processes, such as sorption and different types of diffusion, in addition to the usual visco-thermo-inertial interactions. The two-scale asymptotic method of homogenization for periodic media is successively used to derive the macroscopic equations describing sound propagation through the material. This allowed us to conclude that the macroscopic mass balance is significantly modified by sorption, inter-scale (micro- to/from nanopore scales) mass diffusion, and inter-scale (pore to/from micro- and nanopore scales) pressure diffusion. This modification is accounted for by the dynamic compressibility of the effective saturating fluid that presents atypical properties that lead to slower speed of sound and higher sound attenuation, particularly at low frequencies. In contrast, it is shown that the physical processes occurring at the micro-nano-scale do not affect the macroscopic fluid flow through the material. The developed theory is exemplified by introducing an analytical model for multiscale sorptive granular materials, which is experimentally validated by comparing its predictions with acoustic measurements on granular activated carbons. Furthermore, we provide empirical evidence supporting an alternative method for measuring sorption and mass diffusion properties of multiscale sorptive materials using sound waves.

Single Nanopore Investigations with Ion Conductance Microscopy

PubMed Central

Chen, Chiao-Chen; Zhou, Yi; Baker, Lane A.

2011-01-01

A three-electrode scanning ion conductance microscope (SICM) was used to investigate the local current-voltage properties of a single nanopore. In this experimental configuration, the response measured is a function of changes in the resistances involved in the pathways of ion migration. Single nanopore membranes utilized in this study were prepared with an epoxy painting procedure to isolate a single nanopore from a track-etch multi-pore membrane. Current-voltage responses measured with the SICM probe in the vicinity of a single nanopore were investigated in detail and agreed well with equivalent circuit models proposed in this study. With this modified SICM, the current-voltage responses characterized for the case of a single cylindrical pore and a single conical pore exhibit distinct conductance properties that originate from the geometry of nanopores. PMID:21923184

Effects of nanoporous anodic titanium oxide on human adipose derived stem cells.

PubMed

Malec, Katarzyna; Góralska, Joanna; Hubalewska-Mazgaj, Magdalena; Głowacz, Paulina; Jarosz, Magdalena; Brzewski, Pawel; Sulka, Grzegorz D; Jaskuła, Marian; Wybrańska, Iwona

The aim of current bone biomaterials research is to design implants that induce controlled, guided, successful, and rapid healing. Titanium implants are widely used in dental, orthopedic, and reconstructive surgery. A series of studies has indicated that cells can respond not only to the chemical properties of the biomaterial, but also, in particular, to the changes in surface topography. Nanoporous materials remain in focus of scientific queries due to their exclusive properties and broad applications. One such material is nanostructured titanium oxide with highly ordered, mutually perpendicular nanopores. Nanoporous anodic titanium dioxide (TiO 2 ) films were fabricated by a three-step anodization process in propan-1,2,3-triol-based electrolyte containing fluoride ions. Adipose-derived stem cells offer many interesting opportunities for regenerative medicine. The important goal of tissue engineering is to direct stem cell differentiation into a desired cell lineage. The influence of nanoporous TiO 2 with pore diameters of 80 and 108 nm on cell response, growth, viability, and ability to differentiate into osteoblastic lineage of human adipose-derived progenitors was explored. Cells were harvested from the subcutaneous abdominal fat tissue by a simple, minimally invasive, and inexpensive method. Our results indicate that anodic nanostructured TiO 2 is a safe and nontoxic biomaterial. In vitro studies demonstrated that the nanotopography induced and enhanced osteodifferentiation of human adipose-derived stem cells from the abdominal subcutaneous fat tissue.

Nanopore sequencing in microgravity

PubMed Central

McIntyre, Alexa B R; Rizzardi, Lindsay; Yu, Angela M; Alexander, Noah; Rosen, Gail L; Botkin, Douglas J; Stahl, Sarah E; John, Kristen K; Castro-Wallace, Sarah L; McGrath, Ken; Burton, Aaron S; Feinberg, Andrew P; Mason, Christopher E

2016-01-01

Rapid DNA sequencing and analysis has been a long-sought goal in remote research and point-of-care medicine. In microgravity, DNA sequencing can facilitate novel astrobiological research and close monitoring of crew health, but spaceflight places stringent restrictions on the mass and volume of instruments, crew operation time, and instrument functionality. The recent emergence of portable, nanopore-based tools with streamlined sample preparation protocols finally enables DNA sequencing on missions in microgravity. As a first step toward sequencing in space and aboard the International Space Station (ISS), we tested the Oxford Nanopore Technologies MinION during a parabolic flight to understand the effects of variable gravity on the instrument and data. In a successful proof-of-principle experiment, we found that the instrument generated DNA reads over the course of the flight, including the first ever sequenced in microgravity, and additional reads measured after the flight concluded its parabolas. Here we detail modifications to the sample-loading procedures to facilitate nanopore sequencing aboard the ISS and in other microgravity environments. We also evaluate existing analysis methods and outline two new approaches, the first based on a wave-fingerprint method and the second on entropy signal mapping. Computationally light analysis methods offer the potential for in situ species identification, but are limited by the error profiles (stays, skips, and mismatches) of older nanopore data. Higher accuracies attainable with modified sample processing methods and the latest version of flow cells will further enable the use of nanopore sequencers for diagnostics and research in space. PMID:28725742

In-situ grown nanoporous Zn-Cu catalysts on brass foils for enhanced electrochemical reduction of carbon dioxide

NASA Astrophysics Data System (ADS)

Hu, Hanjun; Tang, Yang; Hu, Qing; Wan, Pingyu; Dai, Liming; Yang, Xiao Jin

2018-07-01

In-situ grown nanoporous Zn-Cu catalysts were prepared by simply annealing a commercial brass foil at 500 °C in air, followed by electrochemical reduction. During the annealing process, Zn preferentially melted and migrated out of the framework of the alloy to form a thin layer of ZnO on its surface. Subsequent electroreduction created nanoporous Zn-enriched surface. The Zn concentration increased from 36% to 50% by 10 min, to 81% by 3 h, and to 87% by 12 h annealing treatment while the average pore size decreased from 290 nm to 120 nm as the annealing time increased from 1 h to 12 h. Faradaic efficiency of CO2 reduction to CO and HCOOH was enhanced by nearly 4 and 6 times, respectively, as compared to untreated brass foils. The nanoporous Zn-Cu catalyst presented a stable ratio of CO/H2 and a steady working current density in a continuous electrolysis of 18 h in 0.5 M KHCO3 solution.

Highly active thermally stable nanoporous gold catalyst

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

Biener, Juergen; Wittstock, Arne; Biener, Monika M.

In one embodiment, a system includes a nanoporous gold structure and a plurality of oxide particles deposited on the nanoporous gold structure; the oxide particles are characterized by a crystalline phase. In another embodiment, a method includes depositing oxide nanoparticles on a nanoporous gold support to form an active structure and functionalizing the deposited oxide nanoparticles.

Understanding Radionuclide Interactions with Layered Materials

NASA Astrophysics Data System (ADS)

Wang, Y.

2015-12-01

Layered materials play an important role in nuclear waste management and environmental cleanup. Better understanding of radionuclide interactions with those materials is critical for engineering high-performance materials for various applications. This presentation will provide an overview on radionuclide interactions with two general categories of layered materials - cationic clays and anionic clays - from a perspective of nanopore confinement. Nanopores are widely present in layered materials, either as the interlayers or as inter-particle space. Nanopore confinement can significantly modify chemical reactions in those materials. This effect may cause the preferential enrichment of radionuclides in nanopores and therefore directly impact the mobility of the radionuclides. This effect also implies that conventional sorption measurements using disaggregated samples may not represent chemical conditions in actual systems. The control of material structures on ion exchange, surface complexation, and diffusion in layered materials will be systematically examined, and the related modeling approaches will be discussed. This work was performed at Sandia National Laboratories, which is a multiprogram laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the DOE under contract DE-AC04-94AL8500.

Urea adsorption by activated carbon prepared from palm kernel shell

NASA Astrophysics Data System (ADS)

Ooi, Chee-Heong; Sim, Yoke-Leng; Yeoh, Fei-Yee

2017-07-01

Dialysis treatment is crucial for patients suffer from renal failure. The dialysis system removes the uremic toxin to a safe level in a patient's body. One of the major limitations of the current hemodialysis system is the capability to efficiently remove uremic toxins from patient's body. Nanoporous materials can be applied to improve the treatment. Palm kernel shell (PKS) biomass generated from palm oil mills can be utilized to prepare high quality nanoporous activated carbon (AC) and applied for urea adsorption in the dialysis system. In this study, AC was prepared from PKS via different carbonization temperatures and followed by carbon dioxide gas activation processes. The physical and chemical properties of the samples were studied. The results show that the porous AC with BET surface areas ranging from 541 to 622 m2g-1 and with total pore volumes varying from 0.254 to 0.297 cm3g-1, are formed with different carbonization temperatures. The equilibrium constant for urea adsorption by AC samples carbonized at 400, 500 and 600 °C are 0.091, 0.287 and 0.334, respectively. The increase of carbonization temperatures from 400 to 600 °C resulted in the increase in urea adsorption by AC predominantly due to increase in surface area. The present study reveals the feasibility of preparing AC with good porosity from PKS and potentially applied in urea adsorption application.

Signal and Noise in FET-Nanopore Devices.

PubMed

Parkin, William M; Drndić, Marija

2018-02-23

The combination of a nanopore with a local field-effect transistor (FET-nanopore), like a nanoribbon, nanotube, or nanowire, in order to sense single molecules translocating through the pore is promising for DNA sequencing at megahertz bandwidths. Previously, it was experimentally determined that the detection mechanism was due to local potential fluctuations that arise when an analyte enters a nanopore and constricts ion flow through it, rather than the theoretically proposed mechanism of direct charge coupling between the DNA and nanowire. However, there has been little discussion on the experimentally observed detection mechanism and its relation to the operation of real devices. We model the intrinsic signal and noise in such an FET-nanopore device and compare the results to the ionic current signal. The physical dimensions of DNA molecules limit the change in gate voltage on the FET to below 40 mV. We discuss the low-frequency flicker noise (<10 kHz), medium-frequency thermal noise (<100 kHz), and high-frequency capacitive noise (>100 kHz) in FET-nanopore devices. At bandwidths dominated by thermal noise, the signal-to-noise ratio in FET-nanopore devices is lower than in the ionic current signal. At high frequencies, where noise due to parasitic capacitances in the amplifier and chip is the dominant source of noise in ionic current measurements, high-transconductance FET-nanopore devices can outperform ionic current measurements.

Activated carbon material

DOEpatents

Evans, A. Gary

1978-01-01

Activated carbon particles for use as iodine trapping material are impregnated with a mixture of selected iodine and potassium compounds to improve the iodine retention properties of the carbon. The I/K ratio is maintained at less than about 1 and the pH is maintained at above about 8.0. The iodine retention of activated carbon previously treated with or coimpregnated with triethylenediamine can also be improved by this technique. Suitable flame retardants can be added to raise the ignition temperature of the carbon to acceptable standards.

Bulk synthesis of nanoporous palladium and platinum powders

DOEpatents

Robinson, David B [Fremont, CA; Fares, Stephen J [Pleasanton, CA; Tran, Kim L [Livermore, CA; Langham, Mary E [Pleasanton, CA

2012-04-17

Disclosed is a method for providing nanoporous palladium and platinum powders. These materials were synthesized on milligram to gram scales by chemical reduction of tetrahalo-complexes with ascorbate in a concentrated aqueous surfactant at temperatures between -20.degree. C. and 30.degree. C. The prepared particles have diameters of approximately 50 nm, wherein each particle is perforated by pores having diameters of approximately 3 nm, as determined by electron tomography. These materials are of potential value for hydrogen and electrical charge storage applications.

Bulk synthesis of nanoporous palladium and platinum powders

DOEpatents

Robinson, David B; Fares, Stephen J; Tran, Kim L; Langham, Mary E

2014-04-15

Disclosed is a method for providing nanoporous palladium and platinum powders. These materials were synthesized on milligram to gram scales by chemical reduction of tetrahalo-complexes with ascorbate in a concentrated aqueous surfactant at temperatures between -20.degree. C. and 30.degree. C. The prepared particles have diameters of approximately 50 nm, wherein each particle is perforated by pores having diameters of approximately 3 nm, as determined by electron tomography. These materials are of potential value for hydrogen and electrical charge storage applications.

Effect of ultraviolet illumination and ambient gases on the photoluminescence and electrical properties of nanoporous silicon layer for organic vapor sensor.

PubMed

Atiwongsangthong, Narin

2012-08-01

The purpose of this research, the nanoporous silicon layer were fabricated and investigated the physical properties such as photoluminescence and the electrical properties in order to develop organic vapor sensor by using nanoporous silicon. The Changes in the photoluminescence intensity of nanoporous silicon samples are studied during ultraviolet illumination in various ambient gases such as nitrogen, oxigen and vacuum. In this paper, the nanoporous silicon layer was used as organic vapor adsorption and sensing element. The advantage of this device are simple process compatible in silicon technology and usable in room temperature. The structure of this device consists of nanoporous silicon layer which is formed by anodization of silicon wafer in hydrofluoric acid solution and aluminum electrode which deposited on the top of nanoporous silicon layer by evaporator. The nanoporous silicon sensors were placed in a gas chamber with various organic vapor such as ethanol, methanol and isopropyl alcohol. From studying on electrical characteristics of this device, it is found that the nanoporous silicon layer can detect the different organic vapor. Therefore, the nanoporous silicon is important material for organic vapor sensor and it can develop to other applications about gas sensors in the future.

Carbon nanotube composite materials

DOEpatents

O'Bryan, Gregory; Skinner, Jack L; Vance, Andrew; Yang, Elaine Lai; Zifer, Thomas

2015-03-24

A material consisting essentially of a vinyl thermoplastic polymer, un-functionalized carbon nanotubes and hydroxylated carbon nanotubes dissolved in a solvent. Un-functionalized carbon nanotube concentrations up to 30 wt % and hydroxylated carbon nanotube concentrations up to 40 wt % can be used with even small concentrations of each (less than 2 wt %) useful in producing enhanced conductivity properties of formed thin films.

Nanoporous Monolithic Microsphere Arrays Have Anti-Adhesive Properties Independent of Humidity

PubMed Central

Eichler-Volf, Anna; Xue, Longjian; Kovalev, Alexander; Gorb, Elena V.; Gorb, Stanislav N.; Steinhart, Martin

2016-01-01

Bioinspired artificial surfaces with tailored adhesive properties have attracted significant interest. While fibrillar adhesive pads mimicking gecko feet are optimized for strong reversible adhesion, monolithic microsphere arrays mimicking the slippery zone of the pitchers of carnivorous plants of the genus Nepenthes show anti-adhesive properties even against tacky counterpart surfaces. In contrast to the influence of topography, the influence of relative humidity (RH) on adhesion has been widely neglected. Some previous works deal with the influence of RH on the adhesive performance of fibrillar adhesive pads. Commonly, humidity-induced softening of the fibrils enhances adhesion. However, little is known on the influence of RH on solid anti-adhesive surfaces. We prepared polymeric nanoporous monolithic microsphere arrays (NMMAs) with microsphere diameters of a few 10 µm to test their anti-adhesive properties at RHs of 2% and 90%. Despite the presence of continuous nanopore systems through which the inner nanopore walls were accessible to humid air, the topography-induced anti-adhesive properties of NMMAs on tacky counterpart surfaces were retained even at RH = 90%. This RH-independent robustness of the anti-adhesive properties of NMMAs significantly contrasts the adhesion enhancement by humidity-induced softening on nanoporous fibrillar adhesive pads made of the same material. PMID:28773497

Fabrication of Subnanometer-Precision Nanopores in Hexagonal Boron Nitride

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

Gilbert, S. Matt; Dunn, Gabriel; Azizi, Amin

Here, we demonstrate the fabrication of individual nanopores in hexagonal boron nitride (h-BN) with atomically precise control of the pore shape and size. Previous methods of pore production in other 2D materials typically create pores with irregular geometry and imprecise diameters. In contrast, other studies have shown that with careful control of electron irradiation, defects in h-BN grow with pristine zig-zag edges at quantized triangular sizes, but they have failed to demonstrate production and control of isolated defects. In this work, we combine these techniques to yield a method in which we can create individual size-quantized triangular nanopores through anmore » h-BN sheet. The pores are created using the electron beam of a conventional transmission electron microscope; which can strip away multiple layers of h-BN exposing single-layer regions, introduce single vacancies, and preferentially grow vacancies only in the single-layer region. We further demonstrate how the geometry of these pores can be altered beyond triangular by changing beam conditions. Precisely size- and geometry-tuned nanopores could find application in molecular sensing, DNA sequencing, water desalination, and molecular separation.« less

Fabrication of Subnanometer-Precision Nanopores in Hexagonal Boron Nitride

DOE PAGES

Gilbert, S. Matt; Dunn, Gabriel; Azizi, Amin; ...

2017-11-08

Here, we demonstrate the fabrication of individual nanopores in hexagonal boron nitride (h-BN) with atomically precise control of the pore shape and size. Previous methods of pore production in other 2D materials typically create pores with irregular geometry and imprecise diameters. In contrast, other studies have shown that with careful control of electron irradiation, defects in h-BN grow with pristine zig-zag edges at quantized triangular sizes, but they have failed to demonstrate production and control of isolated defects. In this work, we combine these techniques to yield a method in which we can create individual size-quantized triangular nanopores through anmore » h-BN sheet. The pores are created using the electron beam of a conventional transmission electron microscope; which can strip away multiple layers of h-BN exposing single-layer regions, introduce single vacancies, and preferentially grow vacancies only in the single-layer region. We further demonstrate how the geometry of these pores can be altered beyond triangular by changing beam conditions. Precisely size- and geometry-tuned nanopores could find application in molecular sensing, DNA sequencing, water desalination, and molecular separation.« less

DNA Origami-Graphene Hybrid Nanopore for DNA Detection.

PubMed

Barati Farimani, Amir; Dibaeinia, Payam; Aluru, Narayana R

2017-01-11

DNA origami nanostructures can be used to functionalize solid-state nanopores for single molecule studies. In this study, we characterized a nanopore in a DNA origami-graphene heterostructure for DNA detection. The DNA origami nanopore is functionalized with a specific nucleotide type at the edge of the pore. Using extensive molecular dynamics (MD) simulations, we computed and analyzed the ionic conductivity of nanopores in heterostructures carpeted with one or two layers of DNA origami on graphene. We demonstrate that a nanopore in DNA origami-graphene gives rise to distinguishable dwell times for the four DNA base types, whereas for a nanopore in bare graphene, the dwell time is almost the same for all types of bases. The specific interactions (hydrogen bonds) between DNA origami and the translocating DNA strand yield different residence times and ionic currents. We also conclude that the speed of DNA translocation decreases due to the friction between the dangling bases at the pore mouth and the sequencing DNA strands.

Super flame-retardant lightweight rime-like carbon-phenolic nanofoam

PubMed Central

Cheng, Haiming; Hong, Changqing; Zhang, Xinghong; Xue, Huafei; Meng, Songhe; Han, Jiecai

2016-01-01

The desire for lightweight nanoporous materials with high-performance thermal insulation and efficient anti-ablation resistance for energy conservation and thermal protection/insulation has greatly motivated research and development recently. The main challenge to synthesize such lightweight materials is how to balance the relationship of low thermal conductivity and flame retardancy. Herein, we propose a new concept of lightweight “rime-like” structured carbon-phenolic nanocomposites to solve this problem, where the 3D chopped network-structured carbon fiber (NCF) monoliths are incorporated with nanoporous phenolic aerogel to retain structural and functional integrity. The nanometer-scaled porous phenolic (NP) was synthesized through polymerization-induced phase separation and ambient pressure drying using phenolic resin (PR) solution as reaction source, ethylene glycol (EG) as solvent and hexamethylenetetramine (HMTA) as catalyst. We demonstrate that the as-prepared NCF-NP nanocomposite exhibits with a low density of 0.25–0.35 g/cm3, low thermal conductivity of 0.125 Wm−1K−1 and outstanding flame retardancy exceeding 2000 °C under arc-jet wind tunnel simulation environment. Our results show that the synthesis strategy is a promising approach for producing nanocomposites with excellent high-temperature heat blocking property. PMID:27629114

Nanoporous mannitol carrier prepared by non-organic solvent spray drying technique to enhance the aerosolization performance for dry powder inhalation

PubMed Central

Peng, Tingting; Zhang, Xuejuan; Huang, Ying; Zhao, Ziyu; Liao, Qiuying; Xu, Jing; Huang, Zhengwei; Zhang, Jiwen; Wu, Chuan-yu; Pan, Xin; Wu, Chuanbin

2017-01-01

An optimum carrier rugosity is essential to achieve a satisfying drug deposition efficiency for the carrier based dry powder inhalation (DPI). Therefore, a non-organic spray drying technique was firstly used to prepare nanoporous mannitol with small asperities to enhance the DPI aerosolization performance. Ammonium carbonate was used as a pore-forming agent since it decomposed with volatile during preparation. It was found that only the porous structure, and hence the specific surface area and carrier density were changed at different ammonium carbonate concentration. Furthermore, the carrier density was used as an indication of porosity to correlate with drug aerosolization. A good correlation between the carrier density and fine particle fraction (FPF) (r2 = 0.9579) was established, suggesting that the deposition efficiency increased with the decreased carrier density. Nanoporous mannitol with a mean pore size of about 6 nm exhibited 0.24-fold carrier density while 2.16-fold FPF value of the non-porous mannitol. The enhanced deposition efficiency was further confirmed from the pharmacokinetic studies since the nanoporous mannitol exhibited a significantly higher AUC0-8h value than the non-porous mannitol and commercial product Pulmicort. Therefore, surface modification by preparing nanoporous carrier through non-organic spray drying showed to be a facile approach to enhance the DPI aerosolization performance. PMID:28462948

Three-Dimensional Morphological and Chemical Evolution of Nanoporous Stainless Steel by Liquid Metal Dealloying [3D Morphological and Chemical Evolution of Nanoporous Stainless Steel by Liquid Metal Dealloying

DOE PAGES

Zhao, Chonghang; Wada, Takeshi; De Andrade, Vincent; ...

2017-09-04

Nanoporous materials, especially those fabricated by liquid metal dealloying processes, possess great potential in a wide range of applications due to their high surface area, bicontinuous structure with both open pores for transport and solid phase for conductivity or support, and low material cost. Here, we used X-ray nanotomography and X-ray fluorescence microscopy to reveal the three-dimensional (3D) morphology and elemental distribution within materials. Focusing on nanoporous stainless steel, we evaluated the 3D morphology of the dealloying front and established a quantitative processing-structure-property relationship at a later stage of dealloying. The morphological differences of samples created by liquid metal dealloyingmore » and aqueous dealloying methods were also discussed. Here, we concluded that it is particularly important to consider the dealloying, coarsening, and densification mechanisms in influencing the performance-determining, critical 3D parameters, such as tortuosity, pore size, porosity, curvature, and interfacial shape.« less

Three-Dimensional Morphological and Chemical Evolution of Nanoporous Stainless Steel by Liquid Metal Dealloying [3D Morphological and Chemical Evolution of Nanoporous Stainless Steel by Liquid Metal Dealloying

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

Zhao, Chonghang; Wada, Takeshi; De Andrade, Vincent

Nanoporous materials, especially those fabricated by liquid metal dealloying processes, possess great potential in a wide range of applications due to their high surface area, bicontinuous structure with both open pores for transport and solid phase for conductivity or support, and low material cost. Here, we used X-ray nanotomography and X-ray fluorescence microscopy to reveal the three-dimensional (3D) morphology and elemental distribution within materials. Focusing on nanoporous stainless steel, we evaluated the 3D morphology of the dealloying front and established a quantitative processing-structure-property relationship at a later stage of dealloying. The morphological differences of samples created by liquid metal dealloyingmore » and aqueous dealloying methods were also discussed. Here, we concluded that it is particularly important to consider the dealloying, coarsening, and densification mechanisms in influencing the performance-determining, critical 3D parameters, such as tortuosity, pore size, porosity, curvature, and interfacial shape.« less

Langevin and Fokker-Planck analyses of inhibited molecular passing processes controlling transport and reactivity in nanoporous materials

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

Wang, Chi-Jen; Ackerman, David M.; Slowing, Igor I.

2014-07-14

Inhibited passing of reactant and product molecules within the linear pores of nanoporous catalytic materials strongly reduces reactivity. The dependence of the passing propensity P on pore radius R is analyzed utilizing Langevin dynamics to account for solvent effects. We find that P~(R-R c) σ, where passing is sterically blocked for R≤R c, with σ below the transition state theory value. Deeper insight comes from analysis of the corresponding high-dimensional Fokker-Planck equation, which facilitates an effective small-P approximation, and dimensional reduction enabling utilization of conformal mapping ideas. We analyze passing for spherical molecules and also assess the effect of rotationalmore » degrees of freedom for elongated molecules.« less

Integrating Sub-3 nm Plasmonic Gaps into Solid-State Nanopores.

PubMed

Shi, Xin; Verschueren, Daniel; Pud, Sergii; Dekker, Cees

2018-05-01

Plasmonic nanopores combine the advantages of nanopore sensing and surface plasmon resonances by introducing confined electromagnetic fields to a solid-state nanopore. Ultrasmall nanogaps between metallic nanoantennas can generate the extremely enhanced localized electromagnetic fields necessary for single-molecule optical sensing and manipulation. Challenges in fabrication, however, hamper the integration of such nanogaps into nanopores. Here, a top-down approach for integrating a plasmonic antenna with an ultrasmall nanogap into a solid-state nanopore is reported. Employing a two-step e-beam lithography process, the reproducible fabrication of nanogaps down to a sub-1 nm scale is demonstrated. Subsequently, nanopores are drilled through the 20 nm SiN membrane at the center of the nanogap using focused-electron-beam sculpting with a transmission electron microscope, at the expense of a slight gap expansion for the smallest gaps. Using this approach, sub-3 nm nanogaps can be readily fabricated on solid-state nanopores. The functionality of these plasmonic nanopores for single-molecule detection is shown by performing DNA translocations. These integrated devices can generate intense electromagnetic fields at the entrance of the nanopore and can be expected to find applications in nanopore-based single-molecule trapping and optical sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single Nanoparticle Translocation Through Chemically Modified Solid Nanopore

NASA Astrophysics Data System (ADS)

Tan, Shengwei; Wang, Lei; Liu, Hang; Wu, Hongwen; Liu, Quanjun

2016-02-01

The nanopore sensor as a high-throughput and low-cost technology can detect single nanoparticle in solution. In the present study, the silicon nitride nanopores were fabricated by focused Ga ion beam (FIB), and the surface was functionalized with 3-aminopropyltriethoxysilane to change its surface charge density. The positively charged nanopore surface attracted negatively charged nanoparticles when they were in the vicinity of the nanopore. And, nanoparticle translocation speed was slowed down to obtain a clear and deterministic signal. Compared with previous studied small nanoparticles, the electrophoretic translocation of negatively charged polystyrene (PS) nanoparticles (diameter ~100 nm) was investigated in solution using the Coulter counter principle in which the time-dependent nanopore current was recorded as the nanoparticles were driven across the nanopore. A linear dependence was found between current drop and biased voltage. An exponentially decaying function ( t d ~ e -v/v0 ) was found between the duration time and biased voltage. The interaction between the amine-functionalized nanopore wall and PS microspheres was discussed while translating PS microspheres. We explored also translocations of PS microspheres through amine-functionalized solid-state nanopores by varying the solution pH (5.4, 7.0, and 10.0) with 0.02 M potassium chloride (KCl). Surface functionalization showed to provide a useful step to fine-tune the surface property, which can selectively transport molecules or particles. This approach is likely to be applied to gene sequencing.

Polyethylene-Carbon Nanotube Composite Film Deposited by Cold Spray Technique

NASA Astrophysics Data System (ADS)

Ata, Nobuhisa; Ohtake, Naoto; Akasaka, Hiroki

2017-10-01

Carbon nanotubes (CNTs) are high-performance materials because of their superior electrical conductivity, thermal conductivity, and self-lubrication, and they have been studied for application to polymer composite materials as fillers. However, the methods of fabricating polymer composites with CNTs, such as injection molding, are too complicated for industrial applications. We propose a simple cold spray (CS) technique to obtain a polymer composite of polyethylene (PE) and CNTs. The composite films were deposited by CS on polypropylene and nano-porous structured aluminum substrates. The maximum thickness of the composite film was approximately 1 mm. Peaks at G and D bands were observed in the Raman spectra of the films. Scanning electron microscopy images of the film surface revealed that PE particles were melted by the acceleration gas and CNTs were attached with melted PE. The PE particles solidified after contact with the substrate. These results indicate that PE-CNT composite films were successfully deposited on polypropylene and nano-porous structured aluminum substrates by CS.

Method for synthesizing carbon nanotubes

DOEpatents

Fan, Hongyou

2012-09-04

A method for preparing a precursor solution for synthesis of carbon nanomaterials, where a polar solvent is added to at least one block copolymer and at least one carbohydrate compound, and the precursor solution is processed using a self-assembly process and subsequent heating to form nanoporous carbon films, porous carbon nanotubes, and porous carbon nanoparticles.

Microporous novolac-derived carbon beads/sulfur hybrid cathode for lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Choudhury, Soumyadip; Krüner, Benjamin; Massuti-Ballester, Pau; Tolosa, Aura; Prehal, Christian; Grobelsek, Ingrid; Paris, Oskar; Borchardt, Lars; Presser, Volker

2017-07-01

Novolac-derived nanoporous carbon beads were used as conductive matrix for lithium-sulfur battery cathodes. We employed a facile self-emulsifying synthesis to obtain sub-micrometer novolac-derived carbon beads with nanopores. After pyrolysis, the carbon beads showed already a specific surface area of 640 m2 g-1 which was increased to 2080 m2 g-1 after physical activation. The non-activated and the activated carbon beads represent nanoporous carbon with a medium and a high surface area, respectively. This allows us to assess the influence of the porosity on the electrochemical performance of lithium-sulfur battery cathodes. The carbon/sulfur hybrids were obtained from two different approaches of sulfur infiltration: melt-infusion of sulfur (annealing) and in situ formation of sulfur from sodium thiosulfate. The best performance (∼880 mAh gsulfur-1 at low charge rate; 5th cycle) and high performance stability (>600 mAh gsulfur-1 after 100 cycles) were found for the activated carbon beads when using melt infusion of sulfur.

Ion dynamics in porous carbon electrodes in supercapacitors using in situ infrared spectroelectrochemistry.

PubMed

Richey, Francis W; Dyatkin, Boris; Gogotsi, Yury; Elabd, Yossef A

2013-08-28

Electrochemical double layer capacitors (EDLCs), or supercapacitors, rely on electrosorption of ions by porous carbon electrodes and offer a higher power and a longer cyclic lifetime compared to batteries. Ionic liquid (IL) electrolytes can broaden the operating voltage window and increase the energy density of EDLCs. Herein, we present direct measurements of the ion dynamics of 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide in an operating EDLC with electrodes composed of porous nanosized carbide-derived carbons (CDCs) and nonporous onion-like carbons (OLCs) with the use of in situ infrared spectroelectrochemistry. For CDC electrodes, IL ions (both cations and anions) were directly observed entering and exiting CDC nanopores during charging and discharging of the EDLC. Conversely, for OLC electrodes, IL ions were observed in close proximity to the OLC surface without any change in the bulk electrolyte concentration during charging and discharging of the EDLC. This provides experimental evidence that charge is stored on the surface of OLCs in OLC EDLCs without long-range ion transport through the bulk electrode. In addition, for CDC EDLCs with mixed electrolytes of IL and propylene carbonate (PC), the IL ions were observed entering and exiting CDC nanopores, while PC entrance into the nanopores was IL concentration dependent. This work provides direct experimental confirmation of EDLC charging mechanisms that previously were restricted to computational simulations and theories. The experimental measurements presented here also provide deep insights into the molecular level transport of IL ions in EDLC electrodes that will impact the design of the electrode materials' structure for electrical energy storage.

Nanopatterned carbon films with engineered morphology by direct carbonization of UV-stabilized block copolymer films.

PubMed

Wang, Yong; Liu, Jinquan; Christiansen, Silke; Kim, Dong Ha; Gösele, Ulrich; Steinhart, Martin

2008-11-01

Nanopatterned thin carbon films were prepared by direct and expeditious carbonization of the block copolymer polystyrene- block-poly(2-vinylpyridine) (PS- b-P2VP) without the necessity of slow heating to the process temperature and of addition of further carbon precursors. Carbonaceous films having an ordered "dots-on-film" surface topology were obtained from reverse micelle monolayers. The regular nanoporous morphology of PS- b-P2VP films obtained by subjecting reverse micelle monolayers to swelling-induced surface reconstruction could likewise be transferred to carbon films thus characterized by ordered nanopit arrays. Stabilization of PS- b-P2VP by UV irradiation and the concurrent carbonization of both blocks were key to the conservation of the film topography. The approach reported here may enable the realization of a broad range of nanoscaled architectures for carbonaceous materials using a block copolymer ideally suited as a template because of the pronounced repulsion between its blocks and its capability to form highly ordered microdomain structures.

Cavitation and pore blocking in nanoporous glasses.

PubMed

Reichenbach, C; Kalies, G; Enke, D; Klank, D

2011-09-06

In gas adsorption studies, porous glasses are frequently referred to as model materials for highly disordered mesopore systems. Numerous works suggest that an accurate interpretation of physisorption isotherms requires a complete understanding of network effects upon adsorption and desorption, respectively. The present article deals with nitrogen and argon adsorption at different temperatures (77 and 87 K) performed on a series of novel nanoporous glasses (NPG) with different mean pore widths. NPG samples contain smaller mesopores and significantly higher microporosity than porous Vycor glass or controlled pore glass. Since the mean pore width of NPG can be tuned sensitively, the evolution of adsorption characteristics with respect to a broadening pore network can be investigated starting from the narrowest nanopore width. With an increasing mean pore width, a H2-type hysteresis develops gradually which finally transforms into a H1-type. In this connection, a transition from a cavitation-induced desorption toward desorption controlled by pore blocking can be observed. Furthermore, we find concrete hints for a pore size dependence of the relative pressure of cavitation in highly disordered pore systems. By comparing nitrogen and argon adsorption, a comprehensive insight into adsorption mechanisms in novel disordered materials is provided. © 2011 American Chemical Society

Nanoporous hard data: optical encoding of information within nanoporous anodic alumina photonic crystals

NASA Astrophysics Data System (ADS)

Santos, Abel; Law, Cheryl Suwen; Pereira, Taj; Losic, Dusan

2016-04-01

Herein, we present a method for storing binary data within the spectral signature of nanoporous anodic alumina photonic crystals. A rationally designed multi-sinusoidal anodisation approach makes it possible to engineer the photonic stop band of nanoporous anodic alumina with precision. As a result, the transmission spectrum of these photonic nanostructures can be engineered to feature well-resolved and selectively positioned characteristic peaks across the UV-visible spectrum. Using this property, we implement an 8-bit binary code and assess the versatility and capability of this system by a series of experiments aiming to encode different information within the nanoporous anodic alumina photonic crystals. The obtained results reveal that the proposed nanosized platform is robust, chemically stable, versatile and has a set of unique properties for data storage, opening new opportunities for developing advanced nanophotonic tools for a wide range of applications, including sensing, photonic tagging, self-reporting drug releasing systems and secure encoding of information.Herein, we present a method for storing binary data within the spectral signature of nanoporous anodic alumina photonic crystals. A rationally designed multi-sinusoidal anodisation approach makes it possible to engineer the photonic stop band of nanoporous anodic alumina with precision. As a result, the transmission spectrum of these photonic nanostructures can be engineered to feature well-resolved and selectively positioned characteristic peaks across the UV-visible spectrum. Using this property, we implement an 8-bit binary code and assess the versatility and capability of this system by a series of experiments aiming to encode different information within the nanoporous anodic alumina photonic crystals. The obtained results reveal that the proposed nanosized platform is robust, chemically stable, versatile and has a set of unique properties for data storage, opening new opportunities for

Tailored nanoporous coatings fabricated on conformable polymer substrates.

PubMed

Poxson, David J; Mont, Frank W; Cho, Jaehee; Schubert, E Fred; Siegel, Richard W

2012-11-01

Nanoporous coatings have become the subject of intense investigation, in part because they have been shown to have unique and tailorable physical properties that can depart greatly from their dense or macroscopic counterparts. Nanoporous coatings are frequently fabricated utilizing oblique-angle or glancing-angle physical vapor-phase deposition techniques. However, a significant limitation for such coatings exists; they are almost always deposited on smooth and rigid planar substrates, such as silicon and glass. This limitation greatly constrains the applicability, tailorability, functionality and even the economic viability, of such nanoporous coatings. Here, we report our findings on nanoporous/polymer composite systems (NPCS) fabricated by utilizing oblique-angle electron-beam methodology. These unique composite systems exhibit several favorable characteristics, namely, (i) fine-tuned control over coating nanoporosity and thickness, (ii) excellent adhesion between the nanoporous coating and polymer substrate, (iii) the ability to withstand significant and repeated bending, and (iv) the ability to be molded conformably on two and three-dimensional surfaces while closely retaining the composite system's designed nanoporous film structure and, hence, properties.

Roles of Chemical Functionality and Pore Curvature in the Design of Nanoporous Proton Conductors

DOE PAGES

Jackson, Grayson L.; Perroni, Dominic V.; Mahanthappa, Mahesh K.

2017-10-03

Nanoporous proton-transporting media are critical components in fuel cells and other electrochemical devices, yet general molecular design criteria for new materials with enhanced performance remain obscure. Aqueous lyotropic liquid crystals (LLCs) comprise a platform for detailed studies of the molecular-level features governing proton transport in monodisperse, water-filled nanopores lined with well-defined chemical functionalities. Here, we report new alkylsulfonic acid LLCs that exhibit H+ conductivities as high as σ = 380 mS/cm at 80°C, which rival those of more acidic, perfluorinated polymers, thus demonstrating that the acidity of the pore functionality is not the sole determinant of proton transport. Direct experimentalmore » comparisons of LLCs with convex and concave nanopores of similar dimensions indicate that H+ conductivities therein sensitively depend on the hydration state of the acid functionalities and the pore curvature. These experiments suggest that judicious manipulation of pore curvature provides a new means for optimizing the activities of proton-exchange membranes and nanoporous solid acid catalysts.« less

Carbon coated anatase TiO2 mesocrystals enabling ultrastable and robust sodium storage

NASA Astrophysics Data System (ADS)

Zhang, Weifeng; Lan, Tongbin; Ding, Tianli; Wu, Nae-Lih; Wei, Mingdeng

2017-08-01

Nanoporous anatase TiO2 mesocrystals with tunable architectures and crystalline phases were successfully fabricated in the presence of the butyl oleate and oleylamine. Especially, the introduced surfactants served as a carbon source, bring a uniform carbon layer (about 2-8 nm) for heightening the electronic conductivity. The carbon coated TiO2 mesocrystals assembled from crystalline tiny subunits have more space sites for sodium-ion storage. When the material was applied as an electrode material in rechargeable sodium-ion batteries, it exhibited a superior capacity of about 90 mA h g-1 at 20 C (1 C = 168 mA g-1) and a highly reversible capacity for 5000 cycles, which is the longest cycle life reported for sodium storage in TiO2 electrodes.

Polyelectrolyte layer-by-layer deposition in cylindrical nanopores.

PubMed

Lazzara, Thomas D; Lau, K H Aaron; Abou-Kandil, Ahmed I; Caminade, Anne-Marie; Majoral, Jean-Pierre; Knoll, Wolfgang

2010-07-27

Layer-by-layer (LbL) deposition of polyelectrolytes within nanopores in terms of the pore size and the ionic strength was experimentally studied. Anodic aluminum oxide (AAO) membranes, which have aligned, cylindrical, nonintersecting pores, were used as a model nanoporous system. Furthermore, the AAO membranes were also employed as planar optical waveguides to enable in situ monitoring of the LbL process within the nanopores by optical waveguide spectroscopy (OWS). Structurally well-defined N,N-disubstituted hydrazine phosphorus-containing dendrimers of the fourth generation, with peripherally charged groups and diameters of approximately 7 nm, were used as the model polyelectrolytes. The pore diameter of the AAO was varied between 30-116 nm and the ionic strength was varied over 3 orders of magnitude. The dependence of the deposited layer thickness on ionic strength within the nanopores is found to be significantly stronger than LbL deposition on a planar surface. Furthermore, deposition within the nanopores can become inhibited even if the pore diameter is much larger than the diameter of the G4-polyelectrolyte, or if the screening length is insignificant relative to the dendrimer diameter at high ionic strengths. Our results will aid in the template preparation of polyelectrolyte multilayer nanotubes, and our experimental approach may be useful for investigating theories regarding the partitioning of nano-objects within nanopores where electrostatic interactions are dominant. Furthermore, we show that the enhanced ionic strength dependence of polyelectrolyte transport within the nanopores can be used to selectively deposit a LbL multilayer atop a nanoporous substrate.

Nanopore-based fourth-generation DNA sequencing technology.

PubMed

Feng, Yanxiao; Zhang, Yuechuan; Ying, Cuifeng; Wang, Deqiang; Du, Chunlei

2015-02-01

Nanopore-based sequencers, as the fourth-generation DNA sequencing technology, have the potential to quickly and reliably sequence the entire human genome for less than $1000, and possibly for even less than $100. The single-molecule techniques used by this technology allow us to further study the interaction between DNA and protein, as well as between protein and protein. Nanopore analysis opens a new door to molecular biology investigation at the single-molecule scale. In this article, we have reviewed academic achievements in nanopore technology from the past as well as the latest advances, including both biological and solid-state nanopores, and discussed their recent and potential applications. Copyright © 2015 The Authors. Production and hosting by Elsevier Ltd.. All rights reserved.

Nanoporous Gold for Enzyme Immobilization.

PubMed

Stine, Keith J; Jefferson, Kenise; Shulga, Olga V

2017-01-01

Nanoporous gold (NPG) is a material of emerging interest for immobilization of biomolecules, especially enzymes. The material provides a high surface area form of gold that is suitable for physisorption or for covalent modification by self-assembled monolayers. The material can be used as a high surface area electrode and with immobilized enzymes can be used for amperometric detection schemes. NPG can be prepared in a variety of formats from alloys containing between 20 and 50 % atomic composition of gold and less noble element(s) by dealloying procedures. Materials resembling NPG can be prepared by hydrothermal and electrodeposition methods. Related high surface area gold structures have been prepared using templating approaches. Covalent enzyme immobilization can be achieved by first forming a self-assembled monolayer on NPG bearing a terminal reactive functional group followed by conjugation to the enzyme through amide linkages to lysine residues. Enzymes can also be entrapped by physisorption or immobilized by electrostatic interactions.

Materials Genome in Action: Identifying the Performance Limits of Physical Hydrogen Storage

PubMed Central

2017-01-01

The Materials Genome is in action: the molecular codes for millions of materials have been sequenced, predictive models have been developed, and now the challenge of hydrogen storage is targeted. Renewably generated hydrogen is an attractive transportation fuel with zero carbon emissions, but its storage remains a significant challenge. Nanoporous adsorbents have shown promising physical adsorption of hydrogen approaching targeted capacities, but the scope of studies has remained limited. Here the Nanoporous Materials Genome, containing over 850 000 materials, is analyzed with a variety of computational tools to explore the limits of hydrogen storage. Optimal features that maximize net capacity at room temperature include pore sizes of around 6 Å and void fractions of 0.1, while at cryogenic temperatures pore sizes of 10 Å and void fractions of 0.5 are optimal. Our top candidates are found to be commercially attractive as “cryo-adsorbents”, with promising storage capacities at 77 K and 100 bar with 30% enhancement to 40 g/L, a promising alternative to liquefaction at 20 K and compression at 700 bar. PMID:28413259

Materials genome in action: Identifying the performance limits of physical hydrogen storage

DOE PAGES

Thornton, Aaron W.; Simon, Cory M.; Kim, Jihan; ...

2017-03-08

The Materials Genome is in action: the molecular codes for millions of materials have been sequenced, predictive models have been developed, and now the challenge of hydrogen storage is targeted. Renewably generated hydrogen is an attractive transportation fuel with zero carbon emissions, but its storage remains a significant challenge. Nanoporous adsorbents have shown promising physical adsorption of hydrogen approaching targeted capacities, but the scope of studies has remained limited. Here the Nanoporous Materials Genome, containing over 850 000 materials, is analyzed with a variety of computational tools to explore the limits of hydrogen storage. Optimal features that maximize net capacitymore » at room temperature include pore sizes of around 6 Å and void fractions of 0.1, while at cryogenic temperatures pore sizes of 10 Å and void fractions of 0.5 are optimal. Finally, our top candidates are found to be commercially attractive as “cryo-adsorbents”, with promising storage capacities at 77 K and 100 bar with 30% enhancement to 40 g/L, a promising alternative to liquefaction at 20 K and compression at 700 bar.« less

Materials genome in action: Identifying the performance limits of physical hydrogen storage

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

Thornton, Aaron W.; Simon, Cory M.; Kim, Jihan

The Materials Genome is in action: the molecular codes for millions of materials have been sequenced, predictive models have been developed, and now the challenge of hydrogen storage is targeted. Renewably generated hydrogen is an attractive transportation fuel with zero carbon emissions, but its storage remains a significant challenge. Nanoporous adsorbents have shown promising physical adsorption of hydrogen approaching targeted capacities, but the scope of studies has remained limited. Here the Nanoporous Materials Genome, containing over 850 000 materials, is analyzed with a variety of computational tools to explore the limits of hydrogen storage. Optimal features that maximize net capacitymore » at room temperature include pore sizes of around 6 Å and void fractions of 0.1, while at cryogenic temperatures pore sizes of 10 Å and void fractions of 0.5 are optimal. Finally, our top candidates are found to be commercially attractive as “cryo-adsorbents”, with promising storage capacities at 77 K and 100 bar with 30% enhancement to 40 g/L, a promising alternative to liquefaction at 20 K and compression at 700 bar.« less

Immobilization of glucose oxidase into a nanoporous TiO₂ film layered on metallophthalocyanine modified vertically-aligned carbon nanotubes for efficient direct electron transfer.

PubMed

Cui, Hui-Fang; Zhang, Kuan; Zhang, Yong-Fang; Sun, Yu-Long; Wang, Jia; Zhang, Wei-De; Luong, John H T

2013-08-15

Glucose oxidase (GOD) was adsorbed into a nanoporous TiO₂ film layered on the surface of an iron phthalocyanine (FePc) vertically-aligned carbon nanotube (CNT) modified electrode. A Nafion film was then dropcast on the electrode's surface to improve operational and storage stabilities of the GOD-based electrode. Scanning electron microscopy (SEM) micrographs revealed the formation of FePc and nanoporous TiO₂ nanoparticles along the sidewall and the tip of CNTs. Cyclic voltammograms of the GOD electrode in neutral PBS exhibited a pair of well-defined redox peaks, attesting the direct electron transfer of GOD (FAD/FADH₂) with the underlying electrode. The potential of glucose electro-oxidation under nitrogen was ∼+0.12 V with an oxidation current density of 65.3 μA cm(-2) at +0.77 V. Voltammetric and amperometric responses were virtually unaffected by oxygen, illustrating an efficient and fast direct electron transfer. The modification of the CNT surface with FePc resulted in a biosensor with remarkable detection sensitivity with an oxygen-independent bioelectrocatalysis. In deaerated PBS, the biosensor displayed average response time of 12 s, linearity from 50 μM to 4 mM, and a detection limit of 30 μM (S/N=3) for glucose. Copyright © 2013 Elsevier B.V. All rights reserved.

Efficient Fabrication of Nanoporous Si and Si/Ge Enabled by a Heat Scavenger in Magnesiothermic Reactions

PubMed Central

Luo, Wei; Wang, Xingfeng; Meyers, Colin; Wannenmacher, Nick; Sirisaksoontorn, Weekit; Lerner, Michael M.; Ji, Xiulei

2013-01-01

Magnesiothermic reduction can directly convert SiO2 into Si nanostructures. Despite intense efforts, efficient fabrication of highly nanoporous silicon by Mg still remains a significant challenge due to the exothermic reaction nature. By employing table salt (NaCl) as a heat scavenger for the magnesiothermic reduction, we demonstrate an effective route to convert diatom (SiO2) and SiO2/GeO2 into nanoporous Si and Si/Ge composite, respectively. Fusion of NaCl during the reaction consumes a large amount of heat that otherwise collapses the nano-porosity of products and agglomerates silicon domains into large crystals. Our methodology is potentially competitive for a practical production of nanoporous Si-based materials. PMID:23860418

Efficient fabrication of nanoporous si and Si/Ge enabled by a heat scavenger in magnesiothermic reactions.

PubMed

Luo, Wei; Wang, Xingfeng; Meyers, Colin; Wannenmacher, Nick; Sirisaksoontorn, Weekit; Lerner, Michael M; Ji, Xiulei

2013-01-01

Magnesiothermic reduction can directly convert SiO2 into Si nanostructures. Despite intense efforts, efficient fabrication of highly nanoporous silicon by Mg still remains a significant challenge due to the exothermic reaction nature. By employing table salt (NaCl) as a heat scavenger for the magnesiothermic reduction, we demonstrate an effective route to convert diatom (SiO2) and SiO2/GeO2 into nanoporous Si and Si/Ge composite, respectively. Fusion of NaCl during the reaction consumes a large amount of heat that otherwise collapses the nano-porosity of products and agglomerates silicon domains into large crystals. Our methodology is potentially competitive for a practical production of nanoporous Si-based materials.

Nanoporous Materials for the Onboard Storage of Natural Gas.

PubMed

Kumar, K Vasanth; Preuss, Kathrin; Titirici, Maria-Magdalena; Rodríguez-Reinoso, Francisco

2017-02-08

Climate change, global warming, urban air pollution, energy supply uncertainty and depletion, and rising costs of conventional energy sources are, among others, potential socioeconomic threats that our community faces today. Transportation is one of the primary sectors contributing to oil consumption and global warming, and natural gas (NG) is considered to be a relatively clean transportation fuel that can significantly improve local air quality, reduce greenhouse-gas emissions, and decrease the energy dependency on oil sources. Internal combustion engines (ignited or compression) require only slight modifications for use with natural gas; rather, the main problem is the relatively short driving distance of natural-gas-powered vehicles due to the lack of an appropriate storage method for the gas, which has a low energy density. The U.S. Department of Energy (DOE) has set some targets for NG storage capacity to obtain a reasonable driving range in automotive applications, ruling out the option of storing methane at cryogenic temperatures. In recent years, both academia and industry have foreseen the storage of natural gas by adsorption (ANG) in porous materials, at relatively low pressures and ambient temperatures, as a solution to this difficult problem. This review presents recent developments in the search for novel porous materials with high methane storage capacities. Within this scenario, both carbon-based materials and metal-organic frameworks are considered to be the most promising materials for natural gas storage, as they exhibit properties such as large surface areas and micropore volumes, that favor a high adsorption capacity for natural gas. Recent advancements, technological issues, advantages, and drawbacks involved in natural gas storage in these two classes of materials are also summarized. Further, an overview of the recent developments and technical challenges in storing natural gas as hydrates in wetted porous carbon materials is also included

Method to fabricate functionalized conical nanopores

DOEpatents

Small, Leo J.; Spoerke, Erik David; Wheeler, David R.

2016-07-12

A pressure-based chemical etch method is used to shape polymer nanopores into cones. By varying the pressure, the pore tip diameter can be controlled, while the pore base diameter is largely unaffected. The method provides an easy, low-cost approach for conically etching high density nanopores.

Controlling Ionic Transport for Device Design in Synthetic Nanopores

NASA Astrophysics Data System (ADS)

Kalman, Eric Boyd

Polymer nanopores present a number of behaviors not seen in microscale systems, such as ion current rectification, ionic selectivity, size exclusion and potential dependent ion concentrations in and near the pore. The existence of these effects stems from the small size of nanopores with respect to the characteristic length scales of surface interactions at the interface between the nanopore surface and the solution within it. The large surface-to-volume ratio due to the nanoscale geometry of a nanopore, as well as similarity in scale between geometry and interaction demands the solution interact with the nanopore walls. As surfaces in solution almost always carry residual charge, these surface forces are primarily the electrostatic interactions between the charge groups on the pore surface and the ions in solution. These interactions may be used by the experimentalist to control ionic transport through synthetic nanopores, and use them as a template for the construction of devices. In this research, we present our work on creating a number of ionic analogs to seminal electronic devices, specifically diodes, and transistors, by controlling ionic transport through the electrostatic interactions between a single synthetic nanopore and ions. Control is achieved by "doping" the effective charge carrier concentration in specific regions of the nanopore through manipulation of the pore's surface charge. This manipulation occurs through two mechanisms: chemical modification of the surface charge and electrostatic manipulation of the local internal nanopore potential using a gate electrode. Additionally, the innate selectivity of the charged nanopores walls allows for the separation of charges in solution. This well-known effect, which spawns measureable quantities, the streaming potential and current, has been used to create nanoscale water desalination membranes. We attempt to create a device using membranes with large nanopore densities for the desalination of water

Propylene/propane permeation properties of ethyl cellulose (EC) mixed matrix membranes fabricated by incorporation of nanoporous graphene nanosheets

PubMed Central

Yuan, Bingbing; Sun, Haixiang; Wang, Tao; Xu, Yanyan; Li, Peng; Kong, Ying; Niu, Q. Jason

2016-01-01

Nanopore containing graphene nanosheets were synthesized by graphene oxide and a reducing agent using a facile hydrothermal treatment in sodium hydroxide media. The as-prepared nanoporous graphene was incorporated into ethyl cellulose (EC) to prepare the mixed matrix membranes (MMMs) for C3H6/C3H8 separation. Transmission electron microscopy (TEM) photograph and X-ray photoelectron spectroscopy (XPS) analysis of nanoporous graphene nanosheets indicated that the structure of nano-pore was irregular and the oxygen-containing groups in the surface were limited. More importantly, the as-prepared MMMs presented better separation performance than that of pristine EC membrane due to simultaneous enhancement of C3H6 permeability and ideal selectivity. The ideal selectivity of the MMMs with 1.125 wt‰ nanoporous graphene content for C3H6/C3H8 increased from 3.45 to 10.42 and the permeability of C3H6 increased from 57.9 Barrer to 89.95 Barrer as compared with the pristine membrane. The presumed facilitated mechanism was that the high specific surface area of nanoporous graphene in polymer matrix increased the length of the tortuous pathway formed by nanopores for the gas diffusion as compared with the pristine graphene nanosheets, and generated a rigidified interface between the EC chains and fillers, thus enhanced the diffusivity selectivity. Therefore, it is expected that nanoporous graphene would be effective material for the C3H6/C3H8 separation. PMID:27352851

Nanoporous Materials in Atmosphere Revitalization. Chapter 1

NASA Technical Reports Server (NTRS)

Hernandez-Maldonado, J.; Ishikawa, Yasuyuki; Luna, Bernadette; Junaedi, Christian; Mulloth, Lila; Perry, Jay L.; Raptis, Raphael G.; Roychoudhury, Subir

2012-01-01

Atmospheric Revitalization (AR) is the term the National Aeronautics and Space Administration (NASA) uses to encompass the engineered systems that maintain a safe, breathable gaseous atmosphere inside a habitable space cabin. An AR subsystem is a key part of the Environmental Control and Life Support (ECLS) system for habitable space cabins. The ultimate goal for AR subsystem designers is to 'close the loop', that is, to capture gaseous human metabolic products, specifically water vapor (H2O) and Carbon dioxide (CO2), for maximal Oxygen (o2) recovery and to make other useful resources from these products. The AR subsystem also removes trace chemical contaminants from the cabin atmosphere to preserve cabin atmospheric quality, provides O2 and may include instrumentation to monitor cabin atmospheric quality. Long duration crewed space exploration missions require advancements in AR process technologies in order to reduce power consumption and mass and to increase reliability compared to those used for shorter duration missions that are typically limited to Low Earth Orbit. For example, current AR subsystems include separate processors and process air flow loops for removing metabolic CO2 and volatile organic tract contaminants (TCs). Physical adsorbents contained in fixed, packed beds are employed in these processors. Still, isolated pockets of high carbon dioxide have been suggested as a trigger for crew headaches and concern persists about future cabin ammonia (NH3) levels as compared with historical flights. Developers are already focused on certain potential advancements. ECLS systems engineers envision improving the AR subsystem by combining the functions of TC control and CO2 removal into a single regenerable process and moving toward structured sorbents - monoliths - instead of granular material. Monoliths present a lower pressure drop and eliminate particle attrition problems that result from bed containment. New materials and configurations offer promise for

Nanoporous hard data: optical encoding of information within nanoporous anodic alumina photonic crystals.

PubMed

Santos, Abel; Law, Cheryl Suwen; Pereira, Taj; Losic, Dusan

2016-04-21

Herein, we present a method for storing binary data within the spectral signature of nanoporous anodic alumina photonic crystals. A rationally designed multi-sinusoidal anodisation approach makes it possible to engineer the photonic stop band of nanoporous anodic alumina with precision. As a result, the transmission spectrum of these photonic nanostructures can be engineered to feature well-resolved and selectively positioned characteristic peaks across the UV-visible spectrum. Using this property, we implement an 8-bit binary code and assess the versatility and capability of this system by a series of experiments aiming to encode different information within the nanoporous anodic alumina photonic crystals. The obtained results reveal that the proposed nanosized platform is robust, chemically stable, versatile and has a set of unique properties for data storage, opening new opportunities for developing advanced nanophotonic tools for a wide range of applications, including sensing, photonic tagging, self-reporting drug releasing systems and secure encoding of information.

Interruption of Hydrogen Bonding Networks of Water in Carbon Nanotubes Due to Strong Hydration Shell Formation.

PubMed

Oya, Yoshifumi; Hata, Kenji; Ohba, Tomonori

2017-10-24

We present the structures of NaCl aqueous solution in carbon nanotubes with diameters of 1, 2, and 3 nm based on an analysis performed using X-ray diffraction and canonical ensemble Monte Carlo simulations. Anomalously longer nearest-neighbor distances were observed in the electrolyte for the 1-nm-diameter carbon nanotubes; in contrast, in the 2 and 3 nm carbon nanotubes, the nearest-neighbor distances were shorter than those in the bulk electrolyte. We also observed similar properties for water in carbon nanotubes, which was expected because the main component of the electrolyte was water. However, the nearest-neighbor distances of the electrolyte were longer than those of water in all of the carbon nanotubes; the difference was especially pronounced in the 2-nm-diameter carbon nanotubes. Thus, small numbers of ions affected the entire structure of the electrolyte in the nanopores of the carbon nanotubes. The formation of strong hydration shells between ions and water molecules considerably interrupted the hydrogen bonding between water molecules in the nanopores of the carbon nanotubes. The hydration shell had a diameter of approximately 1 nm, and hydration shells were thus adopted for the nanopores of the 2-nm-diameter carbon nanotubes, providing an explanation for the large difference in the nearest-neighbor distances between the electrolyte and water in these nanopores.

Computational Screening of Nanoporous Materials for Hexane and Heptane Isomer Separation

DOE PAGES

Chung, Yongchul G.; Bai, Peng; Haranczyk, Maciej; ...

2017-07-05

Computational high-throughput screening was carried out to assess a large number of experimentally reported metal–organic frameworks (MOFs) and zeolites for their utility in hexane isomer separation. Through the paper, we identified many MOFs and zeolites with high selectivity (S L+M > 10) for the group of n-hexane, 2-methylpentane, and 3-methylpentane (linear and monobranched isomers) versus 2,2-dimethylbutane and 2,3-dimethylbutane (dibranched isomers). This group of selective sorbents includes VICDOC (Fe 2(BDP) 3), a MOF with triangular pores that is known to exhibit high isomer selectivity and capacity. For three of these structures, the adsorption isotherms for a 10-component mixture of hexane andmore » heptane isomers were calculated. Subsequent simulations of column breakthrough curves showed that the DEYVUA MOF exhibits a longer process cycle time than VICDOC MOF or MRE zeolite, which are previously reported, high-performing materials, illustrating the importance of capacity in designing MOFs for practical applications. Among the identified candidates, we synthesized and characterized a MOF in a new copper form with high predicted adsorbent capacity (q L+M > 1.2 mol/L) and moderately high selectivity (S L+M ≈ 10). In conclusion, we examined the role of pore shape in hexane isomer separations, especially of triangular-shaped pores. We show through the potential energy surface and three-dimensional siting analyses that linear alkanes do not populate the corners of narrow triangular channels and that structures with nontriangular pores can efficiently separate hexane isomers. Detailed thermodynamic analysis illustrates how differences in the free energy of adsorption contribute to shape-selective separation in nanoporous materials.« less

Computational Screening of Nanoporous Materials for Hexane and Heptane Isomer Separation

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

Chung, Yongchul G.; Bai, Peng; Haranczyk, Maciej

Computational high-throughput screening was carried out to assess a large number of experimentally reported metal–organic frameworks (MOFs) and zeolites for their utility in hexane isomer separation. Through the paper, we identified many MOFs and zeolites with high selectivity (S L+M > 10) for the group of n-hexane, 2-methylpentane, and 3-methylpentane (linear and monobranched isomers) versus 2,2-dimethylbutane and 2,3-dimethylbutane (dibranched isomers). This group of selective sorbents includes VICDOC (Fe 2(BDP) 3), a MOF with triangular pores that is known to exhibit high isomer selectivity and capacity. For three of these structures, the adsorption isotherms for a 10-component mixture of hexane andmore » heptane isomers were calculated. Subsequent simulations of column breakthrough curves showed that the DEYVUA MOF exhibits a longer process cycle time than VICDOC MOF or MRE zeolite, which are previously reported, high-performing materials, illustrating the importance of capacity in designing MOFs for practical applications. Among the identified candidates, we synthesized and characterized a MOF in a new copper form with high predicted adsorbent capacity (q L+M > 1.2 mol/L) and moderately high selectivity (S L+M ≈ 10). In conclusion, we examined the role of pore shape in hexane isomer separations, especially of triangular-shaped pores. We show through the potential energy surface and three-dimensional siting analyses that linear alkanes do not populate the corners of narrow triangular channels and that structures with nontriangular pores can efficiently separate hexane isomers. Detailed thermodynamic analysis illustrates how differences in the free energy of adsorption contribute to shape-selective separation in nanoporous materials.« less

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 and Carbon Hybrid Materials as Anodes for Sodium-Ion Batteries.

PubMed

Zhong, Xiongwu; Wu, Ying; Zeng, Sifan; Yu, Yan

2018-02-12

Sodium-ion batteries (SIBs) have attracted much attention for application in large-scale grid energy storage owing to the abundance and low cost of sodium sources. However, low energy density and poor cycling life hinder practical application of SIBs. Recently, substantial efforts have been made to develop electrode materials to push forward large-scale practical applications. Carbon materials can be directly used as anode materials, and they show excellent sodium storage performance. Additionally, designing and constructing carbon hybrid materials is an effective strategy to obtain high-performance anodes for SIBs. In this review, we summarize recent research progress on carbon and carbon hybrid materials as anodes for SIBs. Nanostructural design to enhance the sodium storage performance of anode materials is discussed, and we offer some insight into the potential directions of and future high-performance anode materials for SIBs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

3-D simulation of nanopore structure for DNA sequencing.

PubMed

Park, Jun-Mo; Pak, Y Eugene; Chun, Honggu; Lee, Jong-Ho

2012-07-01

In this paper, we propose a method for simulating nanopore structure by using conventional 3-D simulation tool to mimic the I-V behavior of the nanopore structure. In the simulation, we use lightly doped silicon for ionic solution where some parameters like electron affinity and dielectric constant are fitted to consider the ionic solution. By using this method, we can simulate the I-V behavior of nanopore structure depending on the location and the size of the sphere shaped silicon oxide which is considered to be an indicator of a DNA base. In addition, we simulate an Ionic Field Effect Transistor (IFET) which has basically the nanopore structure, and show that the simulated curves follow sufficiently the I-V behavior of the measurement data. Therefore, we think it is reasonable to apply parameter modeling mentioned above to simulate nanopore structure. The key idea is to modify electron affinity of silicon which is used to mimic the KCl solution to avoid band bending and depletion inside the nanopore. We could efficiently utilize conventional 3-D simulation tool to simulate the I-V behavior of nanopore structures.

Biological Nanopores: Confined Spaces for Electrochemical Single-Molecule Analysis.

PubMed

Cao, Chan; Long, Yi-Tao

2018-02-20

Nanopore sensing is developing into a powerful single-molecule approach to investigate the features of biomolecules that are not accessible by studying ensemble systems. When a target molecule is transported through a nanopore, the ions occupying the pore are excluded, resulting in an electrical signal from the intermittent ionic blockade event. By statistical analysis of the amplitudes, duration, frequencies, and shapes of the blockade events, many properties of the target molecule can be obtained in real time at the single-molecule level, including its size, conformation, structure, charge, geometry, and interactions with other molecules. With the development of the use of α-hemolysin to characterize individual polynucleotides, nanopore technology has attracted a wide range of research interest in the fields of biology, physics, chemistry, and nanoscience. As a powerful single-molecule analytical method, nanopore technology has been applied for the detection of various biomolecules, including oligonucleotides, peptides, oligosaccharides, organic molecules, and disease-related proteins. In this Account, we highlight recent developments of biological nanopores in DNA-based sensing and in studying the conformational structures of DNA and RNA. Furthermore, we introduce the application of biological nanopores to investigate the conformations of peptides affected by charge, length, and dipole moment and to study disease-related proteins' structures and aggregation transitions influenced by an inhibitor, a promoter, or an applied voltage. To improve the sensing ability of biological nanopores and further extend their application to a wider range of molecular sensing, we focus on exploring novel biological nanopores, such as aerolysin and Stable Protein 1. Aerolysin exhibits an especially high sensitivity for the detection of single oligonucleotides both in current separation and duration. Finally, to facilitate the use of nanopore measurements and statistical analysis

Nanoporous Polymer Films of Cyanate Ester Resins Designed by Using Ionic Liquids as Porogens

NASA Astrophysics Data System (ADS)

Fainleib, Alexander; Vashchuk, Alina; Starostenko, Olga; Grigoryeva, Olga; Rogalsky, Sergiy; Nguyen, Thi-Thanh-Tam; Grande, Daniel

2017-02-01

Novel nanoporous film materials of thermostable cyanate ester resins (CERs) were generated by polycyclotrimerization of dicyanate ester of bisphenol E in the presence of varying amounts (from 20 to 40 wt%) of an ionic liquid (IL), i.e., 1-heptylpyridinium tetrafluoroborate, followed by its quantitative extraction after complete CER network formation. The completion of CER formation and IL extraction was assessed using gel fraction content determination, FTIR, 1H NMR, and energy-dispersive X-ray spectroscopy (EDX). SEM and DSC-based thermoporometry analyses demonstrated the formation of nanoporous structures after IL removal from CER networks, thus showing the effective role of IL as a porogen. Pore sizes varied from 20 to 180 nm with an average pore diameter of around 45-60 nm depending on the initial IL content. The thermal stability of nanoporous CER-based films was investigated by thermogravimetric analysis.

Hyper-dendritic nanoporous zinc foam anodes

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

Chamoun, Mylad; Hertzberg, Benjamin J.; Gupta, Tanya

The low cost, significant reducing potential, and relative safety of the zinc electrode is a common hope for a reductant in secondary batteries, but it is limited mainly to primary implementation due to shape change. In this work we exploit such shape change for the benefit of static electrodes through the electrodeposition of hyper-dendritic nanoporous zinc foam. Electrodeposition of zinc foam resulted in nanoparticles formed on secondary dendrites in a three-dimensional network with a particle size distribution of 54.1 - 96.0 nm. The nanoporous zinc foam contributed to highly oriented crystals, high surface area and more rapid kinetics in contrastmore » to conventional zinc in alkaline mediums. The anode material presented had a utilization of ~ 88% at full depth-of-discharge at various rates indicating a superb rate-capability. The rechargeability of Zn⁰/Zn²⁺ showed significant capacity retention over 100 cycles at a 40% depth-of-discharge to ensure that the dendritic core structure was imperforated. The dendritic architecture was densified upon charge-discharge cycling and presented superior performance compared to bulk zinc electrodes.« less

Hyper-dendritic nanoporous zinc foam anodes

DOE PAGES

Chamoun, Mylad; Hertzberg, Benjamin J.; Gupta, Tanya; ...

2015-04-24

The low cost, significant reducing potential, and relative safety of the zinc electrode is a common hope for a reductant in secondary batteries, but it is limited mainly to primary implementation due to shape change. In this work we exploit such shape change for the benefit of static electrodes through the electrodeposition of hyper-dendritic nanoporous zinc foam. Electrodeposition of zinc foam resulted in nanoparticles formed on secondary dendrites in a three-dimensional network with a particle size distribution of 54.1 - 96.0 nm. The nanoporous zinc foam contributed to highly oriented crystals, high surface area and more rapid kinetics in contrastmore » to conventional zinc in alkaline mediums. The anode material presented had a utilization of ~ 88% at full depth-of-discharge at various rates indicating a superb rate-capability. The rechargeability of Zn⁰/Zn²⁺ showed significant capacity retention over 100 cycles at a 40% depth-of-discharge to ensure that the dendritic core structure was imperforated. The dendritic architecture was densified upon charge-discharge cycling and presented superior performance compared to bulk zinc electrodes.« less

Nanopore thin film enabled optical platform for drug loading and release.

PubMed

Song, Chao; Che, Xiangchen; Que, Long

2017-08-07

In this paper, a drug loading and release device fabricated using nanopore thin film and layer-by-layer (LbL) nanoassembly is reported. The nanopore thin film is a layer of anodic aluminum oxide (AAO), consisting of honeycomb-shape nanopores. Using the LbL nanoassembly process, the drug, using gentamicin sulfate (GS) as the model, can be loaded into the nanopores and the stacked layers on the nanopore thin film surface. The drug release from the device is achieved by immersing it into flowing DI water. Both the loading and release processes can be monitored optically. The effect of the nanopore size/volume on drug loading and release has also been evaluated. Further, the neuron cells have been cultured and can grow normally on the nanopore thin film, verifying its bio-compatibility. The successful fabrication of nanopore thin film device on silicon membrane render it as a potential implantable controlled drug release device.

Graphene Nanopores for Protein Sequencing.

PubMed

Wilson, James; Sloman, Leila; He, Zhiren; Aksimentiev, Aleksei

2016-07-19

An inexpensive, reliable method for protein sequencing is essential to unraveling the biological mechanisms governing cellular behavior and disease. Current protein sequencing methods suffer from limitations associated with the size of proteins that can be sequenced, the time, and the cost of the sequencing procedures. Here, we report the results of all-atom molecular dynamics simulations that investigated the feasibility of using graphene nanopores for protein sequencing. We focus our study on the biologically significant phenylalanine-glycine repeat peptides (FG-nups)-parts of the nuclear pore transport machinery. Surprisingly, we found FG-nups to behave similarly to single stranded DNA: the peptides adhere to graphene and exhibit step-wise translocation when subject to a transmembrane bias or a hydrostatic pressure gradient. Reducing the peptide's charge density or increasing the peptide's hydrophobicity was found to decrease the translocation speed. Yet, unidirectional and stepwise translocation driven by a transmembrane bias was observed even when the ratio of charged to hydrophobic amino acids was as low as 1:8. The nanopore transport of the peptides was found to produce stepwise modulations of the nanopore ionic current correlated with the type of amino acids present in the nanopore, suggesting that protein sequencing by measuring ionic current blockades may be possible.

A Protein Nanopore-Based Approach for Bacteria Sensing

NASA Astrophysics Data System (ADS)

Apetrei, Aurelia; Ciuca, Andrei; Lee, Jong-kook; Seo, Chang Ho; Park, Yoonkyung; Luchian, Tudor

2016-11-01

We present herein a first proof of concept demonstrating the potential of a protein nanopore-based technique for real-time detection of selected Gram-negative bacteria ( Pseudomonas aeruginosa or Escherichia coli) at a concentration of 1.2 × 108 cfu/mL. The anionic charge on the bacterial outer membrane promotes the electrophoretically driven migration of bacteria towards a single α-hemolysin nanopore isolated in a lipid bilayer, clamped at a negative electric potential, and followed by capture at the nanopore's mouth, which we found to be described according to the classical Kramers' theory. By using a specific antimicrobial peptide as a putative molecular biorecognition element for the bacteria used herein, we suggest that the detection system can combine the natural sensitivity of the nanopore-based sensing techniques with selective biological recognition, in aqueous samples, and highlight the feasibility of the nanopore-based platform to provide portable, sensitive analysis and monitoring of bacterial pathogens.

Nanopore Electrochemistry: A Nexus for Molecular Control of Electron Transfer Reactions

PubMed Central

2018-01-01

Pore-based structures occur widely in living organisms. Ion channels embedded in cell membranes, for example, provide pathways, where electron and proton transfer are coupled to the exchange of vital molecules. Learning from mother nature, a recent surge in activity has focused on artificial nanopore architectures to effect electrochemical transformations not accessible in larger structures. Here, we highlight these exciting advances. Starting with a brief overview of nanopore electrodes, including the early history and development of nanopore sensing based on nanopore-confined electrochemistry, we address the core concepts and special characteristics of nanopores in electron transfer. We describe nanopore-based electrochemical sensing and processing, discuss performance limits and challenges, and conclude with an outlook for next-generation nanopore electrode sensing platforms and the opportunities they present. PMID:29392173

Nanopore Kinetic Proofreading of DNA Sequences

NASA Astrophysics Data System (ADS)

Ling, Xinsheng Sean

The concept of DNA sequencing using the time dependence of the nanopore ionic current was proposed in 1996 by Kasianowicz, Brandin, Branton, and Deamer (KBBD). The KBBD concept has generated tremendous amount interests in recent decade. In this talk, I will review the current understanding of the DNA ``translocation'' dynamics and how it can be described by Schrodinger's 1915 paper on first-passage-time distribution function. Schrodinger's distribution function can be used to give a rigorous criterion for achieving nanopore DNA sequencing which turns out to be identical to that of gel electrophoresis used by Sanger in the first-generation Sanger method. A nanopore DNA sequencing technology also requires discrimination of bases with high accuracies. I will describe a solid-state nanopore sandwich structure that can function as a proofreading device capable of discriminating between correct and incorrect hybridization probes with an accuracy rivaling that of high-fidelity DNA polymerases. The latest results from Nanjing will be presented. This work is supported by China 1000-Talent Program at Southeast University, Nanjing, China.

Synthesis and applications of nanoporous perovskite metal oxides

PubMed Central

Huang, Xiubing; Zhao, Guixia

2018-01-01

Perovskite-type metal oxides have been widely investigated and applied in various fields in the past several decades due to their extraordinary variability of compositions and structures with targeted physical and chemical properties (e.g., redox behaviour, oxygen mobility, electronic and ionic conductivity). Recently, nanoporous perovskite metal oxides have attracted extensive attention because of their special morphology and properties, as well as superior performance. This minireview aims at summarizing and reviewing the different synthesis methods of nanoporous perovskite metal oxides and their various applications comprehensively. The correlations between the nanoporous structures and the specific performance of perovskite oxides are summarized and highlighted. The future research directions of nanoporous perovskite metal oxides are also prospected. PMID:29862001

Streaming current magnetic fields in a charged nanopore.

PubMed

Mansouri, Abraham; Taheri, Peyman; Kostiuk, Larry W

2016-11-11

Magnetic fields induced by currents created in pressure driven flows inside a solid-state charged nanopore were modeled by numerically solving a system of steady state continuum partial differential equations, i.e., Poisson, Nernst-Planck, Ampere and Navier-Stokes equations (PNPANS). This analysis was based on non-dimensional transport governing equations that were scaled using Debye length as the characteristic length scale, and applied to a finite length cylindrical nano-channel. The comparison of numerical and analytical studies shows an excellent agreement and verified the magnetic fields density both inside and outside the nanopore. The radially non-uniform currents resulted in highly non-uniform magnetic fields within the nanopore that decay as 1/r outside the nanopore. It is worth noting that for either streaming currents or streaming potential cases, the maximum magnetic field occurred inside the pore in the vicinity of nanopore wall, as opposed to a cylindrical conductor that carries a steady electric current where the maximum magnetic fields occur at the perimeter of conductor. Based on these results, it is suggested and envisaged that non-invasive external magnetic fields readouts generated by streaming/ionic currents may be viewed as secondary electronic signatures of biomolecules to complement and enhance current DNA nanopore sequencing techniques.

Streaming current magnetic fields in a charged nanopore

NASA Astrophysics Data System (ADS)

Mansouri, Abraham; Taheri, Peyman; Kostiuk, Larry W.

2016-11-01

Magnetic fields induced by currents created in pressure driven flows inside a solid-state charged nanopore were modeled by numerically solving a system of steady state continuum partial differential equations, i.e., Poisson, Nernst-Planck, Ampere and Navier-Stokes equations (PNPANS). This analysis was based on non-dimensional transport governing equations that were scaled using Debye length as the characteristic length scale, and applied to a finite length cylindrical nano-channel. The comparison of numerical and analytical studies shows an excellent agreement and verified the magnetic fields density both inside and outside the nanopore. The radially non-uniform currents resulted in highly non-uniform magnetic fields within the nanopore that decay as 1/r outside the nanopore. It is worth noting that for either streaming currents or streaming potential cases, the maximum magnetic field occurred inside the pore in the vicinity of nanopore wall, as opposed to a cylindrical conductor that carries a steady electric current where the maximum magnetic fields occur at the perimeter of conductor. Based on these results, it is suggested and envisaged that non-invasive external magnetic fields readouts generated by streaming/ionic currents may be viewed as secondary electronic signatures of biomolecules to complement and enhance current DNA nanopore sequencing techniques.

Streaming current magnetic fields in a charged nanopore

PubMed Central

Mansouri, Abraham; Taheri, Peyman; Kostiuk, Larry W.

2016-01-01

Magnetic fields induced by currents created in pressure driven flows inside a solid-state charged nanopore were modeled by numerically solving a system of steady state continuum partial differential equations, i.e., Poisson, Nernst-Planck, Ampere and Navier-Stokes equations (PNPANS). This analysis was based on non-dimensional transport governing equations that were scaled using Debye length as the characteristic length scale, and applied to a finite length cylindrical nano-channel. The comparison of numerical and analytical studies shows an excellent agreement and verified the magnetic fields density both inside and outside the nanopore. The radially non-uniform currents resulted in highly non-uniform magnetic fields within the nanopore that decay as 1/r outside the nanopore. It is worth noting that for either streaming currents or streaming potential cases, the maximum magnetic field occurred inside the pore in the vicinity of nanopore wall, as opposed to a cylindrical conductor that carries a steady electric current where the maximum magnetic fields occur at the perimeter of conductor. Based on these results, it is suggested and envisaged that non-invasive external magnetic fields readouts generated by streaming/ionic currents may be viewed as secondary electronic signatures of biomolecules to complement and enhance current DNA nanopore sequencing techniques. PMID:27833119

In vitro proliferation and osteogenic differentiation of mesenchymal stem cells on nanoporous alumina

PubMed Central

Song, Yuanhui; Ju, Yang; Song, Guanbin; Morita, Yasuyuki

2013-01-01

Cell adhesion, migration, and proliferation are significantly affected by the surface topography of the substrates on which the cells are cultured. Alumina is one of the most popular implant materials used in orthopedics, but few data are available concerning the cellular responses of mesenchymal stem cells (MSCs) grown on nanoporous structures. MSCs were cultured on smooth alumina substrates and nanoporous alumina substrates to investigate the interaction between surface topographies of nanoporous alumina and cellular behavior. Nanoporous alumina substrates with pore sizes of 20 nm and 100 nm were used to evaluate the effect of pore size on MSCs as measured by proliferation, morphology, expression of integrin β1, and osteogenic differentiation. An MTT assay was used to measure cell viability of MSCs on different substrates, and determined that cell viability decreased with increasing pore size. Scanning electron microscopy was used to investigate the effect of pore size on cell morphology. Extremely elongated cells and prominent cell membrane protrusions were observed in cells cultured on alumina with the larger pore size. The expression of integrin β1 was enhanced in MSCs cultured on porous alumina, revealing that porous alumina substrates were more favorable for cell growth than smooth alumina substrates. Higher levels of osteoblastic differentiation markers such as alkaline phosphatase, osteocalcin, and mineralization were detected in cells cultured on alumina with 100 nm pores compared with cells cultured on alumina with either 20 nm pores or smooth alumina. This work demonstrates that cellular behavior is affected by variation in pore size, providing new insight into the potential application of this novel biocompatible material for the developing field of tissue engineering. PMID:23935364

Nanoporous TiO2 nanoparticle assemblies with mesoscale morphologies: nano-cabbage versus sea-anemone

NASA Astrophysics Data System (ADS)

Darbandi, Masih; Gebre, Tesfaye; Mitchell, Lucas; Erwin, William; Bardhan, Rizia; Levan, M. Douglas; Mochena, Mogus D.; Dickerson, James H.

2014-05-01

We report the novel synthesis of nanoporous TiO2 nanoparticle ensembles with unique mesoscale morphologies. Constituent nanoparticles evolved into multifaceted assemblies, exhibiting excellent crystallinity and enhanced photocatalytic activity compared with commercial TiO2. Such materials could be exploited for applications, like organic pollutant degradation.We report the novel synthesis of nanoporous TiO2 nanoparticle ensembles with unique mesoscale morphologies. Constituent nanoparticles evolved into multifaceted assemblies, exhibiting excellent crystallinity and enhanced photocatalytic activity compared with commercial TiO2. Such materials could be exploited for applications, like organic pollutant degradation. Electronic supplementary information (ESI) available: Synthesis and characterization procedures, TEM/XRD of samples prepared at different temperature and water content, table of nitrogen adsorption-desorption values of different samples. See DOI: 10.1039/c3nr06154j

Raman Scattering in a New Carbon Material

NASA Technical Reports Server (NTRS)

Voronov, O. A.; Street, K. W., Jr.

2010-01-01

Samples of a new carbon material, Diamonite-B, were fabricated under high pressure from a commercial carbon black--identified as mixed fullerenes. The new material is neither graphite-like nor diamond-like, but exhibits electrical properties close to graphite and mechanical properties close to diamond. The use of Raman spectroscopy to investigate the vibrational dynamics of this new carbon material and to provide structural characterization of its short-, medium- and long-range order is reported. We also provide the results of investigations of these samples by high-resolution electron microscopy and X-ray diffraction. Hardness, electrical conductivity, thermal conductivity and other properties of this new material are compared with synthetic graphite-like and diamond-like materials, two other phases of synthetic bulk carbon.

Nanoporous Polymer Films of Cyanate Ester Resins Designed by Using Ionic Liquids as Porogens.

PubMed

Fainleib, Alexander; Vashchuk, Alina; Starostenko, Olga; Grigoryeva, Olga; Rogalsky, Sergiy; Nguyen, Thi-Thanh-Tam; Grande, Daniel

2017-12-01

Novel nanoporous film materials of thermostable cyanate ester resins (CERs) were generated by polycyclotrimerization of dicyanate ester of bisphenol E in the presence of varying amounts (from 20 to 40 wt%) of an ionic liquid (IL), i.e., 1-heptylpyridinium tetrafluoroborate, followed by its quantitative extraction after complete CER network formation. The completion of CER formation and IL extraction was assessed using gel fraction content determination, FTIR, 1 H NMR, and energy-dispersive X-ray spectroscopy (EDX). SEM and DSC-based thermoporometry analyses demonstrated the formation of nanoporous structures after IL removal from CER networks, thus showing the effective role of IL as a porogen. Pore sizes varied from ~20 to ~180 nm with an average pore diameter of around 45-60 nm depending on the initial IL content. The thermal stability of nanoporous CER-based films was investigated by thermogravimetric analysis.

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH 4-CO 2-H 2O) Interactions in Shale Nanopores under Reservoir Conditions

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

Wang, Yifeng

2016-04-29

Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO 2 and H 2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested asmore » an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH 4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4-CO 2-H 2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4-CO 2-H 2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.« less

Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions.

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

Wang, Yifeng

Shale is characterized by the predominant presence of nanometer-scale (1-100 nm) pores. The behavior of fluids in those pores directly controls shale gas storage and release in shale matrix and ultimately the wellbore production in unconventional reservoirs. Recently, it has been recognized that a fluid confined in nanopores can behave dramatically differently from the corresponding bulk phase due to nanopore confinement (Wang, 2014). CO 2 and H 2O, either preexisting or introduced, are two major components that coexist with shale gas (predominately CH 4) during hydrofracturing and gas extraction. Note that liquid or supercritical CO 2 has been suggested asmore » an alternative fluid for subsurface fracturing such that CO 2 enhanced gas recovery can also serve as a CO 2 sequestration process. Limited data indicate that CO 2 may preferentially adsorb in nanopores (particularly those in kerogen) and therefore displace CH4 in shale. Similarly, the presence of water moisture seems able to displace or trap CH 4 in shale matrix. Therefore, fundamental understanding of CH 4-CO 2-H 2O behavior and their interactions in shale nanopores is of great importance for gas production and the related CO 2 sequestration. This project focuses on the systematic study of CH 4-CO 2-H 2O interactions in shale nanopores under high-pressure and high temperature reservoir conditions. The proposed work will help to develop new stimulation strategies to enable efficient resource recovery from fewer and less environmentally impactful wells.« less

[Carbon fiber-reinforced plastics as implant materials].

PubMed

Bader, R; Steinhauser, E; Rechl, H; Siebels, W; Mittelmeier, W; Gradinger, R

2003-01-01

Carbon fiber-reinforced plastics have been used clinically as an implant material for different applications for over 20 years.A review of technical basics of the composite materials (carbon fibers and matrix systems), fields of application,advantages (e.g., postoperative visualization without distortion in computed and magnetic resonance tomography), and disadvantages with use as an implant material is given. The question of the biocompatibility of carbon fiber-reinforced plastics is discussed on the basis of experimental and clinical studies. Selected implant systems made of carbon composite materials for treatments in orthopedic surgery such as joint replacement, tumor surgery, and spinal operations are presented and assessed. Present applications for carbon fiber reinforced plastics are seen in the field of spinal surgery, both as cages for interbody fusion and vertebral body replacement.

Rectification of nanopores in aprotic solvents - transport properties of nanopores with surface dipoles

NASA Astrophysics Data System (ADS)

Plett, Timothy; Shi, Wenqing; Zeng, Yuhan; Mann, William; Vlassiouk, Ivan; Baker, Lane A.; Siwy, Zuzanna S.

2015-11-01

Nanopores have become a model system to understand transport properties at the nanoscale. We report experiments and modeling of ionic current in aprotic solvents with different dipole moments through conically shaped nanopores in a polycarbonate film and through glass nanopipettes. We focus on solutions of the salt LiClO4, which is of great importance in modeling lithium based batteries. Results presented suggest ion current rectification observed results from two effects: (i) adsorption of Li+ ions to the pore walls, and (ii) a finite dipole moment rendered by adsorbed solvent molecules. Properties of surfaces in various solvents were probed by means of scanning ion conductance microscopy, which confirmed existence of an effectively positive surface potential in aprotic solvents with high dipole moments.Nanopores have become a model system to understand transport properties at the nanoscale. We report experiments and modeling of ionic current in aprotic solvents with different dipole moments through conically shaped nanopores in a polycarbonate film and through glass nanopipettes. We focus on solutions of the salt LiClO4, which is of great importance in modeling lithium based batteries. Results presented suggest ion current rectification observed results from two effects: (i) adsorption of Li+ ions to the pore walls, and (ii) a finite dipole moment rendered by adsorbed solvent molecules. Properties of surfaces in various solvents were probed by means of scanning ion conductance microscopy, which confirmed existence of an effectively positive surface potential in aprotic solvents with high dipole moments. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06340j

DNA origami nanopores: developments, challenges and perspectives

NASA Astrophysics Data System (ADS)

Hernández-Ainsa, Silvia; Keyser, Ulrich F.

2014-11-01

DNA nanotechnology has enabled the construction of DNA origami nanopores; synthetic nanopores that present improved capabilities for the area of single molecule detection. Their extraordinary versatility makes them a new and powerful tool in nanobiotechnology for a wide range of important applications beyond molecular sensing. In this review, we briefly present the recent developments in this emerging field of research. We discuss the current challenges and possible solutions that would enhance the sensing capabilities of DNA origami nanopores. Finally, we anticipate novel avenues for future research and highlight a range of exciting ideas and applications that could be explored in the near future.

Effect of pH on ion current through conical nanopores

NASA Astrophysics Data System (ADS)

Chander, M.; Kumar, R.; Kumar, S.; Kumar, N.

2018-05-01

Here, we examined ionic current behavior of conical nanopores at different pH and a fixed ion concentration of potassium halide (KCl). Conical shaped nanopores have been developed by chemical etching technique in polyethylene terephthalate (PET) membrane/foil of thickness 12 micron. For this we employed a self-assembled electrochemical cell having two chambers and the foil was fitted in the centre of cell. The nanopores were produced in the foil using etching and stopping solutions. The experimental results show that ionic current rectification (ICR) occurs through synthesized conical nanopores. Further, ion current increases significantly with increase of voltage from the base side of nanopores to the tip side at fixed pH of electrolyte.

Superdiffusive gas recovery from nanopores

NASA Astrophysics Data System (ADS)

Wu, Haiyi; He, Yadong; Qiao, Rui

2016-11-01

Understanding the recovery of gas from reservoirs featuring pervasive nanopores is essential for effective shale gas extraction. Classical theories cannot accurately predict such gas recovery and many experimental observations are not well understood. Here we report molecular simulations of the recovery of gas from single nanopores, explicitly taking into account molecular gas-wall interactions. We show that, in very narrow pores, the strong gas-wall interactions are essential in determining the gas recovery behavior both quantitatively and qualitatively. These interactions cause the total diffusion coefficients of the gas molecules in nanopores to be smaller than those predicted by kinetic theories, hence slowing down the rate of gas recovery. These interactions also lead to significant adsorption of gas molecules on the pore walls. Because of the desorption of these gas molecules during gas recovery, the gas recovery from the nanopore does not exhibit the usual diffusive scaling law (i.e., the accumulative recovery scales as R ˜t1 /2 ) but follows a superdiffusive scaling law R ˜tn (n >0.5 ), which is similar to that observed in some field experiments. For the system studied here, the superdiffusive gas recovery scaling law can be captured well by continuum models in which the gas adsorption and desorption from pore walls are taken into account using the Langmuir model.

Incorporating poly(3-hexyl thiophene) into orthogonally aligned cylindrical nanopores of titania for optoelectronics

DOE PAGES

Nagpure, Suraj; Browning, James F.; Rankin, Stephen E.

2016-11-03

Here, the incorporation of hole conducting polymer poly(3-hexyl thiophene) (P3HT) into the 8-9 nm cylindrical nanopores of titania is investigated using films with a unique orthogonally oriented hexagonal close packed mesostructure. The films are synthesized using evaporation induced self-assembly (EISA) with Pluronic triblock copolymer F127 as the structure directing agent. The orthogonally oriented cylindrical nanopore structure was chosen over a cubic structure because confinement in uniform cylindrical channels is hypothesized to enhance hole conductivity of P3HT by inducing local polymer chain ordering. Orthogonal orientation of the cylindrical nanopores is achieved by modifying the substrate (FTO-coated glass slides) with crosslinked F127.more » After thermal treatment to remove organic templates from the films, P3HT is infiltrated into the nanopores by spin coating a 1 wt% P3HT solution in chlorobenzene onto the titania films followed by thermal annealing under vacuum at 200 °C. The results show that infiltration is essentially complete after 30 minutes of annealing, with little or no further infiltration thereafter. A final infiltration depth of ~14 nm is measured for P3HT into the nanopores of titania using neutron reflectometry measurements. Photoluminescence measurements demonstrate that charge transfer at the P3HT-TiO 2 interface improves as the P3HT is infiltrated into the pores, suggesting that an active organic-inorganic heterojuction is formed in the materials.« less

Incorporating poly(3-hexyl thiophene) into orthogonally aligned cylindrical nanopores of titania for optoelectronics

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

Nagpure, Suraj; Browning, James F.; Rankin, Stephen E.

Here, the incorporation of hole conducting polymer poly(3-hexyl thiophene) (P3HT) into the 8-9 nm cylindrical nanopores of titania is investigated using films with a unique orthogonally oriented hexagonal close packed mesostructure. The films are synthesized using evaporation induced self-assembly (EISA) with Pluronic triblock copolymer F127 as the structure directing agent. The orthogonally oriented cylindrical nanopore structure was chosen over a cubic structure because confinement in uniform cylindrical channels is hypothesized to enhance hole conductivity of P3HT by inducing local polymer chain ordering. Orthogonal orientation of the cylindrical nanopores is achieved by modifying the substrate (FTO-coated glass slides) with crosslinked F127.more » After thermal treatment to remove organic templates from the films, P3HT is infiltrated into the nanopores by spin coating a 1 wt% P3HT solution in chlorobenzene onto the titania films followed by thermal annealing under vacuum at 200 °C. The results show that infiltration is essentially complete after 30 minutes of annealing, with little or no further infiltration thereafter. A final infiltration depth of ~14 nm is measured for P3HT into the nanopores of titania using neutron reflectometry measurements. Photoluminescence measurements demonstrate that charge transfer at the P3HT-TiO 2 interface improves as the P3HT is infiltrated into the pores, suggesting that an active organic-inorganic heterojuction is formed in the materials.« less

Nanoporous carbon derived from agro-waste pineapple leaves for supercapacitor electrode

NASA Astrophysics Data System (ADS)

Sodtipinta, Jedsada; Amornsakchai, Taweechai; Pakawatpanurut, Pasit

2017-09-01

By using KOH as the chemical activating agent in the synthesis, the activated carbon derived from pineapple leaf fiber (PALF) was prepared. The structure, morphology, and the surface functional groups of the as-prepared activated carbon were investigated using x-ray diffraction, field emission scanning electron microscope equipped with energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. The electrochemical behavior and performance of the as-synthesized activated carbon electrode were measured using the cyclic voltammetry and the electrochemical impedance spectroscopy in 1 M Na2SO4 electrolyte solution in three-electrode setup. The activated carbon electrode exhibited the specific capacitance of 131.3 F g-1 at a scan rate of 5 mV s-1 with excellent cycling stability. The capacitance retention after 1000 cycles was about 97% of the initial capacitance at a scan rate of 30 mV s-1. Given these good electrochemical properties along with the high abundance of PALF, this activated carbon electrode has the potential to be one of the materials for future large-scale production of the electrochemical capacitors. Invited talk at 5th Thailand International Nanotechnology Conference (Nano Thailand-2016), 27-29 November 2016, Nakhon Ratchasima, Thailand.

Tunable Impedance Spectroscopy Sensors via Selective Nanoporous Materials.

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

Nenoff, Tina M.; Small, Leo J

Impedance spectroscopy was leveraged to directly detect the sorption of I 2 by selective adsorption into nanoporous metal organic frameworks (MOF). Films of three different types of MOF frameworks, respectively, were drop cast onto platinum interdigitated electrodes, dried, and exposed to gaseous I 2 at 25, 40, or 70 C. The MOF frameworks varied in topology from small pores (equivalent to I 2 diameter) to large pore frameworks. The combination of the chemistry of the framework and pore size dictated quantity and kinetics of I 2 adsorption. Air, argon, methanol, and water were found to produce minimal changes in ZIF-8more » impedance. Independent of MOF framework characteristics, all resultant sensors showed high response to I 2 in air. As an example of sensor output, I 2 was readily detected at 25 C in air within 720 s of exposure, using an un-optimized sensor geometry with a small pored MOF. Further optimization of sensor geometry, decreasing MOF film thicknesses and maximizing sensor capacitance, will enable faster detection of trace I 2 .« less

Nanopore fabricated in pyramidal HfO2 film by dielectric breakdown method

NASA Astrophysics Data System (ADS)

Wang, Yifan; Chen, Qi; Deng, Tao; Liu, Zewen

2017-10-01

The dielectric breakdown method provides an innovative solution to fabricate solid-state nanopores on insulating films. A nanopore generation event via this method is considered to be caused by random charged traps (i.e., structural defects) and high electric fields in the membrane. Thus, the position and number of nanopores on planar films prepared by the dielectric breakdown method is hard to control. In this paper, we propose to fabricate nanopores on pyramidal HfO2 films (10-nm and 15-nm-thick) to improve the ability to control the location and number during the fabrication process. Since the electric field intensity gets enhanced at the corners of the pyramid-shaped film, the probability of nanopore occurrence at vertex and edge areas increases. This priority of appearance provides us chance to control the location and number of nanopores by monitoring a sudden irreversible discrete increase in current. The experimental results showed that the probability of nanopore occurrence decreases in an order from the vertex area, the edge area to the side face area. The sizes of nanopores ranging from 30 nm to 10 nm were obtained. Nanopores fabricated on the pyramid-shaped HfO2 film also showed an obvious ion current rectification characteristic, which might improve the nanopore performance as a biomolecule sequencing platform.

Probing the size of proteins with glass nanopores

NASA Astrophysics Data System (ADS)

Steinbock, L. J.; Krishnan, S.; Bulushev, R. D.; Borgeaud, S.; Blokesch, M.; Feletti, L.; Radenovic, A.

2014-11-01

Single molecule studies using nanopores have gained attention due to the ability to sense single molecules in aqueous solution without the need to label them. In this study, short DNA molecules and proteins were detected with glass nanopores, whose sensitivity was enhanced by electron reshaping which decreased the nanopore diameter and created geometries with a reduced sensing length. Further, proteins having molecular weights (MW) ranging from 12 kDa to 480 kDa were detected, which showed that their corresponding current peak amplitude changes according to their MW. In the case of the 12 kDa ComEA protein, its DNA-binding properties to an 800 bp long DNA molecule was investigated. Moreover, the influence of the pH on the charge of the protein was demonstrated by showing a change in the translocation direction. This work emphasizes the wide spectrum of detectable molecules using nanopores from glass nanocapillaries, which stand out because of their inexpensive, lithography-free, and rapid manufacturing process.Single molecule studies using nanopores have gained attention due to the ability to sense single molecules in aqueous solution without the need to label them. In this study, short DNA molecules and proteins were detected with glass nanopores, whose sensitivity was enhanced by electron reshaping which decreased the nanopore diameter and created geometries with a reduced sensing length. Further, proteins having molecular weights (MW) ranging from 12 kDa to 480 kDa were detected, which showed that their corresponding current peak amplitude changes according to their MW. In the case of the 12 kDa ComEA protein, its DNA-binding properties to an 800 bp long DNA molecule was investigated. Moreover, the influence of the pH on the charge of the protein was demonstrated by showing a change in the translocation direction. This work emphasizes the wide spectrum of detectable molecules using nanopores from glass nanocapillaries, which stand out because of their

Oxygen Reduction at Very Low Overpotential on Nanoporous Ag Catalysts

DOE PAGES

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

2015-05-07

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

Recent patents of nanopore DNA sequencing technology: progress and challenges.

PubMed

Zhou, Jianfeng; Xu, Bingqian

2010-11-01

DNA sequencing techniques witnessed fast development in the last decades, primarily driven by the Human Genome Project. Among the proposed new techniques, Nanopore was considered as a suitable candidate for the single DNA sequencing with ultrahigh speed and very low cost. Several fabrication and modification techniques have been developed to produce robust and well-defined nanopore devices. Many efforts have also been done to apply nanopore to analyze the properties of DNA molecules. By comparing with traditional sequencing techniques, nanopore has demonstrated its distinctive superiorities in main practical issues, such as sample preparation, sequencing speed, cost-effective and read-length. Although challenges still remain, recent researches in improving the capabilities of nanopore have shed a light to achieve its ultimate goal: Sequence individual DNA strand at single nucleotide level. This patent review briefly highlights recent developments and technological achievements for DNA analysis and sequencing at single molecule level, focusing on nanopore based methods.

Impedance nanopore biosensor: influence of pore dimensions on biosensing performance.

PubMed

Kant, Krishna; Yu, Jingxian; Priest, Craig; Shapter, Joe G; Losic, Dusan

2014-03-07

Knowledge about electrochemical and electrical properties of nanopore structures and the influence of pore dimensions on these properties is important for the development of nanopore biosensing devices. The aim of this study was to explore the influence of nanopore dimensions (diameter and length) on biosensing performance using non-faradic electrochemical impedance spectroscopy (EIS). Nanoporous alumina membranes (NPAMs) prepared by self-ordered electrochemical anodization of aluminium were used as model nanopore sensing platforms. NPAMs with different pore diameters (25-65 nm) and lengths (4-18 μm) were prepared and the internal pore surface chemistry was modified by covalently attaching streptavidin and biotin. The performance of this antibody nanopore biosensing platform was evaluated using various concentrations of biotin as a model analyte. EIS measurements of pore resistivity and conductivity were carried out for pores with different diameters and lengths. The results showed that smaller pore dimensions of 25 nm and pore lengths up to 10 μm provide better biosensing performance.

Nanoporous Ag prepared from the melt-spun Cu-Ag alloys

NASA Astrophysics Data System (ADS)

Li, Guijing; Song, Xiaoping; Sun, Zhanbo; Yang, Shengchun; Ding, Bingjun; Yang, Sen; Yang, Zhimao; Wang, Fei

2011-07-01

Nanoporous Ag ribbons with different morphology and porosity were achieved by the electrochemical corrosion of the melt-spun Cu-Ag alloys. The Cu-rich phase in the alloys was removed, resulting in the formation of the nanopores distributed across the whole ribbon. It is found that the structures, morphology and porosity of the nanoporous Ag ribbons were dependent on the microstructures of the parent alloys. The most of ligaments presented a rod-like shape due to the formation of pseudoeutectic microstructure in the melt-spun Cu 55Ag 45 and Cu 70Ag 30 alloys. For nanoporous Ag prepared from Cu 85Ag 15 alloys, the ligaments were camber-like because of the appearance of the divorced microstructures. Especially, a novel bamboo-grove-like structure could be observed at the cross-section of the nanoporous Ag ribbons. The experiment reveals that nanoporous Ag ribbons exhibited excellent enhancement of surface-enhanced Raman scattering (SERS) effect, but a slight difference existed due to the discrepancy of their morphology.

Multifunctional carbon nanoelectrodes fabricated by focused ion beam milling.

PubMed

Thakar, Rahul; Weber, Anna E; Morris, Celeste A; Baker, Lane A

2013-10-21

We report a strategy for fabrication of sub-micron, multifunctional carbon electrodes and application of these electrodes as probes for scanning electrochemical microscopy (SECM) and scanning ion conductance microscopy (SICM). The fabrication process utilized chemical vapor deposition of parylene, followed by thermal pyrolysis to form conductive carbon and then further deposition of parylene to form an insulation layer. To achieve well-defined electrode geometries, two methods of electrode exposure were utilized. In the first method, carbon probes were masked in polydimethylsiloxane (PDMS) to obtain a cone-shaped electrode. In the second method, the electrode area was exposed via milling with a focused ion beam (FIB) to reveal a carbon ring electrode, carbon ring/platinum disk electrode, or carbon ring/nanopore electrode. Carbon electrodes were batch fabricated (~35/batch) through the vapor deposition process and were characterized with scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), and cyclic voltammetry (CV) measurements. Additionally, Raman spectroscopy was utilized to examine the effects of Ga(+) ion implantation, a result of FIB milling. Constant-height, feedback mode SECM was performed with conical carbon electrodes and carbon ring electrodes. We demonstrate the utility of carbon ring/nanopore electrodes with SECM-SICM to simultaneously collect topography, ion current and electrochemical current images. In addition, carbon ring/nanopore electrodes were utilized in substrate generation/tip collection (SG/TC) SECM. In SG/TC SECM, localized delivery of redox molecules affords a higher resolution, than when the redox molecules are present in the bath solution. Multifunctional geometries of carbon electrode probes will find utility in electroanalytical applications, in general, and more specifically with electrochemical microscopy as discussed herein.

The role of nanopore shape in surface-induced crystallization

NASA Astrophysics Data System (ADS)

Diao, Ying; Harada, Takuya; Myerson, Allan S.; Alan Hatton, T.; Trout, Bernhardt L.

2011-11-01

Crystallization of a molecular liquid from solution often initiates at solid-liquid interfaces, and nucleation rates are generally believed to be enhanced by surface roughness. Here we show that, on a rough surface, the shape of surface nanopores can also alter nucleation kinetics. Using lithographic methods, we patterned polymer films with nanopores of various shapes and found that spherical nanopores 15-120 nm in diameter hindered nucleation of aspirin crystals, whereas angular nanopores of the same size promoted it. We also show that favourable surface-solute interactions are required for angular nanopores to promote nucleation, and propose that pore shape affects nucleation kinetics through the alteration of the orientational order of the crystallizing molecule near the angles of the pores. Our findings have clear technological implications, for instance in the control of pharmaceutical polymorphism and in the design of ‘seed’ particles for the regulation of crystallization of fine chemicals.

Porous MnCo2O4 as superior anode material over MnCo2O4 nanoparticles for rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Baji, Dona Susan; Jadhav, Harsharaj S.; Nair, Shantikumar V.; Rai, Alok Kumar

2018-06-01

Pyro synthesis is a method to coat nanoparticles by uniform layer of carbon without using any conventional carbon source. The resultant carbon coating can be evaporated in the form of CO or CO2 at high temperature with the creation of large number of nanopores on the sample surface. Hence, a porous MnCo2O4 is successfully synthesized here with the same above strategy. It is believed that the electrolyte can easily permeate through these nanopores into the bulk of the sample and allow rapid access of Li+ ions during charge/discharge cycling. In order to compare the superiority of the porous sample synthesized by pyro synthesis method, MnCo2O4 nanoparticles are also synthesized by sol-gel synthesis method at the same parameters. When tested as anode materials for lithium ion battery application, porous MnCo2O4 electrode shows high capacity with long lifespan at all the investigated current rates in comparison to MnCo2O4 nanoparticles electrode.

Formation and photopatterning of nanoporous titania thin films

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

Park, Oun-Ho; Cheng, Joy Y.; Kim, Hyun Suk

2007-06-04

Photopatternable nanoporous titania thin films were generated from mixtures of an organic diblock copolymer, poly(styrene-b-ethylene oxide) (PS-b-PEO), and an oligomeric titanate (OT) prepared from a chelated titanium isopropoxide. The PS-b-PEO templates well-defined microdomains in thin films of the mixtures, which upon thermal treatment at 450 deg. C, become nanopores in titania. Average pore size and porosity are controlled by the molecular weight and loading level of the PS-b-PEO, respectively. Patterns of nanoporous titania were created by selectively exposing UV light on the mixture films. The UV irradiation destroys the chelating bond and induces the cross-linking reaction of the OT. Subsequentmore » wet development followed by thermal treatment gives patterned nanoporous films of anatase phase titania.« less

Effect of Interface Structure on Mechanical Properties of Advanced Composite Materials

PubMed Central

Gan, Yong X.

2009-01-01

This paper deals with the effect of interface structures on the mechanical properties of fiber reinforced composite materials. First, the background of research, development and applications on hybrid composite materials is introduced. Second, metal/polymer composite bonded structures are discussed. Then, the rationale is given for nanostructuring the interface in composite materials and structures by introducing nanoscale features such as nanopores and nanofibers. The effects of modifying matrices and nano-architecturing interfaces on the mechanical properties of nanocomposite materials are examined. A nonlinear damage model for characterizing the deformation behavior of polymeric nanocomposites is presented and the application of this model to carbon nanotube-reinforced and reactive graphite nanotube-reinforced epoxy composite materials is shown. PMID:20054466

Study of polymer molecules and conformations with a nanopore

DOEpatents

Golovchenko, Jene A.; Li, Jiali; Stein, Derek; Gershow, Marc H.

2013-03-12

The invention features methods for evaluating the conformation of a polymer, for example, for determining the conformational distribution of a plurality of polymers and to detect binding or denaturation events. The methods employ a nanopore which the polymer, e.g., a nucleic acid, traverses. As the polymer traverses the nanopore, measurements of transport properties of the nanopore yield data on the conformation of the polymer.

Study of polymer molecules and conformations with a nanopore

DOEpatents

Golovchenko, Jene A.; Li, Jiali; Stein, Derek; Gershow, Marc H.

2010-12-07

The invention features methods for evaluating the conformation of a polymer, for example, for determining the conformational distribution of a plurality of polymers and to detect binding or denaturation events. The methods employ a nanopore which the polymer, e.g., a nucleic acid, traverses. As the polymer traverses the nanopore, measurements of transport properties of the nanopore yield data on the conformation of the polymer.

Study of polymer molecules and conformations with a nanopore

DOEpatents

Golovchenko, Jene A; Li, Jiali; Stein, Derek; Gershow, Marc H

2015-03-03

The invention features methods for evaluating the conformation of a polymer, for example, for determining the conformational distribution of a plurality of polymers and to detect binding or denaturation events. The methods employ a nanopore which the polymer, e.g., a nucleic acid, traverses. As the polymer traverses the nanopore, measurements of transport properties of the nanopore yield data on the conformation of the polymer.

Embedded CMOS basecalling for nanopore DNA sequencing.

PubMed

Chengjie Wang; Junli Zheng; Magierowski, Sebastian; Ghafar-Zadeh, Ebrahim

2016-08-01

DNA sequencing based on nanopore sensors is now entering the marketplace. The ability to interface this technology to established CMOS microelectronics promises significant improvements in functionality and miniaturization. Among the key functions to benefit from this interface will be basecalling, the conversion of raw electronic molecular signatures to nucleotide sequence predictions. This paper presents the design and performance potential of custom CMOS base-callers embedded alongside nanopore sensors. A basecalliing architecture implemented in 32-nm technology is discussed with the ability to process the equivalent of 20 human genomes per day in real-time at a power density of 5 W/cm2 assuming a 3-mer nanopore sensor.

Modulation of Molecular Flux Using a Graphene Nanopore Capacitor.

PubMed

Shankla, Manish; Aksimentiev, Aleksei

2017-04-20

Modulation of ionic current flowing through nanoscale pores is one of the fundamental biological processes. Inspired by nature, nanopores in synthetic solid-state membranes are being developed to enable rapid analysis of biological macromolecules and to serve as elements of nanofludic circuits. Here, we theoretically investigate ion and water transport through a graphene-insulator-graphene membrane containing a single, electrolyte-filled nanopore. By means of all-atom molecular dynamics simulations, we show that the charge state of such a graphene nanopore capacitor can regulate both the selectivity and the magnitude of the nanopore ionic current. At a fixed transmembrane bias, the ionic current can be switched from being carried by an equal mixture of cations and anions to being carried almost exclusively by either cationic or anionic species, depending on the sign of the charge assigned to both plates of the capacitor. Assigning the plates of the capacitor opposite sign charges can either increase the nanopore current or reduce it substantially, depending on the polarity of the bias driving the transmembrane current. Facilitated by the changes of the nanopore surface charge, such ionic current modulations are found to occur despite the physical dimensions of the nanopore being an order of magnitude larger than the screening length of the electrolyte. The ionic current rectification is accompanied by a pronounced electro-osmotic effect that can transport neutral molecules such as proteins and drugs across the solid-state membrane and thereby serve as an interface between electronic and chemical signals.

Anti-reflective nanoporous silicon for efficient hydrogen production

DOEpatents

Oh, Jihun; Branz, Howard M

2014-05-20

Exemplary embodiments are disclosed of anti-reflective nanoporous silicon for efficient hydrogen production by photoelectrolysis of water. A nanoporous black Si is disclosed as an efficient photocathode for H.sub.2 production from water splitting half-reaction.

Balancing size exclusion and adsorption of polymers in nanopores

NASA Astrophysics Data System (ADS)

Kim, Won; Ryu, Chang Y.

2006-03-01

The liquid chromatography at critical condition (LCCC) presents the condition, at which the size exclusion and adsorption of polymer chains are balanced upon interactions with nanoporous substrates. In this study, we investigate how the polymer interactions with nanopores are affected by the solvent quality and nanopore size. Specifically, we measure the retention times of monodisperse polystyrenes in C18-bonded nanoporous silica column as a function of molecular weight, when a mixed solvent of methylene chloride and acetonitrile are used as elutent. C18-bonded silica particles with 70, 100, and 250 A pore size are used as a stationary phase to study how the transition from SEC-like to IC-like retention behavior depends on the condition of temperature and solvent composition. To locate the LCCC at various nanopore sizes, the temperature and solvent composition have been varied from 0 to 60 C and from 51 to 62 v/v% of methylene chloride, respectively.

Integrated nanopore sensing platform with sub-microsecond temporal resolution

PubMed Central

Rosenstein, Jacob K; Wanunu, Meni; Merchant, Christopher A; Drndic, Marija; Shepard, Kenneth L

2012-01-01

Nanopore sensors have attracted considerable interest for high-throughput sensing of individual nucleic acids and proteins without the need for chemical labels or complex optics. A prevailing problem in nanopore applications is that the transport kinetics of single biomolecules are often faster than the measurement time resolution. Methods to slow down biomolecular transport can be troublesome and are at odds with the natural goal of high-throughput sensing. Here we introduce a low-noise measurement platform that integrates a complementary metal-oxide semiconductor (CMOS) preamplifier with solid-state nanopores in thin silicon nitride membranes. With this platform we achieved a signal-to-noise ratio exceeding five at a bandwidth of 1 MHz, which to our knowledge is the highest bandwidth nanopore recording to date. We demonstrate transient signals as brief as 1 μs from short DNA molecules as well as current signatures during molecular passage events that shed light on submolecular DNA configurations in small nanopores. PMID:22426489

Capacitance of Nanoporous Carbon-Based Supercapacitors Is a Trade-Off between the Concentration and the Separability of the Ions.

PubMed

Burt, Ryan; Breitsprecher, Konrad; Daffos, Barbara; Taberna, Pierre-Louis; Simon, Patrice; Birkett, Greg; Zhao, X S; Holm, Christian; Salanne, Mathieu

2016-10-06

Nanoporous carbon-based supercapacitors store electricity through adsorption of ions from the electrolyte at the surface of the electrodes. Room temperature ionic liquids, which show the largest ion concentrations among organic liquid electrolytes, should in principle yield larger capacitances. Here, we show by using electrochemical measurements that the capacitance is not significantly affected when switching from a pure ionic liquid to a conventional organic electrolyte using the same ionic species. By performing additional molecular dynamics simulations, we interpret this result as an increasing difficulty of separating ions of opposite charges when they are more concentrated, that is, in the absence of a solvent that screens the Coulombic interactions. The charging mechanism consistently changes with ion concentration, switching from counterion adsorption in the diluted organic electrolyte to ion exchange in the pure ionic liquid. Contrarily to the capacitance, in-pore diffusion coefficients largely depend on the composition, with a noticeable slowing of the dynamics in the pure ionic liquid.

Relationship between pore size and reversible and irreversible immobilization of ionic liquid electrolytes in porous carbon under applied electric potential

DOE PAGES

Mahurin, Shannon M.; Mamontov, Eugene; Thompson, Matthew W.; ...

2016-10-04

Transport of electrolytes in nanoporous carbon-based electrodes largely defines the function and performance of energy storage devices. Here, using molecular dynamics simulation and quasielastic neutron scattering, we investigate the microscopic dynamics of a prototypical ionic liquid electrolyte, [emim][Tf 2N], under applied electric potential in carbon materials with 6.7 nm and 1.5 nm pores. The simulations demonstrate the formation of dense layers of counter-ions near the charged surfaces, which is reversible when the polarity is reversed. In the experiment, the ions immobilized near the surface manifest themselves in the elastic scattering signal. The experimentally observed ion immobilization near the wall ismore » fully reversible as a function of the applied electric potential in the 6.7 nm, but not in the 1.5 nm nanopores. In the latter case, remarkably, the first application of the electric potential leads to apparently irreversible immobilization of cations or anions, depending on the polarity, near the carbon pore walls. This unexpectedly demonstrates that in carbon electrode materials with the small pores, which are optimal for energy storage applications, the polarity of the electrical potential applied for the first time after the introduction of an ionic liquid electrolyte may define the decoration of the small pore walls with ions for prolonged periods of time and possibly for the lifetime of the electrode.« less

Significant Effect of Pore Sizes on Energy Storage in Nanoporous Carbon Supercapacitors.

PubMed

Young, Christine; Lin, Jianjian; Wang, Jie; Ding, Bing; Zhang, Xiaogang; Alshehri, Saad M; Ahamad, Tansir; Salunkhe, Rahul R; Hossain, Shahriar A; Khan, Junayet Hossain; Ide, Yusuke; Kim, Jeonghun; Henzie, Joel; Wu, Kevin C-W; Kobayashi, Naoya; Yamauchi, Yusuke

2018-04-20

Mesoporous carbon can be synthesized with good control of surface area, pore-size distribution, and porous architecture. Although the relationship between porosity and supercapacitor performance is well known, there are no thorough reports that compare the performance of numerous types of carbon samples side by side. In this manuscript, we describe the performance of 13 porous carbon samples in supercapacitor devices. We suggest that there is a "critical pore size" at which guest molecules can pass through the pores effectively. In this context, the specific surface area (SSA) and pore-size distribution (PSD) are used to show the point at which the pore size crosses the threshold of critical size. These measurements provide a guide for the development of new kinds of carbon materials for supercapacitor devices. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Removal of nano and microparticles by granular filter media coated with nanoporous aluminium oxide.

PubMed

Lau, B L T; Harrington, G W; Anderson, M A; Tejedor, I

2004-01-01

Conventional filtration was designed to achieve high levels of particle and pathogen removal. Previous studies have examined the possibility of modifying filtration media to improve their ability to remove microorganisms and viruses. Although these studies have evaluated filter media coatings for this purpose, none have evaluated nanoscale particle suspensions as coating materials. The overall goal of this paper is to describe the preliminary test results of nanoporous aluminium oxide coated media that can be used to enhance filtration of nano and microparticles. Filtration tests were carried out using columns packed with uncoated and coated forms of granular anthracite or granular activated carbon. A positive correlation between isoelectric pH of filter media and particle removal was observed. The modified filter media with a higher isoelectric pH facilitated better removal of bacteriophage MS2 and 3 microm latex microspheres, possibly due to increased favorable electrostatic interactions.

Single Protein Structural Analysis with a Solid-state Nanopore Sensor

NASA Astrophysics Data System (ADS)

Li, Jiali; Golovchenko, Jene; McNabb, David

2005-03-01

We report on the use of solid-state nanopore sensors to detect single polypeptides. These solid-state nanopores are fabricated in thin membranes of silicon nitride by ion beam sculpting...[1]. When an electrically biased nanopore is exposed to denatured proteins in ionic solution, discrete transient electronic signals: current blockages are observed. We demonstrate examples of such transient electronic signals for Bovine Serum Albumin (BSA) and human placental laminin M proteins in Guanidine hydrochloride solution, which suggest that these polypeptides are individually translocating through the nanopore during the detecting process. The amplitude of the current blockages is proportional to the bias voltage. No transient current blockages are observed when proteins are not present in the solution. To probe protein-folding state, pH and temperature dependence experiments are performed. The results demonstrate a solid-state nanopore sensor can be used to detect and analyze single polypeptide chains. Similarities and differences with signals obtained from double stranded DNA in a solid-state nanopore and single stranded DNA in a biological nanopore are discussed. [.1] Li, J., D. Stein, C. McMullan, D. Branton, M.J. Aziz, and J.A. Golovchenko, Ion-beam sculpting at nanometre length scales. Nature, 2001. 412(12 July): p. 166-169.

Nanoporous Pirani sensor based on anodic aluminum oxide

NASA Astrophysics Data System (ADS)

Jeon, Gwang-Jae; Kim, Woo Young; Shim, Hyun Bin; Lee, Hee Chul

2016-09-01

A nanoporous Pirani sensor based on anodic aluminum oxide (AAO) is proposed, and the quantitative relationship between the performance of the sensor and the porosity of the AAO membrane is characterized with a theoretical model. The proposed Pirani sensor is composed of a metallic resistor on a suspended nanoporous membrane, which simultaneously serves as the sensing area and the supporting structure. The AAO membrane has numerous vertically-tufted nanopores, resulting in a lower measurable pressure limit due to both the increased effective sensing area and the decreased effective thermal loss through the supporting structure. Additionally, the suspended AAO membrane structure, with its outer periphery anchored to the substrate, known as a closed-type design, is demonstrated using nanopores of AAO as an etch hole without a bulk micromachining process used on the substrate. In a CMOS-compatible process, a 200 μm × 200 μm nanoporous Pirani sensor with porosity of 25% was capable of measuring the pressure from 0.1 mTorr to 760 Torr. With adjustment of the porosity of the AAO, the measurable range could be extended toward lower pressures of more than one decade compared to a non-porous membrane with an identical footprint.

Lead carbonate scintillator materials

DOEpatents

Derenzo, Stephen E.; Moses, William W.

1991-01-01

Improved radiation detectors containing lead carbonate or basic lead carbonate as the scintillator element are disclosed. Both of these scintillators have been found to provide a balance of good stopping power, high light yield and short decay constant that is superior to other known scintillator materials. The radiation detectors disclosed are favorably suited for use in general purpose detection and in medical uses.

The Utility of Nanopore Technology for Protein and Peptide Sensing.

PubMed

Robertson, Joseph W F; Reiner, Joseph E

2018-06-28

Resistive-pulse nanopore sensing enables label-free single-molecule analysis of a wide range of analytes. An increasing number of studies have demonstrated the feasibility and usefulness of nanopore sensing for protein and peptide characterization. Nanopores offer the potential to study a variety of protein-related phenomena that includes unfolding kinetics, differences in unfolding pathways, protein structure stability and free energy profiles of DNA-protein and RNA-protein binding. In addition to providing a tool for fundamental protein characterization, nanopores have also been used as highly selective protein detectors in various solution mixtures and conditions. This review highlights these and other developments in the area of nanopore-based protein and peptide detection. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Preparation and electrochemical performances of nanoporous/cracked cobalt oxide layer for supercapacitors

NASA Astrophysics Data System (ADS)

Gobal, Fereydoon; Faraji, Masoud

2014-12-01

Nanoporous/cracked structures of cobalt oxide (Co3O4) electrodes were successfully fabricated by electroplating of zinc-cobalt onto previously formed TiO2 nanotubes by anodizing of titanium, leaching of zinc in a concentrated alkaline solution and followed by drying and annealing at 400 °C. The structure and morphology of the obtained Co3O4 electrodes were characterized by X-ray diffraction, EDX analysis and scanning electron microscopy. The results showed that the obtained Co3O4 electrodes were composed of the nanoporous/cracked structures with an average pore size of about 100 nm. The electrochemical capacitive behaviors of the nanoporous Co3O4 electrodes were investigated by cyclic voltammetry, galvanostatic charge-discharge studies and electrochemical impedance spectroscopy in 1 M NaOH solution. The electrochemical data demonstrated that the electrodes display good capacitive behavior with a specific capacitance of 430 F g-1 at a current density of 1.0 A g-1 and specific capacitance retention of ca. 80 % after 10 days of being used in electrochemical experiments, indicating to be promising electroactive materials for supercapacitors. Furthermore, in comparison with electrodes prepared by simple cathodic deposition of cobalt onto TiO2 nanotubes(without dealloying procedure), the impedance studies showed improved performances likely due to nanoporous/cracked structures of electrodes fabricated by dealloying of zinc, which provide fast ion and electron transfer routes and large reaction surface area with the ensued fast reaction kinetics.

Nanopores and nucleic acids: prospects for ultrarapid sequencing

NASA Technical Reports Server (NTRS)

Deamer, D. W.; Akeson, M.

2000-01-01

DNA and RNA molecules can be detected as they are driven through a nanopore by an applied electric field at rates ranging from several hundred microseconds to a few milliseconds per molecule. The nanopore can rapidly discriminate between pyrimidine and purine segments along a single-stranded nucleic acid molecule. Nanopore detection and characterization of single molecules represents a new method for directly reading information encoded in linear polymers. If single-nucleotide resolution can be achieved, it is possible that nucleic acid sequences can be determined at rates exceeding a thousand bases per second.

Carbon Fiber Reinforced Carbon-Al-Cu Composite for Friction Material.

PubMed

Cui, Lihui; Luo, Ruiying; Ma, Denghao

2018-03-31

A carbon/carbon-Al-Cu composite reinforced with carbon fiber 2.5D-polyacrylonitrile-based preforms was fabricated using the pressureless infiltration technique. The Al-Cu alloy liquids were successfully infiltrated into the C/C composites at high temperature and under vacuum. The mechanical and metallographic properties, scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive spectroscopy (EDS) of the C/C-Al-Cu composites were analyzed. The results showed that the bending property of the C/C-Al-Cu composites was 189 MPa, whereas that of the pure carbon slide material was only 85 MPa. The compressive strength of C/C-Al-Cu was 213 MPa, whereas that of the pure carbon slide material was only 102 MPa. The resistivity of C/C-Al-Cu was only 1.94 μΩm, which was lower than that of the pure carbon slide material (29.5 μΩm). This finding can be attributed to the "network conduction" structure. Excellent wettability was observed between Al and the carbon matrix at high temperature due to the existence of Al₄C₃. The friction coefficients of the C/C, C/C-Al-Cu, and pure carbon slide composites were 0.152, 0.175, and 0.121, respectively. The wear rate of the C/C-Al-Cu composites reached a minimum value of 2.56 × 10 -7 mm³/Nm. The C/C-Al-Cu composite can be appropriately used as railway current collectors for locomotives.

Facile preparation of porous carbon from coffee bean waste using low temperature solvothermal method

NASA Astrophysics Data System (ADS)