Video Processing Electrophoretic Measurements under High Electric Fields for Sub-millimeter Particles in Oil.

Electrokinetic properties such as the mobility, surface charge, and zeta potential of sub-millimeter particles are vital parameters in various industrial applications. Their measurement and control in aqueous media have been extensively studied. However, despite their growing importance, the electrokinetic properties of organic solvents have not been studied as thoroughly as those of aqueous media. An electrophoresis cell with a microscope monitor was designed for the electrokinetic studies of sub-millimeter particles in cyclohexane, which is a solvent with very low permittivity. The movement of large particles in the range of 4 ~ 478 µm was successfully traced under a strong electric voltage up to 1100 V, even without the addition of surfactants. The particle sizes were at least 300 times larger than those reported previously. By applying electric fields up to 55 kV/m, the electrophoretic mobilities were measured to be of the order of 10-9 to 10-7 m2/V∙s through image processing of the recorded particle movement. Five organic sub-millimeter particles had charge densities in the range of -3.5 ~ 4.4 e/µm2, and polyethersulfone particles showed extremely high mobilities. The surface charge of organic and inorganic particles is mainly generated by the dissociation of hydroxide groups or by the protonation to surface Lewis base oxygen atoms.

Tailoring the Structure of Chitosan-Based Porous Carbon Nanofiber Architectures toward Efficient Capacitive Charge Storage and Capacitive Deionization.

Carbon nanoarchitectures derived from biobased building blocks are potential sustainable alternatives to electrode materials generated with petroleum-derived resources. We aim at developing a fundamental understanding on the connection between the structure and electrochemical performance of porous carbon nanofiber (PCNF) architectures from the polysaccharide chitosan as a biobased building block. We fabricated a range of PCNF architectures from the chitosan carbon precursor and tailored their structure by varying the amount and molecular weight of the sacrificial pore-forming polymer poly(ethylene oxide). The morphology (high-resolution scanning electron microscopy), carbon structure (X-ray diffraction, transmission electron microscopy), pore network (N2 gas adsorption, small-angle X-ray scattering), and surface/bulk composition (X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy) were studied in detail together with a comprehensive electrochemical analysis on the fabricated electrodes. In supercapacitor devices, the best-performing freestanding electrode had (1) a high accessible surface area (as,BET ≈ 700 m2 g-1) and hierarchical pore network (micro- and mesopores) providing a fast ion diffusion process, high specific capacitance, and rate capability, (2) surface chemistry allowing a high Coulombic efficiency by avoiding parasitic Faradaic side reactions, and (3) a unique turbostratic carbon nanostructure leading to low charge transfer resistance while keeping good electrical conductivity. This electrode exhibited good stability over 2000 cycles (at 2 A g-1) with high capacitance retention (>80%) and charge efficiency (>90%). In the capacitive deionization (CDI) device, our electrode demonstrated an ultrahigh salt adsorption capacity of 23.6 mg g-1, which is among the state-of-the-art values reported for a biobased carbon. A high charge efficiency (85%) was achieved during the CDI process using low-cost materials, in contrast to similarly performing devices fabricated with expensive ion exchange membranes or petroleum-based carbon precursors. Our results demonstrate that inexpensive chitosan-based materials can be readily transformed in one carbonization step without any aggressive activating chemicals into tailor-made hierarchically ordered state-of-the-art carbon materials for charge storage devices.

Ultrafine self-N-doped porous carbon nanofibers with hierarchical pore structure utilizing a biobased chitosan precursor.

Ultrafine porous carbon nanofiber network with ~40 nm fiber diameter is realized for the first time utilizing a biobased polymer as carbon precursor. A simple one-step carbonization procedure is applied to convert the electrospun chitosan/poly(ethylene oxide) nanofibers to self-N-doped ultrafine hierarchically porous carbon nanofiber interconnected web. The pore formation process is governed by the immiscible nature of the two polymers and the sacrificial character of poly(ethylene oxide) with low carbon yield at the carbonization temperature (800 °C). The obtained porous scaffold has a high specific surface area (564 m2 g-1), high micro (0.22 cm3 g-1) as well as meso/macropore volume (0.28 cm3 g-1). Structural analysis indicates high graphitic content and the existence of turbostratic carbon typical for carbon fibers derived from otherwise synthetic polymer precursors. X-ray photoelectron spectroscopy confirms the presence of an N-doped structure with dominating graphitic N, together with a smaller amount of pyridinic N. The prepared electrode exhibits good electrochemical performance as a supercapacitor device. The excellent charge storage characteristics are attributed to the unique ultrafine hierarchical nanoarchitecture and the interconnected N-doped carbon structure. This green material holds great promise for the realization of more sustainable high-performance energy storage devices.

Adsorption Properties of Methane, Ethane, and Hexane on Mesoporous Organic Polymers Prepared by the Flash Freezing Method.

Mesoporous organic polymers, including poly(p-phenylene ether-sulfone) (PES), polysulfone (PSF), poly(bisphenol A-carbonate) (PC), and polyvinyl chloride (PVC), were prepared by the previously reported flash freezing method. For the four polymers, the vapor adsorption of water and hydrocarbons (C2H6, C3H8, and C6H14) was examined. PVC showed that the hydrocarbon adsorption was more selective than water adsorption. The isosteric heats of adsorption were determined from the temperature dependence of the vapor adsorption of the hydrocarbons and water. This showed the weak interaction of PVC with water and its stronger (but not too strong) interaction with hydrocarbons. The hydrophobicity and mesoporosity of PVC were determined to be suitable for such selective adsorption of hydrocarbons compared to that of water with low energy consumption during the desorption process of the hydrocarbons. Mesoporous PVC should considered a candidate for the recovery of flammable gases from water/hydrocarbon mixtures.

Bushy sphere dendrites with husk-shaped branches axially spreading out from the core for photo-catalytic oxidation/remediation of toxins.

This work describes densely interlinked bushy "tree-like chains" characterized by neatly branched sphere dendrites (bushy sphere dendrites, BSD) with long fan-like, husk-shaped branching paths that extend longitudinally from the core axis of the {110}-exposed plane. We confirmed that the hierarchical dendrite surfaces created bowls of swirled caves along the tree-tube in the mat-like branches. These surfaces had high-index catalytic site facets associated with the formation of ridges/defects on the dominant {110}-top-cover surface. These swirled caves along the branches were completely filled with 50-100 nm poly-CN nano-sphere-fossils with orb-like appearance. Such structural features are key issues of the inherent surface reactivity of a powerful catalyst/trapper, enabling photocatalytic oxidation and trapping of extremely toxic arsenite (AsO33-) species and photo-induced recovery of arsenate (AsO43-) products from catalyst surfaces. The light-induced release of produced AsO43- from BSD indicates (i) highly controlled waste collection/management (i.e., recovery), (ii) low cost and ecofriendly photo-adsorbent, (iii) selective trapping of real sample water to produce water-free arsenite species; (iv) multiple reuse cycles of catalysts (i.e., reduced waste volume). Matrixed dendrites, covered with 3D microscopic sphere cores that capture solar-light, trap toxins, and are triggered by light, were designed. These dendrites can withstand indoor and outdoor recovery of toxins from water sources.

Effective, Low-Cost Recovery of Toxic Arsenate Anions from Water by Using Hollow-Sphere Geode Traps.

Because of the devastating impact of arsenic on terrestrial and aquatic organisms, the recovery, removal, disposal, and management of arsenic-contaminated water is a considerable challenge and has become an urgent necessity in the field of water treatment. This study reports the controlled fabrication of a low-cost adsorbent based on microscopic C-,N-doped NiO hollow spheres with geode shells composed of poly-CN nanospherical nodules (100 nm) that were intrinsically stacked and wrapped around the hollow spheres to form a shell with a thickness of 500-700 nm. This C-,N-doped NiO hollow-sphere adsorbent (termed CNN) with multiple diffusion routes through open pores and caves with connected open macro/meso windows over the entire surface and well-dispersed hollow-sphere particles that create vesicle traps for the capture, extraction, and separation of arsenate (AsO43- ) species from aqueous solution. The CNN structures are considered to be a potentially attractive adsorbent for AsO43- species due to 1) superior removal and trapping capacity from water samples and 2) selective trapping of AsO43- from real water samples that mainly contained chloride and nitrate anions and Fe2+ , and Mn2+ , Ca2+ , and Mg2+ cations. The structural stability of the hierarchal geodes was evident after 20 cycles without any significant decrease in the recovery efficiency of AsO43- species. To achieve low-cost adsorbents and toxic-waste management, this superior CNN AsO43- dead-end trapping and recovery system evidently enabled the continuous control of AsO43- disposal in water-scarce environments, presents a low-cost and eco-friendly adsorbent for AsO43- species, and selectively produced water-free arsenate species. These CNN geode traps show potential as excellent adsorbent candidates in environment remediation tools and human healthcare.

Mechanically Induced Opening-Closing Action of Binaphthyl Molecular Pliers: Digital Phase Transition versus Continuous Conformational Change.

Reversible dynamic control of structure is a significant challenge in molecular nanotechnology. Previously, we have reported a mechanically induced continuous (analog) conformational variation in an amphiphilic binaphthyl, where closing of molecular pliers was achieved by compression of a molecular monolayer composed of these molecules at the air-water interface. In this work we report that a phase transition induced by an applied mechanical stress enables discontinuous digital (1/0) opening of simple binaphthyl molecular pliers. A lipid matrix at the air-water interface promotes the formation of quasi-stable nanocrystals, in which binaphthyl molecules have an open transoid configuration. The crystallization/dissolution of quasi-stable binaphthyl crystals with accompanying conformational change is reversible and repeatable.

Hydrophilic polymer nanofibre networks for rapid removal of aromatic compounds from water.

Hydrophobic mesoporous polymer nanofibre networks were converted to hydrophilic ones by a mild sulfonation reaction. The resultant mesoporous polystyrene with a large free surface area effectively captured water-soluble dye molecules and allowed aromatic compounds to rapidly permeate into the internal binding sites.

Flash freezing route to mesoporous polymer nanofibre networks.

There are increasing requirements worldwide for advanced separation materials with applications in environmental protection processes. Various mesoporous polymeric materials have been developed and they are considered as potential candidates. It is still challenging, however, to develop economically viable and durable separation materials from low-cost, mass-produced materials. Here we report the fabrication of a nanofibrous network structure from common polymers, based on a microphase separation technique from frozen polymer solutions. The resulting polymer nanofibre networks exhibit large free surface areas, exceeding 300 m(2) g(-1), as well as small pore radii as low as 1.9 nm. These mesoporous polymer materials are able to rapidly adsorb and desorb a large amount of carbon dioxide and are also capable of condensing organic vapours. Furthermore, the nanofibres made of engineering plastics with high glass transition temperatures over 200 °C exhibit surprisingly high, temperature-dependent adsorption of organic solvents from aqueous solution.

Ultrafast viscous permeation of organic solvents through diamond-like carbon nanosheets.

Chemical, petrochemical, energy, and environment-related industries strongly require high-performance nanofiltration membranes applicable to organic solvents. To achieve high solvent permeability, filtration membranes must be as thin as possible, while retaining mechanical strength and solvent resistance. Here, we report on the preparation of ultrathin free-standing amorphous carbon membranes with Young's moduli of 90 to 170 gigapascals. The membranes can separate organic dyes at a rate three orders of magnitude greater than that of commercially available membranes. Permeation experiments revealed that the hard carbon layer has hydrophobic pores of ~1 nanometer, which allow the ultrafast viscous permeation of organic solvents through the membrane.

Manganese oxyhydroxide and oxide nanofibers for high efficiency degradation of organic pollutants.

Ultrathin MnOOH nanofibers were synthesized on a large scale from diluted Mn(NO(3))(2) aqueous solution at room temperature. These MnOOH nanofibers were shape-reservedly converted into Mn(3)O(4) and MnO(2) nanofibers by post-heat treatment in air at 400 °C and 600 °C for 1 h, respectively. The morphology and crystalline structures of the nanofibers were characterized by electronic microscopes and x-ray diffraction. These nanofibers had good crystalline structures. These nanofibers were in bundles with a diameter of 25 nm composed of 3-5 nm fine crystalline nanofibers. The Mn(3)O(4) nanofibers had a specific surface area of 71 m(2) g(-1) and demonstrated highly catalytic degradation of the organic pollutant methylene blue with the assistance of H(2)O(2) at room temperature.

Thermal and mechanical properties of dried foam films and their incorporation of water-soluble compounds.

Dried foam films (DFFs), which are free-standing reversed bilayers covering the holes of micrometers, are obtained by using several types of surfactants. In this article, we examined the formation of DFFs from a wide range of surfactants, systematically changing the headgroup, the counterion, the length and number of alkyl chains, and so forth. Some DFFs showed thermal stability higher than 150 degrees C. The interaction among headgroups in each monolayer of DFFs significantly contributed to the high thermal stability. The elastic moduli of DFFs were in the range of 4-42 MPa, as determined by a nanoindentation technique using AFM. A nonionic surfactant (Brij-35) formed stable DFFs only when urea was incorporated to form hydrogen bonds with the ethylene oxide units. The thermal stability of DPC (dodecylphosphocholine) films was increased up to 220 degrees C by adding Cd(2+) because of the formation of a coordination network with the phosphate groups. Then the elastic modulus increased from 15 to 32 MPa. It was also possible to incorporate polyelectrolytes (Na(2)SiO(3) and PAH) and a cadmium polynuclear complex ([Cd(10)(SCH(2)CH(2)OH)(16)] x (ClO(4))(4)) into the interlayer space of DFFs by tuning the proximal electrostatic interaction with the headgroups of surfactants.

Ultrafast permeation of water through protein-based membranes.

Pressure-driven filtration by porous membranes is widely used in the production of drinking water from ground and surface water. Permeation theory predicts that filtration rate is proportional to the pressure difference across the filtration membrane and inversely proportional to the thickness of the membrane. However, these membranes need to be able to withstand high water fluxes and pressures, which means that the active separation layers in commercial filtration systems typically have a thickness of a few tens to several hundreds of nanometres. Filtration performance might be improved by the use of ultrathin porous silicon membranes or carbon nanotubes immobilized in silicon nitride or polymer films, but these structures are difficult to fabricate. Here, we report a new type of filtration membrane made of crosslinked proteins that are mechanically robust and contain channels with diameters of less than 2.2 nm. We find that a 60-nm-thick membrane can concentrate aqueous dyes from fluxes up to 9,000 l h(-1) m(-2) bar(-1), which is approximately 1,000 times higher than the fluxes that can be withstood by commercial filtration membranes with similar rejection properties. Based on these results and molecular dynamics simulations, we propose that protein-surrounded channels with effective lengths of less than 5.8 nm can separate dye molecules while allowing the ultrafast permeation of water at applied pressures of less than 1 bar.

Bio-detection of dipeptides by the ZrO2/PVA/Cyt.c multilayer film.

The adsorption mechanism of dipeptides namely Gly-Glu, Asp-Glu with protein layer was successfully examined on cytochrome c (Cyt.c) surface probing by fluorescent dye molecule. Molecularly thin Cyt.c layer was immobilized on poly(vinyl alcohol) (PVA) coated zirconium oxide (ZrO2) gel films by electrostatic interaction. Denaturation of Cyt.c was minimized on sol-gel derived ZrO2-gel film by PVA. The conformation of immobilized protein was verified by FTIR-ATR measurements. The fluorescent dye molecule was easily bound on the Cyt.c layer. The dye adsorbed protein thin film was soaked in two different dipeptides solution with various concentrations. The adsorption of dipeptides on Cyt.c thin film and consequent desorption of fluorescent dye from Cyt.c layer in dipeptide solutions was monitored by UV-vis absorption, fluorescence spectroscopy and quartz crystal microbalance method. The ion exchange mechanism on protein surface between fluorescent dye and dipeptides is thought to be responsible for dye desorption and formation of relatively strong electrostatic bonding between dipeptides with protein. The adsorption behavior curve of dipeptides was analyzed by Hill equation. The number of functional group together with size of dipeptides play an important role for different adsorption parameters obtained from this model.

Ultrathin nanofibrous films prepared from cadmium hydroxide nanostrands and anionic surfactants.

We developed a simple fabrication method of ultrathin nanofibrous films from the dispersion of cadmium hydroxide nanostrands and anionic surfactants. The nanostrands were prepared in a dilute aqueous solution of cadmium chloride by using 2-aminoethanol. They were highly positively charged and gave bundlelike fibers upon mixing an aqueous solution of anionic surfactant. The nanostrand/surfactant composite fibers were filtered on an inorganic membrane filter. The resultant nanofibrous film was very uniform in the area of a few centimeters square when the thickness was not less than 60 nm. The films obtained with sodium tetradecyl sulfate (STS) had a composition close to the electroneutral complex, [Cd37(OH)68(H2O)n] x 6(STS), as confirmed by energy dispersive X-ray analysis. They were water-repellent with a contact angle of 117 degrees, and the value slightly decreased with the alkyl chain length of anionic surfactants. Ultrathin nanofibrous films were stable enough to be used for ultrafiltration at pressure difference of 90 kPa. We could effectively separate Au nanoparticles of 40 nm at an extremely high filtration rate of 14000 L/(h m2 bar).

Time-dependent growth of zinc hydroxide nanostrands and their crystal structure.

Positively-charged crystalline zinc hydroxide nanostrands with a diameter of 2 nm and a length of a few micrometres rapidly grew in dilute aqueous solution of zinc nitrate and aminoethanol. The nanostrands were composed of hexagonal clusters of [Zn(61)(OH)(116)(H(2)O)(n)](6+).

Nanomechanical properties of reversed surfactant bilayers formed in micrometre-sized holes.

Nanomechanical properties of free-standing reversed surfactant bilayers, dried foam films (DFFs), were examined via AFM by fitting local force-indentation curves with a Hertzian model. The Young's moduli of four kinds of bilayers were in a range of 10-30 MPa.

Surfactant-assisted fabrication of free-standing inorganic sheets covering an array of micrometre-sized holes.

Thin inorganic membranes are of importance to a number of applications such as sensing, catalysis and separation. Here, we present a method to fabricate free-standing sheets of various inorganic materials such as C, Si, Pt, Fe and CdSe with thicknesses ranging from a few to a hundred nanometres. First, an array of holes in a flat substrate was uniformly covered by dried-foam-film (DFF) self-standing reversed bilayers of surfactants. As the surfactant bilayers are sufficiently robust to allow deposition of amorphous films, a variety of inorganic films were then fabricated on the DFFs using physical deposition techniques such as sputtering, electron-beam deposition and thermal deposition. The films thus obtained showed improved thermal stability compared with the DFFs. This fabrication method therefore provides a flexible and reliable way to readily produce free-standing inorganic multilayered structures.