Nanoconfinement of Carbon Dioxide within Interfacial Aqueous/Ionic Liquid Systems.

Nanoporous, gas-selective membranes have shown encouraging results for the removal of CO2 from flue gas, yet the optimal design for such membranes is often unknown. Therefore, we used molecular dynamics simulations to elucidate the behavior of CO2 within aqueous and ionic liquid (IL) systems ([EMIM][TFSI] and [OMIM][TFSI]), both confined individually and as an interfacial aqueous/IL system. We found that within aqueous systems the mobility of CO2 is reduced due to interactions between the CO2 oxygens and hydroxyl groups on the pore surface. Within the IL systems, we found that confinement has a greater effect on the [EMIM][TFSI] system as opposed to the [OMIM][TFSI] system. Paradoxically, the larger and more asymmetrical [OMIM]+ molecule undergoes less efficient packing, resulting in fewer confinement effects. Free energy surfaces of the nanoconfined aqueous/IL interface demonstrate that CO2 will transfer spontaneously from the aqueous to the IL phase.

Ultrahard nanotwinned cubic boron nitride.

Cubic boron nitride (cBN) is a well known superhard material that has a wide range of industrial applications. Nanostructuring of cBN is an effective way to improve its hardness by virtue of the Hall-Petch effect--the tendency for hardness to increase with decreasing grain size. Polycrystalline cBN materials are often synthesized by using the martensitic transformation of a graphite-like BN precursor, in which high pressures and temperatures lead to puckering of the BN layers. Such approaches have led to synthetic polycrystalline cBN having grain sizes as small as ∼14 nm (refs 1, 2, 4, 5). Here we report the formation of cBN with a nanostructure dominated by fine twin domains of average thickness ∼3.8 nm. This nanotwinned cBN was synthesized from specially prepared BN precursor nanoparticles possessing onion-like nested structures with intrinsically puckered BN layers and numerous stacking faults. The resulting nanotwinned cBN bulk samples are optically transparent with a striking combination of physical properties: an extremely high Vickers hardness (exceeding 100 GPa, the optimal hardness of synthetic diamond), a high oxidization temperature (∼1,294 °C) and a large fracture toughness (>12 MPa m(1/2), well beyond the toughness of commercial cemented tungsten carbide, ∼10 MPa m(1/2)). We show that hardening of cBN is continuous with decreasing twin thickness down to the smallest sizes investigated, contrasting with the expected reverse Hall-Petch effect below a critical grain size or the twin thickness of ∼10-15 nm found in metals and alloys.

Metal-Organic Framework (MOF) Nanorods, Nanotubes, and Nanowires.

New mechanisms for the controlled growth of one-dimensional (1D) metal-organic framework (MOF) nano- and superstructures under size-confinement and surface-directing effects have been discovered. Through applying interfacial synthesis templated by track-etched polycarbonate (PCTE) membranes, congruent polycrystalline zeolitic imidazolate framework-8 (ZIF-8) solid nanorods and hollow nanotubes were found to form within 100 nm membrane pores, while single crystalline ZIF-8 nanowires grew inside 30 nm pores, all of which possess large aspect ratios up to 60 and show preferential crystal orientation with the {100} planes aligned parallel to the long axis of the pore. Our findings provide a generalizable method for controlling size, morphology, and lattice orientation of MOF nanomaterials.

Thermal conductivity and nanocrystalline structure of platinum deposited by focused ion beam.

Pt deposited by focused ion beam (FIB) is a common material used for attachment of nanosamples, repair of integrated circuits, and synthesis of nanostructures. Despite its common use little information is available on its thermal properties. In this work, Pt deposited by FIB is characterized thermally, structurally, and chemically. Its thermal conductivity is found to be substantially lower than the bulk value of Pt, 7.2 W m(-1) K(-1) versus 71.6 W m(-1) K(-1) at room temperature. The low thermal conductivity is attributed to the nanostructure of the material and its chemical composition. Pt deposited by FIB is shown, via aberration corrected TEM, to be a segregated mix of nanocrystalline Pt and amorphous C with Ga and O impurities. Ga impurities mainly reside in the Pt while O is homogeneously distributed throughout. The Ga impurity, small grain size of the Pt, and the amorphous carbon between grains are the cause for the low thermal conductivity of this material. Since Pt deposited by FIB is a common material for affixing samples, this information can be used to assess systematic errors in thermal characterization of different nanosamples. This application is also demonstrated by thermal characterization of two carbon nanofibers and a correction using the reported thermal properties of the Pt deposited by FIB.

Porous ice phases with VI and distorted VII structures constrained in nanoporous silica.

High-pressure compression of water contained in nanoporous silica allowed fabrication of novel porous ice phases as a function of pressure. The starting liquid nanoporous H2O transformed to ice VI and VII at 1.7 and 2.5 GPa, respectively, which are 0.6 and 0.4 GPa higher than commonly accepted pressures for bulk H2O. The continuous increase of pressure drives the formation of a tetragonally distorted VII structure with the space group I4mm, rather than a cubic Pn3m phase in bulk ice. The enhanced incompressibility of the tetragonal ice is related to the unique nanoporous configuration, and the distortion ratio c/a gradually increases with increasing pressure. The structural changes and enhanced thermodynamic stability may be interpreted by the two-dimensional distribution of silanol groups on the porous silica surfaces and the associated anisotropic interactions with H2O at the interfaces.

Atomic layer deposition of L-alanine polypeptide.

L-Alanine polypeptide thin films were synthesized via atomic layer deposition (ALD). Instead of using an amino acid monomer as the precursor, an L-alanine amino acid derivatized with a protecting group was used to prevent self-polymerization, increase the vapor pressure, and allow linear cycle-by-cycle growth emblematic of ALD. The successful deposition of a conformal polypeptide film has been confirmed by FTIR, TEM, and Mass Spectrometry, and the ALD process has been extended to polyvaline.

Polymer-graphene nanocomposites as ultrafast-charge and -discharge cathodes for rechargeable lithium batteries.

Electroactive polymers are a new generation of "green" cathode materials for rechargeable lithium batteries. We have developed nanocomposites combining graphene with two promising polymer cathode materials, poly(anthraquinonyl sulfide) and polyimide, to improve their high-rate performance. The polymer-graphene nanocomposites were synthesized through a simple in situ polymerization in the presence of graphene sheets. The highly dispersed graphene sheets in the nanocomposite drastically enhanced the electronic conductivity and allowed the electrochemical activity of the polymer cathode to be efficiently utilized. This allows for ultrafast charging and discharging; the composite can deliver more than 100 mAh/g within just a few seconds.

DNA translocation through an array of kinked nanopores.

Synthetic solid-state nanopores are being intensively investigated as single-molecule sensors for detection and characterization of DNA, RNA and proteins. This field has been inspired by the exquisite selectivity and flux demonstrated by natural biological channels and the dream of emulating these behaviours in more robust synthetic materials that are more readily integrated into practical devices. So far, the guided etching of polymer films, focused ion-beam sculpting, and electron-beam lithography and tuning of silicon nitride membranes have emerged as three promising approaches to define synthetic solid-state pores with sub-nanometre resolution. These procedures have in common the formation of nominally cylindrical or conical pores aligned normal to the membrane surface. Here we report the formation of 'kinked' silica nanopores, using evaporation-induced self-assembly, and their further tuning and chemical derivatization using atomic-layer deposition. Compared with 'straight through' proteinaceous nanopores of comparable dimensions, kinked nanopores exhibit up to fivefold reduction in translocation velocity, which has been identified as one of the critical issues in DNA sequencing. Additionally, we demonstrate an efficient two-step approach to create a nanopore array exhibiting nearly perfect selectivity for ssDNA over dsDNA. We show that a coarse-grained drift-diffusion theory with a sawtooth-like potential can reasonably describe the velocity and translocation time of DNA through the pore. By control of pore size, length and shape, we capture the main functional behaviours of protein pores in our solid-state nanopore system.

Templated growth of platinum nanowheels using the inhomogeneous reaction environment of bicelles.

Novel platinum nanowheels were synthesized by the reduction of aqueous platinum complex with ascorbic acid in the presence of disk-like bicelles. The platinum nanowheels possess thickened centers and flared edges that are connected by dendritic platinum nanosheets. This structural complexity can be attributed to the inhomogeneous micro-environment of the templating bicelles consisting of a central bi-layer region and a high curvature rim. The formation mechanism of the nanowheels was investigated by imaging nanostructures at different stages of the reaction. The templating bicelles were also imaged by TEM with the aid of negative staining. The variation of reaction parameters including platinum concentration, temperature, and total concentration of surfactants (CTAB + FC7) led to other types of platinum nanostructures, such as circular dendritic nanosheets with a tunable diameter and rectangular dendritic nanosheets. Interestingly, under irradiation by a TEM electron beam, the dendritic nanosheet portion of the nanowheels transforms into a metastable holey sheet. In addition, the platinum nanowheels have an electrochemical active surface area comparable to that of ETEK platinum black and thus are expected to have potential applications in catalysis.

Grain size dependent high-pressure elastic properties of ultrafine micro/nanocrystalline grossular.

We have performed sound velocity and unit cell volume measurements of three synthetic, ultrafine micro/nanocrystalline grossular samples up to 50 GPa using Brillouin spectroscopy and synchrotron X-ray diffraction. The samples are characterized by average grain sizes of 90 nm, 93 nm and 179 nm (hereinafter referred to as samples Gr90, Gr93, and Gr179, respectively). The experimentally determined sound velocities and elastic properties of Gr179 sample are comparable with previous measurements, but slightly higher than those of Gr90 and Gr93 under ambient conditions. However, the differences diminish with increasing pressure, and the velocity crossover eventually takes place at approximately 20-30 GPa. The X-ray diffraction peaks of the ultrafine micro/nanocrystalline grossular samples significantly broaden between 15-40 GPa, especially for Gr179. The velocity or elasticity crossover observed at pressures over 30 GPa might be explained by different grain size reduction and/or inhomogeneous strain within the individual grains for the three grossular samples, which is supported by both the pressure-induced peak broadening observed in the X-ray diffraction experiments and transmission electron microscopy observations. The elastic behavior of ultrafine micro/nanocrystalline silicates, in this case, grossular, is both grain size and pressure dependent.

Donor-acceptor biomorphs from the ionic self-assembly of porphyrins.

Microscale four-leaf clover-shaped structures are formed by self-assembly of anionic and cationic porphyrins. Depending on the metal complexed in the porphyrin macrocycle (Zn or Sn), the porphyrin cores are either electron donors or electron acceptors. All four combinations of these two metals in cationic tetra(N-ethanol-4-pyridinium)porphyrin and anionic tetra(sulfonatophenyl)porphyrin result in related cloverlike structures with similar crystalline packing indicated by X-ray diffraction patterns. The clover morphology transforms as the ionic strength and temperature of the self-assembly reaction are increased, but the structures maintain 4-fold symmetry. The ability to alter the electronic and photophysical properties of these solids (e.g., by altering the metals in the porphyrins) and to vary cooperative interactions between the porphyrin subunits raises the possibility of producing binary solids with tunable functionality. For example, we show that the clovers derived from anionic Zn porphyrins (electron donors) and cationic Sn porphyrins (electron acceptors) are photoconductors, but when the metals are reversed in the two porphyrins, the resulting clovers are insulators.

Tailoring anisotropic wetting properties on submicrometer-scale periodic grooved surfaces.

The use of simple plasma treatments and polymer deposition to tailor the anisotropic wetting properties of one-dimensional (1D) submicrometer-scale grooved surfaces, fabricated using interferometric lithography in photoresist polymer films, is reported. Strongly anisotropic wetting phenomena are observed for as-prepared 1D grooved surfaces for both positive and negative photoresists. Low-pressure plasma treatments with different gas compositions (e.g., CHF(3), CF(4), O(2)) are employed to tailor the anisotropic wetting properties from strongly anisotropic and hydrophobic to hydrophobic with very high contact angle and superhydrophilic with a smaller degree of wetting anisotropy and without changing the structural anisotropy. The change of the surface wetting properties for these 1D patterned surfaces is attributed to a change in surface chemical composition, monitored using XPS. In addition, the initial anisotropic wetting properties on 1D patterned samples could be modified by coating plasma treated samples with a thin layer of polymer. We also demonstrated that the wetting properties of 1D grooved surfaces in a Si substrate could be tuned with similar plasma treatments. The ability to tailor anisotropic wetting on 1D patterned surfaces will find many applications in microfluidic devices, lab-on-a-chip systems, microreactors, and self-cleaning surfaces.

Evolution of dendritic platinum nanosheets into ripening-resistant holey sheets.

Under electron-beam irradiation, dendritic platinum nanosheets structurally evolve into metastable "holey" nanosheets. Monte Carlo simulations of this structural transformation agree well with electron microscope images detailing the ripening process. The experiments and simulations show that nanoscale holes of a critical size are persistent and give holey sheets their morphological stability and sustained high surface area. Platinum nanostructures composed of these holey nanosheets exhibit improved durability in electrocatalytic reactions due to their remarkable ripening resistance.

Macrovoid-Inhibited PVDF Hollow Fiber Membranes via Spinning Process Delay for Direct Contact Membrane Distillation.

A polyvinylidene fluoride (PVDF) hollow fiber membrane was fabricated through water-induced dope crystallization by allowing a facile spinning process delay (SPD) in the nonsolvent-induced phase separation (NIPS) process for direct contact membrane distillation (DCMD). The SPD was achieved by the addition of a small amount of water to the PVDF dope solution that was held in a closed container for a particular time. The crystalline property of the PVDF dope solution was investigated by differential scanning calorimetry. The obtained PVDF hollow fiber membranes were characterized with different techniques, including field emission scanning electron microscopy, X-ray diffraction, and the mechanical strength. Both the formation mechanism and properties were studied for the membranes with different SPD times. The results showed that macrovoid-inhibited PVDF membranes were obtained from 12 days of the SPD via the crystallization-dominated membrane formation process. The obtained membrane 4D-12 exhibited desirable membrane structure and properties for DCMD, which includes an improved liquid entry pressure of 2.25 bar, a surface water contact angle of 129°, a maximum pore size of 0.40 µm, and a mean pore size of 0.34 µm. The membrane 4D-12 possessed a twofold increase in both energy efficiency and permeate water flux in DCMD and stable permeate water flux and salt rejection through 224 h of continuous desalination operation. Compared to the commonly used approach by adding chemicals to the external coagulant, the SPD method provided a low-cost and environmentally friendly alternative to pursuing the macrovoid-free PVDF membranes for DCMD.

Crystal Chemistry of Carnotite in Abandoned Mine Wastes.

The crystal chemistry of carnotite (prototype formula: K2(UO2)2(VO4)2·3H2O) occurring in mine wastes collected from Northeastern Arizona was investigated by integrating spectroscopy, electron microscopy, and x-ray diffraction analyses. Raman spectroscopy confirms that the uranyl vanadate phase present in the mine waste is carnotite, rather than the rarer polymorph vandermeerscheite. X-ray diffraction patterns of the carnotite occurring in these mine wastes are in agreement with those reported in the literature for a synthetic analog. Carbon detected in this carnotite was identified as organic carbon inclusions using transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) analyses. After excluding C and correcting for K-drift from the electron microprobe analyses, the composition of the carnotite was determined as 8.64% K2O, 0.26% CaO, 61.43% UO3, 20.26% V2O5, 0.38% Fe2O3, and 8.23% H2O. The empirical formula, (K1.66 Ca0.043 Al(OH)2+ 0.145 Fe(OH)2+ 0.044)((U0.97)O2)2((V1.005)O4)2·4H2O of the studied carnotite, with an atomic ratio 1.9:2:2 for K:U:V, is similar to the that of carnotite (K2(UO2)2(VO4)2·3H2O) reported in the literature. Lattice spacing data determined using selected area electron diffraction (SAED)-TEM suggests: (1) complete amorphization of the carnotite within 120 s of exposure to the electron beam and (2) good agreement of the measured d-spacings for carnotite in the literature. Small Differences between the measured and literature d-spacing values are likely due to the varying degree of hydration between natural and synthetic materials. Such information about the crystal chemistry of carnotite in mine wastes is important for an improved understanding of the occurrence and reactivity of U, V, and other elements in the environment.

Synthesis of platinum nanowheels using a bicellar template.

Disk-like surfactant bicelles provide a unique meso-structured reaction environment for templating the wet-chemical reduction of platinum(II) salt by ascorbic acid to produce platinum nanowheels. The Pt wheels are 496 +/-55 nm in diameter and possess thickened centers and radial dendritic nanosheets (about 2-nm in thickness) culminating in flared dendritic rims. The structural features of the platinum wheels arise from confined growth of platinum within the bilayer that is also limited at edges of the bicelles. The size of CTAB/FC7 bicelles is observed to evolve with the addition of Pt(II) complex and ascorbic acid. Synthetic control is demonstrated by varying the reaction parameters including metal salt concentration, temperature, and total surfactant concentration. This study opens up opportunities for the use of other inhomogeneous soft templates for synthesizing metals, metal alloys, and possibly semiconductors with complex nanostructures.

Directed aerosol writing of ordered silica nanostructures on arbitrary surfaces with self-assembling inks.

This paper reports the fabrication of micro- and macropatterns of ordered mesostructured silica on arbitrary flat and curved surfaces using a facile robot-directed aerosol printing process. Starting with a homogenous solution of soluble silica, ethanol, water, and surfactant as a self-assembling ink, a columnated stream of aerosol droplets is directed to the substrate surface. For deposition at room temperature droplet coalescence on the substrates and attendant solvent evaporation result in continuous, highly ordered mesophases. The pattern profiles are varied by changing any number of printing parameters such as material deposition rate, printing speed, and aerosol-head temperature. Increasing the aerosol temperature results in a decrease of the mesostructure ordering, since faster solvent evaporation and enhanced silica condensation at higher temperatures kinetically impede the molecular assembly process. This facile technique provides powerful control of the printed materials at both the nanoscale and microscale through chemical self-assembly and robotic engineering, respectively.

Author Correction: Ultra-thin enzymatic liquid membrane for CO2 separation and capture.

The original version of this Article contained an error in the spelling of the author Stanley S. Chou, which was incorrectly given as Stan Chou. This has now been corrected in both the PDF and HTML versions of the Article.

Ultra-thin enzymatic liquid membrane for CO2 separation and capture.

The limited flux and selectivities of current carbon dioxide membranes and the high costs associated with conventional absorption-based CO2 sequestration call for alternative CO2 separation approaches. Here we describe an enzymatically active, ultra-thin, biomimetic membrane enabling CO2 capture and separation under ambient pressure and temperature conditions. The membrane comprises a ~18-nm-thick close-packed array of 8 nm diameter hydrophilic pores that stabilize water by capillary condensation and precisely accommodate the metalloenzyme carbonic anhydrase (CA). CA catalyzes the rapid interconversion of CO2 and water into carbonic acid. By minimizing diffusional constraints, stabilizing and concentrating CA within the nanopore array to a concentration 10× greater than achievable in solution, our enzymatic liquid membrane separates CO2 at room temperature and atmospheric pressure at a rate of 2600 GPU with CO2/N2 and CO2/H2 selectivities as high as 788 and 1500, respectively, the highest combined flux and selectivity yet reported for ambient condition operation.