Ionic Conductance through Graphene: Assessing Its Applicability as a Proton Selective Membrane.

Inspired by recent reports on possible proton conductance through graphene, we have investigated the behavior of pristine graphene and defect engineered graphene membranes for ionic conductance and selectivity with the goal of evaluating a possibility of its application as a proton selective membrane. The averaged conductance for pristine chemical vapor deposited (CVD) graphene at pH1 is ∼4 mS/cm2 but varies strongly due to contributions from the unavoidable defects in our CVD graphene. From the variations in the conductance with electrolyte strength and pH, we can conclude that pristine graphene is fairly selective and the conductance is mainly due to protons. Engineering of the defects with ion beam (He+, Ga+) irradiation and plasma (N2 and H2) treatment showed improved areal conductance with high proton selectivity mostly for He-ion beam and H2 plasma treatments, which agrees with primarily vacancy-free type of defects produced in these cases confirmed by Raman analysis.

Voltage gated inter-cation selective ion channels from graphene nanopores.

With the ability to selectively control ionic flux, biological protein ion channels perform a fundamental role in many physiological processes. For practical applications that require the functionality of a biological ion channel, graphene provides a promising solid-state alternative, due to its atomic thinness and mechanical strength. Here, we demonstrate that nanopores introduced into graphene membranes, as large as 50 nm in diameter, exhibit inter-cation selectivity with a ∼20× preference for K+ over divalent cations and can be modulated by an applied gate voltage. Liquid atomic force microscopy of the graphene devices reveals surface nanobubbles near the pore to be responsible for the observed selective behavior. Molecular dynamics simulations indicate that translocation of ions across the pore likely occurs via a thin water layer at the edge of the pore and the nanobubble. Our results demonstrate a significant improvement in the inter-cation selectivity displayed by a solid-state nanopore device and by utilizing the pores in a de-wetted state, offers an approach to fabricate selective graphene membranes that does not rely on the fabrication of sub-nm pores.

Adsorption of Molecular Nitrogen in Electrical Double Layers near Planar and Atomically Sharp Electrodes.

The adsorption of gas molecules at electrode-electrolyte interfaces is an important step in electrochemical reactions. Using molecular dynamics simulations, we investigate the adsorption of dissolved N2 in the electrical double layers (EDLs) of an aqueous electrolyte near planar and 1 nm radius spherical carbon electrodes. The adsorption of N2 is found to be overall enriched near neutral electrodes regardless of their surface curvature, although it can be locally enriched or depleted depending on the distance from the electrode surface. In comparison, the adsorption of N2 in the EDL near negatively charged electrodes is found to increase under a moderate surface charge density, but decrease under a high surface charge density, especially near a planar electrode. By analyzing the potential of mean force for dissolved N2, the solvent-induced effects are found to play important roles in influencing the adsorption of N2 in the EDLs. The adsorption behavior of N2 molecules, especially their dependence on the surface charge and curvature of electrodes, is further rationalized by examining the structure of interfacial water molecules, their interference with the hydration shell of N2, and their modification by the electrification of electrodes.

Antibacterial dental adhesive resins containing nitrogen-doped titanium dioxide nanoparticles.

The development of dental adhesive resins with long-lasting antibacterial properties is a possible solution to overcome the problem of secondary caries in modern adhesive dentistry. OBJECTIVES: (i) Synthesis and characterization of nitrogen-doped titanium dioxide nanoparticles (N_TiO2), (ii) topographical, compositional and wettability characterization of thin-films (unaltered and experimental) and, (iii) antibacterial efficacy of N_TiO2-containing dental adhesives against Streptococcus mutans biofilms. MATERIALS AND METHODS: Nanoparticles were synthesized and characterized using different techniques. Specimens (diameter = 12 mm, thickness ≅ 15 µm) of OptiBond Solo Plus (Kerr Corp., USA) and experimental adhesives [50, 67 and 80% (v/v)] were fabricated, photopolymerized (1000 mW/cm2, 1 min) and UV-sterilized (254 nm, 800,000 µJ/cm2) for microscopy, spectroscopy, wettability and antibacterial testing. Wettability was assessed with a contact angle goniometer by dispensing water droplets (2 µL) onto four random locations of each specimen (16 drops/group). Drop profiles were recorded (1 min, 25 frames/s, 37 °C) and contact angles were calculated at time = 0 s (θINITIAL) and time = 59 s (θFINAL). Antibacterial testing was performed by growing S. mutans (UA159-ldh, JM10) biofilms for either 3 or 24 h (anaerobic conditions, 37 °C) with or without continuous light irradiation (410 ±â€¯10 nm, 3 h = 38.75 J/cm2, 24 h = 310.07 J/cm2) against the surfaces of sterile specimens. RESULTS: N_TiO2 was successfully prepared using solvothermal methods. Doped-nanoparticles displayed higher light absorption levels when compared to undoped titania. Experimental adhesives demonstrated superior antibacterial efficacy in dark conditions. CONCLUSIONS: The findings presented herein suggest that N_TiO2 is a feasible antibacterial agent against cariogenic biofilms.

A physical catalyst for the electrolysis of nitrogen to ammonia.

Ammonia synthesis consumes 3 to 5% of the world's natural gas, making it a significant contributor to greenhouse gas emissions. Strategies for synthesizing ammonia that are not dependent on the energy-intensive and methane-based Haber-Bosch process are critically important for reducing global energy consumption and minimizing climate change. Motivated by a need to investigate novel nitrogen fixation mechanisms, we herein describe a highly textured physical catalyst, composed of N-doped carbon nanospikes, that electrochemically reduces dissolved N2 gas to ammonia in an aqueous electrolyte under ambient conditions. The Faradaic efficiency (FE) achieves 11.56 ± 0.85% at -1.19 V versus the reversible hydrogen electrode, and the maximum production rate is 97.18 ± 7.13 µg hour-1 cm-2. The catalyst contains no noble or rare metals but rather has a surface composed of sharp spikes, which concentrates the electric field at the tips, thereby promoting the electroreduction of dissolved N2 molecules near the electrode. The choice of electrolyte is also critically important because the reaction rate is dependent on the counterion type, suggesting a role in enhancing the electric field at the sharp spikes and increasing N2 concentration within the Stern layer. The energy efficiency of the reaction is estimated to be 5.25% at the current FE of 11.56%.

Author Correction: Facile emulsion mediated synthesis of phase-pure diopside nanoparticles.

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Facile emulsion mediated synthesis of phase-pure diopside nanoparticles.

Diopside is a common natural pyroxene that is rarely found in a pure state, since magnesium is often partially substituted by iron, and other elements (sodium and aluminum) are often present. This pyroxene, along with feldspars and olivines, is common in concrete. As the prospective license renewal of light water reactors to 80 years of operation has raised concerns on the effects of radiation in the concrete biological shield surrounding the reactors, mineral nanoparticles can be valuable to perform amorphization studies to inform predictive models of mechanical properties of irradiated concrete. The synthesis of diopside nanoparticles was achieved in this study using a reverse-micelle sol-gel method employing TEOS, calcium chloride and Mg(MeO)2 in a methanol/toluene solution. Tert-butylamine and water were used as hydrolysis agents, and dodecylamine as a surfactant. The resulting amorphous precursor was centrifuged to remove organics and fired at 800 °C. Additional reaction with hydrogen peroxide was used to remove amine remnants. TEM and SEM examinations revealed a product comprised of 50-100 nm diameter nanoparticles. XRD indicated phase pure diopside and BET indicated a surface area of 63.5 m2/g before peroxide treatment, which at a bulk density of 3.4 g/cm3 is equivalent to particles with diameter of 28 nm.

Nano-scale synthesis of the complex silicate minerals forsterite and enstatite.

Olivine is a relatively common family of silicate minerals in many terrestrial and extraterrestrial environments, and is also useful as a refractory ceramic. A capability to synthesize fine particles of olivine will enable additional studies on surface reactivity under geologically relevant conditions. This paper presents a method for the synthesis of nanocrystalline samples of the magnesium end-member, forsterite (Mg2SiO4) in relatively large batches (15-20g) using a sol-gel/surfactant approach. Magnesium methoxide and tetraethylorthosilicate (TEOS) are refluxed in a toluene/methanol mixture using dodecylamine as a surfactant and tert-butyl amine and water as hydrolysis agents. This material is then cleaned and dried, and fired at 800°C. Post-firing reaction in hydrogen peroxide was used to remove residual organic surfactant. X-ray diffraction showed that a pure material resulted, with a BET surface area of up to 76.6m2/g. The results of a preliminary attempt to use this approach to synthesize nano-scale orthopyroxene (MgSiO3) are also reported.

Atomistic-Scale Simulations of Defect Formation in Graphene under Noble Gas Ion Irradiation.

Despite the frequent use of noble gas ion irradiation of graphene, the atomistic-scale details, including the effects of dose, energy, and ion bombardment species on defect formation, and the associated dynamic processes involved in the irradiations and subsequent relaxation have not yet been thoroughly studied. Here, we simulated the irradiation of graphene with noble gas ions and the subsequent effects of annealing. Lattice defects, including nanopores, were generated after the annealing of the irradiated graphene, which was the result of structural relaxation that allowed the vacancy-type defects to coalesce into a larger defect. Larger nanopores were generated by irradiation with a series of heavier noble gas ions, due to a larger collision cross section that led to more detrimental effects in the graphene, and by a higher ion dose that increased the chance of displacing the carbon atoms from graphene. Overall trends in the evolution of defects with respect to a dose, as well as the defect characteristics, were in good agreement with experimental results. Additionally, the statistics in the defect types generated by different irradiating ions suggested that the most frequently observed defect types were Stone-Thrower-Wales (STW) defects for He(+) irradiation and monovacancy (MV) defects for all other ion irradiations.

Focused helium-ion beam irradiation effects on electrical transport properties of few-layer WSe2: enabling nanoscale direct write homo-junctions.

Atomically thin transition metal dichalcogenides (TMDs) are currently receiving significant attention due to their promising opto-electronic properties. Tuning optical and electrical properties of mono and few-layer TMDs, such as tungsten diselenide (WSe2), by controlling the defects, is an intriguing opportunity to synthesize next generation two dimensional material opto-electronic devices. Here, we report the effects of focused helium ion beam irradiation on the structural, optical and electrical properties of few-layer WSe2, via high resolution scanning transmission electron microscopy, Raman spectroscopy, and electrical transport measurements. By controlling the ion irradiation dose, we selectively introduce precise defects in few-layer WSe2 thereby locally tuning the resistivity and transport properties of the material. Hole transport in the few layer WSe2 is degraded more severely relative to electron transport after helium ion irradiation. Furthermore, by selectively exposing material with the ion beam, we demonstrate a simple yet highly tunable method to create lateral homo-junctions in few layer WSe2 flakes, which constitutes an important advance towards two dimensional opto-electronic devices.

Polarization Control via He-Ion Beam Induced Nanofabrication in Layered Ferroelectric Semiconductors.

Rapid advances in nanoscience rely on continuous improvements of material manipulation at near-atomic scales. Currently, the workhorse of nanofabrication is resist-based lithography and its various derivatives. However, the use of local electron, ion, and physical probe methods is expanding, driven largely by the need for fabrication without the multistep preparation processes that can result in contamination from resists and solvents. Furthermore, probe-based methods extend beyond nanofabrication to nanomanipulation and to imaging which are all vital for a rapid transition to the prototyping and testing of devices. In this work we study helium ion interactions with the surface of bulk copper indium thiophosphate CuM(III)P2X6 (M = Cr, In; X= S, Se), a novel layered 2D material, with a Helium Ion Microscope (HIM). Using this technique, we are able to control ferrielectric domains and grow conical nanostructures with enhanced conductivity whose material volumes scale with the beam dosage. Compared to the copper indium thiophosphate (CITP) from which they grow, the nanostructures are oxygen rich, sulfur poor, and with virtually unchanged copper concentration as confirmed by energy-dispersive X-ray spectroscopy (EDX). Scanning electron microscopy (SEM) imaging contrast as well as scanning microwave microscopy (SMM) measurements suggest enhanced conductivity in the formed particles, whereas atomic force microscopy (AFM) measurements indicate that the produced structures have lower dissipation and are softer as compared to the CITP.

Graphene engineering by neon ion beams.

Achieving the ultimate limits of lithographic resolution and material performance necessitates engineering of matter with atomic, molecular, and mesoscale fidelity. With the advent of scanning helium ion microscopy, maskless He(+) and Ne(+) beam lithography of 2D materials, such as graphene-based nanoelectronics, is coming to the forefront as a tool for fabrication and surface manipulation. However, the effects of using a Ne focused-ion-beam on the fidelity of structures created out of 2D materials have yet to be explored. Here, we will discuss the use of energetic Ne ions in engineering graphene nanostructures and explore their mechanical, electromechanical and chemical properties using scanning probe microscopy (SPM). By using SPM-based techniques such as band excitation (BE) force modulation microscopy, Kelvin probe force microscopy (KPFM) and Raman spectroscopy, we are able to ascertain changes in the mechanical, electrical and optical properties of Ne(+) beam milled graphene nanostructures and surrounding regions. Additionally, we are able to link localized defects around the milled graphene to ion milling parameters such as dwell time and number of beam passes in order to characterize the induced changes in mechanical and electromechanical properties of the graphene surface.

Development of in situ Electrochemical Small-Angle Neutron Scattering (eSANS) for Simultaneous Structure and Redox Characterization of Nanoparticles.

An in situ electrochemical small-angle neutron scattering (eSANS) method was developed to measure simultaneously the redox properties and size, shape and interactions of solution-dispersed nanomaterials. By combining multi-step potentials and chronocoulometry readout with SANS, the structure and redox properties of engineered nanomaterials are followed in one experiment. Specifically, ZnO nanoparticles were examined as dilute dispersions in pH buffered deuterium oxide solutions under negative electrode potentials. The ZnO disk-shaped nanoparticles undergo an irreversible size transformation upon reduction at the vitreous carbon electrode. The decrease in average nanoparticle size near a current maximum shows the reduction reaction from ZnO to Zn occurs. The eSANS method provides nanometer scale sensitivity to nanoparticle size and shape changes due to an electrochemical reaction that is crucial to understand in energy, healthcare, and other applications.

Maskless Lithography and in situ Visualization of Conductivity of Graphene using Helium Ion Microscopy.

The remarkable mechanical and electronic properties of graphene make it an ideal candidate for next generation nanoelectronics. With the recent development of commercial-level single-crystal graphene layers, the potential for manufacturing household graphene-based devices has improved, but significant challenges still remain with regards to patterning the graphene into devices. In the case of graphene supported on a substrate, traditional nanofabrication techniques such as e-beam lithography (EBL) are often used in fabricating graphene nanoribbons but the multi-step processes they require can result in contamination of the graphene with resists and solvents. In this letter, we report the utility of scanning helium ion lithography for fabricating functional graphene nanoconductors that are supported directly on a silicon dioxide layer, and we measure the minimum feature size achievable due to limitations imposed by thermal fluctuations and ion scattering during the milling process. Further we demonstrate that ion beams, due to their positive charging nature, may be used to observe and test the conductivity of graphene-based nanoelectronic devices in situ.

Correlating high power conversion efficiency of PTB7:PC71BM inverted organic solar cells with nanoscale structures.

Advances in material design and device engineering led to inverted organic solar cells (i-OSCs) with superior power conversion efficiencies (PCEs) compared to their "conventional" counterparts, in addition to the well-known better ambient stability. Here, we report an in-depth morphology study of the i-OSC active and cathode modifying layers, employing a model system with a well-established bulk-heterojunction, PTB7:PC71BM as the active layer and poly-[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) as the cathode surface modifying layer. We have also identified the role of a processing additive, 1,8-diiodooctane (DIO), used in the spin-casting of the active layer to increase PCE. Using various characterization techniques, we demonstrate that the high PCEs of i-OSCs are due to the diffusion of electron-accepting PC71BM into the PFN layer, resulting in improved electron transport. The diffusion occurs when residual solvent molecules in the spun-cast film act as a plasticizer. Addition of DIO to the casting solution results in more PC71BM diffusion and therefore more efficient electron transport. This work provides important insight and guidance to further enhancement of i-OSC performance by materials and interface engineering.

Degradation of Trichloroethene with a Novel Ball Milled Fe-C Nanocomposite.

Nanoscale zero-valent iron (NZVI) is effective in reductively degrading dense non-aqueous phase liquids (DNAPLs), such as trichloroethene (TCE), in groundwater (i.e., dechlorination) although the NZVI technology itself still suffers from high material costs and inability to target hydrophobic contaminants in source zones. To address these problems, we developed a novel, inexpensive iron-carbon (Fe-C) nanocomposite material by simultaneously milling micron-size iron and activated carbon powder. Microscopic and X-ray diffraction (XRD) characterization of the composite material revealed that nanoparticles of Fe were dispersed in activated carbon and a new iron carbide phase was formed. Bench-scale studies showed that this material instantaneously sorbed >90% of TCE from aqueous solutions and subsequently decomposed TCE into non-chlorinated products. Compared to milled Fe, Fe-C nanocomposite dechlorinated TCE at a slightly slower rate and favored the production of ethene over other TCE degradation products such as C3--C6 compounds. When placed in hexane-water mixture, the Fe-C nanocomposite materials are preferentially partitioned into the organic phase, indicating the ability of the composite materials to target DNAPL during remediation.

Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes.

Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5-10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance.

Scalable production of microbially mediated zinc sulfide nanoparticles and application to functional thin films.

A series of semiconducting zinc sulfide (ZnS) nanoparticles were scalably, reproducibly, controllably and economically synthesized with anaerobic metal-reducing Thermoanaerobacter species. These bacteria reduced partially oxidized sulfur sources to sulfides that extracellularly and thermodynamically incorporated with zinc ions to produce sparingly soluble ZnS nanoparticles with ∼5nm crystallites at yields of ∼5gl(-1)month(-1). A predominant sphalerite formation was facilitated by rapid precipitation kinetics, a low cation/anion ratio and a higher zinc concentration compared to background to produce a naturally occurring hexagonal form at the low temperature, and/or water adsorption in aqueous conditions. The sphalerite ZnS nanoparticles exhibited narrow size distribution, high emission intensity and few native defects. Scale-up and emission tunability using copper doping were confirmed spectroscopically. Surface characterization was determined using Fourier transform infrared and X-ray photoelectron spectroscopies, which confirmed amino acid as proteins and bacterial fermentation end products not only maintaining a nano-dimensional average crystallite size, but also increasing aggregation. The application of ZnS nanoparticle ink to a functional thin film was successfully tested for potential future applications.

Identifying active functionalities on few-layered graphene catalysts for oxidative dehydrogenation of isobutane.

The general consensus in the studies of nanostructured carbon catalysts for oxidative dehydrogenation (ODH) of alkanes to olefins is that the oxygen functionalities generated during synthesis and reaction are responsible for the catalytic activity of these nanostructured carbons. Identification of the highly active oxygen functionalities would enable engineering of nanocarbons for ODH of alkanes. Few-layered graphenes were used as model catalysts in experiments to synthesize reduced graphene oxide samples with varying oxygen concentrations, to characterize oxygen functionalities, and to measure the activation energies for ODH of isobutane. Periodic density functional theory calculations were performed on graphene nanoribbon models with a variety of oxygen functionalities at the edges to calculate their thermal stability and to model reaction mechanisms for ODH of isobutane. Comparing measured and calculated thermal stability and activation energies leads to the conclusion that dicarbonyls at the zigzag edges and quinones at armchair edges are appropriately balanced for high activity, relative to other model functionalities considered herein. In the ODH of isobutane, both dehydrogenation and regeneration of catalytic sites are relevant at the dicarbonyls, whereas regeneration is facile compared with dehydrogenation at quinones. The catalytic mechanism involves weakly adsorbed isobutane reducing functional oxygen and leaving as isobutene, and O2 in the feed, weakly adsorbed on the hydrogenated functionality, reacting with that hydrogen and regenerating the catalytic sites.

Solvent-type-dependent polymorphism and charge transport in a long fused-ring organic semiconductor.

Crystalline polymorphism of organic semiconductors is among the critical factors in determining the structure and properties of the resultant organic electronic devices. Herein we report for the first time a solvent-type-dependent polymorphism of a long fused-ring organic semiconductor and its crucial effects on charge transport. A new polymorph of 5,11-bis(triethylsilylethynyl)anthradithiophene (TES ADT) is obtained using solvent-assisted crystallization, and the crystalline polymorphism of TES ADT thin films is correlated with their measured hole mobilities. The best-performing organic thin film transistors of the two TES ADT polymorphs show subthreshold slopes close to 1 V dec(-1), and threshold voltages close to zero, indicating that the density of traps at the semiconductor-dielectric interface is negligible in these devices and the observed up to 10-fold differences in hole mobilities of devices fabricated with different solvents are largely resultant from the presence of two TES ADT polymorphs. Moreover, our results suggest that the best-performing TES ADT devices reported in the literature correspond to the new polymorph identified in this study, which involves crystallization from a weakly polar solvent (such as toluene and chloroform).