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Ion exchange is one of the most interesting processes occurring at the interface between aqueous solutions and polymers, such as the well-known Nafion. If the exchanged ions have different diffusion coefficients, this interchange generates local electric fields which can be harnessed to drive fluid motion. In this work, we show how it is possible to design and fabricate self-propelling microswimmers based on Nafion, driven by ion-exchange, and fueled by innocuous salts. These Nafion micromotors are made using colloidal lithography by micro/nanostructuring Nafion in the form of asymmetric rods. These microswimmers exhibit fascinating collective motion in water driven by the interplay of their self-generated chemical/electric fields and their capability to pump matter nearby towards the collective motile structure. The pumping activity of the microswimmers induces the formation of growing mobile clusters, whose velocity increases with size. Such dynamic structures are able to trap nearby micro/nano-objects while purifying the liquid, which acts both as the transport media and as fuel. Such phenomenology opens the door to potential applications in water remediation that are currently under development.
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An accurate knowledge of the parameters governing the kinetics of block copolymer self-assembly is crucial to model the time- and temperature-dependent evolution of pattern formation during annealing as well as to predict the most efficient conditions for the formation of defect-free patterns. Here, the self-assembly kinetics of a lamellar PS-b-PMMA block copolymer under both isothermal and non-isothermal annealing conditions are investigated by combining grazing-incidence small-angle X-ray scattering (GISAXS) experiments with a novel modelling methodology that accounts for the annealing history of the block copolymer film before it reaches the isothermal regime. Such a model allows conventional studies in isothermal annealing conditions to be extended to the more realistic case of non-isothermal annealing and prediction of the accuracy in the determination of the relevant parameters, namely the correlation length and the growth exponent, which define the kinetics of the self-assembly.
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One of the most striking properties of Nafion is the formation of a long-range solute exclusion zone (EZ) in contact with water. The mechanism of formation of this EZ has been the subject of a controversial and long-standing debate. Previous studies by Schurr et al. and Florea et al. root the explanation of this phenomenon in the ion-exchange properties of Nafion, which generates ion diffusion and ion gradients that drive the repulsion of solutes by diffusiophoresis. Here we have evaluated separately the electrophoretic and chemiphoretic contributions to multi-ionic diffusiophoresis using differently charged colloidal tracers as solutes to identify better their contribution in the EZ formation. Our experimental results, which are also supported by numerical simulations, show that the electric field, built up due to the unequal diffusion coefficients of the exchanged ions, is the dominant parameter behind such interfacial phenomenon in the presence of alkali metal chlorides. The EZ formation depends on the interplay of the electric field with the zeta potential of the solute and can be additionally modulated by changing ion diffusion coefficients or adding salts. As a consequence, we show that not all solutes can be expelled from the Nafion interface and hence the EZ is not always formed. This study thus provides a more detailed description of the origin and dynamics of this phenomenon and opens the door to the rational use of this active interface for many potential applications.
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Platinum thin films activated ex situ by oxygen plasma become reduced by the combined effect of an intense soft X-ray photon beam and condensed water. The evolution of the electronic structure of the surface has been characterized by near-ambient-pressure photoemission and mimics the inverse two-step sequence observed in the electro-oxidation of platinum, i.e. the surface-oxidized platinum species are reduced first and then the adsorbed species desorb in a second step leading to a surface dominated by metallic platinum. The comparison with measurements performed under high-vacuum conditions suggests that the reduction process is mainly induced by the reactive species generated by the radiolysis of water. When the photon flux is decreased, then the reduction process becomes slower.
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The development of effective autonomous micro- and nanomotors relies on controlling fluid motion at interfaces. One of the main challenges in the engineering of such artificial machines is the quest for efficient mechanisms to power them without using external driving forces. In the past decade, there has been an important increase of man-made micro- and nanomotors fueled by self-generated physicochemical gradients. Impressive proofs of concept of multitasking machines have been reported demonstrating their capabilities for a plethora of applications. While the progress toward applications is promising, there are still open questions on fundamental physicochemical aspects behind the mechanical actuation, which require more experimental and theoretical efforts. These efforts are not merely academic but will open the door for an efficient and practical implementation of such promising devices. In this Account, we focus on chemically driven motors whose motion is the result of a complex interplay of chemical reactions and (electro)hydrodynamic phenomena. A reliable study of these processes is rather difficult with mobile objects like swimming motors. However, pumps, which are the immobilized motor counterparts, emerge as simple manufacturing and well-defined platforms for a better experimental probing of the mechanisms and key parameters controlling the actuation. Here we review some recent studies using a new methodology that has turned out to be very helpful to characterize micropump chemomechanics. The aim was to identify the redox role of the motor components, to map the chemical reaction, and to quantify the relevant electrokinetic parameters (e.g., electric field and fluid flow). This was achieved by monitoring the velocity of differently charged tracers and by fluorescence imaging of the chemical species involved in the chemical reaction, for example, proton gradients. We applied these techniques to different systems of interest. First, we probed bimetallic pumps as counterparts of the pioneering bimetallic swimmers. We corroborated that fluid motion was due to a self-generated electro-osmotic mechanism driven by the redox decomposition of H2O2. In addition, we analyzed by simulations the key parameters that yield an optimized operation. Moreover, we accomplished a better assessment of the importance of surface chemistry on the metal electrochemical response, highlighting its relevance in controlling the redox role of the metals and motion direction. Second, we focused on metallic and semiconductor micropumps to analyze light-controlled motion mechanisms through photoelectrochemical decomposition of fuels. These pumps were driven by visible light and could operate using just water as fuel. In these systems, we found a very interesting competition between two different mechanisms for fluid propulsion, namely, light-activated electro-osmosis and light-insensitive diffusio-osmosis, stemming from different chemical pathways in the fuel decomposition. In this case, surface roughness becomes a pivotal parameter to enhance or depress one mechanism over the other. These examples demonstrate that pumps are practical platforms to explore operating mechanisms and to quantify their performance. Additionally, they are suitable systems to test novel fuels or motor materials. This knowledge is extensible to swimmers providing not only fundamental understanding of their locomotion mechanisms but also useful clues for their design and optimization.
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One-dimensional (1D) nanostructured surfaces based on high-density arrays of nanowires and nanotubes of photoactive titanium dioxide (TiO2) present a tunable wetting behavior from superhydrophobic to superhydrophilic states. These situations are depicted in a reversible way by simply irradiating with ultraviolet light (superhydrophobic to superhydrophilic) and storage in dark. In this article, we combine in situ environmental scanning electron microscopy (ESEM) and near ambient pressure photoemission analysis (NAPP) to understand this transition. These experiments reveal complementary information at microscopic and atomic level reflecting the surface wettability and chemical state modifications experienced by these 1D surfaces upon irradiation. We pay special attention to the role of the water condensation mechanisms and try to elucidate the relationship between apparent water contact angles of sessile drops under ambient conditions at the macroscale with the formation of droplets by water condensation at low temperature and increasing humidity on the nanotubes' surfaces. Thus, for the as-grown nanotubes, we reveal a metastable and superhydrophobic Cassie state for sessile drops that tunes toward water dropwise condensation at the microscale compatible with a partial hydrophobic Wenzel state. For the UV-irradiated surfaces, a filmwise wetting behavior is observed for both condensed water and sessile droplets. NAPP analyses show a hydroxyl accumulation on the as-grown nanotubes surfaces during the exposure to water condensation conditions, whereas the water filmwise condensation on a previously hydroxyl enriched surface is proved for the superhydrophilic counterpart.
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The generation of reactive oxygen species (ROS) via the Fenton reaction has received significant attention for widespread applications. This reaction can be triggered by zero-valent metal nanoparticles by converting externally added H2O2 into hydroxyl radicals (ËOH) in acidic media. To avoid the addition of external additives or energy supply, developing self-sustained catalytic systems enabling onsite production of H2O2 at a neutral pH is crucial. Here, we present novel galvanic nanocells (GNCs) based on metallic Fe/Au bilayers on arrays of nanoporous silica nanostructures for the generation of self-sustained Fenton reactions. These GNCs exploit the large electrochemical potential difference between the Fe and Au layers to enable direct H2O2 production and efficient release of Fe2+ in water at neutral pH, thereby triggering the Fenton reaction. Additionally, the GNCs promote Fe2+/Fe3+ circulation and minimize side reactions that passivate the iron surface to enhance their reactivity. The capability to directly trigger the Fenton reaction in water at pH 7 is demonstrated by the fast degradation and mineralization of organic pollutants, by using tiny amounts of catalyst. The self-generated H2O2 and its transformation into ËOH in a neutral environment provide a promising route not only in environmental remediation but also to produce therapeutic ROS and address the limitations of Fenton catalytic nanostructures.
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Although molecular metals have been known for decades, their insolubility, low vapor pressure, and synthesis routes have prevented them from being integrated into electronic devices. We have prepared stable colloidal solutions of the organic metal TTF-TCNQ that overcome such difficulties. The solutions contain well-dispersed nanoparticles stabilized by long alkyl chain amines. They afford soluble powders by evaporation and homogeneous thin films by drop-casting. Powders and films show room temperature conductivities in the 0.01-0.1 S cm(-1) range.
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Water becomes ordered in the form of hexagonal ice at room temperature under controlled humidity conditions upon confinement in the nanometer range between protective graphene sheets and crystalline (111) surfaces with hexagonal symmetry of the alkali earth fluoride BaF2. Interfacial water/substrate pseudoepitaxy turns out to be a critical parameter since ice is only formed when the lattice mismatch is small, an observation based on the absence of ice on (111) surfaces of isostructural CaF2.
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Chemically propelled micropumps are promising wireless systems to autonomously drive fluid flows for many applications. However, many of these systems are activated by nocuous chemical fuels, cannot operate at high salt concentrations, or have difficulty for controlling flow directionality. In this work we report on a self-driven polymer micropump fueled by salt which can trigger both radial and unidirectional fluid flows. The micropump is based on the cation-exchanger Nafion, which produces chemical gradients and local electric fields capable to trigger interfacial electroosmotic flows. Unidirectional pumping is predicted by simulations and achieved experimentally by nanostructuring Nafion into microarrays with a fine tune modulation of surrounding surface zeta potentials. Nafion micropumps work in a wide range of salt concentrations, are reusable, and can be fueled by different salt cations. We demonstrate that they work with the common water-contaminant cadmium, using the own capture of this ion as fuel to drive fluid pumping. Thus, this system has potential for efficient and fast water purification strategies for environmental remediation. Unidirectional Nafion pumps also hold promise for effective analyte delivery or preconcentration for (bio)sensing assays.
Asunto(s)
Nanoestructuras , Agua , Electroósmosis , Polímeros de FluorocarbonoRESUMEN
The metallic and semiconducting character of a large family of organic materials based on the electron donor molecule tetrathiafulvalene (TTF) is rooted in the partial oxidation (charge transfer or mixed valency) of TTF derivatives leading to partially filled molecular orbital-based electronic bands. The intrinsic structure of such complexes, with segregated donor and acceptor molecular chains or planes, leads to anisotropic electronic properties (quasi one-dimensional or two-dimensional) and morphology (needle-like or platelet-like crystals). Recently, such materials have been synthesized as nanoparticles by intentionally frustrating the intrinsic anisotropic growth. X-ray photoemission spectroscopy (XPS) has emerged as a valuable technique to characterize the transfer of charge due to its ability to discriminate the different chemical environments or electronic configurations manifested by chemical shifts of core level lines in high-resolution spectra. Since the photoemission process is inherently fast (well below the femtosecond time scale), dynamic processes can be efficiently explored. We determine here the fingerprint of partial oxidation on the photoemission lines of nanoparticles of selected TTF-based conductors.
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We have studied the adsorption properties of a charge donor organic molecule, tetrathiafulvalene (TTF), on the (110) surfaces of silver and gold by means of the generalized gradient approach of the density functional theory using periodic slab models. This molecule is the core building block of a host of molecular materials exhibiting extremely reach phase diagrams with a variety of ground states. The interfaces formed with metallic surfaces have received only limited attention, despite of their relevance. We have determined the stable adsorption sites for two unit cells representing high and low coverage, which are determinant for the adsorption properties of TTF on the surface. The preferential chemisorption is via the direct interaction of sulfur atoms with the Ag or Au atoms on top sites. All adsorbed TTF are more stable than gas phase TTF. The simulation of the vibrational spectra has permitted us to find the fingerprints of these structures to characterize them on this surface. The donor nature of TTF induces charge transfer to the metallic surfaces.
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The silver-copper mixed oxide AgCuO(2) (also formulated as Ag(2)Cu(2)O(4)) possesses a peculiar electronic structure in which both Ag and Cu are partially oxidized, with the charge being delocalized among the three elements in the oxide. Accordingly, a quasi-metallic behavior should be expected for this oxide, and indeed bulk transport measurements show conductivity values that are orders of magnitude higher than for other members of this novel oxide family. The presence of silver makes thermal sintering an inadequate method to evaluate true conductivity, and thus such measurements were performed on low density pellets, giving an underestimated value for the conductivity. In the present work we present a new synthetic route for AgCuO(2) based on mild hydrothermal reactions that has yielded unprecedented large AgCuO(2) single-crystals well over 1 µm in size using temperatures as low as 88 °C. We have used a dual beam instrument to apply nanocontacts to those crystals, allowing the in situ measurement of transport properties of AgCuO(2) single crystals. The results show a linear relationship between applied current and measured voltage. The conductivity values obtained are 50 to 300 times higher than those obtained for bulk low density AgCuO(2) pellets, thus confirming the high conductivity of this oxide and therefore supporting the delocalized charge observed by spectroscopic techniques.
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High-density and high-resolution line and space patterns on surfaces are obtained by directed self-assembly of lamella-forming block copolymers (BCPs) using wide-stripe chemical guiding patterns. When the width of the chemical pattern is larger than the half-pitch of the BCP, the interaction energy between each BCP domain and the surface is crucial to obtain the desired segregated film morphology. We investigate how the intermixing between BCPs and polymer brush molecules on the surface influences the optimal surface and interface free energies to obtain a proper BCP alignment. We have found that computational models successfully predict the experimentally obtained guided patterns if the penetrability of the brush layer is taken into account instead of a hard, impenetrable surface. Experiments on directed self-assembly of lamella-forming poly(styrene- block-methyl methacrylate) using chemical guiding patterns corroborate the models used in the simulations, where the values of the surface free energy between the BCP and the guiding and background stripes are accurately determined using an experimental method based on the characterization of contact angles in droplets formed after dewetting of homopolymer blends.
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Time resolution is one of the most severe limitations of scanning probe microscopies (SPMs), since the typical image acquisition times are in the order of several seconds or even few minutes. As a consequence, the characterization of dynamical processes occurring at surfaces (e.g. surface diffusion, film growth, self-assembly and chemical reactions) cannot be thoroughly addressed by conventional SPMs. To overcome this limitation, several years ago we developed a first prototype of the FAST module, an add-on instrument capable of driving a commercial scanning tunneling microscope (STM) at and beyond video rate frequencies. Here we report on a fully redesigned version of the FAST module, featuring improved performance and user experience, which can be used both with STMs and atomic force microscopes (AFMs), and offers additional capabilities such as an atom tracking mode. All the new features of the FAST module, including portability between different commercial instruments, are described in detail and practically demonstrated.
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The determination of nanomechanical properties is an intensive topic of study in several fields of nanophysics, from surface and materials science to biology. At the same time, amplitude modulation force microscopy is one of the most established techniques for nanoscale characterization. In this work, we combine these two topics and propose a method able to extract quantitative nanomechanical information from higher harmonic amplitude imaging in atomic force microscopy. With this method it is possible to discriminate between different materials in the stiffness range of 1-3â¯GPa, in our case thin films of PS-PMMA based block copolymers. We were able to obtain a critical lateral resolution of less than 20â¯nm and discriminate between materials with less than a 1â¯GPa difference in modulus. We show that within this stiffness range, reliable values of the Young's moduli can be obtained under usual imaging conditions and with standard dynamic AFM probes.
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Self-propelled micro/nanomotors that can transform chemical energy from the surrounding environment into mechanical motion are cutting edge nanotechnologies with potential applications in biomedicine and environmental remediation. These applications require full understanding of the propulsion mechanisms to improve the performance and controllability of the motors. In this work, we demonstrate that there are two competing chemomechanical mechanisms at semiconductor/metal (Si/Pt) micromotors in a pump configuration under visible light exposure. The first propulsion mechanism is driven by an electro-osmotic process stemmed from a photoactivation reaction mediated by H2O2, which takes place in two separated redox reactions at the Si and Pt interfaces. One reaction involves the oxidation of H2O2 at the silicon side, and the other the H2O2 reduction at the metal side. The second mechanism is not light responsive and is triggered by the redox decomposition of H2O2 exclusively at the Pt surface. We show that it is possible to enhance/suppress one mechanism over the other by tuning the surface roughness of the micromotor metal. More specifically, the actuation mechanism can be switched from light-controlled electrokinetics to light-insensitive diffusio-osmosis by only increasing the metal surface roughness. The different actuation mechanisms yield strikingly different fluid flow velocities, electric fields, and light sensitivities. Consequently, these findings are very relevant and can have a remarkable impact on the design and optimization of photoactivated catalytic devices and, in general, on bimetallic or insulating-metallic motors.
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We present a combined theoretical and experimental study of the dependence of resonant higher harmonics of rectangular cantilevers of an atomic force microscope (AFM) as a function of relevant parameters such as the cantilever force constant, tip radius and free oscillation amplitude as well as the stiffness of the sample's surface. The simulations reveal a universal functional dependence of the amplitude of the 6th harmonic (in resonance with the 2nd flexural mode) on these parameters, which can be expressed in terms of a gun-shaped function. This analytical expression can be regarded as a practical tool for extracting qualitative information from AFM measurements and it can be extended to any resonant harmonics. The experiments confirm the predicted dependence in the explored 3-45 N/m force constant range and 2-345 GPa sample's stiffness range. For force constants around 25 N/m, the amplitude of the 6th harmonic exhibits the largest sensitivity for ultrasharp tips (tip radius below 10 nm) and polymers (Young's modulus below 20 GPa).
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In recent years, block copolymer lithography has emerged as a viable alternative technology for advanced lithography. In chemical-epitaxy-directed self-assembly, the interfacial energy between the substrate and each block copolymer domain plays a key role on the final ordering. Here, we focus on the experimental characterization of the chemical interactions that occur at the interface built between different chemical guiding patterns and the domains of the block copolymers. We have chosen hard X-ray high kinetic energy photoelectron spectroscopy as an exploration technique because it provides information on the electronic structure of buried interfaces. The outcome of the characterization sheds light onto key aspects of directed self-assembly: grafted brush layer, chemical pattern creation and brush/block co-polymer interface.