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Functionalisation of technological nanopores and investigation of their transport properties have attracted considerable interest from scientific as from technological point of view, among others due to their potential regarding molecular transport design. Asymmetric design of nanopore structure and functionalisation is expected to trigger increased and directed transport of ionic species. Based on this motivation, we demonstrate a layer-selective polymer functionalisation in a mesoporous double layer thin film to generate nanoscale step gradient architectures with asymmetric charge distribution by taking advantage of co-condensation and polymer modification techniques. Thereby, mesoporous silica and co-condensed mesoporous amino silica thin films are combined to double layered films with a film thickness of 300 – 400 nm in both sequential arrangements, respectively. Iniferter initiated polymerisation is used to selectively functionalise only the amino silica layer with polymers such as poly(2-(methacryloyloxy)ethyltrimethylammonium chloride) (PMETAC) in a grafting from approach. Investigation of the ionic pore accessibility of the mesoporous double layered films before and after layer-selective polymer functionalisation shows that the ionic pore accessibility is dominated by the bottom layer when overcoming the electrostatic repulsion of the top layer.

Nickel cobalt layered double hydroxide (NiCo-LDH)-based materials have recently emerged as catalysts for important electrochemical applications. However, they frequently suffer from low electrical conductivity and agglomeration, which in turn impairs their performance. Herein, we present a catalyst design based on integrated, self-supported nickel nanotube networks (Ni-NTNWs) loaded with NiCo-LDH nanosheets, which represents a binder-free, hierarchically nanostructured electrode architecture combining continuous conduction paths and openly accessible macropores of low tortuosity with an ultrahigh density of active sites. Similar to macroscale metallic foams, the NTNWs serve as three-dimensionally interconnected, robust frameworks for the deposition of active material, but are structured in the submicron range. Our synthesis is solely based on scalable approaches, namely templating with commercial track-etched membranes, electroless plating, and electrodeposition. Morphological and compositional characterization proved the successful decoration of the inner and outer nanotube surfaces with a conformal NiCo-LDH layer. Ni-NTNW electrodes and hydroxide-decorated variants showed excellent performance in glucose sensing. The highest activity was achieved for the catalyst augmented with NiCo-LDH nanosheets, which surpassed the modification with pure Ni(OH)2. Despite its low thickness of 20 µm, the optimized catalyst layer provided an outstanding sensitivity of 4.6 mA mM−1 cm−2, a low detection limit of 0.2 µM, a fast response time of 5.3 s, high selectivity and stability, and two linear ranges covering four orders of magnitude, up to 2.5 mM analyte. As such, derivatized interconnected metal nano-networks represent a promising design paradigm for highly miniaturized yet effective catalyst electrodes and electrochemical sensors.

Electroless plating is a powerful tool in nanofabrication and is available for many of the noble transition metals. There is, however, a striking lack of electroless plating procedures for the rarer platinum-group metals. In this work, two plating baths for nanoscale iridium coatings are developed and their conformality and nanofabrication potential are showcased by coating ion-track-etched polycarbonate membranes, creating Ir nanotubes in the process. Both plating solutions yield morphologically different deposits, indicating that the microstructure of the film can be tuned by adjusting the composition of the plating bath. The catalytic performance of the deposited materials is investigated by using membrane-embedded nanotubes as catalysts for the reduction of 4-nitrophenol and methyl orange by borohydride, showing remarkable activity and stability. Operation in flow-through configuration, in which the metallized membrane is implemented as a microreactor greatly enhances the interaction with the catalyst surface, considerably increasing product yield. The results highlight the potential of Ir nanoplating for realizing sophisticated nanostructures and heterogeneous catalysts, but also illustrate the intricacies related to the complex chemistry of electroless Ir plating baths.

Owing to their large surface area, continuous conduction paths, high activity and pronounced anisotropy, nanowires are pivotal for a wide range of applications, yet far from thermodynamic equilibri...

The understanding and design of wetting-transport and wetting-charge-transport interplay in nanometer-sized pores is a still not fully understood key step in improving nanopore transport-related applications. A control of mesopore wettability accompanied by pore filling and ionic mesopore accessibility analysis is expected to deliver major insights into this interplay of nanoscale pore wetting and transport. For a systematic understanding, we demonstrate a gradual adjustment of nanopore ionic accessibility by gradually tuning silica nanopore wettability using chemical vapor phase deposition of 1H,1H,2H,2H-perfluorooctyl dimethylchlorosilane. The mutual influence of wetting on liquid imbibition, condensation, and molecular transport as well as on heat transfer were studied by ellipsometry, cyclic voltammetry and boiling experiments, respectively. A multi-methodical analytic approach was used to directly couple wetting properties of mesoporous silica thin films to ionic mesopore accessibility allowing us to determine two different ion transport mechanisms based on three defined wetting regimes as well as a threshold hydrophobicity suppressing pore accessibility. Furthermore, boiling experiments showed a clear increase in nucleation site density upon changing the wettability of the mesoporous surfaces from hydrophilic to hydrophobic. Hence, these results provide insights into the complex interplay of pore wall functionalization, wetting, and charge-dependent nanopore properties.

Due to its simplicity, flexibility and conformity, electroless plating presents itself as an attractive route towards functional metal nanostructures. Despite the importance for creating multimetallic materials with enhanced properties, the complex interactions between the components in electroless plating baths make alloy formations a challenging objective. In this work, we outline an electroless plating strategy fabricating Pd−Pt alloy nanomaterials, which is based on arbitrarily miscible plating baths for the individual metals. To demonstrate the excellent nanoscale conformity and homogeneity of our plating system, we apply it to ion track‐etched polymer templates with large inner surfaces as ambitious substrates, resulting in the formation of 3D free‐standing PdₓPt₁₀₀₋ₓ‐nanotube‐networks (NTNWs). Based on the electro‐oxidation of methanol as a model reaction, we utilize the compositional freedom provided by our syntheses for optimizing the catalytic performance of our metal NTNWs, which heavily depends on the Pd−Pt ratio. Within our system, the highest surface normalized activity was found for the Pd₂₀Pt₈₀ NTNW, reaching more than a two‐fold increase of the peak current density in comparison to pure Pt. Overall, our reaction system provides a versatile toolkit for fabricating intricate Pd−Pt nanostructures of arbitrary elemental composition, and constitutes a starting point for designing new electroless alloy plating baths.

Many nanofabrication processes require sophisticated equipment, elevated temperature, vacuum or specific atmospheric conditions, templates, and exotic chemicals, which severely hamper their implementation in real-world applications. In this study, we outline a fully wet-chemical procedure for equipping a 3D carbon felt (CF) substrate with a multifunctional, titania nanospike-supported Pt-Pd nanoparticle (Pt-Pd-TiO2@CF) layer in a facile and scalable manner. The nanostructure, composition, chemical speciation, and formation of the material was meticulously investigated, evidencing the conformal coating of the substrate with a roughened layer of nanocrystalline rutile spikes by chemical bath deposition from Ti3+ solutions. The spikes are densely covered by bimetallic nanoparticles of 4.4 ± 1.1 nm in size, which were produced by autocatalytic Pt deposition onto Pd seeds introduced by Sn2+ ionic layer adsorption and reaction. The as-synthesized nanocomposite was applied to the (photo)electro-oxidation of formic acid (FA), exhibiting a superior performance compared to Pt-plated, Pd-seeded CF (Pt-Pd@CF) and commercial Pt-C, indicating the promoting electrocatalytic role of the TiO2 support. Upon UV-Vis illumination, the performance of the Pt-Pd-TiO2@CF electrode is remarkably increased (22-fold), generating a current density of 110 mA cm-2, distinctly outperforming titania-free Pt-Pd@CF (5 mA cm-2) and commercial Pt-C (6 mA cm-2) reference catalysts. In addition, the Pt-Pd-TiO2@CF showed a much better stability, characterized by a very high poisoning tolerance for in situ-generated CO intermediates, whose formation is hindered in the presence of TiO2. This overall performance boost is attributed to a dual enhancement mechanism (∼30% electrocatalytic and ∼70% photoelectrocatalytic). The photogenerated electrons from the TiO2 conduction band enrich the electron density of the Pt nanoparticles, promoting the generation of active oxygen species on their surfaces from adsorbed oxygen and water molecules, which facilitate the direct FA electro-oxidation into CO2.

Nano-objects are favored structures for applications such as catalysis and sensing. Although they already provide a large surface-to-volume ratio, this ratio can be further increased by shape-selective plating of the nanostructure surfaces. This process combines the conformity of autocatalytic deposition with the defined nucleation and growth characteristics of colloidal nanoparticle syntheses. However, many aspects of such reactions are still not fully understood. In this study, we investigate in detail the growth of spiky nickel nanotubes in polycarbonate template membranes. One distinctive feature of our synthesis is the simultaneous growth of nanospikes on both the inside and outside of nanotubes while the tubes are still embedded in the polymer. This is achieved by combining the plating process with locally enhanced in situ etching of the poylmer template, for which we propose a theory. Electron microscopy investigations reveal twinning defects as the driving force for the growth of crystalline nanospikes. Deposit crystallinity is ensured by the reducing agent hydrazine. Iminodiacetic acid is not only used as a complexing agent during synthesis but apparently also acts as a capping agent and limits random nucleation on the spike facets. Finally, we apply our synthesis to templates with interconnected pores to obtain free-standing spiky nickel nanotube networks, demonstrating its ability to homogeneously coat substrates with extended inner surfaces and to operate in nanoscale confinement.

Bioinspired solid-state nanopores and nanochannels have attracted interest in the last two decades, as they are envisioned to advance future sensing, energy conversion, and separation concepts. Although much effort has been made regarding functionalization of these materials, multifunctionality and accurate positioning of functionalities with nanoscale precision still remain challenging. However, this precision is necessary to meet transport performance and complexity of natural pores in living systems, which are often based on nonequilibrium states and compartmentalization. In this work, a nanolocal functionalization and simultaneous localized sensing strategy inside a filtering mesoporous film using precisely placed plasmonic metal nanoparticles inside mesoporous films with pore accessibility control is demonstrated. A single layer of gold nanoparticles is incorporated into mesoporous thin films with precise spatial control along the nanoscale layer thickness. The local surface plasmon resonance is applied to induce a photopolymerization leading to a nanoscopic polymer shell around the particles and thus nanolocal polymer placement inside the mesoporous material. As near-field modes are sensitive to the dielectric properties of their surrounding, the in situ sensing capability is demonstrated using UV–vis spectroscopy. It is demonstrated that the sensing sensitivity only slightly decreases upon functionalization. The presented nanolocal placement of responsive functional polymers into nanopores offers a simultaneous filtering and nanoscopic readout function. Such a nanoscale local control is envisioned to have a strong impact onto the development of new transport and sensor concepts, especially as the system can be developed into higher complexity using different metal nanoparticles and additional design of mesoporous film filtering properties.

Bioinspired solid-state nanopores and nanochannels have attracted interest in the last two decades, as they are envisioned to advance future sensing, energy conversion, and separation concepts. Although much effort has been made regarding functionalization of these materials, multifunctionality and accurate positioning of functionalities with nanoscale precision still remain challenging. However, this precision is necessary to meet transport performance and complexity of natural pores in living systems, which are often based on nonequilibrium states and compartmentalization. In this work, a nanolocal functionalization and simultaneous localized sensing strategy inside a filtering mesoporous film using precisely placed plasmonic metal nanoparticles inside mesoporous films with pore accessibility control is demonstrated. A single layer of gold nanoparticles is incorporated into mesoporous thin films with precise spatial control along the nanoscale layer thickness. The local surface plasmon resonance is applied to induce a photopolymerization leading to a nanoscopic polymer shell around the particles and thus nanolocal polymer placement inside the mesoporous material. As near-field modes are sensitive to the dielectric properties of their surrounding, the in situ sensing capability is demonstrated using UV–vis spectroscopy. It is demonstrated that the sensing sensitivity only slightly decreases upon functionalization. The presented nanolocal placement of responsive functional polymers into nanopores offers a simultaneous filtering and nanoscopic readout function. Such a nanoscale local control is envisioned to have a strong impact onto the development of new transport and sensor concepts, especially as the system can be developed into higher complexity using different metal nanoparticles and additional design of mesoporous film filtering properties.

Abstract Mass activity and long-term stability are two major issues in current fuel cell catalyst designs. While supported catalysts normally suffer from poor long-term stability but show high mass activity, unsupported catalysts tend to perform better in the first point while showing deficits in the latter one. In this study, a facile synthesis route towards self-supported metallic electrocatalyst nanoarchitectures with both aspects in mind is outlined. This procedure consists of a palladium seeding step of ion track-etched polymer templates followed by a nickel electrodeposition and template dissolution. With this strategy, free-standing nickel nanowire networks which contain palladium nanoparticles only in their outer surface are obtained. These networks are tested in anodic half-cell measurements for demonstrating their capability of oxidising methanol in alkaline electrolytes. The results from the electrochemical experiments show that this new catalyst is more tolerant towards high methanol concentrations (up to $${5}\,\hbox{mol}\,\hbox{L}^{-1}$$ 5 mol L - 1 ) than a commercial carbon supported palladium nanoparticle catalyst and provides a much better long-term stability during potential cycling. Graphical Abstract

In this study, molecular beam epitaxy is utilized to stabilize a nanostructured thin-film magnet consisting of a soft magnetic Y2Co17 exchange coupled to hard magnetic YCo5. While, typically, a phase decomposition can be obtained in rare-earth cobalt systems only by the addition of further elements like Cu, Fe, and Zr and complex heat treatments, here we directly induce phase separation by growth kinetics. The resulting nanoscale architecture, as revealed by cross-sectional transmission electron microscopy, is composed of a network of coherently interlinked and aligned Y2Co17 and YCo5 building blocks. The formation of coherent precipitations is facilitated by the perfectly matching lattice constants, atomic species, and crystal symmetry of the two phases with vastly different magnetocrystalline anisotropies. The hard magnetic phase induces an aligned uniaxial anisotropy in Y2Co17, resulting in substantial coercivity associated with enhanced energy products. This work highlights the importance of thin-film epitaxy in understanding magnetic hardening mechanisms and suggests strategies for a rational design of future sustainable magnetic systems.

Recent advances in microelectromechanical systems (MEMS) based chips for in situ transmission electron microscopy are opening exciting new avenues in nanoscale research. The capability to perform current-voltage measurements while simultaneously analyzing the corresponding structural, chemical or even electronic structure changes during device operation would be a major breakthrough in the field of nanoelectronics. In this work we demonstrate for the first time how to electrically contact and operate a lamella cut from a resistive random access memory (RRAM) device based on a Pt/HfO2/TiN metal-insulator-metal (MIM) structure. The device was fabricated using a focused ion beam (FIB) instrument and an in situ lift-out system. The electrical switching characteristics of the electron-transparent lamella were comparable to a conventional reference device. The lamella structure was initially found to be in a low resistance state and could be reset progressively to higher resistance states by increasing the positive bias applied to the Pt anode. This could be followed up with unipolar set/reset operations where the current compliance during set was limited to 400 µA. FIB structures allowing to operate and at the same time characterize electronic devices will be an important tool to improve RRAM device performance based on a microstructural understanding of the switching mechanism.

Pt-decorated $$\hbox {TiO}_{2}$$ nanotubes Pt@TiO2 are prepared only by applying a set of facile wet-chemical redox reactions to ion track-etched polycarbonate templates. First, a homogeneous layer of Pt nanoparticles is deposited onto the complex template surface by reducing potassium tetrachloroplatinate with absorbed dimethylaminoborane. Second, the template is coated with a conformal $$\hbox {TiO}_{2}$$ layer, using a chemical bath deposition reaction based on titanium(III) chloride. After the removal of the template, the rutile-type $$\hbox {TiO}_{2}$$ nanotubes remain decorated with Pt nanoparticles and nanoparticle-clusters on their outside. During the process, neither vacuum techniques nor external current sources or addition of heat are employed. The crystallinity, composition, and morphology of the composite nanotubes are analysed by X-ray diffraction, scanning and transmission electron microscopy as well as by energy-dispersive X-ray spectroscopy. Finally, the obtained materials are examplarily applied in the electrooxidation of ethanol and formic acid, and their performances have been evaluated. Compared to conventional carbon black-supported Pt nanoparticles, the Pt@TiO2 nanotubes show higher reaction rates. Mass activities of 2.36 $$\hbox {A}\hbox { mg}_{\rm Pt}^{-1}\hbox { cm}^{-2}$$ are reached in ethanol oxidation and 7.56 $$\hbox {A}\hbox { mg}_{\rm Pt}^{-1}\hbox { cm}^{-2}$$ in the formic acid oxidation. The present structures are able to exploit the synergy of Pt and $$\hbox {TiO}_{2}$$ with a bifunctional mechanism to result in powerful but easy-to-fabricate catalyst structures. They represent an easily producible type of composite nanostructures which can be applied in various fields such as in catalytics and sensor technology.

In paper-based devices, capillary fluid flow is based on length-scale selective functional control within a hierarchical porous system. The fluid flow can be tuned by altering the paper preparation process, which controls parameters such as the paper grammage. Interestingly, the fiber morphology and nanoporosity are often neglected. In this work, porous voids are incorporated into paper by the combination of dense or mesoporous ceramic silica coatings with hierarchically porous cotton linter paper. Varying the silica coating leads to significant changes in the fluid flow characteristics, up to the complete water exclusion without any further fiber surface hydrophobization, providing new approaches to control fluid flow. Additionally, functionalization with redox-responsive polymers leads to reversible, dynamic gating of fluid flow in these hybrid paper materials, demonstrating the potential of length scale specific, dynamic, and external transport control.

The application of electroless plating to porous template membranes displays an important route towards one-dimensional metal nanostructures such as nanotubes. For this reaction class, activation pretreatments are required to introduce catalyst seeds, which initiate surface-selective metal deposition from the metastable plating baths. Hitherto, these pretreatments are performed as a means to an end to ensure reliable metal film nucleation, and introduce often undesired contaminations. In this work, we demonstrate that the seeding step can be recognized as a synthetic tool to purposefully adjust the chemical composition of electrolessly plated nanomaterials. By consecutive application of several interfacial reactions (polymer swelling, reducing agent absorption, metal nanoparticle nucleation, autocatalytic metal deposition), we fabricate gold-platinum nanotubes of well-defined composition. Aside strictly monometallic gold and platinum nanotubes, bimetallic nanotubes are produced which consist of platinum nanoparticies embedded in gold walls. As shown in the electrooxidation of formic acid, the nanotube composition has a pronounced impact on the properties of the resulting materials and can be used to enhance the catalyst performance. The outlined strategy provides a versatile route towards sets of compositionally varying metal nanostructures and allows to examine and to exploit multi-element synergies. (C) 2016 Elsevier B.V. All rights reserved.

The fabrication of ordered superstructures composed of nano- and microscale building blocks is of tremendous interest. In this work, we present a versatile approach for the synthesis of hierarchical and free-standing metal architectures of high structural complexity. Using the ion-track etching technique, hierarchically porous polycarbonate membranes are obtained, which are employed as nanocasting templates. Pore filling is accomplished by the two complementary wet-chemical techniques electrodeposition and electroless plating. Depending on the pore filling mechanism and the template structure, a wide range of novel metal nano-/micro-architectures can be realized. The products can be characterized as hierarchical assemblies of 1D structures (nanotubes, nanowires, microwires, nanorods). With electrodeposition, complete pore filling is achieved, which results in the formation of wire-based morphologies. Special attention is dedicated to the controlled partial filling of the pores with electroless plating, which allows the simultaneous deposition of tubes and – depending on the conformity of the plating reaction and the deposition time – narrower arrays of tubes, wires or rods. To demonstrate the favorable functional properties of the obtainable products, a silver-based wire-tube assembly is employed in the enzyme-free and selective electrochemical detection of hydrogen peroxide. An excellent sensitivity of 1340 μA mM −1 cm −2 and a fast response time of

The Bi1/2Na1/2TiO3-based materials exhibit the largest electric-field-induced strains among lead-free piezoceramics and are considered as promising candidates for actuation applications. A typical representative of this group is (1-x)Bi1/2Na1/2TiO3-xSrTiO3, where its excellent electromechanical properties were recently related to the existence of a core–shell microstructure. Although the latter was also reported in other Bi1/2Na1/2TiO3-based ceramics, the formation mechanism remains unknown. In the present work we therefore first investigated the solid-state reaction occurring during calcination using simultaneous thermogravimetric analysis, X-ray diffraction, scanning and transmission electron microscopy. The reaction occurred in two steps, whereby the cores and shells had different formation reaction temperatures, which resulted in a metastable heterogeneous microstructure. Furthermore, a series of sintered samples with different relative densities, grain sizes, and core densities was prepared. Modifications of these microstructural parameters resulted in variation of the maximal strain by 17% and in the electric-field required to trigger the phase transitions by 38%.

Electroless plating of magnetic materials on catalytically active noble metal seeds is a powerful tool to design highly efficient recyclable catalysts. For the electroless plating procedure of metallic nanotubes in porous polymer templates, a sensitisation and activation process of the template is necessary. Therefore, metallic seeds are created on the surface of the polymer, which then enable the selective heterogeneous nucleation of a metal film on the template's surface. By choosing the metals for seeds and structures wisely, different functional materials can be purposefully combined. In this work magnetically recoverable catalysts were designed, which consist of magnetic NiCo nanotubes as carrier for catalytically active Pd seeds. The synthesised catalyst structures were thoroughly characterised by SEM, TEM, EDX, XRD, XPS, ICP-OES, VSM and then tested in the 4-nitrophenol reduction reaction, which was monitored by UV-Vis spectroscopy. After the reaction the structures were recycled and reused without a decrease in activity.

The method of electroless plating offers a facile synthesis route to high-aspect ratio metal nanotubes. Despite the simplicity of the method, the traditional approach involves hazardous and toxic chemicals; to change this Green Chemistry has come into play. Since both, nanotechnology and Green Chemistry, have become important research topics, the combination of these offers new opportunities. According to the concept of Green Chemistry, Pd nanotubes were produced by using nonhazardous chemicals. The challenge was to rebuild the sensitisation and activation process of electroless plating and to find green reaction parameters for controlling the auto-catalysed heterogeneous nucleation of Pd. The produced Pd nanotubes were characterised by SEM and EDX. Furthermore TEM characterisation was done for determining the structural properties of Pd NTs. The efficiency of the reaction was quantified by ICP-OES and XPS measurements. To illustrate that green synthesized nanomaterials can be compared with conventionally prepared catalysts, the Pd nanotubes were tested in a model reaction to determine their catalytic activity. For this purpose the reduction of 4-nitrophenol to 4-aminophenol with NaBH4 was chosen, which also finds application in the synthesis of acetaminophen.

Functionalized ordered mesoporous materials are relevant in technologies, such as drug release, sensing, and separation. To design functionality, the silica framework can be functionalized with responsive molecules or polymers. Often, the pH value in those hybrid materials determines performance. Even though pH/pKa differences between polymers in bulk solutions and nanoscale confinement have been observed, the influence of confinement on pH- and pore filling dependent polyelectrolyte oligomer chain charge has yet not been investigated systematically. Here, mesoporous silica films are functionalized with (2-dimethylamino)ethyl methacrylate) (DMAEMA) and 2-(methacryloyloxy)ethyl phosphate (MEP) oligomers using photoiniferter initiated polymerization. This approach allows a controlled and environmentally friendly mesopore functionalization in water. The obtained oligomer functionalized pores are tunable with respect to pore filling. For both, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(2-(methacryloxy)ethyl phosphate) (PMEP), the charge generation inside mesopore confinement is significantly delayed toward harsher pH conditions resulting in pKa shifts of 1���2 pH units. Polymer amount and ionic strength show to further influence the pKa of PDMAEMA in mesopores. The technological importance of the pH value in confinement and its effect on enzyme stabilization is demonstrated. Lipase from Aspergillus oryzae loses its activity upon encapsulation in silica nanoparticles at pH values where the enzyme is stable in bulk solution.

We present a versatile approach for the fabrication of well-defined networks of interconnected metal nanotubes, which applies electroless plating to ion-track-etched polymer templates that enclose designed pore networks. In order to obtain self-supporting structures, the deposition reactions must be optimized to yield conformal nanoscale metal films on microstructured substrates possessing extensive inner surfaces. Using this route, gold, copper, silver, nickel, and platinum nanotube net-works are synthesized. The resulting structures can be handled macroscopically and combine a large surface area with continuous mass transport and conduction pathways, rendering them promising for application in, for example, electrocatalysis and sensing. This potential is demonstrated by employing a gold nanotube network for the amperometric detection of hydrogen peroxide, in which excellent sensitivity, catalyst utilization, and stability is achieved.

The electrode material in all-vanadium redox flow batteries often consists of fibrous carbon felts. It is believed that surface functional groups such as carboxyl and hydroxyl groups, e.g. introduced by heat-treatment, increase the activity of the carbon electrodes due to a facilitated electron transfer. However, other properties of the carbon material have not been investigated in detail. In this paper, the structure of morphologically different carbon materials, such as graphite flakes, two carbon blacks and a carbon fiber material, was correlated with the electrochemical activity obtained by cyclic voltammetry in a three-electrode configuration in vanadyl sulfate solution. Furthermore, the respective carbon materials were heat-treated in air at 400 °C and the corresponding structural changes in sp2 carbon content and amount and kind of surface functional groups determined by NEXAFS analysis were correlated with the activity. Our work shows that the sp2 carbon content on the surface is an important parameter significantly affecting the activity. The results can be utilized to choose a suitable carbon powder material to impregnate the felts in order to increase their reactive surface area.

We replicate the unique pore structure of ion-track etched polymers with carbon using an organic sol-gel precursor strategy. First, phenol resin is cross-linked in the membrane pores, followed by selective dissolution of the template matrix and carbonization at a temperature of 550 degrees C. The potential to create nanomaterials of novel morphology is demonstrated by synthesizing free-standing, interconnected networks composed of aligned carbon nanowires of defined or modulated diameter.

Nanotube assemblies represent an emerging class of advanced functional materials, whose utility is however hampered by intricate production processes. In this work, three classes of nanotube networks (monometallic, bimetallic, and metal oxide) are synthesized solely using facile redox reactions and Commercially available ion track membranes. First,, the disordered pores of an ion track membrane are widened by chemical etching; resulting in the formation of a strongly interconnected pore network. Replicating this template structure with electroless copper plating yields a monolithic film composed, of crossing metal nanotubes. We show that the parent material can be easily transformed into bimetallic or oxidic derivatives by applying a second electroless plating or thermal oxidation step. These treatments retain the monolithic network structure but result in the formation of core shell nanotubes of altered composition (thermal oxidation: Cu2O-CuO); electroless nickel coating: Cu-Ni). The obtained nanomaterials are applied in the enzyme-free electrochemical detection of glucose, showing very high sensitivities between 2.27 and 2.83 A M-1 cm(-2). Depending on the-material composition, varying reactivities were observed: While copper oxidation reduces the response to glucose, it is increased in the case of nickel modification, albeit at the cost of decreased. selectivity. The performance of the materials is explained by the network architecture, which combines the advantages of one-dimensional nano-objects (continuous, conduction pathways, high surface area) with those of a self-supporting, open-porous superstructure (binder-free catalyst layer, efficient diffusion). In summary, this novel synthetic approach provides a fast, scalable, and flexible route toward free-standing nanotube arrays of high compositional complexity.

The synthesis of bimetallic nanostructures using galvanic replacement displays a versatile route toward efficient catalysts for fuel cell reactions. We show that electrolessly plated Ag nanotubes (NTs) are a unique template for the synthesis of double-walled Ag – Pt NTs. After replacement reaction, different dealloying protocols are applied to adjust the residual Ag content. The structures were thoroughly characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy, providing evidence of a hollow tube structure composed of Ag – Pt alloy. Experiments under harsh conditions reveal, that a significant amount of Ag remain in the NTs, which strongly affects the methanol oxidation performance. With optimized Ag – Pt ratio, the specific activity of Pt / C catalysts can be outperformed. From the obtained results, we emphasize that each effort using galvanic replacement should be accompanied by detailed compositional analysis.