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Wir berichten über eine Weiterentwicklung auf Grundlage der analytischen Ultrazentrifugation, durch welche Partikelgrößen direkt in Lösung mit Sub-nm-Auflösung charakterisiert werden können. Erreicht wird diese Auflösung durch die simultane Messung von UV/Vis-Spektren, während die einzelnen Komponenten der Mischung hydrodynamisch aufgetrennt werden. Durch die Aufrüstung der analytischen Ultrazentrifuge mit einem neuartigen Multiwellenlängendetektor wird der traditionellen hydrodynamischen Charakterisierung eine weitere spektrale Dimension hinzugefügt, was den Informationsgehalt vervielfacht. Die Leistungsfähigkeit der Messmethode wird durch die Charakterisierung von CdTe-Nanopartikeln verdeutlicht, wobei keine Aufreinigung und Fraktionierung der Nanopartikeln in einzelne, scheinbar monodisperse Fraktionen erforderlich ist. Durch unsere Untersuchungen konnten wir zum ersten Mal die reinen spektralen Eigenschaften und Bandlücken von diskreten CdTe-Nanopartikelspezies in einer Mischung messen. published

For the integration of responsive molecular units into chemically stable metal–organic frameworks (MOFs), the luminescent ligand 9-fluoreneone-2,7-dicarboxylic acid (H2FDC) was utilised in a reaction with Zr4+. The resulting framework has fcu topology and is permanently porous with a BET surface area of 1428 m2 g–1. The MOF shows guest-responsive fluorescent properties and is therefore suitable for application in sensing of solvent vapours. Saturated vapours of non-polar aromatic and non-aromatic compounds can be distinguished on the basis of their shifts in the fluorescence emission peak. Polar solvents are also distinguishable, whereas aprotic solvents induce a hypsochromic and protic solvents a bathochromic shift. Furthermore, different alcohols can be distinguished from each other. In the case of water, the significant dependence of the emission wavelength on the concentration demonstrates the potential of the MOF as a humidity sensor.

We report the size-dependent structural, surface, colloidal, and thermal properties of the well-known refractory material titanium diboride prepared at the nanoscale by a size-controlled inorganic molten-salt technique. A combined analysis of the powder X-ray diffraction data through a modified Williamson–Hall plot, a size–strain plot, and Rietveld fitting methods indicates that TiB2 nanocrystals with average crystallite sizes smaller than D ≈ 22 nm prefer to form defects at the titanium site rather than experience strain. The resulting composition is Ti1–xB2 [x = 0.03(1)–0.08(1)]. The size-induced defect formation is accompanied by anisotropic lattice contraction that decreases primarily the cell parameter c. Transmission electron microscopy revealed that the nanocrystals are embedded in an amorphous matrix. A comparison between the electron spin resonance spectra of bulk and nanosized samples indicated that only the nanosized samples yield observable signals. This signal is associated with unpaired electrons trapped in the boron–oxygen species that surround the Ti1–xB2 nanocrystals. These species provide stability to the Ti1–xB2 nanocrystals in aqueous dispersions, as evidenced by electrokinetic measurements. Upon heating under an Ar atmosphere, the boron–oxygen species evaporate from ca. 1000 °C, and the Ti vacancies in the interior nanocrystalline core vanish. TiB2 nanocrystals show excellent chemical stability against decomposition up to 1500 °C.

We investigate the degradation of organic solar cells based on an oligothiophene (DCV5T-Me) small molecule donor and the acceptor C60. Two different flexible, transparent bottom electrode types are employed: a transparent metal electrode (TME) and silver nanowires (AgNWs). They exhibit high optical transparency up to 86% and a sheet resistance as low as 12Ω/□. Power conversion efficiencies of 7.0%, 5.7%, and 7.2% on TME, AgNWs, and indium tin oxide (ITO, reference) are reached, respectively. The solar cells are protected against moisture ingress utilizing a flexible alumina thin-film, exhibiting water vapor transmission rates down to 3 × 10(-5) g m(-2) day(-1) at 38 °C and 90% relative humidity (RH). Implementation of this ultrabarrier as top and bottom encapsulation enables fabrication of fully flexible devices. A decrease in PCE to 80% of initial values is observed after 1000 ± 50 h on flexible, encapsulated TME but only 20 ± 5 h on AgNWs in a climate of 38 °C/50% RH. Degradation in AgNW-based devices is attributed to electrode decomposition.

We report on an efficient assembly approach to a variety of electrostatically stabilized all-inorganic semiconductor nanocrystals (NCs) via their linking with appropriate ions into multibranched gel networks. These all-inorganic non-ordered 3D assemblies can combine strong interparticle coupling which facilitates charge transport between the NCs with their diverse morphology, composition, size, and functional capping ligands. Moreover, the resulting dry gels (aerogels) are highly porous monolithic structures, which preserve the quantum confinement of their building blocks. The inorganic semiconductor aerogel made of 4.5 nm CdSe colloidal NCs, capped with iodide ions and bridged with Cd2+ ions, exhibited a surface area as high as 146 m2/g.

Here, the surface functionalization of CdSe and CdSe/CdS core/shell nanocrystals (NCs) with compact chloride and indium-chloride-complex ligands is reported. The ligands provide not only short interparticle distances but additionally control doping and passivation of surface trap states, leading to enhanced electronic coupling in NC-based arrays. The solids based on these NCs show an excellent electronic transport behavior after heat treatment at the relatively low temperature of 190 °C. Indeed, the indium-chlorido-capped 4.5 nm CdSe NC based thin-film field-effect transistor reaches a saturation mobility of μ = 4.1 cm2 (V s)−1 accompanied by a low hysteresis, while retaining the typical features of strongly quantum confined semiconductor NCs. The capping with chloride ions preserves the high photoluminescence quantum yield (≈66%) of CdSe/CdS core/shell NCs even when the CdS shell is relatively thin (six monolayers). The simplicity of the chemical incorporation of chlorine and indium species via solution ligand exchange, the efficient electronic passivation of the NC surface, as well as their high stability as dispersions make these materials especially attractive for wide-area solution-processable fabrication of NC-based devices.

Multi-metallic aerogels have recently emerged as a novel and promising class of unsupported electrocatalyst materials due to their high catalytic activity and improved durability for various electrochemical reactions. Aerogels can be prepared by a spontaneous one-step gelation process, where the chemical co-reduction of metal precursors and the prompt formation of nanochain-containing hydrogels, as a preliminary stage for the preparation of aerogels, take place. However, detailed knowledge about the homogeneity and chemical distribution of these three-dimensional Pd-Pt aerogels at the nano-scale as well as at the macro-scale is still unclear. Therefore, we used a combination of spectroscopic and microscopic techniques to obtain a better insight into the structure and elemental distribution of the various Pd-rich Pd-Pt aerogels prepared by the spontaneous one-step gelation process. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) in combination with energy-dispersive X-ray spectroscopy (EDX) were employed in this work to uncover the structural architecture and chemical composition of the various Pd-rich Pd-Pt aerogels over a broad length range. The Pd80Pt20, Pd60Pt40 and Pd50Pt50 aerogels showed heterogeneity in the chemical distribution of the Pt and Pd atoms inside the macroscopic nanochain-network. The features of mono-metallic clusters were not detected by EXAFS or STEM-EDX, indicating alloyed nanoparticles. However, the local chemical composition of the Pd-Pt alloys strongly varied along the nanochains and thus within a single aerogel. To determine the electrochemically active surface area (ECSA) of the Pd-Pt aerogels for application in electrocatalysis, we used the electrochemical CO stripping method. Due to their high porosity and extended network structure, the resulting values of the ECSA for the Pd-Pt aerogels were higher than that for a commercially available unsupported Pt black catalyst. We show that the Pd-Pt aerogels possess a high utilization of catalytically active centers for electrocatalytic applications based on the nanostructured bimetallic framework. Knowledge about the homogeneity and chemical distribution of the bimetallic aerogels can help to further optimize their preparation by the spontaneous one-step gelation process and to tune their electrocatalytic reactivity.

The optical properties of semiconductor nanocrystals (SC NCs) are largely controlled by their size and surface chemistry, i.e., the chemical composition and thickness of inorganic passivation shells and the chemical nature and number of surface ligands as well as the strength of their bonds to surface atoms. The latter is particularly important for CdTe NCs, which - together with alloyed CdxHg1-xTe - are the only SC NCs that can be prepared in water in high quality without the need for an additional inorganic passivation shell. Aiming at a better understanding of the role of stabilizing ligands for the control of the application-relevant fluorescence features of SC NCs, we assessed the influence of two of the most commonly used monodentate thiol ligands, thioglycolic acid (TGA) and mercaptopropionic acid (MPA), on the colloidal stability, photoluminescence (PL) quantum yield (QY), and PL decay behavior of a set of CdTe NC colloids. As an indirect measure for the strength of the coordinative bond of the ligands to SC NC surface atoms, the influence of the pH (pD) and the concentration on the PL properties of these colloids was examined in water and D2O and compared to the results from previous dilution studies with a set of thiol-capped Cd1-xHgxTe SC NCs in D2O. As a prerequisite for these studies, the number of surface ligands was determined photometrically at different steps of purification after SC NC synthesis with Ellman's test. Our results demonstrate ligand control of the pH-dependent PL of these SC NCs, with MPA-stabilized CdTe NCs being less prone to luminescence quenching than TGA-capped ones. For both types of CdTe colloids, ligand desorption is more pronounced in H2O compared to D2O, underlining also the role of hydrogen bonding and solvent molecules.

We proposed and demonstrated the first account of large-area, semi-transparent, tandem photosensitive nanocrystal skins (PNSs) constructed on flexible substrates operating on the principle of photogenerated potential buildup, which avoid the need for applying an external bias and circumvent the current-matching limitation between junctions. We successfully fabricated and operated the tandem PNSs composed of single monolayers of colloidal water-soluble CdTe and CdHgTe nanocrystals (NCs) in adjacent junctions on a Kapton polymer tape. Owing to the usage of a single NC layer in each junction, noise generation was significantly reduced while keeping the resulting PNS films considerably transparent. In each junction, photogenerated excitons are dissociated at the interface of the semi-transparent Al electrode and the NC layer, with holes migrating to the contact electrode and electrons trapped in the NCs. As a result, the tandem PNSs lead to an open-circuit photovoltage buildup equal to the sum of those of the two single junctions, exhibiting a total voltage buildup of 128.4 mV at an excitation intensity of 75.8 mu W cm(-2) at 350 nm. Furthermore, we showed that these flexible PNSs could be bent over 3.5 mm radius of curvature and cut out in arbitrary shapes without damaging the operation of individual parts and without introducing any significant loss in the total sensitivity. These findings indicate that the NC skins are promising as building blocks to make low-cost, flexible, large-area UV/visible sensing platforms with highly efficient full-spectrum conversion.

Developing novel electrode materials is a substantial issue to improve the performance of lithium ion batteries. In the present study, single phase Ti–Sn alloys with different Sn contents of 1 to 10 at% were used to fabricate Ti–Sn–O nanotubes via a straight-forward anodic oxidation step in an ethylene glycol-based solution containing NH4F. Various characterization tools such as SEM, EDXS, TEM, XPS and Raman spectroscopy were used to characterize the grown nanotube films. Our results reveal the successful formation of mixed TiO2/SnO2 nanotubes in the applied voltage range of 10–40 V. The as-formed nanotubes are amorphous and their dimensions are precisely controlled by tuning the formation voltage which turns Ti–Sn–O nanotubes into highly attractive materials for various applications. As an example, the Ti–Sn–O nanotubes offer promising properties as anode materials in lithium ion batteries. The electrochemical performance of the grown nanotubes was evaluated against a Li/Li+ electrode at a current density of 504 μA cm−2. The results demonstrate that TiO2/SnO2 nanotubes prepared at 40 V on a TiSn1 alloy substrate display an average 1.4 fold increase in areal capacity with excellent cycling stability over more than 400 cycles compared to the pure TiO2 nanotubes fabricated and tested under identical conditions. This electrode was tested at current densities of 50, 100, 252, 504 and 1008 μA cm−2 exhibiting average capacities of 780, 660, 490, and 405 μA cm−2 (i.e. 410, 345, 305 and 212 mA h g−1), respectively. The remarkably improved electrochemical performance is attributed to enhanced lithium ion diffusion which originates from the presence of SnO2 nanotubes and the high surface area of the mixed oxide tubes. The TiO2/SnO2 electrodes retain their original tubular structure after electrochemical cycling with only slight changes in their morphology.

The n‐type semiconductor system Bi2Te3Bi2Se3 is known as a low‐temperature thermoelectric material with a potentially high efficiency. Herein, a facile approach is reported to synthesize core/shell heterostructured Bi2Te2Se/Bi2Te3 nanosheets (NSs) with lateral dimensions of 1–3 μm and thickness of about 50 nm. Bi2Te3 and Bi2Se3, as well as heterostructured Bi2Te2Se/Bi2Te3 NSs are obtained via colloidal synthesis. Heterostructured NSs show an inhomogeneous distribution of the chalcogen atoms forming selenium and tellurium‐rich layers across the NS thickness, resulting in a core/shell structure. Detailed morphological studies reveal that these structures contain nanosized pores. These features contribute to the overall thermoelectric properties of the material, inducing strong phonon scattering at grain boundaries in compacted solids. NSs are processed into nanostructured bulks through spark plasma sintering of dry powders to form a thermoelectric material with high power factor. Electrical characterization of our materials reveals a strong anisotropic behavior in consolidated pellets. It is further demonstrated that by simple thermal annealing, core/shell structure can be controllably transformed into alloyed one. Using this approach pellets with Bi2Te2.55Se0.45 composition are obtained, which exhibit low thermal conductivity and high power factor for in‐plane direction with zT of 1.34 at 400 K.

DNA nanostructures provide a powerful platform for the programmable assembly of nanomaterials. Here this approach is extended to synthesize rod-like gold nanoparticles in a full DNA controlled manner. The approach is based on DNA molds containing elongated cavities. Gold is deposited inside the molds using a seeded-growth procedure. By carefully exploring the growth parameters it is shown that gold nanostructures with aspect ratios of up to 7 can be grown from single seeds. The highly anisotropic growth is in this case controlled only by the rather soft and porous DNA walls. The optimized seeded growth procedure provides a robust and simple routine to achieve continuous gold nanostructures using DNA templating.

Diffusion-limited cluster aggregation (DLCA) is a well established model for the formation of highly porous low-density non-equilibrium structures. One of the main conclusions of the previous studies considering this model is that the rotational diffusion of aggregating clusters does not change their structure characterized by a universal fractal dimension of $d_f=1.7-1.8$. In contradiction to this assumption, we demonstrate that the rotation movement of clusters significantly changes the structure of forming aggregates. The fractal dimension of rotating clusters is lower than the one found in the standard DLCA model and decreases with the increasing ratio of rotational and translational diffusion constants $D_r/D_t$, which offers a possibility to tune the structures of the aggregates below the conventional DLCA fractal dimension limit., 5 pages, 4 figures

Electrocatalysis plays a prominent role in renewable energy conversion and storage, enabling a number of sustainable processes for future technologies. There are generally three strategies to improve the efficiency (or activity) of the electrocatalysts: i) increasing the intrinsic activity of the catalyst itself, ii) improving the exposure of active sites, and iii) accelerating mass transfer during catalysis (both reactants and products). These strategies are not mutually exclusive and can ideally be addressed simultaneously, leading to the largest improvements in activity. Aerogels, as featured by large surface area, high porosity, and self-supportability, provide a platform that matches all the aforementioned criteria for the design of efficient electrocatalysts. The field of aerogel synthesis has seen much progress in recent years, mainly thanks to the rapid development of nanotechnology. Employing precursors with different properties enables the resulting aerogel with targeted catalytic properties and improved performances. Here, the design strategies of aerogel catalysts are demonstrated, and their performance for several electrochemical reactions is reviewed. The common principles that govern electrocatalysis are further discussed for each category of reactions, thus serving as a guide to the development of future aerogel electrocatalysts.

Tuning the surface structure at the atomic level is of primary importance to simultaneously meet the electrocatalytic performance and stability criteria required for the development of low-temperature proton-exchange membrane fuel cells (PEMFCs). However, transposing the knowledge acquired on extended, model surfaces to practical nanomaterials remains highly challenging. Here, we propose ‘surface distortion’ as a novel structural descriptor, which is able to reconciliate and unify seemingly opposing notions and contradictory experimental observations in regards to the electrocatalytic oxygen reduction reaction (ORR) reactivity. Beyond its unifying character, we show that surface distortion is pivotal to rationalize the electrocatalytic properties of state-of-the-art of PtNi/C nanocatalysts with distinct atomic composition, size, shape and degree of surface defectiveness under a simulated PEMFC cathode environment. Our study brings fundamental and practical insights into the role of surface defects in electrocatalysis and highlights strategies to design more durable ORR nanocatalysts. Tuning surface structure is key for electrocatalytic performance and stability of proton-exchange membrane fuel cells. Surface distortion as a structural descriptor can help to clarify the role of surface defects and to design enhanced nanocatalysts.

Carbon nanomaterials such as carbon blacks are intrinsically hydrophobic with limited wettability in aqueous media, thus restricting their potential applications. To improve their hydrophilicity, common methods tend to utilize harmful chemicals and conditions, such as a mixture of KMnO4 and H2SO4 or a complex and expensive synthesis setup. In our work, we report a simple method to improve the wettability of these materials by a mechanochemical treatment completed within 1 h at room-temperature utilizing a NH3 solution. Besides increasing the specific surface area of the carbon black from 67 m2·g−1 up to 307 m2·g−1, our process also incorporates nitrogen- and oxygen-containing functional groups into the carbon. This reduces the contact angle from 80° to 30°, confirming an enhanced wettability. Our work presents an easy, fast, and straightforward pathway towards the functionalization of carbon nanomaterials and can be of use in various applications where aqueous wettability is advantageous.

Tris(3,5-dimethylpyrazolyl)arsane (1) is introduced as a low-cost and convenient to handle arsenic precursor for the straight Forward synthesis of InAs Quantum dots (QDs). Transamination of 1 with the solvent oleylamine (OLAH) gives trioleylarsane (As(OLA)3) which in the presence of the reducing agents diisobutylaluminum hydride (DIBAL-H) or trioleylphosphane (P(OLA)3) yields InAs QDs via a typical hot injection approach. The size of the obtained InAs core QDs are tuned by varying the reaction time, the amount of the applied reducing agent, or even more effectively by changing the Indium and/or zinc halide precursors, InX3, and ZnX2 (Cl, Br, or I). Passivation of the resulting InAs particles with a protective ZnS or ZnSe shell results in improved photoluminescence of the core/shell QDs covering a spectral range between 600 and 1150 nm.

In this study we report on mechanical properties of molded, single component Al2O3, Ga2O3, Fe2O3, and ZrO2 as well as mixed aerogels, made from yttrium stabilized zirconia, yttrium aluminum garnet, and zinc aluminum spinel. Initially all aerogels were produced equally in molded bodies by a facile epoxy method and were annealed afterward at 300 °C. Then we performed uniaxial pressure tests on cylindrical aerogel monoliths to gain Young's modulus which depends on composition, density, and post-treatment. Already pure aerogels like ZrO2 show well-promising Young's modulus of 10.7 MPa, whereas most popular SiO2 materials display a modulus between 2 and 3 MPa at comparable densities. Moreover we focused on Al2O3 aerogels which exhibit high stability and interesting densification behavior depending on the annealing temperature. On the basis of this observation, we combined the toughness of the Al2O3 scaffold with the extraordinary hardness of ZrO2, by adding up to 20 atom % Zr, to increase the specific Young's modulus. For the mixed material with a Zr content of 20 atom %, we reach a record value for compressible aerogels of 125 MPa mL g-1.

Polymer electrolyte fuel cells (PEFCs) widespread commercialization is hindered by the devices’ limited durability, in terms caused by the corrosion of the carbon support used in the Pt-based PEFC catalysts. Using unsupported electrocatalysts could mitigate such durability issues, but little is known regarding the manner in which their processing into catalyst layers (CLs) affects pore size distribution (PSD) and PEFC performance. Thus, we have used a computational model to investigate the modes of agglomerate packing in CLs made from unsupported Pt3Ni nanochain ensembles (aerogels) or Pt black, and complemented this analysis with focused ion beam scanning electron microscopy tomography of corresponding real CLs. 3D structures, PSDs and tortuosities were obtained for real and computed CLs and were found to be in good agreement. The Pt black CL mainly exhibits large and straight pores (>100 nm wide), while the Pt3Ni aerogel CL mostly features small and twisted pores (< 100 nm wide) that cause the significantly poorer O2 mass transport (vs. Pt black) observed in PEFC experiments. Moreover, this modeling approach leads to key insights on the working principle of a filler material used for positively shifting the average PSD and improving the PEFC performance of the Pt3Ni CL., Journal of the Electrochemical Society, 165 (2), ISSN:0013-4651, ISSN:1945-7111

Many different aerogel materials are known to be accessible via the controlled destabilization of the respective nanoparticle suspensions. Especially for applications in heterogeneous catalysis such materials with high specific surface areas are highly desirable. Here, a facile method to obtain a mixed ZnPd/ZnO aerogel via a reductive treatment of a preformed Pd/ZnO aerogel is presented. Different morphologies of the Pd/ZnO aerogels could be achieved by controlling the destabilization of the ZnO sol. All aerogels show a high CO2 selectivity of up to 96% and a very good activity in methanol steam reforming that delivers hydrogen, which is one of the most important fuels for future energy concepts. The method presented is promising for different transition metal/metal oxide systems and hence opens a path to a huge variety of materials.

The absolute electronic energy levels in Hg-doped CdTe semiconductor nanocrystals (CdHgTe NCs) with varying sizes/volumes and Hg contents are determined by using cyclic voltammetry (CV) measurements and density functional theory (DFT) -based calculations. The electrochemical measurements demonstrate several distinct characteristic features in the form of oxidation and reduction peaks in the voltammograms, where the peak positions are dependent on the volume of CdHgTe NCs as well as on their composition. The estimated absolute electronic energy levels for three different volumes, namely 22, 119 and 187 nm(3) with 2.7±0.3 % of Hg content, show strong volume dependence. The volume-dependent shift in the characteristic reduction and oxidation peak potential scan can be attributed to the alteration in the energetic band positions owing to the quantum confinement effect. Moreover, the composition (Cd/Hg=98.3/1.7 and 97.0/3.0) -dependent alteration in the electronic energy levels of CdHgTe NCs for two different samples with similar volumes (ca. 124±5 nm(3) ) are shown. Thus obtained electronic energy level values of CdHgTe NCs as a function of volume and composition demonstrate good congruence with the corresponding absorption and emission spectral data, as well as with DFT-based calculations. DFT calculations reveal that incorporation of Hg into CdTe NCs mostly affects the energy levels of conduction band edge, whereas the valence band edge remains almost unaltered.

One plausible approach to endow aerogels with specific properties while preserving their other attributes is to fine-tune the building blocks. However, the preparation of metallic aerogels with designated properties, for example catalytically beneficial morphologies and transition-metal doping, still remains a challenge. Here, we report on the first aerogel electrocatalyst composed entirely of alloyed PdNi hollow nanospheres (HNSs) with controllable chemical composition and shell thickness. The combination of transition-metal doping, hollow building blocks, and the three-dimensional network structure make the PdNi HNS aerogels promising electrocatalysts for ethanol oxidation. The mass activity of the Pd83 Ni17 HNS aerogel is 5.6-fold higher than that of the commercial Pd/C catalyst. This work expands the exploitation of the electrocatalysis properties of aerogels through the morphology and composition control of its building blocks.

Eine gezielte Verbesserung der Baueinheiten ist eine naheliegende Herangehensweise, um Aerogele mit herausragenden Eigenschaften zu versehen und gleichzeitig ihre Vorzuge zu erhalten. Bestimmte Eigenschaften, wie die Optimierung der Morphologie fur katalytische Anwendungen oder die Ubergangsmetalldotierung in metallischen Aerogelen, sind jedoch nach wie vor schwer zu realisieren. In diesem Zusammenhang prasentieren wir hier erstmalig elektrokatalytisch aktive Aerogele, welche sich vollstandig aus legierten PdNi-Hohlnanospharen (HNS) aufbauen und deren chemische Zusammensetzung und Schalendicke gezielt eingestellt werden kann. Die Kombination von Ubergangsmetalldotierung mit hohlen Baueinheiten in einem dreidimensionalen Netzwerk machen PdNi-HNS-Aerogele zu vielversprechenden Elektrokatalysatoren fur die Ethanoloxidation. Gegenuber dem kommerziellen Pd/C-Katalysator zeigt das Pd83Ni17-HNS-Aerogel eine 5.6-fach hohere Massenaktivitat. Durch diese Arbeit wird die Nutzbarkeit von metallischen Aerogelen in der Elektrokatalyse erweitert, indem die Morphologie und Zusammensetzung der Baueinheiten gezielt kontrolliert werden.

Recent years have seen an increasing research effort focused on nanoscaling of metal borides, a class of compounds characterized by a variety of crystal structures and bonding interactions. Despite being subject to an increasing number of studies in the application field, comprehensive studies of the size-dependent structural changes of metal borides are limited. In this work, size-dependent microstructural analysis of the VB2 nanocrystals prepared by means of a size-controlled colloidal solution synthesis is carried out using X-ray powder diffraction. The contributions of crystallite size and strain to X-ray line broadening is separated by introducing a modified Williamson–Hall method taking into account different reflection profile shapes. For average crystallite sizes smaller than ca. 20 nm, a remarkable increase of lattice strain is observed together with a significant contraction of the hexagonal lattice decreasing primarily the cell parameter c. Exemplary density-functional theory calculations suppo...

In this work, the band-emissions of both the magic-sized clusters (MSCs) and nanosized quantum dots (QDs) of cadmium arsenide (Cd3As2) are studied versus time during the hot-bubbling synthesis. The syntheses are performed by introducing the ex-situ produced H3As into the hot-surfactant solutions dissolved with cadmium oleate and ligand molecules. It is found that the MSCs are produced within 4.0 min because of the color change of the solution. However, these clusters are not stable, and the peak of the photoabsorption shifts from 528 to 540 nm with the growth time. Across a shallow energy barrier, the MSCs grow into nanosized quantum dots whose photoluminescence wavelengths are found to extend into the NIR region (λ > 1480 nm) after a growth period of ∼45.0 min. The quantum yield of the band emissions ranges 2.5–8.0% during the growth of Cd3As2 QDs. Analyses from the time-resolved fluorescence decay profiles suggest that the ultrafast exciton radiative decays are the dominant recombination in the Cd3As2 M...

Here, we present a ligand exchange of long insulating molecules with short, robust, and environmentally friendly iodide ions via a mild flocculation of PbSe nanocrystals (NCs). This ligand exchange leads to the formation of stable colloidal solutions in various polar solvents and in a broad concentration range via electrostatic repulsion. The iodide capping ligands preserve the electronic structure and maintain the optical properties of the PbSe NCs, both in solution and in the form of solid films. The spin-coated PbSe NC solids exhibit good transport characteristics with electron mobilities in the linear and saturation regimes reaching (2.1 +/- 0.3) cm(2)/(V center dot s) and (2.9 +/- 0.4) cm(2)/(V center dot s), respectively. This opens up opportunities for the low-cost and low-temperature fabrication of NC thin films being attractive for applications in the fields of electronics and optoelectronics.

Electrode material characteristics need to be improved urgently to fulfill the requirements for high performance lithium ion batteries. Herein, we report the use of the two-phase alloy Ti80Co20 for...

The physicochemical details of the well-established template-assisted electrodeposition process for metal nanowire fabrication are investigated with respect to the physical origination for template geometry limitation. The overall process of metal reduction inside anodized Al2 O3 (AAO) is divided into three parts: i) the electrochemical reduction at the pore bottom, ii) the diffusion of the electrolytic species, and iii) the capacitive interaction between pore surface and electrolyte. The results show that the reduction of Ni is controlled by the degree of electrode recession, i.e., the pore depth. Applying Cottrell's equation to pulsed electrodeposition enables experimental access to diffusion coefficients (DNi2+). This gives a gradient in DNi2+ along with the filling process. The switch-over from crystallization to diffusion control is investigated to depend on temperature and pore length. Additionally, the electrode surface capacitance scales non-linearly with the pore depth. This is deduced as a consequence of electrostatic surface-electrolyte interaction. A minimum in the electrode capacitance at a pore length of 48 μm is identified as the point with maximum thickness of a double-layer-type surface effect to the electrolyte. The results extend the template's role from simply geometrically limiting metal growth and explain occurring process issues when filling especially high-aspect-ratio pores.

51Cr-labeled, superparamagnetic, iron oxide nanoparticles (51Cr-SPIOs) and 65Zn-labeled CdSe/CdS/ZnS-quantum dots (65Zn-Qdots) were prepared using an easy, on demand, exchange-labeling technique and their particokinetic parameters were studied in mice after intravenous injection. The results indicate that the application of these heterologous isotopes can be used to successfully mark the nanoparticles during initial distribution and organ uptake, although the 65Zn-label appeared not to be fully stable. As the degradation of the nanoparticles takes place, the individual transport mechanisms for the different isotopes must be carefully taken into account. Although this variation in transport paths can bring new insights with regard to the respective trace element homeostasis, it can also limit the relevance of such trace material-based approaches in nanobioscience. By monitoring 51Cr-SPIOs after oral gavage, the gastrointestinal non-absorption of intact SPIOs in a hydrophilic or lipophilic surrounding was measured in mice with such high sensitivity for the first time. After intravenous injection, polymer-coated, 65Zn-Qdots were mainly taken up by the liver and spleen, which was different from that of ionic 65ZnCl2. Following the label for 4 weeks, an indication of substantial degradation of the nanoparticles and the release of the label into the Zn pool was observed. Confocal microscopy of rat liver cryosections (prepared 2 h after intravenous injection of polymer-coated Qdots) revealed a colocalization with markers for Kupffer cells and liver sinusoidal endothelial cells (LSEC), but not with hepatocytes. In J774 macrophages, fluorescent Qdots were found colocalized with lysosomal markers. After 24 h, no signs of degradation could be detected. However, after 12 weeks, no fluorescent nanoparticles could be detected in the liver cryosections, which would confirm our 65Zn data showing a substantial degradation of the polymer-coated CdSe/CdS/ZnS-Qdots in the liver.

The surfactant polyvinylpyrrolidone (PVP) commonly used to synthesize silver nanowires (AgNW) in solution is known to negatively affect the performance of nanowire-based thin film electrodes. An insulating shell of the polymer hinders tight contact between the nanowires themselves and between the nanowires and substrate, resulting in high sheet resistance of the freshly prepared nanowire films. Here, we develop a simple low-temperature method allowing us to reduce the sheet resistance of AgNW networks and simultaneously improving the optical transmittance. The method is based on the capacity of PVP to absorb moisture which results in a strong decrease in the glass transition temperature of the polymer. The latter leads to softening effects, causing a reduced wire contact resistance already at 60 °C for 90 nm thick AgNWs and even at 45 °C for 35 nm thick AgNWs. As a result, the sheet resistances of the thin film electrodes treated by our method are near to the values conventionally obtained after thermal annealing at temperatures between 140–250 °C. Our humidity assisted low temperature approach is especially advantageous for organic electronics and fabricating devices on thermally sensitive transparent flexible foils.

A class of 3D PdNi bimetallic nano-materials with porous nanostructures is synthesized using a facile and versatile approach at room temperature. Due to their porous nanostructures, their clean surfaces, as well as the synergistic effect between their compositions, the as-prepared PdNi exhibit greatly enhanced activity and stability towards methanol electrooxidation in an alkaline medium, holding great promise in fuel cells.

Aerogels assembled from colloidal metal or semiconductor nanocrystals (NCs) feature large surface area, ultralow density, and high porosity, thus rendering them attractive in various applications, such as catalysis, sensors, energy storage, and electronic devices. Morphological and structural modification of the aerogel backbones while maintaining the aerogel properties enables a second stage of the aerogel research, which is defined as hierarchical aerogels. Different from the conventional aerogels with nanowire-like backbones, those hierarchical aerogels are generally comprised of at least two levels of architectures, i.e., an interconnected porous structure on the macroscale and a specially designed configuration at local backbones at the nanoscale. This combination "locks in" the inherent properties of the NCs, so that the beneficial genes obtained by nanoengineering are retained in the resulting monolithic hierarchical aerogels. Herein, groundbreaking advances in the design, synthesis, and physicochemical properties of the hierarchical aerogels are reviewed and organized in three sections: i) pure metallic hierarchical aerogels, ii) semiconductor hierarchical aerogels, and iii) metal/semiconductor hybrid hierarchical aerogels. This report aims to define and demonstrate the concept, potential, and challenges of the hierarchical aerogels, thereby providing a perspective on the further development of these materials.

Semiconductor nanostructures such as CdSe quantum dots and colloidal nanoplatelets exhibit remarkable optical properties, making them interesting for applications in optoelectronics and photocatalysis. For both areas of application a detailed understanding of the electronic structure is essential to achieve highly efficient devices. The electronic structure can be probed using the fact that optical properties of semiconductor nanoparticles are found to be extremely sensitive to the presence of excess charges that can for instance be generated by means of an electrochemical charge transfer via an electrode. Here we present the use of EMAS as a versatile spectroelectrochemical method to obtain absolute band edge positions of CdSe nanostructures versus a well-defined reference electrode under ambient conditions. In this, the spectral properties of the nanoparticles are monitored with respect to an applied electrochemical potential. We developed a bleaching model that yields the lowest electronic state in the conduction band of the nanostructures. A change in the band edge positions caused by quantum confinement is shown both for CdSe quantum dots and for colloidal nanoplatelets. In the case of CdSe quantum dots these findings are in good agreement with tight binding calculations. The method presented is not limited to CdSe nanostructures but can be used as a universal tool. Hence, this technique allows the determination of absolute band edge positions of a large variety of materials used in various applications.

Gels and aerogels derived from colloidal nanoparticles not only own the advantages of the traditional aerogels like ultra-low density, large surface area and high porosity, but also retain some of the unique properties of the nanoparticles. These characteristics endow such new types of materials with the possibility of promising applications. In this review, we focus on the function-led design of aerogels from the 3D assembly of 0D spherical particles, 1D nanowires, and 2D nanosheets, and especially their applications in catalysis, sensing, optoelectronics, pollutant adsorbents/filtration, and beyond.

We report on a novel and simple approach to surface ligand design of CdSe-based nanocrystals (NCs) with biocompatible, heterobifunctional polyethylene glycol (PEG) molecules. This method provides high transfer yields of the NCs into aqueous media with preservation of the narrow and symmetric emission bands of the initial organic-capped NCs regardless of their interior crystal structure and surface chemistry. The PEG-functionalized NCs show small sizes, high photoluminescence quantum yields of up to 75%, as well as impressive optical and colloidal stability. This universal approach is applied to different fluorescent nanomaterials (CdSe/CdS, CdSe/CdSCdxZn1–xS, and CdSe/CdS/ZnS), extending the great potential of organic-capped NCs for biological applications.

TiO2 nanotubes (NTs) synthesized by electrochemical anodization are discussed as very promising anodes for lithium ion batteries, owing to their high structural stability, high surface area, safety, and low production cost. However, their poor electronic conductivity and low Li+ ion diffusivity are the main drawbacks that prevent them from achieving high electrochemical performance. Herein, we report the fabrication of a novel ternary carbon nanotubes (CNTs)@TiO2/CoO nanotubes composite by a two-step synthesis method. The preparation includes an initial anodic fabrication of well-ordered TiO2/CoO NTs from a Ti-Co alloy, followed by growing of CNTs horizontally on the top of the oxide films using a simple spray pyrolysis technique. The unique 1D structure of such a hybrid nanostructure with the inclusion of CNTs demonstrates significantly enhanced areal capacity and rate performances compared to pure TiO2 and TiO2/CoO NTs, without CNTs tested under identical conditions. The findings reveal that CNTs provide a highly conductive network that improves Li+ ion diffusivity, promoting a strongly favored lithium insertion into the TiO2/CoO NT framework, and hence resulting in high capacity and an extremely reproducible high rate capability.

Tri(pyrazolyl)phosphanes (5R1,R2) are utilized as an alternative, cheap and low-toxic phosphorus source for the convenient synthesis of InP/ZnS quantum dots (QDs). From these precursors, remarkably long-term stable stock solutions (>6 months) of P(OLA)3 (OLAH = oleylamine) are generated from which the respective pyrazoles are conveniently recovered. P(OLA)3 acts simultaneously as phosphorus source and reducing agent in the synthesis of highly emitting InP/ZnS core/shell QDs. These QDs are characterized by a spectral range between 530-620 nm and photoluminescence quantum yields (PL QYs) between 51-62%. A proof-of-concept white light-emitting diode (LED) applying the InP/ZnS QDs as color conversion layer was built to demonstrate their applicability and processibility.

The formation of self-assembled monolayers on surfaces is often likely to be accompanied by the formation of byproducts, whose identification holds clues to the reaction mechanism but is difficult due to the minute amounts produced. We now report a successful identification of self-assembly byproducts using gold aerogel with a large specific surface area, a procedure likely to be applicable generally. Like a thin gold layer on a flat substrate, the aerogel surface is alkylated with n-butyl-d

Highly active and durable oxygen reduction catalysts are needed to reduce the costs and enhance the service life of polymer electrolyte fuel cells (PEFCs). This can be accomplished by alloying Pt with a transition metal (for example Ni) and by eliminating the corrodible, carbon-based catalyst support. However, materials combining both approaches have seldom been implemented in PEFC cathodes. In this work, an unsupported Pt-Ni alloy nanochain ensemble (aerogel) demonstrates high current PEFC performance commensurate with that of a carbon-supported benchmark (Pt/C) following optimization of the aerogel's catalyst layer (CL) structure. The latter is accomplished using a soluble filler to shift the CL's pore size distribution towards larger pores which improves reactant and product transport. Chiefly, the optimized PEFC aerogel cathodes display a circa 2.5-fold larger surface-specific ORR activity than Pt/C and maintain 90 % of the initial activity after an accelerated stress test (vs. 40 % for Pt/C).

Microfluidic devices present the basis of modern life sciences and chemical information processing. To control the flow and to allow optical readout, a reliable sensor material that can be easily utilized for microfluidic systems is in demand. Here, we present a new optical readout system for pH sensing based on pH sensitive, photoluminescent glutathione capped cadmium telluride quantum dots that are covalently immobilized in a poly(acrylate) hydrogel. For an applicable pH sensing the generated hybrid material is integrated in a microfluidic sensor chip setup. The hybrid material not only allows in situ readout, but also possesses valve properties due to the swelling behavior of the poly(acrylate) hydrogel. In this work, the swelling property of the hybrid material is utilized in a microfluidic valve seat, where a valve opening process is demonstrated by a fluid flow change and in situ monitored by photoluminescence quenching. This discrete photoluminescence detection (ON/OFF) of the fluid flow change (OFF/ON) enables upcoming chemical information processing., MF and SL gratefully acknowledge the cluster of Excellence “Center for Advancing Electronics Dresden (CfAED) for financial and assistant support. AD thanks the Government of the Russian Federation (Grant 074-U01) through ITMO Post-Doctoral Fellowship and the European Social Fund (ESF) for financing within the project “ChemIT”.

We report on a simple and effective technique of tuning the colloidal solubility of inorganic-capped CdSe and CdSe/CdS core/shell nanocrystals (NCs) from highly polar to nonpolar media using n-butylamine molecules. The introduction of the short and volatile organic amine mainly results in a modification of the labile diffusion region of the inorganic-capped NCs, enabling a significant extension of their dispersibility and improving the ability to form long-range assemblies. Moreover, the hybrid n-butylamine/inorganic capping can be thermally decomposed under mild heat treatment, making this approach of surface functionalization well-compatible with a low-temperature, solution-processed device fabrication. Particularly, a field-effect transistor-based on n-butylamine/Ga-I-complex-capped 4.5 nm CdSe NC solids shows excellent transport characteristics with electron mobilities up to 2 cm2/(V·s) and a high current modulation value (>104) at a low operation voltage (

Mixed aerogels from semiconductor and metal nanoparticles represent an outstanding hybrid material with exceptional properties due to two striking advantages: the creation of a huge quantity of semiconductor-metal interfaces combined with a highly porous three-dimensional nanostructured network. We present a versatile synthetic pathway towards hybrid aerogels built up by joint gelation of CdTe and noble metal nanoparticles (Au, Pd and bimetallic Au/Pd). A straightforward HO treatment inducing gel formation is developed as a more elegant alternative compared to the established photooxidation approach. The use of HO allows a reproducible, simple and mild gel formation which can be easily upscaled. The tremendous influence of the HO concentration on gelation mechanism and gelation kinetics is revealed by photoluminescence quantum yield (PLQY) determinations. Resulting gels are extensively characterized via transmission electron microscopy (TEM), scanning TEM (STEM), energy dispersive X-ray analysis (EDX) as well as photoluminescence (PL) spectroscopy and PL lifetime measurements. By varying the composition of the herein presented noble metal nanoparticles in a controlled fashion the range of semiconductor-metal hybrid aerogels is widened, which demonstrates the versatility and consistency of our approach. This synthetic flexibility grants access to a variety of different mixed hybrid aerogels which are of high significance for catalytic, sensing and photonic applications., Parts of TEM investigations have been carried out at the Leibniz-Institut für Polymerforschung Dresden e.V. Access to their TEM facility is gratefully acknowledged. AD thanks the Government of the Russian Federation (Grant 074-U01) through ITMO Post-Doctoral Fellowship.

There is significant interest in high-performance materials that can directly and efficiently capture water vapor, particularly from air. Herein, we report a class of novel porous carbon cuboids with unusual ultra-hydrophilic properties, over which the synergistic effects between surface heterogeneity and micropore architecture is maximized, leading to the best atmospheric water-capture performance among porous carbons to date, with a water capacity of up to 9.82 mmol g(-1) at P/P0 =0.2 and 25 °C (20% relative humidity or 6000 ppm). Benefiting from properties, such as defined morphology, narrow pore size distribution, and high heterogeneity, this series of functional carbons may serve as model materials for fundamental research on carbon chemistry and the advance of new types of materials for water-vapor capture as well as other applications requiring combined highly hydrophilic surface chemistry, developed hierarchical porosity, and excellent stability.