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The development of thin-film thermoelectric applications in sensing and energy harvesting can benefit largely from suitable deposition methods for earth-abundant materials. In this study, p-type copper oxide thin films have been prepared on soda lime silicate glass by direct current (DC) magnetron sputtering at room temperature from a pure copper metallic target in an argon atmosphere, followed by subsequent annealing steps at 300 °C under various atmospheres, namely air (CuO:air), nitrogen (CuO:N) and oxygen (CuO:O). The resultant films have been studied to understand the influence of various annealing atmospheres on the structural, spectroscopic and thermoelectric properties. X-ray diffraction (XRD) patterns of the films showed reflexes that could be assigned to those of crystalline CuO with a thin mixed Cu(I)Cu(II) oxide, which was also observed by near edge X-ray absorption fine structure spectroscopy (NEXAFS). The positive Seebeck coefficient (S) reached values of up to 204 μV K−1, confirming the p-type behavior of the films. Annealing under oxygen provided a significant improvement in the electrical conductivity up to 50 S m−1, resulting in a power factor of 2 μW m−1 K−2. The results reveal the interplay between the intrinsic composition and the thermoelectric performance of mixed copper oxide thin films, which can be finely adjusted by simply varying the annealing atmosphere.

The mechanochemical formation of the ionic cocrystals of glucose (Glc) and sodium salts Glc2NaCl·H2O (1) and Glc2NaX (X = Br (2), I (3)) is presented. Products are formed by co-milling Glc with thr...

We present an in situ triple coupling of synchrotron X-ray diffraction with Raman spectroscopy, and thermography to study milling reactions in real time. This combination of methods allows a correlation of the structural evolution with temperature information. The temperature information is crucial for understanding both the thermodynamics and reaction kinetics. The reaction mechanisms of three prototypical mechanochemical syntheses, a cocrystal formation, a C@C bond formation (Knoevenagel condensation), and the formation of a manganese-phosphonate, were elucidated. Trends in the temperature development during milling are identified. The heat of reaction and latent heat of crystallization of the product contribute to the overall temperature increase. A decrease in temperature occurs via release of, for example, water as a byproduct. Solid and liquid intermediates are detected. The influence of the mechanical impact could be separated from temperature effects caused by the reaction.

The oxidation of CO is a fundamental model reaction in heterogeneous catalysis. This contribution presents an uncommon approach to investigate a catalytic gas-phase reaction by using colloidal gold and provides a unified picture of the CO oxidation of supported gold nanoparticles at room temperature. Our experiments on ligand-free colloidal gold nanoparticles prove that gold activates molecular oxygen independently from the presence of any support. Isotope experiments along with studies on colloidal stability reveal that the active oxygen species is a stable surface oxide that can be protonated. The role of the support is to provide water for protonation steps. Therefore, the hydrophilicity is the main property of the support which determines the catalytic activity and not, as is often assumed, its acidity or reducibility. The deduced model provides explanations for experimental results described in the literature for various gold catalysts and reaction conditions.

Although the deposition of alternating layers from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and polyaniline (PANI) salts has recently provided a breakthrough in the field of conductive polymers, the cause for the conductivity improvement has remained unclear. In this work, we report a cooperative doping effect between alternating PANI base and PEDOT:PSS layers, resulting in electrical conductivities of 50–100 S cm–1 and power factors of up to 3.0 ± 0.5 μW m–1 K–2, which surpass some of the recent values obtained for protonated PANI/PEDOT:PSS multilayers by a factor of 20. In this case, the simultaneous improvement in the electrical conductivity of both types of layers is caused by the in situ protonation of PANI, which corresponds to the removal of the excess acidic PSS chains from the PEDOT:PSS grains. The interplay between the functional groups’ reactivity and the supramolecular chain reorganization leads to an array of preparation-dependent phenomena, including a stepwise inc...

The mechanochemical synthesis of the zinc N-(phosphonomethyl)glycinate Zn(O3PCH2NH2CH2CO2)·H2O (1) is presented. The structure was solved from powder X-ray diffraction (PXRD) data. In the three-dimensional pillared structure, the Zn atoms are coordinated tetrahedrally. In situ investigations of the reaction process with synchrotron PXRD and Raman spectroscopy reveal a two-step process including the formation of an intermediate.

A newly established in situ technique using Raman spectroscopy was employed for the detailed kinetic investigation of mechanochemical reaction pathways. This approach was applied for the systematic investigation of the direct influence of colliding balls on the reaction rate constants of a mechanochemical cocrystallization reaction. As a model reaction, the mechanochemical cocrystallization of felodipine and the coformer imidazole was investigated. Keeping the total ball mass constant by varying the number of milling balls, our study reveals that the impact of each single collision has a more significant influence on the reaction kinetics than expected.

We demonstrate here a novel laboratory experiment for the synthesis of gold nanoparticles (AuNPs) by using a low energy gold-sputtering method together with a modern, green, and biofriendly deep eutectic solvent (DES). The strategy is straightforward, economical, ecofriendly, rapid, and clean. It yields uniform AuNPs of 5 nm in diameter with high reproducibility. Moreover, catalytic applications of AuNPs in DES are shown by studying the conversion of p-nitrophenol to p-aminophenol. Systematic in situ UV–vis spectra are recorded during the catalytic reaction. While the experimental procedures are simple, our laboratory experiments can be applied in a variety of settings depending upon how detailed the instructor requires the depth of the analyses. The laboratory experiments described herein were successfully conducted and evaluated by students with a bachelor degree.

The cocrystal formation of pyrazinamide (PZA) with malonic acid (MA) was studied in situ. The mechanochemical reaction proceeds via conversion of a crystalline intermediate (PZA:MA II) into the thermodynamically more stable form (PZA:MA I) upon further grinding. The information derived from in situ powder X-ray diffraction (PXRD) enabled the isolation of this new metastable polymorph. On the basis of the PXRD data, the crystal structure of the 1:1 cocrystal PZA:MA II was solved. The polymorphs were further characterized and compared by Raman spectroscopy, solid-state NMR spectroscopy, differential thermal analysis/thermogravimetric analysis, and scanning electron microscopy. Our study demonstrates how monitoring mechanochemical reactions by in situ PXRD can direct the discovery and isolation of even short-lived intermediates not yet accessed by conventional methods.

The effect of the reactant powder mass on reaction times for the mechanochemical formation of a soft matter model system was studied by in situ PXRD. The syntheses were performed at a constant ball mass in a shaker mill with and without glassy SiO2 as an inert additive. Reaction times decreased with the increase of the ball to reactant ratio (BRR). The kinetic influence of the SiO2 powder was excluded. The decrease in the reaction time with decreasing mass of reactants was related to the rise in the stress energy transferred to the powder by a higher ball impact. The BRR had no effect on the induction time. But the product conversion was accelerated by raising the BRR. While a certain temperature is needed for the activation of reactants in the induction phase, the conversion of soft matter reactants is rather controlled by impact than temperature.

A one‐pot synthesis and application of cellulose‐based sensors to efficiently detect various toxic metal ions in aqueous solutions in micromolar quantities is reported. Cellulose microfibers have been functionalized with carbon disulfide in alkaline solution to form cellulose xanthate. The material detects several toxic metal ions such as copper, nickel, or cobalt ions through color change detectable by the naked eye. The optical sensor can be used as an ideal flash test for assessing the quality of drinking water., Cellulose is functionalized in a one‐pot synthesis with xanthate groups. The as‐synthesized material is able to detect toxic copper(II) and nickel(II) ions in micromolar quantities by color change, detectable by the naked eye. The colorimetric sensor can be used as a flash test to assess the quality of drinking water., Humboldt‐Universität zu Berlin International Strategy Office

Biopolymers are very efficient for significant applications ranging from tissue engineering, biological devices to water purification. There is a tremendous potential value of cellulose because of its being the most abundant biopolymer on earth, swellability, and functional groups to be modified. A novel, highly efficient route for the fabrication of mechanically stable and natural hydrogels is described in which cellulose and glycine are dissolved in an alkaline solution of NaOH and neutralized in an acidic solution. The dissolving temperature and the glycine amount are essential parameters for the self-assembly of cellulose chains and for tuning the morphology and the aggregate structures of the resulting hydrogels. Glycine plays the role of a physical crosslinker based on the information obtained from FTIR and Raman spectra. Among the prepared set of hydrogels, CL5Gly30 hydrogels have the highest capacity to absorb water. The prepared CL5Gly30 gels can absorb up to seven times their dry weight due to its porous 3-D network structure. CL5Gly10 hydrogel exhibits 80% deformation under 21 N force executed. The method developed in this article can contribute to the application of heavy metal adsorption in aqueous solutions for water purification and waste management. © 2019 The Authors. 137 published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48380.

We report on structural and electrical characterization of zinc oxide material containing aluminum (Al:ZnO) prepared by a co-precipitation technique using different zinc and aluminum precursors. The as-prepared powders were calcinated and pre-annealed at 600 °C and 1200 °C. These were cold-pressed to pellets and sintered at 1000 °C. We also prepared ZnO material with no Al for comparisons. The electrical and thermal conductivity, as well as the Seebeck coefficient, were measured. These properties were correlated with structural analysis by X-ray diffraction characterization and scanning electron microscopy. The process yields a nanostructured material with much reduced thermal conductivity.

Benzamide has been known for its polymorphism for almost 200 years. Three polymorphic forms are described. To date, it was only possible to crystallize a metastable form in a mixture together with the thermodynamically most stable form I. A complete transformation of form I into the metastable form III by mechanochemical treatment has been achieved. Catalytic amounts of nicotinamide seeds were used to activate the conversion by mechanochemical seeding. NMR experiments indicated that the nicotinamide molecules were incorporated statistically in the crystal lattice of benzamide form III during the conversion. The transformation pathway was evaluated using in situ powder X-ray diffraction.

The stability of different theophylline cocrystals under milling conditions was investigated by competitive cocrystal reactions. To determine the most stable cocrystal form under milling conditions, the active pharmaceutical ingredient theophylline was either ground with two similar coformers (benzoic acid, benzamide, or isonicotinamide), or the existing theophylline cocrystals were ground together with a competitive coformer. All competitive reactions were investigated by in situ powder X-ray diffraction disclosing the formation pathway of the milling processes. On the basis of these milling reactions, a stability order (least to most stable) was derived: tp/bs < tp/ba < tp/ina < bs/ina.

Theoretical and experimental studies indicate that crystal nucleation can take more complex pathways than expected on the ground of the classical nucleation theory. Among these pathways are the formation of pre-nucleation clusters and amorphous precursor phases. A direct in situ observation of the different pathways of nucleation from solution is challenging since the paths can be influenced by heterogeneous nucleation sites, such as container walls. Here, we provide insights into the crystallization process using the in situ combination of an acoustic levitator, Raman spectroscopy, and X-ray scattering. The contactless sample holder enables the observation of homogeneous crystallization processes and the detection of intermediates and final crystalline forms. We provide evidence for the existence of multiple pathways of nucleation based on the investigation of the crystallization of organic molecules from different solvents. Starting from a diluted solution, a supersaturation is reached during the experiment due to the evaporation of the solvent. The highly supersaturated solution reveals different pathways of crystallization. Depending on the degree of supersaturation either the thermodynamically stable or the metastable crystal form is observed.

This contribution investigates the growth mechanism of the Turkevich method. The experimental results provide the missing piece of the mechanistic puzzle which enables the actual control of particle growth in the commonly used Turkevich method. Applying the gained knowledge, the boundary conditions for a successful Turkevich synthesis are deduced. Moreover, the conditions under which the Turkevich method is highly reproducible are derived. Following these conditions, the Turkevich synthesis is modified to reveal small monodisperse particles with an unprecedented reproducibility of ±0.1 nm.

The liquid-assisted grinding cocrystallization of theophylline with benzamide leading to polymorphic compounds was investigated. A solvent screening with 17 different solvents was performed. The dipole moment of the solvent used in the synthesis determines the structure of the polymorphic product. A detailed investigation leads to the determination of the kinetically and thermodynamically favored product. In situ observations of the formation pathway during the grinding process of both polymorphs show that the thermodynamically favored cocrystal is formed in a two-step mechanism with the kinetic cocrystal as an intermediate.

The crystalline cadmium phenylphosphonates Cd(O3PPh)·H2O (1), Cd(HO3PPh)2 (2), and Cd(HO3PPh)2(H2O3PPh) (3) can be synthesized via solid state reactions by grinding together cadmium acetate with the respective equivalents of phenylphosphonic acid. Phosphonates (2) and (3) have not been obtained via any other synthesis method so far. The determination of the crystal structure of the new compounds (2) and (3) based on powder X-ray diffraction (PXRD) data is reported. The milling reactions were investigated using in situ synchrotron PXRD. Based on these data, an identification of intermediates and a detailed analysis of the underlying mechanisms were possible.

We present a facile alternative to other well known strategies for synthesizing flexible thermoelectric materials. Instead of printing thin active layers on flexible substrates or doping conductive polymers, we produce thermoelectric pastes, using a mixture of graphite, copper(I) oxide and polychlorotrifluoroethene. The Seebeck coefficient of the investigated pastes varies between 10 and 600 μV K(-1), while the electrical conductivity spans over an even wider range of 10(-4) to 10(2) S m(-1). Here, the influence of phenomena such as percolation on the electrical transport is revealed. The resulting power factor reaches 5.69 × 10(-4) ± 0.70 × 10(-4) μW m(-1) K(-2) for the graphite-polymer paste, with an unexpected minimum at a graphite molar fraction of approximately 0.4. The values are comparable to those of the powder mixtures, which are slightly higher, but less precisely tunable. Such compounds are further evaluated for practical applications. The graphite-polymer paste is used to exemplify, how a flexible thermoelectric sensor can be easily manufactured, step by step. Our results represent a proof of principle, that thermoelectric pastes are viable alternatives to current solutions. A further expansion of the scope for the composites can be achieved by using high performance thermoelectric materials and conductive polymers.

The crystal structures and syntheses of four different copper(II) phenylphosphonates, the monophenylphosphonates α-, β-, and γ-Cu(O3PC6H5)·H2O (α-CuPhPmH (1) β-CuPhPmH (2) and γ-CuPhPmH (3)), and the diphosphonate Cu(HO3PC6H5)2·H2O (CuPhP2mH (4)), are presented. The compounds were synthesized from solution at room temperature, at elevated temperature, under hydrothermal conditions, and mechanochemical conditions. The structures of α-CuPhPmH (1) and CuPhP2mH (4) were solved from powder X-ray diffraction data. The structure of β-CuPhPmH (2) was solved by single crystal X-ray analysis. The structures were validated by extended X-ray absorption fine structure (EXAFS) and DTA analyses. Disorder of the crystal structure was elucidated by electron diffraction. The relationship between the compounds and their reaction pathways were investigated by in situ synchrotron measurements.

While the field of thermoelectricity continues developing, the academic world is still debating its applicability for wide-scale implementation. The main concerns revolve around its low energy conversion efficiency (5–10%), compared to photovoltaics (up to 46%), and the environmental impact of commonly used materials (e.g. Bi2Te3, PbTe). Although less scrutinized, other fields such as photoelectrochemistry and catalysis have suffered from similar drawbacks. In light of the recent developments, the question arises, if the introduction of hybrid devices combining those renewable energy sources is preferable to the current divided efforts. Several new papers bring arguments in favor of this combined approach, with an efficiency of 16% reported for a triboelectric–thermoelectric–photovoltaic water splitting cell.

An unusually fast and effective synthesis procedure for a host guest system consisting of a metal organic framework (MOF) and a polyoxometalate (POM) is described. The material was synthesised mechanochemically and the evolution of the structure was monitored ex and in situ using synchrotron X-ray diffraction (XRD).

Two divalent manganese aminophosphonates, manganese mono(nitrilotrimethylphosphonate) (MnNP3) and manganese bis(N-(carboxymethyl)iminodi(methylphosphonate)) (Mn(NP2AH)2), have been prepared by mechanochemical synthesis and characterized by powder X-ray diffraction (PXRD). The structure of the novel compound Mn(NP2AH)2 was determined from PXRD data. MnNP3 as well as Mn(NP2AH)2 exhibits a chain-like structure. In both cases, the manganese atom is coordinated by six oxygen atoms in a distorted octahedron. The local coordination around Mn was further characterized by extended X-ray absorption fine structure. The synthesis process was followed in situ by synchrotron X-ray diffraction revealing a three-step reaction mechanism. The as-prepared manganese(II) phosphonates were calcined on air. All samples were successfully tested for their suitability as catalyst material in the oxygen evolution reaction.

The driving forces triggering the formation of co-crystals under milling conditions were investigated by using a set of multicomponent competitive milling reactions. In these reactions, different active pharmaceutical ingredients were ground together with a further compound acting as coformer. The study was based on new co-crystals including the coformer anthranilic acid. The results of the competitive milling reactions indicate that the formation of co-crystals driven by intermolecular recognition are influenced and inhibited by kinetic aspects including the formation of intermediates and the stability of the reactants.

While polymorphism is a common phenomenon in the crystallization processes of organic compounds, polyamorphism has gained importance only recently. Using sophisticated sample environments and applying in situ scattering methods and vibrational spectroscopy, the complete crystallization process of organic compounds from solution can be traced and characterized. Diffuse scattering from amorphous intermediates can be investigated by analyzing the atomic pair distribution function (PDF) to gain further insights into molecular pre-orientation. The crystallization behavior of paracetamol was studied exemplarily under defined, surface-free conditions. Based on the choice of the solvent, the formation of different polymorphs is promoted. The thermodynamically stable form I and the metastable orthorhombic form II could be isolated in pure form directly from solution. For both polymorphs, the crystallization from solution proceeds via a distinct amorphous precursor phase. PDF analyses of these different amorphous states indicate a specific pre-orientation of the analyte molecules introduced by the solvent. The resulting crystalline polymorph is already imprinted in these proto-crystalline precursors. Direct experimental evidence for the polyamorphism of paracetamol is provided.

Pulsed laser ablation in liquids (PLAL) is a versatile route to stable colloids without the need for stabilizing agents. The use of suspensions instead of bulk targets further simplifies the experimental set-up and even improves the productivity. However, the utilization of this approach is hindered by limited knowledge about the underlying mechanisms of the nanoparticle formation. We present the synthesis of copper(i) iodide nanoparticles via ns-pulsed laser irradiation of CuI powder suspended in water or ethyl acetate. A thorough study of the nanoparticle size by transmission electron microscopy reveals a log-normal distribution with a mean diameter of 31 nm (±11 nm) in water and 18 nm (±7 nm) in ethyl acetate. The duration of the laser irradiation appears to have only a minor influence on the size distribution. Selected area diffraction and electron energy-loss spectroscopy verify the chemical composition of the generated CuI nanoparticles. While comparable precursors like CuO and Cu3N follow a reductive ablation mechanism, a fragmentation mechanism is found for CuI. With a productivity of 1.7 μg J(-1) this pulsed laser fragmentation in liquids (PLFL) proves to be an efficient route to colloidal CuI nanoparticles.

Bimetallic nanoparticles (NPs), particularly Au/Pd and Au/Pt, have attracted extensive attention due to their wide-spread application in catalysis, optoelectronics and energy recuperation.[1] Here we have attempted the fabrication of Au/Pt and Au/Pd bimetallic NPs by an energy-efficient eco-friendly microwave methodology. The microwave-assisted reactions enable considerably large product yields over conventional colloidal methods due to (a) almost two-fold increased reaction kinetics, (b) localized superheating at reaction sites and rapid rise of initial temperature.[2] Au NPs (sizes 20 ± 3 nm) are fabricated in the first step followed by the reduction of [PdCl2(NH3)2] or [K2PtCl6]in tetraethylene glycol at 180 ºC for 2 min. Controlling and understanding the atomic structure and elemental distributions of these NPs are crucial for their optimized performances. So, we address the fundamental question of the most likely arrangement of Au and Pd or Pt atoms in these bimetallic NPs prepared under similar conditions by complementary characterizations using UV-Vis spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The UV-Vis spectroscopy reveals the formation of an alloy shell. The extent of depression of the plasmon peak of Au and its blue-shift reveals substantial deposition of Pd atoms on an Au core and significant alloying in comparison to Au/Pt NPs. XRD reveals the gradual shift of the diffraction peak from the position of Au to the position of Pd or Pt with change in composition. XRD supports the formation of a thick alloy shell in these NPs. However, the TEM images reveal a very interesting result. With increase in Pt concentration, the size of the dispersed NPs decreases from 20 ± 3 nm to about 16 nm (± 1 nm) and there is evolution of a bimodal particle size distribution with small particles about 1-2 nm diameters. On the contrary, with increasing Pd concentration, the particle size of the dispersed particles increases to about 32 nm (± 1 nm). This discrepancy of particle size evolution for the two systems arises due to the differences in surface energies (Pt > Pd > Au atoms). Pt atoms tend to diffuse towards the core with the formation of Au nano-islands which eventually segregates leading to a reduction in particle size and bimodal distribution. At higher concentration of Pt, Pt and Au atoms tend to nucleate separately also contribute to the bimodal distribution. While for Au/Pd NPs, we have an Au core with an alloyed shell having higher Pd concentration. This is further supported by experimental evidence by selective etching and dissolution of Au by potassium-iodide solution. Furthermore, the Au/Pd bimetallic NPs are found to possess better catalytic activities in the reduction of 4-nitrophenol to 4-aminophenol than Au/Pt and monometallic NPs.

The metal ion chelating property was conferred onto silicon (Si) and gold (Au) surfaces by direct electrografting of the 4-[(carboxymethyl)thio]benzenediazonium cation (4-CMTBD). Infrared spectroscopic ellipsometry showed the presence of characteristic phenyl and carbonyl vibrational bands on the functionalized surfaces as a proof of existence of surface-bound organic units of 4-[(carboxymethyl)thio]benzene, (4-CMTB). The loss of diazonium group (N≡N+) upon electrografting of 4-CMTBD was investigated using IR spectroscopy. A Faradaic efficiency of about 18.8–20.0% was realized in mass deposition experiments for grafting 4-CMTB on the Au surface using an electrochemical quartz crystal microbalance technique. Raman spectroscopy performed on the Si–(4-CMTB) surface after treatment with copper (Cu) ion solution provided evidence of metal ion chelation based on an observed v(Cu–O) peak at about 487 cm–1 and a v(Cu–S) signal at about 267 cm–1. The binding of Cu ions by the chelating ligands also caused a red sh...

This work reveals that the electrical conductivity σ of a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film can be significantly increased by spin-coating multiple thin layers onto a substrate. Generally, σ can be improved by more than fourfold for multiple layers, as compared to a single thicker one. A gradual enhancement is observed for pristine PEDOT:PSS films (up to 2.10 ± 0.26 S cm–1 for five-layered films), while a plateau in σ at around 200 S cm–1 is reached after only three layers, when using a PEDOT:PSS solution with 5 vol% dimethyl sulfoxide. By contrast, only a small change in σ is observed for single layers of varying thickness. Accordingly, the thermoelectric power factor is also increased by up to 3.4 times for the multiple layers. Based on atomic force microscopy, X-ray photoelectron spectroscopy, UV–vis, and Raman spectroscopy measurements, two mechanisms are also proposed, involving an increase in percolation by inclusion of smaller grains within the existing ones, respectively, a reorganization of the PEDOT:PSS chains. These findings represent a direct strategy for enhancing the thermoelectric performance of conductive polymer films without additional reagents, while the mechanistic insights explain existing literature results.

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.

We present a study on the catalytic reduction of 4-nitrophenol (Nip) to 4-aminophenol (Amp) by sodium borohydride (BH4–) in the presence of metal nanoparticles in aqueous solution. This reaction which proceeds via the intermediate 4-hydroxylaminophenol has been used abundantly as a model reaction to check the catalytic activity of metallic nanoparticles. Here we present a full kinetic scheme that includes the intermediate 4-hydroxylaminophenol. All steps of the reaction are assumed to proceed solely on the surface of metal nanoparticles (Langmuir–Hinshelwood model). The discussion of the resulting kinetic equations shows that there is a stationary state in which the concentration of the intermediate 4-hydroxylaminophenol stays approximately constant. The resulting kinetic expression had been used previously to evaluate the kinetic constants for this reaction. In this stationary state there are isosbestic points in the UV/vis-spectra which are in full agreement with most published data. We compare the full...

In this work, we report the formation and growth mechanisms of gold nanoparticles (AuNPs) in eco-friendly deep eutectic solvents (DES; choline chloride and urea). AuNPs are synthesized on the DES surface via a low-energy sputter deposition method. Detailed small angle X-ray scattering (SAXS), UV-Vis, and cryogenic transmission electron microscopy (cryo-TEM) investigations show the formation of AuNPs of 5 nm diameter. Data analysis reveals that for a prolonged gold-sputtering time there is no change in the size of the particles. Only the concentration of AuNPs increases linearly in time. More surprisingly, the self-assembly of AuNPs into a first and second shell ordered system is observed directly by in situ SAXS for prolonged gold-sputtering times. The self-assembly mechanism is explained by the templating nature of DES combined with the equilibrium between specific physical interaction forces between the AuNPs. A disulfide-based stabilizer, bis((2-mercaptoethyl)trimethylammonium) disulfide dichloride, was applied to suppress the self-assembly. Moreover, the stabilizer even reverses the self-assembled or agglomerated AuNPs back to stable 5 nm individual particles as directly evidenced by UV-Vis. The template behavior of DES is compared to that of nontemplating solvent castor oil. Our results will also pave the way to understand and control the self-assembly of metallic and bimetallic nanoparticles.

The growing challenges of environmental purification by solar photocatalysis, precious-metal-free catalysis, and photocurrent generation in photovoltaic cells receive the utmost global attention. Here we demonstrate a one-pot, green chemical synthesis of a new stable heterostructured, ecofriendly, multifunctional microcomposite that consists of α-Bi2 O3 microneedles intercalated with anchored graphene oxide (GO) microsheets (1.0 wt %) for the above-mentioned applications on a large economical scale. The bare α-Bi2 O3 microneedles display two times better photocatalytic activities than commercial TiO2 (Degussa-P25), whereas the GO-hybridized composite exhibits approximately four to six times enhanced photocatalytic activities than the neat TiO2 photocatalyst in the degradation of colored aromatic organic dyes (crystal violet and rhodamine 6G) under visible-light irradiation (300 W tungsten lamp). The highly efficient activity is associated with the strong surface adsorption ability of GO for aromatic dye molecules, the high carrier acceptability, and the efficient electron-hole pair separation in Bi2 O3 by individual adjoining GO sheets. The introduction of Ag nanoparticles (2.0 wt %) further enhances the photocatalytic performance of the composite over eightfold because of a plasmon-induced electron-transfer process from Ag nanoparticles through the GO sheets into the conduction band of Bi2 O3 . The new composites are also catalytically active and catalyze the reduction of 4-nitrophenol to 4-aminophenol in the presence of borohydride ions. Photoanodes assembled from GO/α-Bi2 O3 and Ag/GO/α-Bi2 O3 composites display an improved photocurrent response (power conversion efficiency ∼20 % higher) over those prepared without GO in dye-sensitized solar cells.

Experimental results for the hypersonic impact of singly charged, mass selected, water clusters at a hard surface demonstrate cooling of the heated cluster by sequential loss of a water molecule. The trends in the experiment are most simply summarized as an evaporation. This behavior is in contrast to the shattering phenomena observed for rare gas clusters. The same information theoretic approach that predicted the shattering transition is fully consistent with the results for the water clusters. It shows that the relatively high binding energy per water monomer is the key reason for the anomalous fragmentation. The tetra coordinated oxygen atom in a cluster does however imply that the fragmentation is not a pure evaporation but has residual elements of a shattering transition. For water clusters the transition is broadened to span the finite range in energy between the onset of boiling and the energy when the solvation of the hydronium ion is over and it is bare.

The synthesis of the polymorphic cocrystal caffeine:anthranilic acid was investigated to obtain a better understanding of the processes leading to the formation of different polymorphic forms. In the case of these cocrystal polymorphs synthesized by liquid-assisted grinding a distinct influence of the dipole moment of the solvent was found. A pre-coordination between the solvent molecules and the caffeine:anthranilic acid cocrystal could be identified in the formation of form II. In the case of form II the solvent can be regarded as a catalyst. The formation pathway of each polymorph was evaluated using synchrotron X-ray diffraction.

Self-assembly of gold nanoparticles was obtained by sputter deposition on DES. SAXS and TEM investigations reveal the formation of spherical nanoparticles with a mean diameter of 5 ± 0.5 nm. For extended sputtering times, the number density of AuNPs increases linearly and a very pronounced 1st and 2nd shell ordering is observed.

Metal nanoparticles have attracted much attention due to their unique properties. Size control provides an effective key to an accurate adjustment of colloidal properties. The common approach to size control is testing different sets of parameters via trial and error. The actual particle growth mechanisms, and in particular the influences of synthesis parameters on the growth process, remain a black box. As a result, precise size control is rarely achieved for most metal nanoparticles. This contribution presents an approach to size control that is based on mechanistic knowledge. It is exemplified for a common silver nanoparticle synthesis, namely, the reduction of AgClO4 with NaBH4. Conducting this approach allowed a well-directed modification of this synthesis that enables, for the first time, the size-controlled production of silver nanoparticles 4–8 nm in radius without addition of any stabilization agent.

Recently, a so-called `crown-jewel' concept of preparation of Au/Pd-based colloidal nanoclusters has been reported [Zhang, Watanabe, Okumura, Haruta & Toshima (2011).Nat. Mater.11, 49–52]. Here, a different way of preparing highly active Au/Pd-based nanoclusters is presented. The origin of the increased activity of Au/Pd-based colloidal bimetallic nanoclusters was unclear up to now. However, it is, in general, accepted that in the nanometre range (1–100 nm) the cluster size, shape and composition affect the structural characteristics (e.g.lattice symmetry, unit cell), electronic properties (e.g.band gap) and chemical properties (e.g.catalytic activity) of a material. Hence, a detailed study of the relationship between the nanostructure of nanoclusters and their catalytic activity is presented here. The results indicate that a high surface-to-volume ratio of the nanoclusters combined with the presence of `both' Au and Pd isolated regions at the surface are crucial to achieve a high catalytic activity. A detailed structure elucidation directly leads to a mechanistic proposal, which indeed explains the higher catalytic activity of Au/Pd-based catalysts compared with pure metallic Au or Pd. The mechanism is based on cascade catalysis induced by a single type of nanoparticle with an intermixed surface of Au and Pd.

Due to its direct correlation to the number of spins within a sample quantitative NMR spectroscopy (qNMR) is a promising method with absolute comparison abilities in complex systems in technical, as well as metrological applications. Most of the samples studied with qNMR are in liquid state in diluted solutions, while gas-phase applications represent a rarely applied case. Commercially available NMR equipment was used for purity assessment of liquid and liquefied hydrocarbons serving as raw materials for production of primary reference gas standards. Additionally, gas-phase studies were performed within an online NMR flow probe, as well as in a high-pressure NMR setup to check feasibility as verification method for the composition of gas mixtures.

Mechanochemical reactions often result in 100% yields of single products, making purifying procedures obsolete. Mechanochemistry is also a sustainable and eco-friendly method. The ever increasing interest in this method is contrasted by a lack in mechanistic understanding of the mechanochemical reactivity and selectivity. Recent in situ investigations provided direct insight into formation pathways. However, the currently available theories do not predict temperature T as an influential factor. Here, we report the first determination of an apparent activation energy for a mechanochemical reaction. In a temperature-dependent in situ study the cocrystallisation of ibuprofen and nicotinamide was investigated as a model system. These experiments provide a pivotal step towards a comprehensive understanding of milling reaction mechanisms.

A new cocrystal of pyrazinamide with oxalic acid was prepared mechanochemically and characterized by PXRD, Raman spectroscopy, solid-state NMR spectroscopy, DTA-TG, and SEM. Based on powder X-ray diffraction data the structure was solved. The formation pathway of the reaction was studied in situ using combined synchrotron PXRD and Raman spectroscopy. Using oxalic acid dihydrate the initially neat grinding turned into a rapid self-accelerated liquid-assisted grinding process by the release of crystallization water. Under these conditions, the cocrystal was formed directly within two minutes.

Metallic nanotips exhibit large electric field enhancements over an extremely broad bandwidth spanning from the optical domain down to static fields. They therefore constitute ideal model systems for the investigation of the inherent frequency scalings of highly nonlinear and strong-field phenomena. Here, we present a comprehensive study of strong-field photoemission from individual metallic nanotips. Combining high local fields and variable-wavelength mid-infrared pulses, we investigate electron dynamics governed by the nanoscale confinement of the optical near-field. In particular, we characterize a transition to sub-cycle, field-driven electron acceleration. The experimental findings are corroborated by semiclassical calculations within a two-step model.

Soda lime silicate glasses are the perfect matrix for embedding and stabilizing metallic, magnetic, and oxide nanoparticles. We emphasize here that silicate glasses are also perfectly suited for studying growth and crystallization mechanisms of nanoparticles under in situ and ex situ conditions with the methods of small angle neutron scattering, small angle X-ray scattering (SAXS), and anomalous SAXS. Combined with transmission electron microscopy, X-ray diffraction, luminescence, and the theory of UV-Vis spectroscopy, a complete characterization can be achieved. We describe two novel crystal formation and growth mechanisms: (i) growth constraint by high viscous shell, and (ii) delayed Ostwald repining. On the basis of this mechanistic understanding, the properties of glasses can be optimized for applications and even novel ceramic and optical devices, such as warm white light Planck emitters can be foreseen.