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When vertically aligned carbon nanotubes (VACNT) are exposed to gases, their dielectric properties may change by mechanisms such as doping effects or a modification of the scattering channels of the mobile charge carriers of the VACNT. This report provides first data of a study which aims at an exploration of such conductivity changes in the THz frequency regime. The test gases are NH3 and SO2 which are known to act as donors, respectively as acceptors when interacting with the carbon nanotubes. Our measurements confirm the doping effects. This may open the way towards gas sensors based on the VACNT interrogated by THz radiation, where the VACNTs act as an accumulation volume for certain species contained in a gas stream. [ABSTRACT FROM AUTHOR]

Water-mediated interactions (WMIs) are responsible for diverse processes in aqueous solutions, including protein folding and nanoparticle aggregation. WMI may be affected by changes in temperature and pressure, and hence, they can alter chemical/physical processes that occur in aqueous environments. Traditionally, attention has been focused on hydrophobic interactions while, in comparison, the role of hydrophilic and hybrid (hydrophobic-hydrophilic) interactions have been mostly overlooked. Here, we study the role of T and P on the WMI between nanoscale (i) hydrophobic-hydrophobic, (ii) hydrophilic-hydrophilic, and (iii) hydrophilic-hydrophobic pairs of (hydroxylated/non-hydroxylated) graphene-based surfaces. We find that hydrophobic, hydrophilic, and hybrid interactions are all sensitive to P. However, while hydrophobic interactions [case (i)] are considerably sensitive to T-variations, hydrophilic [case (ii)] and hybrid interactions [case (iii)] are practically T-independent. An analysis of the entropic and enthalpic contributions to the potential of mean force for cases (i)-(iii) is also presented. Our results are important in understanding T- and P-induced protein denaturation and the interactions of biomolecules in solution, including protein aggregation and phase separation processes. From the computational point of view, the results presented here are relevant in the design of implicit water models for the study of molecular and colloidal/nanoparticle systems at different thermodynamic conditions.

The efficiency of a wet chemical route to synthesize gold nanostructures with tunable size and shape significantly depends on the applied solvent and the interaction of solvent molecules with other species such as gold ions. The ability of the organic solvent N -methyl-2-pyrrolidone (NMP) as a suitable medium for application in star-like gold nanostructure (AuNS) synthesis with a tunable morphology at ambient conditions has been investigated. The time-dependent analysis of the UV-vis absorption spectra of Au III Cl 4 - in a pure NMP solution illustrates the role of NMP as simultaneous complexing and reducing agents. Kinetic studies indicate that Au III Cl 4 - in NMP solution is reduced to Au I Cl 2 - , with no need to use another reducing agent, any external energy sources, or solvent pretreatment. This is because Au I species stay stable in this solution unless poly(vinylpyrrolidone) (PVP) catalyzes their disproportionation. Morphological studies by transmission electron microscopy (TEM) specify the high-yield synthesis of AuNS with monocrystalline spikes in a concentrated NMP solution by PVP. This study illustrates that the presence of seeds, as another agent to catalyze the disproportionation of Au I species, makes it possible to synthesize AuNS in varying concentrations of PVP in this medium. The role of PVP concentration and the presence of seeds in the formation kinetics, morphology, and optical properties is systematically discussed. The results achieved through this study develop a straightforward and safe procedure for AuNS synthesis in high yield in a water-miscible organic polar solvent with tunable morphology and optical properties. Considering the high capability of NMP to dissolve various types of polymers and hydrophobic ligands, synthesizing AuNS in this solvent opens a window to a practical and easy way to fabricate gold-based nanomaterials with fascinating optical properties., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

We perform molecular dynamics simulations to study the effects of temperature and pressure on the water-mediated interaction (WMI) between two nanoscale (apolar) graphene plates at 240 ≤ T ≤ 400 K and -100 ≤ P ≤ 1200 MPa. These are thermodynamic conditions relevant to, for example, cooling-, heating-, compression-, and decompression-induced protein denaturation. We find that at all ( T, P) studied, the potential of mean force between the graphene plates, as a function of plate separation r, exhibits local minima at specific plate separations r = r n that can accommodate n water layers ( n = 0,1,2,3). In particular, our results show that isobaric cooling and isothermal compression have a similar effect on WMI between the plates; both processes tend to suppress the attraction and ultimate collapse of the graphene plates by kinetically trapping the plates at the metastable states with r = r n ( n > 0). In addition, isobaric heating and isothermal decompression also have a similar effect; both processes tend to reduce the range and strength of the interactions between the graphene plates. Interestingly, at low temperatures, the WMI between the plates is affected by crystallization. However, crystallization depends deeply on the water model considered, SPC/E and TIP4P/2005 water models, with the crystallization occurring at different ( T, P) conditions, into different forms of ice.

We perform molecular dynamics simulations to study the effects of temperature on the water-mediated interactions between nanoscale apolar solutes. Specifically, we calculate the potential of mean force (PMF) between two graphene plates immersed in water at 240 ≤ T ≤ 400 K and P = 0.1 MPa. These are thermodynamic conditions relevant to cooling- and heating-induced protein denaturation. It is found that both cooling and heating tend to suppress the attraction, and ultimate collapse, of the graphene plates. However, the underlying role played by water upon heating and cooling is different. Isobaric heating reduces the strength and range of the interactions between the plates. Instead, isobaric cooling stabilizes the plates separations that can accommodate an integer number of water layers between the graphene plates. In particular, the energy barriers separating these plate separations increase linearly with 1/ T. We also explore the sensitivity of the plates PMF to the water model employed. In the case of the TIP4P/2005 model, water confined between the plates crystallizes into a defective bilayer ice at low temperatures, whereas in the case of the SPC/E model, water remains in the liquid state at same thermodynamic conditions. The effects of varying water-graphene interactions on the plates PMF are also studied.

The influence of the composition within multilayered heterostructure oxide semiconductors has a critical impact on the performance of thin-film transistor (TFT) devices. The heterostructures, comprising alternating polycrystalline indium oxide and zinc oxide layers, are fabricated by a facile atomic layer deposition (ALD) process, enabling the tuning of its electrical properties by precisely controlling the thickness of the individual layers. This subsequently results in enhanced TFT performance for the optimized stacked architecture after mild thermal annealing at temperatures as low as 200 °C. Superior transistor characteristics, resulting in an average field-effect mobility (μ sat. ) of 9.3 cm 2 V -1 s -1 ( W/ L = 500), an on/off ratio ( I on / I off ) of 5.3 × 10 9 , and a subthreshold swing of 162 mV dec -1 , combined with excellent long-term and bias stress stability are thus demonstrated. Moreover, the inherent semiconducting mechanism in such multilayered heterostructures can be conveniently tuned by controlling the thickness of the individual layers. Herein, devices comprising a higher In 2 O 3 /ZnO ratio, based on individual layer thicknesses, are predominantly governed by percolation conduction with temperature-independent charge carrier mobility. Careful adjustment of the individual oxide layer thicknesses in devices composed of stacked layers plays a vital role in the reduction of trap states, both interfacial and bulk, which consequently deteriorates the overall device performance. The findings enable an improved understanding of the correlation between TFT performance and the respective thin-film composition in ALD-based heterostructure oxides.

Chemical vapor deposition (CVD) of carbon precursors employing a metal catalyst is a well-established method for synthesizing high-quality single-layer graphene. Yet the main challenge of the CVD process is the required transfer of a graphene layer from the substrate surface onto a chosen target substrate. This process is delicate and can severely degrade the quality of the transferred graphene. The protective polymer coatings typically used generate residues and contamination on the ultrathin graphene layer. In this work, we have developed a graphene transfer process which works without a coating and allows the transfer of graphene onto arbitrary substrates without the need for any additional post-processing. During the course of our transfer studies, we found that the etching process that is usually employed can lead to contamination of the graphene layer with the Faradaic etchant component FeCl 3 , resulting in the deposition of iron oxide Fe x O y nanoparticles on the graphene surface. We systematically analyzed the removal of the copper substrate layer and verified that crystalline iron oxide nanoparticles could be generated in controllable density on the graphene surface when this process is optimized. It was further confirmed that the Fe x O y particles on graphene are active in the catalytic growth of carbon nanotubes when employing a water-assisted CVD process.

We characterize the phase behavior of glassy water by performing extensive out-of-equilibrium molecular dynamics simulations using the TIP4P/2005 water model. Specifically, we study (i) the pressure-induced transformations between low-density (LDA) and high-density amorphous ice (HDA), (ii) the pressure-induced amorphization (PIA) of hexagonal ice (I h ), (iii) the heating-induced LDA-to-HDA transformation at high pressures, (iv) the heating-induced HDA-to-LDA transformation at low and negative pressures, (v) the glass transition temperatures of LDA and HDA as a function of pressure, and (vi) the limit of stability of LDA upon isobaric heating and isothermal decompression (at negative pressures). These transformations are studied systematically, over a wide range of temperatures and pressures, allowing us to construct a P-T phase diagram for glassy TIP4P/2005 water. Our results are in qualitative agreement with experimental observations and with the P-T phase diagram obtained for glassy ST2 water that exhibits a liquid-liquid phase transition and critical point. We also discuss the mechanism for PIA of ice I h and show that this is a two-step process where first, the hydrogen-bond network (HBN) is distorted and then the HBN abruptly collapses. Remarkably, the collapse of the HB in ice I h occurs when the average molecular orientations order, a measure of the tetrahedrality of the HBN, is of the same order as in LDA, suggesting a common mechanism for the LDA-to-HDA and I h -to-HDA transformations.

ZnS nanoparticles have been synthesized on vertically aligned carbon nanotubes by gas-phase conversion of ZnO nanoparticles which have been tethered on vertically aligned carbon nanotubes using atomic layer deposition (ALD). The resulting ZnO@CNT nanocomposite has been converted to ZnS@CNT by reacting it with hydrogen sulfide using thioacetamide as a precursor. The composition of the resulting nanocomposite could be tuned from a mixed ternary ZnS/ZnO@CNT nanocomposite to a pure ZnS@CNT nanocomposite. At the same time, the amount of wurtzite and sphalerite phases varies in the ZnS@CNT nanocomposite. The resulting nanocomposites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), selected area electron diffraction (SAED), ultraviolet-visible diffuse reflectance spectroscopy (UV-VIS DRS) and photoluminescence spectroscopy (PL). Finally, the different nanocomposites were tested for their photocatalytic activity by the photocatalytic decomposition under visible light using methyl orange (MO). Herein a systematic study of the photocatalytic activity of different compositions of ZnS in the ZnS@CNT nanocomposite was performed for the first time.

Low-layered, transparent graphene is accessible by a chemical vapor deposition (CVD) technique on a Ni-catalyst layer, which is deposited on a <100> silicon substrate. The number of graphene layers on the substrate is controlled by the grain boundaries in the Ni-catalyst layer and can be studied by micro Raman analysis. Electrical studies showed a sheet resistance (R(sheet)) of approximately 1435 Ω per □, a contact resistance (R(c)) of about 127 Ω, and a specific contact resistance (R(sc)) of approximately 2.8×10(-4)  Ω cm(2) for the CVD graphene samples. Transistor output characteristics for the graphene sample demonstrated linear current/voltage behavior. A current versus voltage (I(ds)-V(ds)) plot clearly indicates a p-conducting characteristic of the synthesized graphene. Gas-sensor measurements revealed a high sensor activity of the low-layer graphene material towards H(2) and CO. At 300 °C, a sensor response of approximately 29 towards low H(2) concentrations (1 vol %) was observed, which is by a factor of four higher than recently reported., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A 3D hybrid architecture composed of macroscopic, vertically aligned CNT blocks which are formed via a metal catalyzed CVD process followed by deposition of TiO(2) on the CNT side walls in nanocrystalline or amorphous form is presented. The morphology of the deposited TiO(2) can be tailored by the deposition method employed. Depositing TiO(2) from the gas phase by employing the organometallic precursor Ti[OCH(CH(3))(2)](4) leads to formation of nanocrystalline anatase or rutile particles with a dense coverage on the surface and within the 3D CNT scaffold. Phase pure TiO(2) (anatase) is formed between 500 and 700 °C, while higher temperatures resulted in rutile modification of TiO(2). Below 500 °C, TiO(2) forms an amorphous oxide layer. At higher temperatures such initially formed TiO(2) layers segregate into particles which tend to crystallize. In contrast, when generating TiO(2) by oxidation of Ti metal which is deposited by vaporization onto the 3D CNT block array, and subsequently oxidized in air or controlled O(2) atmosphere this leads to a porous layer with a particular nanostructure on top of the CNT blocks. First studies of the fabrication and field emission of the new 3D CNT/TiO(2) hybrid cathodes display good and stable FE characteristics with onset fields for current density of 1 μA cm(-2) of 1.7 to 1.9 V μm(-1), while the average field enhancement factor is in the range between 2000 and 2500 depending on the O(2) base pressure during the measurements., (This journal is © The Royal Society of Chemistry 2011)

A novel molecular approach to the synthesis of polycrystalline Cu-doped ZnO rod-like nanostructures with variable concentrations of introduced copper ions in ZnO host matrix is presented. Spectroscopic (PLS, variable temperature XRD, XPS, ELNES, HERFD) and microscopic (HRTEM) analysis methods reveal the +II oxidation state of the lattice incorporated Cu ions. Photoluminescence spectra show a systematic narrowing (tuning) of the band gap depending on the amount of Cu(II) doping. The advantage of the template assembly of doped ZnO nanorods is that it offers general access to doped oxide structures under moderate thermal conditions. The doping content of the host structure can be individually tuned by the stoichiometric ratio of the molecular precursor complex of the host metal oxide and the molecular precursor complex of the dopant, Di-aquo-bis[2-(methoxyimino)-propanoato]zinc(II) 1 and -copper(II) 2. Moreover, these keto-dioximato complexes are accessible for a number of transition metal and lanthanide elements, thus allowing this synthetic approach to be expanded into a variety of doped 1D metal oxide structures.

Cuprous oxide agglomerates composed of 4-10 nm Cu2O nanoparticles were deposited on multiwalled carbon nanotubes (MWCNTs) and on ZnO/MWCNTs to give binary [Cu2O/MWCNT] and ternary [Cu2O/ZnO/MWCNT] composites. Di-aqua-bis[2-(methoxyimino)propanoato]copper Cu[O2CCCH3NOMe](2)·2H2O 1 in DMF was used as single source precursor for the deposition of nanoscaled Cu2O. The precursor decomposes either in air or under argon to yield CuO2 by in situ redox reaction. Thermogravimetric coupled mass spectroscopic analysis (TG-MS) of 1 revealed that methanol formed during the decomposition of 1 acts as a potential in situ reducing agent. Scanning electron microscopy (SEM) of the binary [Cu2O/MWCNT] nano-composite shows an increase of cuprous oxide loading depending on the precursor amount, along the periphery of the MWCNTs as well as formation of larger particle agglomerates. Transmission electron microscopy (TEM) of the sample shows crystalline domains of size 4-10 nm surrounded by an amorphous region within the larger particles. SEM and TEM of ternary [Cu2O/ZnO/MWCNT] clearly reveal that Cu2O nanoparticles are primarily deposited on ZnO rather than on MWCNTs. The catalytic activities of the [Cu2O/MWCNT] and [Cu2O/ZnO/MWCNT] binary and ternary composites were studied for the selective partial oxidation of ethanol to acetaldehyde with molecular oxygen. While using binary [Cu2O/MWCNT] (13.8 wt% Cu) as catalyst, acetaldehyde was obtained with a yield of 87% at 355 °C (selectivity 96% and conversion 91%). When nanoscale ZnO is present, the resulting [Cu2O/ZnO/MWCNT] composite shows preferential hydrogen and CO2 formation due to the fact that the dehydrogenation and total oxidation pathway is more favoured compared to the binary composite. Significant morphological changes of the catalyst during the catalytic process were observed.

Mass-selected, ligand-free Fe(N) clusters with N = 10-30 atoms (cluster diameter: 0.6-0.9 nm) were implanted into [Al@SiO(x)] surfaces at a low surface coverage corresponding to a few thousandths up to a few hundredths of a monolayer in order to avoid initial cluster agglomeration. These studies are aimed towards gaining an insight into the lower limit of the size regime of carbon nanotube (CNT) growth by employing size-selected sub-nm iron clusters as catalyst or precatalyst precursors for CNT growth. Agglomeration of sub-nm iron clusters to iron nanoparticles with a median size range between three and six nanometres and the CNT formation hence can be observed at CVD growth temperatures of 750 °C. Below 600 °C, no CNT growth is observed.

Gold nanoparticles of 10-24 and 5-8 nm in size were obtained by chemical citrate reduction and UV photoreduction, respectively, on acid-treated multiwalled carbon nanotubes (MWCNTs) and on ZnO/MWCNT composites. The shape and size of the deposited Au nanoparticles were found to be dependent upon the synthetic method used. Single-crystalline, hexagonal gold particles were produced in the case of UV photoreduction on ZnO/MWCNT, whereas spherical Au particles were deposited on MWCNT when the chemical citrate reduction method was used. In the UV photoreduction route, n-doped ZnO serves as the e(-) donor, whereas the solvent is the hole trap. All materials were fully characterised by UV/Vis spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and BET surface analysis. The catalytic activity of the composites was studied for the selective hydrogenation of alpha,beta-unsaturated carbonyl compound 3,7-dimethyl-2,6-octadienal (citral). The Au/ZnO/MWCNT composite favours the formation of unsaturated alcohols (selectivity=50% at a citral conversion of 20%) due to the presence of single-crystalline, hexagonal gold particles, whereas saturated aldehyde formation is favoured in the case of the Au/MWCNT nanocomposite that contains spherical gold particles.

We have developed a chemical vapor deposition (CVD) process for the catalytic growth of carbon nanotubes (CNTs), anchored in a comose-type structure on top of porous alumina substrates. The mass-flow conditions of precursor and carrier gases and temperature distributions in the CVD reactor were studied by transient computational fluid dynamic simulation. Molecular-beam quadrupole mass spectroscopy (MB-QMS) has been used to analyze the gas phase during ferrocene CVD under reaction conditions (1073 K) in the boundary layer near the substrate. Field-emission (FE) properties of the nonaligned CNTs were measured for various coverages and pore diameters of the alumina. Samples with more dense CNT populations provided emitter-number densities up to 48,000 cm(-2) at an electric field of 6 V microm(-1). Samples with fewer but well-anchored CNTs in 22-nm pores yielded the highest current densities. Up to 83 mA cm(-2) at 7 V microm(-1) in dc mode and more than 200 mA cm(-2) at 11 V microm(-1) in pulsed diode operation have been achieved from a cathode size of 24 mm2.

The catalytic CVD synthesis, using propyne as carbon precursor and Fe(NO3)3 as catalyst precursor inside porous alumina, gives carbon nanotube (CNT) bags in a well-arranged two-dimensional order. The tubes have the morphology of bags or fibers, since they are completely filled with smaller helicoidal CNTs. This morphology has so far not been reported for CNTs. Owing to the dense filling of the outer mother CNTs with small helicoidal CNTs, the resulting CNT fibers appear to be stiff and show no sign of inflation, as sometimes observed with hollow CNTs. The fiber morphology was observed by raster electron microscopy (REM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The carbon material is graphitic as deduced from spectroscopic studies (X-ray diffraction, Raman and electron energy-loss spectroscopy (EELS)). From Mössbauer studies, the presence of two different oxidation states (Fe0 and FeIII) of the catalyst is proven. Geometric structuring of the template by two different methods has been studied. Inkjet catalyst printing shows that the tubes can be arranged in defined areas by a simple and easily applied technique. Laser-structuring creates grooves of nanotube fibers embedded in the alumina host. This allows the formation of defined architectures in the microm range. Results on hydrogen absorption and field emission properties of the CNT fibers are reported.

Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. Mössbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the Mössbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From Mössbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active towards formation of carbon nanotubes by a CVD process. Depending on the reaction conditions, the formation of smaller carbon nanotubes inside the interior of larger carbon nanotubes within the alumina pores can be achieved. This behavior can be understood by means of selectively turning on and off the iron catalyst by adjusting the flow rate of the gaseous carbon precursor in the CVD process.