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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.