Photocatalytic active ZnO1-xSx@CNTs heteronanostructures.

Herein, we report on the use of vertically aligned multiwall carbon nanotubes (CNTs) films as support for ZnO/ZnS photocatalytic active nanostructures. The CNTs were synthetized via a hot-filament chemical vapor deposition (HfCVD), using Fe catalyst on top of Al2O3buffer layer. Controlled point defects in the CNTs outer walls were created by exposure to a low pressure nonthermal water vapors diffusive plasma and acted as seeds for subsequent pulsed-electrodeposition of Zn nanoparticles. This was to achieve a direct and improved contact between the nanoparticles and CNTs. To obtain ZnO, ZnS and mix phase of ZnO/ZnS spread on CNTs, the oxidation, sulfurization and 2 steps subsequent annealing in oxygen and sulfur rich atmospheres were applied. High resolution transmission electron microscopy with energy dispersive x-rays spectroscopy in scanning mode, provided the chemical mapping of the structures. X-ray diffraction (XRD) analyses proved the hexagonal phase of ZnO and ZnS, obtained after oxidation in H2O and S vapors, respectively. In the case of the samples obtained by the 2 steps subsequent annealing, XRD showed mainly the presence of ZnO and a small amount of ZnS. The benefit of the secondary annealing in S vapor was seen as an absorption enhancement of the ZnO1-xSx@CNTs sample having the absorption edge at 417 nm, whereas the absorption edge of ZnO@CNTs was 408 nm and of ZnS@CNTs 360 nm. For all the samples, compared to the bare ZnO and ZnS, the absorption red shift was observed which is attributed to the CNTs involvement. Therefore, this study showed the double sides benefit to induce the absorption of ZnO of the visible light, one from S doping and second of CNTs involvement. The absorption enhancement had a positive impact on photocatalytic degradation of methyl blue dye, showing that ZnO1-xSx@CNTs heteronanostructure was the best photocatalyst among the studied samples.

Solution-Processed Functionalized Graphene Film Prepared by Vacuum Filtration for Flexible NO2 Sensors.

Large-scale production of graphene nanosheets (GNSs) has led to the availability of solution-processable GNSs on the commercial scale. The controlled vacuum filtration method is a scalable process for the preparation of wafer-scale films of GNSs, which can be used for gas sensing applications. Here, we demonstrate the use of this deposition method to produce functional gas sensors, using a chemiresistor structure from GNS solution-based techniques. The GNS suspension was prepared by liquid-phase exfoliation (LPE) and transferred to a polyvinylidene fluoride (PVDF) membrane. The effect of non-covalent functionalization with Co-porphyrin and Fe-phthalocyanines on the sensor properties was studied. The pristine and functionalized GNS films were characterized using different techniques such as Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray diffraction (XRD), and electrical characterizations. The morphological and spectroscopic analyses both confirm that the molecules (Co-porphyrin and Fe-phthalocyanine) were successfully adsorbed onto the GNSs surface through π-π interactions. The chemiresistive sensor response of functionalized GNSs toward the low concentrations of nitrogen dioxide (NO2) (0.5-2 ppm) was studied and compared with those of the film of pristine GNSs. The tests on the sensing performance clearly showed sensitivity to a low concentration of NO2 (5 ppm). Furthermore, the chemical modification of GNSs significantly improves NO2 sensing performance compared to the pristine GNSs. The sensor response can be modulated by the type of adsorbed molecules. Indeed, Co-Por exhibited negative responsiveness (the response of Co-Por-GNS sensors and pristine GNS devices was 13.1% and 15.6%, respectively, after exposure to 0.5 ppm of NO2). Meanwhile, Fe-Phc-GNSs induced the opposite behavior resulting in an increase in the sensor response (the sensitivity was 8.3% and 7.8% of Fe-Phc-GNSs and pristine GNSs, respectively, at 0.5 ppm NO2 gas).

Thermal Evolution of C-Fe-Bi Nanocomposite System: From Nanoparticle Formation to Heterogeneous Graphitization Stage.

Carbon xerogel nanocomposites with integrated Bi and Fe particles (C­Bi­Fe) represent an interesting model of carbon nanostructures decorated with multifunctional nanoparticles (NPs) with applicability for electrochemical sensors and catalysts. The present study addresses the fundamental aspects of the catalyzed growth of nano-graphites in C­Bi­Fe systems, relevant in charge transport and thermo-chemical processes. The thermal evolution of a C­Bi­Fe xerogel is investigated using different pyrolysis treatments. At lower temperatures (~750°C), hybrid bismuth iron oxide (BFO) NPs are frequently observed, while graphitization manifests under more specific conditions such as higher temperatures (~1,050°C) and reduction yields. An in situ heating TEM experiment reveals graphitization activity between 800 and 900°C. NP motion is directly correlated with textural changes of the carbon support due to the catalyzed growth of graphitic nanoshells and nanofibers as confirmed by HR-TEM and electron tomography (ET) for the graphitized sample. An exponential growth model for the catalyst dynamics enables the approximation of activation energies as 0.68 and 0.29­0.34 eV during reduction and graphitization stages. The results suggest some similarities with the tip growth mechanism, while oxygen interference and the limited catalyst­feed gas interactions are considered as the main constraints to enhanced growth.

Single-Crystalline Body Centered FeCo Nano-Octopods: From One-Pot Chemical Growth to a Complex 3D Magnetic Configuration.

Single crystalline magnetic FeCo nanostars were prepared using an organometallic approach under mild conditions. The fine-tuning of the experimental conditions allowed the direct synthesis of these nano-octopods with body-centered cubic (bcc) structure through a one-pot reaction, contrarily to the seed-mediated growth classically used. The FeCo nanostars consist of 8 tetrahedrons exposing {311} facets, as revealed by high resolution transmission electron microscopy (HRTEM) imaging and electron tomography (ET), and exhibit a high magnetization comparable with the bulk one (Ms = 235 A·m2·kg-1). Complex 3D spin configurations resulting from the competition between dipolar and exchange interactions are revealed by electron holography. This spin structures are stabilized by the high aspect ratio tetrahedral branches of the nanostars, as confirmed by micromagnetic simulations. This illustrates how magnetic properties can be significantly tuned by nanoscale shape control.

Kinked Silicon Nanowires: Superstructures by Metal-Assisted Chemical Etching.

We report on metal-assisted chemical etching of Si for the synthesis of mechanically stable, hybrid crystallographic orientation Si superstructures with high aspect ratio, above 200. This method sustains high etching rates and facilitates reproducible results. The protocol enables the control of the number, angle, and location of the kinks via successive etch-quench sequences. We analyzed relevant Au mask catalyst features to systematically assess their impact on a wide spectrum of etched morphologies that can be easily attained and customized by fine-tuning of the critical etching parameters. For instance, the designed kinked Si nanowires can be incorporated in biological cells without affecting their viability. An accessible numerical model is provided to explain the etch profiles and the physicochemical events at the Si/Au-electrolyte interface and offers guidelines for the development of finite-element modeling of metal-assisted Si chemical etching.

Carbon Xerogel Nanostructures with Integrated Bi and Fe Components for Hydrogen Peroxide and Heavy Metal Detection.

Multifunctional Bi- and Fe-modified carbon xerogel composites (CXBiFe), with different Fe concentrations, were obtained by a resorcinol-formaldehyde sol-gel method, followed by drying in ambient conditions and pyrolysis treatment. The morphological and structural characterization performed by X-ray diffraction (XRD), Raman spectroscopy, N2 adsorption/desorption porosimetry, scanning electron microscopy (SEM) and scanning/transmission electron microscopy (STEM) analyses, indicates the formation of carbon-based nanocomposites with integrated Bi and Fe oxide nanoparticles. At higher Fe concentrations, Bi-Fe-O interactions lead to the formation of hybrid nanostructures and off-stoichiometric Bi2Fe4O9 mullite-like structures together with an excess of iron oxide nanoparticles. To examine the effect of the Fe content on the electrochemical performance of the CXBiFe composites, the obtained powders were initially dispersed in a chitosan solution and applied on the surface of glassy carbon electrodes. Then, the multifunctional character of the CXBiFe systems is assessed by involving the obtained modified electrodes for the detection of different analytes, such as biomarkers (hydrogen peroxide) and heavy metal ions (i.e., Pb2+). The achieved results indicate a drop in the detection limit for H2O2 as Fe content increases. Even though the current results suggest that the surface modifications of the Bi phase with Fe and O impurities lower Pb2+ detection efficiencies, Pb2+ sensing well below the admitted concentrations for drinkable water is also noticed.

Atomic Step Flow on a Nanofacet.

Crystal growth often proceeds by atomic step flow. When the surface area available for growth is limited, the nucleation and progression of the steps can be affected. This issue is particularly relevant to the formation of nanocrystals. We examine the case of Au-catalyzed GaAs nanowires, which we grow in a transmission electron microscope. Our in situ observations show that atomic layers nucleate at the periphery of the interface between the nanowire and the catalyst droplet. From this starting location, the atomic step flows within a restricted area of hexagonal shape. At specific partial coverages, the monolayer configuration changes abruptly. A simple model based on the geometry of the system and its edge energies explains these observations. In particular, we observe an inversion of the step curvature which reveals that the effective energy per unit length of monolayer edge is much lower at the interface periphery than inside the catalyst droplet.

Three-Dimensional Branched and Faceted Gold-Ruthenium Nanoparticles: Using Nanostructure to Improve Stability in Oxygen Evolution Electrocatalysis.

Achieving stability with highly active Ru nanoparticles for electrocatalysis is a major challenge for the oxygen evolution reaction. As improved stability of Ru catalysts has been shown for bulk surfaces with low-index facets, there is an opportunity to incorporate these stable facets into Ru nanoparticles. Now, a new solution synthesis is presented in which hexagonal close-packed structured Ru is grown on Au to form nanoparticles with 3D branches. Exposing low-index facets on these 3D branches creates stable reaction kinetics to achieve high activity and the highest stability observed for Ru nanoparticle oxygen evolution reaction catalysts. These design principles provide a synthetic strategy to achieve stable and active electrocatalysts.

New insights into the side-face structure, growth aspects, and reactivity of Ag(n) nanoprisms.

We report an improved synthesis of colloidal Ag(n) nanoprisms using carboxyl compounds (citrate or succinate) and long chain macromolecules (polyvinylpyrrolidone (PVP)). The side-facet structure of the triangular nanostructure was determined in detail using electron tomography in scanning transmission mode (3D STEM) and HRTEM. It has been found that they are built up by {100} facets with a single parallel twin plane. The best conditions for producing uniform Ag nanoprisms with tunable sizes and high yields in the presence of carboxyl compounds additive system are described, and a growth mechanism is proposed. This approach provides also a route to synthesize Ag nanodisks and Au-Ag alloyed nanoprisms.

Rapid and Facile Synthesis of Gold Trisoctahedrons for Surface-Enhanced Raman Spectroscopy and Refractive Index Sensing.

Au trisoctahedrons (TOHs) with sharp tips and high-index facets have exceptional properties for diverse applications, such as plasmon-enhanced spectroscopies, catalysis, sensing, and biomedicine. However, the synthesis of Au TOHs remains challenging, and most reported synthetic methods are time-consuming or involve complex steps, hindering the exploration of their potential applications. Herein, we present a facile and fast approach to prepare Au TOHs with high uniformity and good control over the final size and shape, all within less than 10 min of synthesis, for surface-enhanced Raman spectroscopy (SERS) and refractive index sensing. The size of the Au TOHs can be easily tailored over a wide range, from 39 to 268 nm, allowing a tuning of the plasmon resonance at wavelengths from visible to near-infrared regions. The exposed facets of the Au TOHs can also be varied by controlling the growth temperatures. The wide tunability of size and exposed facets of Au TOHs can greatly broaden the range of their applications. We have also encapsulated Au TOHs with zeolite imidazolate framework (ZIF-8), obtaining core-shell hybrid structures. With the ability to tune Au TOH size, we further assessed their SERS performances in function of their size by detecting 2-NaT in solution, exhibiting enhancement factors of the order of 105 with higher values when the LSPR is blue-shifted from the laser excitation wavelength. Au TOHs have been also compared for refractive index sensing applications against Au nanospheres, revealing Au TOHs as better candidates. Overall, this facile and fast method for synthesizing Au TOHs with tunable size and exposed facets simplifies the path toward the exploration of properties and applications of this highly symmetrical and high-index nanostructure.

Electric Field-Induced Nano-Assembly Formation: First Evidence of Silicon Superclusters with a Giant Permanent Dipole Moment.

The outstanding properties of silicon nanoparticles have been extensively investigated during the last few decades. Experimental evidence and applications of their theoretically predicted permanent electric dipole moment, however, have only been reported for silicon nanoclusters (SiNCs) for a size of about one to two nanometers. Here, we have explored the question of whether suitable plasma conditions could lead to much larger silicon clusters with significantly stronger permanent electric dipole moments. A pulsed plasma approach was used for SiNC production and surface deposition. The absorption spectra of the deposited SiNCs were recorded using enhanced darkfield hyperspectral microscopy and compared to time-dependent DFT calculations. Atomic force microscopy and transmission electron microscopy observations completed our study, showing that one-to-two-nanometer SiNCs can, indeed, be used to assemble much larger "superclusters" with a size of tens of nanometers. These superclusters possess extremely high permanent electric dipole moments that can be exploited to orient and guide these clusters with external electric fields, opening the path to the controlled architecture of silicon nanostructures.

One-Step Synthesis of CuxOy/TiO2 Photocatalysts by Laser Pyrolysis for Selective Ethylene Production from Propionic Acid Degradation.

In an effort to produce alkenes in an energy-saving way, this study presents for the first time a photocatalytic process that allows for the obtention of ethylene with high selectivity from propionic acid (PA) degradation. To this end, TiO2 nanoparticles (NPs) modified with copper oxides (CuxOy/TiO2) were synthetised via laser pyrolysis. The atmosphere of synthesis (He or Ar) strongly affects the morphology of photocatalysts and therefore their selectivity towards hydrocarbons (C2H4, C2H6, C4H10) and H2 products. Specifically, CuxOy/TiO2 elaborated under He environment presents highly dispersed copper species and favours the production of C2H6 and H2. On the contrary, CuxOy/TiO2 synthetised under Ar involves copper oxides organised into distinct NPs of ~2 nm diameter and promotes C2H4 as the major hydrocarbon product, with selectivity, i.e., C2H4/CO2 as high as 85% versus 1% obtained with pure TiO2.

Liquid Shear Exfoliation of MoS2: Preparation, Characterization, and NO2-Sensing Properties.

2D materials possess great potential to serve as gas-sensing materials due to their large, specific surface areas and strong surface activities. Among this family, transition metal chalcogenide materials exhibit different properties and are promising candidates for a wide range of applications, including sensors, photodetectors, energy conversion, and energy storage. Herein, a high-shear mixing method has been used to produce multilayered MoS2 nanosheet dispersions. MoS2 thin films were manufactured by vacuum-assisted filtration. The structural morphology of MoS2 was studied using ς-potential, UV-visible, scanning electron microscopy (SEM), atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy (RS). The spectroscopic and microscopic analyses confirm the formation of a high-crystalline MoS2 thin film with good inter-sheet connectivity and relative thickness uniformity. The thickness of the MoS2 layer is measured to be approximately 250 nm, with a nanosheet size of 120 nm ± 40 nm and a number of layers between 6 and 9 layers. Moreover, the electrical characteristics clearly showed that the MoS2 thin film exhibits good conductivity and a linear I-V curve response, indicating good ohmic contact between the MoS2 film and the electrodes. As an example of applicability, we fabricated chemiresistive sensor devices with a MoS2 film as a sensing layer. The performance of the MoS2-chemiresistive sensor for NO2 was assessed by being exposed to different concentrations of NO2 (1 ppm to 10 ppm). This sensor shows a sensibility to low concentrations of 1 ppm, with a response time of 114 s and a recovery time of 420 s. The effect of thin-film thickness and operating temperatures on sensor response was studied. The results show that thinner film exhibits a higher response to NO2; the response decreases as the working temperature increases.

On-chip monitoring of toxic gases: capture and label-free SERS detection with plasmonic mesoporous sorbents.

The detection of the spread of toxic gas molecules in the air at low concentration in the field requires a robust miniaturized system combined with an analytical technique that is portable and able to detect and identify the molecules, as is the case with surface enhanced Raman scattering (SERS). This work aims to address capability gaps faced by first responders in real-time detection, identification and monitoring of neurotoxic gases by developing robust, reliable and reusable SERS microfluidic chips. Thus, the key performance attributes of a portable SERS detection system that must be addressed in detail are its limit of detection, response time and reusability. To this purpose, we integrate a 3D plasmonic architecture based on closely packed mesoporous silica (MCM48) nanospheres decorated with Au nanoparticle arrays, denoted as MCM48@Au, into a Si microfluidic chip designed and used for preconcentration and label-free detection of gases at a trace concentration level. The SERS performance of the plasmonic platform is thoroughly analyzed using DMMP as a model neurotoxic simulant over a 1 cm2 SERS active area and over a range of concentrations from 100 ppbV to 2.5 ppmV. The preconcentration-based SERS signal amplification by the mesoporous silica moieties is evaluated against dense silica counterparts, denoted as Stöber@Au. To assess the potential for applications in the field, the microfluidic SERS chip has been interrogated with a portable Raman spectrometer, evaluated with temporal and spatial resolution and subjected to several gas detection/regeneration cycles. The reusable SERS chip shows exceptional performance for the label-free monitoring of 2.5 ppmV gaseous DMMP.

Synthesis of Few-Layered Transition-Metal Dichalcogenides by Ion Implantation of Chalcogen and Metal Species into Sapphire.

The growth of transition-metal dichalcogenides (TMDCs) has been performed so far using most established thin-film growth techniques (e.g., vapor phase transport, chemical vapor deposition, molecular beam epitaxy, etc.). However, because there exists no self-limiting mechanism for the growth of TMDCs, none of these techniques allows precise control of the number of TMDC layers over large substrate areas. Here, we explore the ion implantation of the parent TMDC atoms into a chemically neutral substrate for the synthesis of TMDC films. The idea is that once all of the ion-implanted species have reacted together, the synthesis reaction stops, thereby effectively stopping growth. In other words, even if there is no self-limiting mechanism, growth stops when the nutrients are exhausted. We have co-implanted Mo and S ions into c-oriented sapphire substrates using various doses corresponding to 1- to 5-layer atom counts. We find that the subsurface region of the sapphire substrates is amorphized by the ion implantation process, at least for implanted doses of 2-layer atom counts and over. For all doses, we have observed the formation of MoS2 material inside the sapphire after postimplantation annealing between 800 and 850 °C. We report that the order of implantation (i.e., whether S or Mo is implanted first) is an important parameter. More precisely, samples for which S is implanted first tend to yield thin crystals with a large lateral extension (more than 200 nm for 5-layer doses) and mainly located at the interface between the amorphized and crystalline sapphire. When Mo is first implanted, the MoS2 crystals still predominantly appear at the amorphous-crystalline interface (which is much rougher), but they are much thicker, suggesting a different nucleation mechanism.

3D analysis of the morphology and spatial distribution of nitrogen in nitrogen-doped carbon nanotubes by energy-filtered transmission electron microscopy tomography.

We present here the application of the energy-filtered transmission electron microscopy (EFTEM) in the tomographic mode to determine the precise 3D distribution of nitrogen within nitrogen-doped carbon nanotubes (N-CNTs). Several tilt series of energy-filtered images were acquired on the K ionization edges of carbon and nitrogen on a multiwalled N-CNT containing a high amount of nitrogen. Two tilt series of carbon and nitrogen 2D maps were then calculated from the corresponding energy-filtered images by using a proper extraction procedure of the chemical signals. Applying iterative reconstruction algorithms provided two spatially correlated C and N elemental-selective volumes, which were then simultaneously analyzed with the shape-sensitive reconstruction deduced from Zero-Loss recordings. With respect to the previous findings, crucial information obtained by analyzing the 3D chemical maps was that, among the two different kind of arches formed in these nanotubes (transversal or rounded ones depending on their morphology), the transversal arches contain more nitrogen than do the round ones. In addition, a detailed analysis of the shape-sensitive volume allowed the observation of an unexpected change in morphology along the tube axis: close to the round arches (with less N), the tube is roughly cylindrical, whereas near the transversal ones (with more N), its shape changes to a prism. This relatively new technique is very powerful in the material science because it combines the ability of the classical electron tomography to solve 3D structures and the chemical selectivity of the EFTEM imaging.

Grid batch-dependent tuning of glow discharge parameters.

Sample preparation on cryo-EM grids can give various results, from very thin ice and homogeneous particle distribution (ideal case) to unwanted behavior such as particles around the "holes" or complexes that do not entirely correspond to the one in solution (real life). We recently run into such a case and finally found out that variations in the 3D reconstructions were systematically correlated with the grid batches that were used. We report the use of several techniques to investigate the grids' characteristics, namely TEM, SEM, Auger spectroscopy and Infrared Interferometry. This allowed us to diagnose the origin of grid preparation problems and to adjust glow discharge parameters. The methods used for each approach are described and the results obtained on a common specific case are reported.

Reactive layer-by-layer deposition of poly(ethylene imine) and a precursor of TiO2: influence of the sodium chloride concentration on the film growth, interaction with hexacyanoferrate anions, and particle distribution in the film.

Films prepared according to a layer-by-layer (LBL) manner find increasing importance in many applications such as coatings with dedicated optical or electronic properties, particularly when including nanomaterials. An alternative way to prepare such hybrid layer-by-layer coatings is to perform sol-gel chemistry in a layer-by-layer manner. In this article, we highlight the importance of the NaCl concentration as a parameter to control the growth as well as the properties of LBL films made from poly(ethylene imine) as the organic counterpart and titanium IV (bisammoniumlactato)dihydroxyde ([Ti(lac)(2)(OH)(2)](2-)) as the precursor of TiO(2). An increase in the sodium chloride concentration leads to the faster growth of the film and to a decrease in the number of hexacyanoferrate anions remaining in the film after a buffer rinse. This may be due to a progressive increase in the fraction of negatively charged TiO(2) as suggested by transmission electron microscopy. In the presence of 0.5 M NaCl, the fraction of TiO(2) is close to 60% in mass. As a surprising finding, the films produced from 0.15 M NaCl are not homogeneously filled with TiO(2) even if the film is produced in an LBL fashion. The increased concentration of TiO(2) at the film-solution interface could constitute a barrier for the incorporation of the negatively charged redox probe.

Simple and rapid gas sensing using a single-walled carbon nanotube field-effect transistor-based logic inverter.

Single-walled carbon nanotubes (SWCNTs) are promising candidates for gas sensing applications, providing an efficient solution to the device miniaturization challenge and allowing low power consumption. SWCNT gas sensors are mainly based on field-effect transistors (SWCNT-FETs) where the modification of the current flowing through the nanotube is used for gas detection. A major limitation of these SWCNT-FETs lies in the difficulty to measure their transfer curves, since the flowing current typically varies between 10-12 and 10-3 A. Thus, voluminous and energy consuming systems are necessary, severely limiting the miniaturization and low energy consumption. Here, we propose an inverter device that combines two SWCNT-FETs which brings a concrete solution to these limitations and simplifies data processing. In this innovative sensing configuration, the gas detection is based on the variation of an electric potential in the volt range instead of a current intensity variation in the microampere range. In this study, the proof of concept is performed using NO2 gas but can be easily extended to a wide range of gases.

High Density of Quantum-Sized Silicon Nanowires with Different Polytypes Grown with Bimetallic Catalysts.

When Si nanowires (NWs) have diameters below about 10 nm, their band gap increases as their diameter decreases; moreover, it can be direct if the material adopts the metastable diamond hexagonal structure. To prepare such wires, we have developed an original variant of the vapor-liquid-solid process based on the use of a bimetallic Cu-Sn catalyst in a plasma-enhanced chemical vapor deposition reactor, which allows us to prevent droplets from coalescing and favors the growth of a high density of NWs with a narrow diameter distribution. Controlling the deposited thickness of the catalyst materials at the sub-nanometer level allows us to get dense arrays (up to 6 × 1010 cm-2) of very-small-diameter NWs of 6 nm on average (standard deviation of 1.6 nm) with crystalline cores of about 4 nm. The transmission electron microscopy analysis shows that both 3C and 2H polytypes are present, with the 2H hexagonal diamond structure appearing in 5-13% of the analyzed NWs per sample.