Enhancing the Properties of Photo-Generated Metallized Nanocomposite Coatings through Thermal Annealing.

In this work, the effect of thermal annealing on silver nanoparticles@polymer (AgNPs@polymer) nanocomposite coatings was investigated. These photo-generated metallized coatings have a spatial distribution of metal nanoparticles, with a depth-wise decrease in their concentration. During annealing, both structural and morphological variations, as well as a spatial reorganization of AgNPs, were observed, both at the surface and in the core of the AgNPs@polymer coating. Owing to their increased mobility, the polymer chains reorganize spontaneously, and, at the same time, a hopping diffusion process, caused by the minimization of the surface energy, promotes the migration and coalescence of the silver nanoparticles towards the surface. The layer of discrete nanoparticles gradually transforms from a weakly percolative assembly to a denser and more networked structure. Consequently, the surface of the coatings becomes significantly more electrically conductive, hydrophobic, and reflective. The general trend is that the thinner the nanohybrid coating, the more pronounced the effect of thermal annealing on its spatial reorganization and properties. These results open up interesting prospects in the field of metallized coating technology and pave the way for integration into a wide variety of devices, e.g., efficient and inexpensive reflectors for energy-saving applications, electrically conductive microdevices, and printed electronic microcircuits.

Dissociation of N2 on a Si(111)-7x7 Surface at Room Temperature.

We demonstrate that the strong N2 bond can be efficiently dissociated at low pressure and ambient temperature on a Si(111)-7x7 surface. The reaction was experimentally investigated by scanning tunnelling microscopy and X-ray photoemission spectroscopy. Experimental and density functional theory results suggest that relatively low thermal energy collision of N2 with the surface can facilitate electron transfer from the Si(111)-7x7 surface to the π*-antibonding orbitals of N2 that significantly weaken the N2 bond. This activated N2 triple bond dissociation on the surface leads to the formation of a Si3 N interface.

Unveiling the Potential of Corn Cob Biochar: Analysis of Microstructure and Composition with Emphasis on Interaction with NO2.

In the context of sustainable solutions, this study examines the pyrolysis process applied to corn cobs, with the aim of producing biochar and assessing its effectiveness in combating air pollution. In particular, it examines the influence of different pyrolysis temperatures on biochar properties. The results reveal a temperature-dependent trend in biochar yield, which peaks at 400 °C, accompanied by changes in elemental composition indicating increased stability and extended shelf life. In addition, high pyrolysis temperatures, above 400 °C, produce biochars with enlarged surfaces and improved pore structures. Notably, the highest pyrolysis temperature explored in this study is 600 °C, which significantly influences the observed properties of biochars. This study also explores the potential of biochar as an NO2 adsorbent, as identified by chemical interactions revealed by X-ray photoelectron spectroscopy (XPS) analysis. This research presents a promising and sustainable approach to tackling air pollution using corn cob biochar, providing insight into optimized production methods and its potential application as an effective NO2 adsorbent to improve air quality.

Escherichia coli Biofilm Formation, Motion and Protein Patterns on Hyaluronic Acid and Polydimethylsiloxane Depend on Surface Stiffness.

The surface stiffness of the microenvironment is a mechanical signal regulating biofilm growth without the risks associated with the use of bioactive agents. However, the mechanisms determining the expansion or prevention of biofilm growth on soft and stiff substrates are largely unknown. To answer this question, we used PDMS (polydimethylsiloxane, 9-574 kPa) and HA (hyaluronic acid gels, 44 Pa-2 kPa) differing in their hydration. We showed that the softest HA inhibited Escherichia coli biofilm growth, while the stiffest PDMS activated it. The bacterial mechanical environment significantly regulated the MscS mechanosensitive channel in higher abundance on the least colonized HA-44Pa, while Type-1 pili (FimA) showed regulation in higher abundance on the most colonized PDMS-9kPa. Type-1 pili regulated the free motion (the capacity of bacteria to move far from their initial position) necessary for biofilm growth independent of the substrate surface stiffness. In contrast, the total length travelled by the bacteria (diffusion coefficient) varied positively with the surface stiffness but not with the biofilm growth. The softest, hydrated HA, the least colonized surface, revealed the least diffusive and the least free-moving bacteria. Finally, this shows that customizing the surface elasticity and hydration, together, is an efficient means of affecting the bacteria's mobility and attachment to the surface and thus designing biomedical surfaces to prevent biofilm growth.

Deep-UV laser direct writing of photoluminescent ZnO submicron patterns: an example of nanoarchitectonics concept.

Micro- and nanopatterning of metal oxide materials is an important process to develop electronic or optoelectronic devices. ZnO is a material of choice for its semiconducting and photoluminescence properties. In the frame of the nanoarchitectonics concept, we have developed and investigated a new process that relies on direct writing laser patterning in the Deep-UV (DUV) range to prepare photoluminescent microstructures of ZnO at room temperature, under air. This process is based on a synthesis of colloidal ZnO nanocrystals (NCs) with a careful choice of the ligands on the surface to obtain an optimal (i) stability of the colloids, (ii) redissolution of the non-insolated parts and (iii) cross-linking of the DUV-insolated parts. The mechanisms of photocrosslinking are studied by different spectroscopic methods. This room temperature process preserves the photoluminescence properties of the NCs and the wavelength used in DUV allows to reach a sub-micrometer resolution, which opens new perspectives for the integration of microstructures on flexible substrates for optoelectronic applications.

Low Metal Loading (Au, Ag, Pt, Pd) Photo-Catalysts Supported on TiO2 for Renewable Processes.

Photo-catalysts based on titanium dioxide, and modified with highly dispersed metallic nanoparticles of Au, Ag, Pd and Pt, either mono- or bi-metallic, have been analyzed by multiple characterization techniques, including XRD, XPS, SEM, EDX, UV-Vis and N2 adsorption/desorption. Mono-metallic photo-catalysts were prepared by wet impregnation, while bi-metallic photocatalysts were obtained via deposition-precipitation (DP). The relationship between the physico-chemical properties and the catalyst's behavior for various photo-synthetic processes, such as carbon dioxide photo-reduction to liquid products and glucose photo-reforming to hydrogen have been investigated. Among the tested materials, the catalysts containing platinum alone (i.e., 0.1 mol% Pt/TiO2) or bi-metallic gold-containing materials (e.g., 1 wt% (AuxAgy)/TiO2 and 1 wt% (AuxPtz)/TiO2) showed the highest activity, presenting the best results in terms of productivity and conversion for both applications. The textural, structural and morphological properties of the different samples being very similar, the main parameters to improve performance were function of the metal as electron sink, together with optoelectronic properties. The high activity in both applications was related to the low band gap, that allows harvesting more energy from a polychromatic light source with respect to the bare TiO2. Overall, high selectivity and productivity were achieved with respect to most literature data.

Activated Carbon/Transition Metal (Ni, In, Cu) Hexacyanoferrate Nanocomposites for Cesium Adsorption.

Transition metal hexacyanoferrate/microporous activated carbon composites were obtained using a simple successive impregnation approach. The effect of metal type (nickel, indium, or copper), and the carbon oxidation on the composite characteristics (porosity, metal structure, and particle size), as well as on the removal efficiency of cesium from aqueous solution was investigated. Successful formation of the desired metal hexacyanoferrate phase was achieved and the size of the metallic nanoparticles and their dispersion in the carbon network was found to depend on the metal type, with the indium and nickel-based materials exhibiting the smallest particle size distribution (< 10 nm). Adsorption tests performed under batch conditions demonstrate that the copper hexacyanoferrate/activated carbon composite present the highest cesium removal capacity from aqueous solution (74.7 mg·g-1) among the three studied metal-based nanocomposites. The carbon oxidation treatment leads to the increase in the number of functional groups to the detriment of the porosity but allows for an improvement in the Cs adsorption capacity. This indicates that the Cs adsorption process is governed by the carbon surface chemistry and not its porosity. Moreover, combining oxidized carbon support with copper hexacyanoferrate induces the highest cesium adsorption capacity (101.5 mg·g-1). This could be related to synergistic effects through two absorption mechanisms, i.e., a cation exchange mechanism of Cs with the metallic hexacyanoferrate phase and Cs adsorption via carbon oxygen surface groups, as demonstrated using X-ray photoelectron spectroscopy (XPS) analyses.

Binary Oxides Prepared by Microwave-Assisted Solution Combustion: Synthesis, Characterization and Catalytic Activity.

Three different alumina-based Ni, Cu, Co oxide catalysts with metal loading of 10 wt %, and labeled 10Ni⁻Al, 10Co⁻Al and 10Cu⁻Al, were prepared by microwave-assisted solution combustion. Their morphological, structural and surface properties were deeply investigated by complementary physico-chemical techniques. Finally, the three materials were tested in CO oxidation used as test reaction for comparing their catalytic performance. The 10Cu⁻Al catalyst was constituted of copper oxide phase, while the 10Ni⁻Al and 10Co⁻Al catalysts showed the presence of "spinels" phases on the surface. The well-crystallized copper oxide phase in the 10Cu⁻Al catalyst, obtained by microwave synthesis, allowed for obtaining very high catalytic activity. With a CO conversion of 100% at 225 °C, the copper containing catalyst showed a much higher activity than that usually measured for catalytic materials of similar composition, thus representing a promising alternative for oxidation processes.

Anisotropic Magneto-Coulomb Properties of 2D-0D Heterostructure Single Electron Device.

Fabrication and spintronics properties of 2D-0D heterostructures are reported. Devices based on graphene ("Gr")-aluminium nanoclusters heterostructures show robust and reproducible single-electron transport features, in addition to spin-dependent functionality when using a top magnetic electrode. The magnetic orientation of this single ferromagnetic electrode enables the modulation of the environmental charge experienced by the aluminium nanoclusters. This anisotropic magneto-Coulomb effect, originating from spin-orbit coupling within the ferromagnetic electrode, provides tunable spin valve-like magnetoresistance signatures without the requirement of spin coherent charge tunneling. These results extend the capability of Gr to act both as electrode and as a platform for the growth of 2D-0D mixed-dimensional van der Waals heterostructures, providing magnetic functionalities in the Coulomb blockade regime on scalable spintronic devices. These heterostructures pave the way towards novel device architectures at the crossroads of 2D material physics and spin electronics.

Large-scale synthesis of fluorinated graphene by rapid thermal exfoliation of highly fluorinated graphite.

Weakly fluorinated graphene nanosheets were efficiently prepared via fast thermal exfoliation of highly fluorinated graphite. This scalable method consists of a fast temperature increase (around 10 °C s-1) of fluorinated HOPG performed under an argon atmosphere, without any post-treatment. The mechanism of exfoliation induced by the defluorination step, evolving volatile fluorocarbons, has been highlighted thanks to thermogravimetric analysis (TGA), high temperature X-ray diffraction (HTK-XRD), X-ray Photoelectron Spectrometry (XPS) studies on temperature, and Raman and infrared spectroscopy. The advantages of the described process are its high-yield for the preparation of fluorinated graphene nanosheets, its ease of implementation and scalability. Moreover, the fluorine content drastically decreases during such a process and graphene layers are slightly functionalized, i.e. conductive contrary to the precursor.

Generating highly reflective and conductive metal layers through a light-assisted synthesis and assembling of silver nanoparticles in a polymer matrix.

The development of metalized surfaces exhibiting mirror properties and/or electric conductivity without heavy equipments and with low metal charge is a big challenge in view of many industrial applications. We report herein on the photo-assembling of silver nanoparticles (AgNPs) in a polymer matrix, carried out within minutes from an acrylate monomer and silver nitrate at room temperature, under air and without any solvents. The top surface of the material gets converted into a continuous silver thin film and a depthwise concentration gradient of AgNPs is created in the polymer, which images the absorption profile of the actinic UV light in the reactive formulation. This specific assembling of the silver@polymer coating induces excellent reflective and conductive properties. The conductance was observed to strongly increase with increasing the exposure from 3 to 30 min due to the formation of a more and more compact metal film. This coating strategy works with a variety of substrates (textile, paper, glass, wood, plastic and stainless steel). Moreover, on flexible surfaces such as textile, the flexibility was preserved. The possibility to use this kind of nanomaterial as a printing ink, with a much lower metal concentration (3 to 5 wt.%) than concurrent inks, was also demonstrated.

Tuning the morphology of silver nanostructures photochemically coated on glass substrates: an effective approach to large-scale functional surfaces.

This paper reports on a simple and environmentally friendly photochemical process capable of generating nano-layers (8-22 nm) of silver nanostructures directly onto glass surfaces. This approach opens the way to large-scale functionalized surfaces with plasmonic properties through a single light-induced processing. Thus, Ag nanostructures top-coated were obtained through photo-reduction, at room temperature, of a photosensitive formulation containing a metal precursor, free from extra toxic stabilizers or reducing agents. The reactive formulation was confined between two glass slides and exposed to a continuous near-UV source. In this way, stable silver nano-layers can be generated directly on the substrate with a very good control of the morphology of as-synthesized nanostructures that allows tailoring the optical properties of the coated layers. The position and width of the corresponding surface plasmon resonance bands can be adjusted over a broad spectral window. By extension, this low-cost and easy-to-apply process can also be used to coat ultra thin layers of metal nanostructures on a variety of substrates. The possibility of controlling of nanostructures shape should achieve valuable developments in many fields, as diverse as plasmonics, surface enhanced Raman scattering, nano-electronic circuitry, or medical devices.

Covalent Functionalization by Cycloaddition Reactions of Pristine Defect-Free Graphene.

Based on a low-temperature scanning tunneling microscopy study, we present a direct visualization of a cycloaddition reaction performed for some specific fluorinated maleimide molecules deposited on graphene. Up to now, it was widely admitted that such a cycloaddition reaction can not happen without pre-existing defects. However, our study shows that the cycloaddition reaction can be carried out on a defect-free basal graphene plane at room temperature. In the course of covalently grafting the molecules to graphene, the sp2 conjugation of carbon atoms was broken, and local sp3 bonds were created. The grafted molecules perturbed the graphene lattice, generating a standing-wave pattern with an anisotropy which was attributed to a (1,2) cycloaddition, as revealed by T-matrix approximation calculations. DFT calculations showed that while both (1,4) and (1,2) cycloadditions were possible on free-standing graphene, only the (1,2) cycloaddition could be obtained for graphene on SiC(0001). Globally averaging spectroscopic techniques, XPS and ARPES, were used to determine the modification in the elemental composition of the samples induced by the reaction, indicating an opening of an electronic gap in graphene.

High Spin Polarization at Ferromagnetic Metal-Organic Interfaces: A Generic Property.

A high spin polarization of states around the Fermi level, EF, at room temperature has been measured in the past at the interface between a few molecular candidates and the ferromagnetic metal Co. Is this promising property for spintronics limited to these candidates? Previous reports suggested that certain conditions, such as strong ferromagnetism, i.e., a fully occupied spin-up d band of the ferromagnet, or the presence of π bonds on the molecule, i.e., molecular conjugation, needed to be met. What rules govern the presence of this property? We have performed spin-resolved photoemission spectroscopy measurements on a variety of such interfaces. We find that this property is robust against changes to the molecule and ferromagnetic metal's electronic properties, including the aforementioned conditions. This affirms the generality of highly spin-polarized states at the interface between a ferromagnetic metal and a molecule and augurs bright prospects toward integrating these interfaces within organic spintronic devices.

Site-selective local fluorination of graphene induced by focused ion beam irradiation.

The functionalization of graphene remains an important challenge for numerous applications expected by this fascinating material. To keep advantageous properties of graphene after modification or functionalization of its structure, local approaches are a promising road. A novel technique is reported here that allows precise site-selective fluorination of graphene. The basic idea of this approach consists in the local radicalization of graphene by focused ion beam (FIB) irradiation and simultaneous introduction of XeF2 gas. A systematic series of experiments were carried out to outline the relation between inserted defect creation and the fluorination process. Based on a subsequent X-ray photoelectron spectroscopy (XPS) analysis, a 6-fold increase of the fluorine concentration on graphene under simultaneous irradiation was observed when compared to fluorination under normal conditions. The fluorine atoms are predominately localized at the defects as indicated from scanning tunneling microscopy (STM). The experimental findings are confirmed by density functional theory which predicts a strong increase of the binding energy of fluorine atoms when bound to the defect sites. The developed technique allows for local fluorination of graphene without using resists and has potential to be a general enabler of site-selective functionalization of graphene using a wide range of gases.