Hydrogen Sensing Mechanism of WS2 Gas Sensors Analyzed with DFT and NAP-XPS.

Nanostructured tungsten disulfide (WS2) is one of the most promising candidates for being used as active nanomaterial in chemiresistive gas sensors, as it responds to hydrogen gas at room temperature. This study analyzes the hydrogen sensing mechanism of a nanostructured WS2 layer using near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory (DFT). The W 4f and S 2p NAP-XPS spectra suggest that hydrogen makes physisorption on the WS2 active surface at room temperature and chemisorption on tungsten atoms at temperatures above 150 °C. DFT calculations show that a hydrogen molecule physically adsorbs on the defect-free WS2 monolayer, while it splits and makes chemical bonds with the nearest tungsten atoms on the sulfur point defect. The hydrogen adsorption on the sulfur defect causes a large charge transfer from the WS2 monolayer to the adsorbed hydrogen. In addition, it decreases the intensity of the in-gap state, which is generated by the sulfur point defect. Furthermore, the calculations explain the increase in the resistance of the gas sensor when hydrogen interacts with the WS2 active layer.

The Role of Cerium Valence in the Conversion Temperature of H2Ti3O7 Nanoribbons to TiO2-B and Anatase Nanoribbons, and Further to Rutile.

CeO2-TiO2 is an important mixed oxide due to its catalytic properties, particularly in heterogeneous photocatalysis. This study presents a straightforward method to obtain 1D TiO2 nanostructures decorated with CeO2 nanoparticles at the surface. As the precursor, we used H2Ti3O7 nanoribbons prepared from sodium titanate nanoribbons by ion exchange. Two cerium sources with an oxidation state of +3 and +4 were used to obtain mixed oxides. HAADF-STEM mapping of the Ce4+-modified nanoribbons revealed a thin continuous layer at the surface of the H2Ti3O7 nanoribbons, while Ce3+ cerium ions intercalated partially between the titanate layers. The phase composition and morphology changes were monitored during calcination between 620 °C and 960 °C. Thermal treatment led to the formation of CeO2 nanoparticles on the surface of the TiO2 nanoribbons, whose size increased with the calcination temperature. The use of Ce4+ raised the temperature required for converting H2Ti3O7 to TiO2-B by approximately 200 °C, and the temperature for the formation of anatase. For the Ce3+ batch, the presence of cerium inhibited the conversion to rutile. Analysis of cerium oxidation states revealed the existence of both +4 and +3 in all calcined samples, regardless of the initial cerium oxidation state.

Eco-Friendly Synthesis of an Oxovanadium(IV)-bis(abietate) Complex with Antimicrobial Action.

The search for less expensive and viable products is always one of the challenges for research development. Commonly, the synthesis of coordination compounds involves expensive ligands, through expensive and low-yield routes, in addition to generating toxic and unusable residues. In this work, the organic ligand used is derived from the resin of a reforestation tree, Pinus elliottii var. elliottii. The synthesis method used Pinus resin and an aqueous solution of vanadium(III) chloride at a temperature of 80 °C. The procedure does not involve organic solvents and does not generate toxic residues, thus imparting the complex formation reaction a green chemistry character. The synthesis resulted in an unprecedented oxovanadium(IV)-bis(abietate) complex, which was characterized by mass spectrometry (MS), chemical analysis (CHN), vibrational (FTIR) and electronic spectra (VISIBLE), X-ray diffraction (XRD), and thermal analysis (TG/DTA). Colorimetric studies were performed according to the CIELAB color space. The structural formula found, consisted of a complex containing two abietate ligands, [VO(C20H29O2)2]. The VO(IV)-bis(abietate) complex was applied against microorganisms and showed promising results in antibacterial and antifungal activity. The best result of inhibitory action was against the strains of Gram-positive bacteria S. aureus and L. monocytogenes, with minimum inhibitory concentration (MIC) values of 62.5 and 125 µmol L−1, respectively. For Gram-negative strains the results were 500 µmol L−1 for E. coli; and 1000 µmol L−1 for Salmonella enterica Typhimurium. Antifungal activity was performed against Candida albicans, where the MIC was 15.62 µmol L−1, and for C. tropicalis it was 62.5 µmol L−1. According to the MFC analysis, the complex presented, in addition to the fungistatic action, a fungicidal action, as there was no growth of fungi on the plates tested. The results found for the tests demonstrate that the VO(IV)-bis(abietate) complex has great potential as an antimicrobial and mainly antifungal agent. In this way, the pigmented ink with antimicrobial activity could be used in environments with a potential risk of contamination, preventing the spread of microorganisms harmful to health.

Polysaccharides as Green Fuels for the Synthesis of MgO: Characterization and Evaluation of Antimicrobial Activities.

The synthesis of structured MgO is reported using feedstock starch (route I), citrus pectin (route II), and Aloe vera (route III) leaf, which are suitable for use as green fuels due to their abundance, low cost, and non-toxicity. The oxides formed showed high porosity and were evaluated as antimicrobial agents. The samples were characterized by energy-dispersive X-ray fluorescence (EDXRF), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The crystalline periclase monophase of the MgO was identified for all samples. The SEM analyses show that the sample morphology depends on the organic fuel used during the synthesis. The antibacterial activity of the MgO-St (starch), MgO-CP (citrus pectin), and MgO-Av (Aloe vera) oxides was evaluated against pathogens Staphylococcus aureus (ATCC 6538P) and Escherichia coli (ATCC 8739). Antifungal activity was also studied against Candida albicans (ATCC 64548). The studies were carried out using the qualitative agar disk diffusion method and quantitative minimum inhibitory concentration (MIC) tests. The MIC of each sample showed the same inhibitory concentration of 400 µg. mL-1 for the studied microorganisms. The formation of inhibition zones and the MIC values in the antimicrobial analysis indicate the effective antimicrobial activity of the samples against the test microorganisms.

Nd3+-Doped TiO2 Nanoparticles as Nanothermometer: High Sensitivity in Temperature Evaluation inside Biological Windows.

TiO2 nanoparticles doped with different amounts of Nd3+ (0.5, 1, and 3 wt.%) were synthetized by the sol-gel method, and evaluated as potential temperature nanoprobes using the fluorescence intensity ratio between thermal-sensitive radiative transitions of the Nd3+. XRD characterization identified the anatase phase in all the doped samples. The morphology of the nanoparticles was observed with SEM, TEM and HRTEM microscopies. The relative amount of Nd3+ in TiO2 was obtained by EDXS, and the oxidation state of titanium and neodymium was investigated via XPS and NEXAFS, respectively. Nd3+ was present in all the samples, unlike titanium, where besides Ti4+, a significantly amount of Ti3+ was observed; the relative concentration of Ti3+ increased as the amount of Nd3+ in the TiO2 nanoparticles increased. The photoluminescence of the synthetized nanoparticles was investigated, with excitation wavelengths of 350, 514 and 600 nm. The emission intensity of the broad band that was associated with the presence of defects in the TiO2, increased when the concentration of Nd3+ was increased. Using 600 nm for excitation, the 4F7/2→4I9/2, 4F5/2→4I9/2 and 4F3/2→4I9/2 transitions of Nd3+ ions, centered at 760 nm, 821 nm, and 880 nm, respectively, were observed. Finally, the effect of temperature in the photoluminescence intensity of the synthetized nanoparticles was investigated, with an excitation wavelength of 600 nm. The spectra were collected in the 288-348 K range. For increasing temperatures, the emission intensity of the 4F7/2→4I9/2 and 4F5/2→4I9/2 transitions increased significantly, in contrast to the 4F3/2→4I9/2 transition, in which the intensity emission decreased. The fluorescence intensity ratio between the transitions I821I880=F5/24I49/2F43/2I49/2 and I760I880=F47/2I49/2F43/2I49/2 were used to calculate the relative sensitivity of the sensors. The relative sensitivity was near 3% K-1 for I760I880 and near 1% K-1 for I821I880.

On the Use of Pulsed UV or Visible Light Activated Gas Sensing of Reducing and Oxidising Species with WO3 and WS2 Nanomaterials.

This paper presents a methodology to quantify oxidizing and reducing gases using n-type and p-type chemiresistive sensors, respectively. Low temperature sensor heating with pulsed UV or visible light modulation is used together with the application of the fast Fourier transform (FFT) to extract sensor response features. These features are further processed via principal component analysis (PCA) and principal component regression (PCR) for achieving gas discrimination and building concentration prediction models with R2 values up to 98% and RMSE values as low as 5% for the total gas concentration range studied. UV and visible light were used to study the influence of the light wavelength in the prediction model performance. We demonstrate that n-type and p-type sensors need to be used together for achieving good quantification of oxidizing and reducing species, respectively, since the semiconductor type defines the prediction model's effectiveness towards an oxidizing or reducing gas. The presented method reduces considerably the total time needed to quantify the gas concentration compared with the results obtained in a previous work. The use of visible light LEDs for performing pulsed light modulation enhances system performance and considerably reduces cost in comparison to previously reported UV light-based approaches.

Stable graphene oxide-gold nanoparticle platforms for biosensing applications.

Graphene oxide-gold nanoparticle (AuNPs@GO) hybrids were fabricated in water dispersions of graphene oxide (GO) and Au precursor completely free of stabilizing agents by UV-light irradiation. Gold nanoparticle (AuNP) nucleation, growth, and stabilization mechanisms at the surface of GO are discussed on the basis of UV-Vis, Raman, IR, and X-Ray photo-spectroscopy studies. The analyses of AuNPs@GO hybrids by transmission electron microscopy (TEM), thermogravimetric (TGA) and electrochemical tests show that they exhibit outstanding chemical, thermal and electrochemical stabilities. Thus, AuNPs@GO biosensing platforms were fabricated for surface enhanced Raman spectroscopy (SERS) detection of crystal violet (CV), a SERS standard molecule, and in a different set of experiments, for flavin adenine dinucleotide (FAD), a flavoprotein coenzyme that plays an important role in many oxidoreductase and reversible redox conversions in biochemical reactions. AuNPs@GO hybrids synthesized by using UV light irradiation show exceptional stability and high intensification of the Raman signals showing that they have high potential for use as biomedical probes for the detection, monitoring, and diagnosis of medical diseases.

Gas Sensing with Iridium Oxide Nanoparticle Decorated Carbon Nanotubes.

The properties of multi-wall carbon nanotubes decorated with iridium oxide nanoparticles (IrOx-MWCNTs) are studied to detect harmful gases such as nitrogen dioxide and ammonia. IrOx nanoparticles were synthetized using a two-step method, based on a hydrolysis and acid condensation growth mechanism. The metal oxide nanoparticles obtained were employed for decorating the sidewalls of carbon nanotubes. Iridium-oxide nanoparticle decorated carbon nanotube material showed higher and more stable responses towards NH3 and NO2 than bare carbon nanotubes under different experimental conditions, establishing the optimal operating temperatures and estimating the limits of detection and quantification. Furthermore, the nanomaterials employed were studied using different morphological and compositional characterization techniques and a gas sensing mechanism is proposed.

Controlling the Formation of Nanocavities in Kirkendall Nanoobjects through Sequential Thermal Ex Situ Oxidation and In Situ Reduction Reactions.

Controlling the porosity, the shape, and the morphology of Kirkendall hollow nanostructures is the key factor to tune the properties of these tailor-made nanomaterials which allow in turn broadening their applications. It is shown that by applying a continuous oxidation to copper nanowires following a temperature ramp protocol, one can synthesize cuprous oxide nanotubes containing periodic copper nanoparticles. A further oxidation of such nanoobjects allows obtaining cupric oxide nanotubes with a bamboo-like structure. On the other hand, by applying a sequential oxidation and reduction reactions to copper nanowires, one can synthesize hollow nanoobjects with complex shapes and morphologies that cannot be obtained using the Kirkendall effect alone, such as necklace-like cuprous oxide nanotubes, periodic solid copper nanoparticles or hollow cuprous oxide nanospheres interconnected with single crystal cuprous oxide nanorods, and aligned and periodic hollow nanospheres embedded in a cuprous oxide nanotube. The strategy demonstrated in this study opens new avenues for the engineering of hollow nanostructures with potential applications in gas sensing, catalysis, and energy storage.

Impact of Synthesis Parameters upon the Electronic Structure in PVD-Deposited CdxZn1-xO Composite Thin Films: An XPS-XANES Investigation.

The impact of different synthesis parameters, such as thickness, postsynthesis annealing temperature, and oxygen gas flow rate, upon the electronic structure is discussed in detail in the present experimental investigation. X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) spectroscopy techniques are used to evaluate the surface electronic properties along with the presence and stability of the CdO2 surface oxide in CdxZn1-xO (x = 0.4) composite thin films. The thin films were synthesized with varying thicknesses using a Cd0.4Zn0.6O (CZO) ceramic and Cd0.4Zn0.6 (CZ) metallic targets and oxygen gas flow rates during magnetron sputtering. The Zn L3,2 edge and O K edge XANES spectra are affected by the oxygen gas flow rate. For the zero rate, an increase in intensity is observed in the Zn L3,2 edge, and notable changes occur in the overall spectral features of the O K edge. In the films synthesized in the presence of oxygen, highly probable O 2p → antibonding Zn 3d electronic transitions decrease the probability of the Zn 2p1/2 → antibonding Zn 3d electronic transition by filling the vacant antibonding Zn 3d states, leading to the reduction in overall intensity in the Zn L3,2 edge. Scanning electron microscopy reveals grain growth with increasing annealing temperature. The annealing induces orbital hybridization, generating new electronic states with higher transition probabilities and intensity enhancement in both Zn L3,2 and O K edges. The presence of the CdO2 surface phase is confirmed by analyzing the Cd 3d5/2 and O 1s XPS core levels. The CdO2 surface phase is observed in the films synthesized using the CZO target for all thicknesses, while the CZ target is only observed for higher thicknesses. Further postsynthesis annealing treatment results in the disappearance of the CdO2 phase. The CdO2 surface phase can be controlled by varying the film thickness and postsynthesis annealing temperature.

Silver Decoration of Vertically Aligned MoS2-MoOx Nanosheets: A Comprehensive XPS Investigation.

This study investigates the simultaneous decoration of vertically aligned molybdenum disulfide nanostructure (VA-MoS2) with Ag nanoparticles (NPs) and nitrogen functionalization. Nitrogen functionalization was achieved through physical vapor deposition (PVD) DC-magnetron sputtering using nitrogen as a reactive gas, aiming to induce p-type behavior in MoS2. The utilization of reactive sputtering resulted in the growth of three-dimensional silver structures on the surface of MoS2, promoting the formation of silver nanoparticles. A comprehensive characterization was conducted to assess surface modifications and analyze chemical and structural changes. X-ray photoelectron spectroscopy (XPS) showed the presence of silver on the MoS2 surface. Scanning electron microscopy (SEM) confirmed successful decoration with silver nanoparticles, showing that deposition time affects the size and distribution of the silver on the MoS2 surface.

Differentiation of petro-sourced plastic microfilaments from organic microfilaments by SEM-EDX in environmental samples.

Quantifying microplastics (MPs) in marine environments is challenging due to the complexities of differentiation from other materials. This study aims to distinguish petro-sourced plastic microfilaments from organic ones in environmental samples using scanning electron microscope coupled with energy dispersive X-ray (SEM-EDX) analysis. Therefore, 38 particles resembling MPs (PRMPs) from sediments and organisms in Madagascar were analyzed. MPs identification thresholds were determined from SEM-EDX analysis of macroplastics and seaweed, the primary sources of microfilaments. SEM-EDX results of the 38 PRMPs were compared with identification/misidentification made by five MPs observation experts. Results indicated that a carbon/oxygen (C/O) ratio >1 distinguished macroplastics and MPs from other sources (seaweed and organic microfilaments). SEM-EDX analysis identified 81.58% of PRMPs as MPs. The average error made by one observer was 36.32%. These findings highlight the need for a method to assess identification error in MPs quantification and recommend SEM-EDX analysis of microfilaments to gauge observer error.

Highly ordered hollow oxide nanostructures: the Kirkendall effect at the nanoscale.

Highly ordered ultra-long oxide nanotubes are fabricated by a simple two-step strategy involving the growth of copper nanowires on nanopatterned template substrates by magnetron sputtering, followed by thermal annealing in air. The formation of such tubular nanostructures is explained according to the nanoscale Kirkendall effect. The concept of this new fabrication route is also extendable to create periodic zero-dimensional hollow nanostructures.

Combining physical vapor deposition structuration with dealloying for the creation of a highly efficient SERS platform.

Nanostructured noble metal thin films are highly studied for their interesting plasmonic properties. The latter can be effectively used for the detection of small and highly diluted molecules by the surface-enhanced Raman scattering (SERS) effect. Regardless of impressive detection limits achieved, synthesis complexity and the high cost of gold restrict its use in devices. Here, we report on a novel two-step approach that combines the deposition of a silver-aluminum thin film with dealloying to design and fabricate efficient SERS platforms. The magnetron sputtering technique was used for the deposition of the alloy thin film to be dealloyed. After dealloying, the resulting silver nanoporous structures revealed two degrees of porosity: macroporosity, associated to the initial alloy morphology, and nanoporosity, related to the dealloying step. The resulting nanoporous columnar structure was finely optimized by tuning deposition (i.e., the alloy chemical composition) and dealloying (i.e., dealloying media) parameters to reach the best SERS properties. These are reported for samples dealloyed in HCl and with 30 atom % of silver at the initial state with a detection limit down to 10-10 mol·L-1 for a solution of rhodamine B.

Mixed oxides with corundum-type structure obtained from recycling can seals as paint pigments: color stability.

Green chromium and red iron oxides are technically important pigments due to their high color intensity, good dispersibility in paints, and superior hiding power. We report on the synthesis of colored pigments of mixed oxides with a corundum-type structure. The pigments are obtained via the addition of coloring ions to boehmite from recycled metallic aluminium. X-ray diffractometry (XRD) and Raman spectroscopy confirmed the crystallographic phase. Additionally, the oxidation state 3+ responsible for the greenish (chromium) and reddish (iron) coloration of the mixed oxides was confirmed by XPS and visible-light absorption measurements. The colorimetric stability of the oxides in acid and alkaline environments was evaluated. After 240 h of exposure to harsh environments, both pigments demonstrated stability and showed no strong color difference.

Regenerated cellulose/chitosan composite aerogel with highly efficient adsorption for anionic dyes.

A novel reusable, high-compressible cotton regenerated cellulose/chitosan composite aerogel (RC/CSCA) was prepared using N-methylmorpholine-N-oxide (NMMO) as the green cellulose solvent, and glutaraldehyde (GA) as the crosslinking agent. The regenerated cellulose obtained from cotton pulp could chemically crosslink with chitosan and GA, to form a stable 3D porous structure. The GA played an essential role in preventing shrinkage and preserving the deformation recovery ability of RC/CSCA. Due to the ultralow density (13.92 mg/cm3), thermal stability (above 300 °C), and high porosity (97.36 %), the positively charged RC/CSCA can be used as a novel biocomposite adsorbent for effective and selective removal of toxic anionic dyes from wastewater, showing an excellent adsorption capacity, environmental adaptability, and recyclability. The maximal adsorption capacity and removal efficiency of RC/CSCA for methyl orange (MO) was 742.68 mg/g and 95.83 %.

Synthesis of Blue Gahnite (ZnAl2O4:Co, Nd): A Cost-Effective Method for Producing Solar-Reflective Pigments for Cool Coatings.

Developing strategies for the green synthesis of novel materials, such as pigments for protection from solar radiation, is a fundamental research subject in material science to mitigate the heat island effect. Within this perspective, the current study reports on the synthesis of blue pigments of ZnAl2O4:M (M = Co2+ and Co2+/Nd3+) using recycled metallic aluminum (discarded can seal) with reflective properties of Near-infrared radiation. The pigments were characterized by XRD, SEM, XPS, UV-Vis, NIR diffuse reflectance spectroscopy, and CIE-1976 L*a*b* color measurements. The wettability of the coatings containing the synthesized pigments was also evaluated. The structural characterization showed that the pigments present the Gahnite crystalline phase. Colorimetric measurements obtained by the CIEL*a*b* method show values correlated to blue pigments attributed to Co2+ ions in tetrahedral sites. The pigments exhibit high near-infrared solar reflectance (with R% ≥ 60%), with an enhancement of nearly 20% for the pigment-containing neodymium when applied in white paint, indicating that the prepared compounds have the potential to be energy-saving color pigments for coatings.

Eco-Friendly Polysaccharide-Based Synthesis of Nanostructured MgO: Application in the Removal of Cu2+ in Wastewater.

The present study described three synthesis routes using different natural polysaccharides as low-cost non-toxic fuels and complexing agents for obtaining MgO. Cassava starch, Aloe vera leaves (mainly acemannan) gel, and citric pectin powder were mixed with magnesium nitrate salt and calcined at 750 °C for 2 h. The samples were named according to the polysaccharide: cassava starch (MgO-St), citrus pectin (MgO-CP), and Aloe vera (MgO-Av). X-ray diffraction identified the formation of a monophasic periclase structure (FCC type) for the three samples. The N2 adsorption/desorption isotherms (B.E.T. method) showed an important difference in textural properties, with a higher pore volume (Vmax = 89.76 cc/g) and higher surface area (SA = 43.93 m2/g) obtained for MgO-St, followed by MgO-CP (Vmax = 11.01 cc/g; SA = 7.01 m2/g) and MgO-Av (Vmax = 6.44 cc/g; SA = 6.63 m2/g). These data were consistent with the porous appearance observed in SEM images. Porous solids are interesting as adsorbents for removing metallic and molecular ions from wastewater. The removal of copper ions from water was evaluated, and the experimental data at equilibrium were adjusted according to the Freundlich, Langmuir, and Temkin isotherms. According to the Langmuir model, the maximum adsorption capacity (qmax) was 6331.117, 5831.244, and 6726.623 mg·g-1 for the adsorbents MgO-St, MgO-Av, and MgO-CP, respectively. The results of the adsorption isotherms indicated that the synthesized magnesium oxides could be used to decrease the amount of Cu2+ ions in wastewater.

Copper(II) and Cobalt(II) Complexes Based on Abietate Ligands from Pinus Resin: Synthesis, Characterization and Their Antibacterial and Antiviral Activity against SARS-CoV-2.

Co-abietate and Cu-abietate complexes were obtained by a low-cost and eco-friendly route. The synthesis process used Pinus elliottii resin and an aqueous solution of CuSO4/CoSO4 at a mild temperature (80 °C) without organic solvents. The obtained complexes are functional pigments for commercial architectural paints with antipathogenic activity. The pigments were characterized by Fourier-transform infrared spectroscopy (FTIR), mass spectrometry (MS), thermogravimetry (TG), near-edge X-ray absorption fine structure (NEXAFS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and colorimetric analysis. In addition, the antibacterial efficiency was evaluated using the minimum inhibitory concentration (MIC) test, and the antiviral tests followed an adaptation of the ISO 21702:2019 guideline. Finally, virus inactivation was measured using the RT-PCR protocol using 10% (w/w) of abietate complex in commercial white paint. The Co-abietate and Cu-abietate showed inactivation of >4 log against SARS-CoV-2 and a MIC value of 4.50 µg·mL-1 against both bacteria Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). The results suggest that the obtained Co-abietate and Cu-abietate complexes could be applied as pigments in architectural paints for healthcare centers, homes, and public places.

Facile fabrication of self-roughened surfaces for superhydrophobic coatings via polarity-induced phase separation strategy.

Rough structures have gained increasing attention since they are essential for surfaces with special wettability, which can be used for various applications. It is still a challenge to find a low-cost and simple way to fabricate rough surfaces despite extensive efforts. Herein, we report a facile strategy to fabricate self-roughened surfaces based on polarity-induced phase separation. The strategy relies on the migration of flexible chains of the nonpolar polysiloxane to airside, driven by surface tension and polarity difference with the polar crosslinker, which forms a self-roughened surface with numerous protrusions. It is worth noting that this strategy does not require strict control of procedures, since it is insensitive to environmental changes unlike other phase separation methods, as shown by the results of systematic studies on several key parameters. Modified fabrics and coatings exhibit excellent superhydrophobicity with a water contact angle higher than 160°. Moreover, due to the strong hydrogen bonds formed by the polar urea groups of the crosslinker with substrates, the abrasion resistance of the coating is significantly enhanced. It is believed that the proposed novel and facile strategy will be a promising candidate for industrial manufacturing.