Breakthroughs in the Design of Novel Carbon-Based Metal Oxides Nanocomposites for VOCs Gas Sensing

Nowadays, the detection of volatile organic compounds (VOCs) at trace levels (down to ppb) is feasible by exploiting ultra-sensitive and highly selective chemoresistors, especially in the field of medical diagnosis. By coupling metal oxide semiconductors (MOS e.g., SnO2, ZnO, WO3, CuO, TiO2 and Fe2O3) with innovative carbon-based materials (graphene, graphene oxide, reduced graphene oxide, single-wall and multi-wall carbon nanotubes), outstanding performances in terms of sensitivity, selectivity, limits of detection, response and recovery times towards specific gaseous targets (such as ethanol, acetone, formaldehyde and aromatic compounds) can be easily achieved. Notably, carbonaceous species, highly interconnected to MOS nanoparticles, enhance the sensor responses by (i) increasing the surface area and the pore content, (ii) favoring the electron migration, the transfer efficiency (spillover effect) and gas diffusion rate, (iii) promoting the active sites concomitantly limiting the nanopowders agglomeration; and (iv) forming nano-heterojunctions. Herein, the aim of the present review is to highlight the above-mentioned hybrid features in order to engineer novel flexible, miniaturized and low working temperature sensors, able to detect specific VOC biomarkers of a human's disease

Low temperature/uv-assisted composites as gas sensors for medical applications

The sensing of gas molecules is of fundamental importance for environmental monitoring, control of chemical processes, medical applications, and so on [1]. Furthermore, recent success in non-invasive medical diagnostics, based on human breath analysis, is pushing forward the development of extremely sensitive gas sensors for ppb detection of specific analytes (e.g. acetone) in a complex gas mixture [1,2]. In recent years, graphene-based gas sensors have attracted much attention and different structures have been developed showing high sensing performances and room temperature working conditions [2]. However, they still suffer from several problems, which could be overcome by covering the graphene surface with metal oxide semiconductors. Furthermore, studies regarding the detection of Volatile Organic Compounds (VOCs) are still at the beginning [3]. Hence, the present work will be aimed at: i) optimizing the synthetic routes of ad hoc composite VOCs sensing materials (based on graphene oxide/SnO2 hybrids); ii) engineering the gas sensor device; and iii) evaluating the sensing performances at both high and mild temperatures (also exploiting the UV light) towards gaseous ethanol, acetone and ethylbenzene. Starting from pure graphite, graphene oxide (GO) powder was synthesized by adopting the Hummer\u2019s modified method, in which the synthetic route was deeply investigated, and several parameters (such as H2O2 concentration) were modulated. Once optimized this step, SnO2 were grown on its surface by hydrothermal method, varying the starting salt precursor/GO weight ratio between 4 and 32. For comparison, pure commercial and home-made SnO2 were also tested. Several physico-chemical analyses were performed to characterize all the as-prepared nanopowders. Subsequently, a homogeneous film was deposited by spraying technique onto Pt-Interdigitated Electrodes (Pt-IDEs). Then, gaseous ethanol (Figure 1) and acetone were sensed, obtaining very promising results for both pure and hybrid materials at 350\ub0C, and at lower temperatures (150\ub0C to 30\ub0C, by exploiting the UV light) for the graphene-based samples

A novel optimized mold release oil-in-water emulsion for polyurethane foams production

Release agents are compounds usually sprayed on the molds surface, forming a thin film that can act as a barrier preventing the sticking. Herein, both physical and chemical optimization of a wax-based O/W emulsion for polyurethane (PU) foams is reported. E_N1.8Cet1.2Ac2.5 sample (where N, Cet and Ac stand for the percentages of linear amine, cetyl alcohol and acetic acid), emulsified by the inversion point method, turned out to have the optimal composition, in terms of smaller oil droplets size (by Dynamic Light Scattering analysis and optical measurements), long-term stability (by Abbe refractometer and backscattering tests), good spreading (contact angle and surface tension measurements) and low corrosion phenomena (by potentiodynamic polarization tests, Scanning Electron Microscopy analysis). Principal Component Analysis helped to find the best correlations among all the investigated variables and to have some predictions on the role of the different raw materials in affecting the final stability of the emulsions

Marble hydrophobicity tuned by Si-based coatings

Hydrophobic polymers applied on stone materials increase their durability against undesired weathering processes [1]. The achievement of a certain degree of surface hydrophobicity (reducing the water permeation) constitutes one of the main research focuses [2]. Herein, two commercial Si-based resins (e.g. Alpha\uaeSI30 and Bluesil\uaeBP9710), directly applied on Carrara marble substrates and a silanization process, by using trichloromethylsilane (TCMS), were adopted. Contact angle measurements were carried out to evaluate the hydrophobic features. Hence, since only in the case of TCMS a good hydrophobicity was achieved (\uf071 around 150\ub0), two commercial polysiloxane-based additives (e.g. TegoPhobe 1500N and TegoPhobe 1650) were added respectively to Alpha\uaeSI30 and Bluesil\uaeBP9710, according to their chemical compatibility. These auxiliary substances allowed to decrease the wettability features of marble. Furthermore, since all the investigated coatings could be used as stone materials protective agents, water capillary absorption and vapor permeability tests were performed. Also, in this case, TCMS revealed to be the most performing one among the adopted silane-based resins, thanks to the drastic reduction of absorbed water and the decrease of vapor permeability within the threshold value of 50%. Finally, the coatings stability was evaluated by accelerated ageing tests. References [1] Cappelletti G., Fermo P., Pino F., Pargoletti E., Pecchioni E., Fratini F., Ruffolo S.A., La Russa M.F., On the role of hydrophobic Si-based protective coatings in limiting mortar deterioration, Environ Sci Pollut Res, 22 (2015) 17733\u201317743. [2] Cappelletti G., Fermo P., Camiloni M., Smart hybrid coatings for natural stones conservation, Progress in Organic Coatings 78 (2015) 511\u2013516

The hydrophobicity modulation of glass and marble materials by different Si-based coatings

Hydrophobic polymers applied on hydroxylated surfaces increase their durability against undesired weathering processes. The achievement of a certain degree of surface hydrophobicity (reducing the water permeation) constitutes one of the main research focuses. Herein, two commercial Si-based resins (e.g. Alpha\uaeSI30 and Bluesil\uaeBP9710), directly applied on both glass and Carrara marble substrates, and a silanization process by using trichloromethylsilane (TCMS) were adopted. Contact angle measurements together with hysteresis determination and Surface Free Energy (SFE) were carried out to evaluate the hydrophobic features. Hence, since only in the case of TCMS a good hydrophobicity was achieved (\uf071 around 150\ub0), two commercial polysiloxane-based additives (e.g. TegoPhobe 1500N and TegoPhobe 1650) were added respectively to Alpha\uaeSI30 and Bluesil\uaeBP9710, according to their chemical compatibility. These auxiliary substances allowed to decrease the wettability features of either glass or marble. Furthermore, since all the investigated coatings could be used as stone materials protective agents, water capillary absorption and vapor permeability tests were performed. Also in this case, TCMS revealed to be the most performing one among the adopted silane-based resins, thanks to the drastic reduction of absorbed water and the decrease of vapor permeability within the threshold value of 50%. Finally, the coatings stability was evaluated by accelerated ageing tests

Ad hoc tailored electrocatalytic MnO2nanorods for the oxygen reduction in aqueous and organic media

Metal-air batteries are one of the most promising electrochemical systems for energy storage and conversion. Herein we report promising results by exploiting manganese dioxide nanoparticles as ORR electrocatalysts. MnO2 nanorods were prepared through a hydrothermal synthesis, i.e. by varying both the salt precursors (Le. manganese sulphate or chloride) and the oxidizing agents (Le. ammonium persulfate or potassium permanganate). All the nanopowders were finely characterized on structural, morphological and surface points of view. Then, their electrocatalytic power was tested either in aqueous 0.1 M potassium hydroxide or in Tetra Ethylene Glycol Dimethyl Ether (TEGDME)/LiNO3 0.5 M electrolytes, by using Gas Diffusion Electrodes (GDEs) and Glassy Carbon (GC) as cathodes, respectively. All the nanoparticles promoted the ORR by causing a shift of the onset potential up to 100 mV in both solvents. Nevertheless, this shift was different according to the solvent/electrolyte used: in the case of the ether-based solvent, different values are obtained by adopting the synthesized MnO2 powders. Thus, we hypothesized that the structural/surface properties of MnO2 samples are leveled in the aqueous medium (Le. in a OH rich solvent, the hydroxyls can interact with the homologs on the MnO2 surface), contrary to what occurs in the organic solvent. Furthermore, a different behavior was observed also on the kinetic point of view thus leading to diverse interpretations of the oxygen reduction mechanism, especially in TEGDME

Detection of VOCs Traces by Graphene Oxide-Metal Oxide Gas Sensors

The sensing of gas molecules is of fundamental importance for environmental monitoring, control of chemical processes, medical applications, and so on [1-3]. In recent years, graphene-based gas sensors have attracted much attention due to enhanced graphene thermo-electric conductivity, surface area and mechanical strength. Thus, different structures have been developed and high sensing performances and room temperature working conditions were achieved [2,4]. However, they still suffer from several problems, which could be overcome by covering the graphene surface with metal oxide nanoparticles [2]. Furthermore, studies regarding the detection of Volatile Organic Compounds (VOCs) are still at the beginning [3]. Hence, the present work will be aimed at: i) optimizing the synthetic routes of ad hoc composite VOCs sensing materials (based on graphene oxide/SnO2 or ZnO hybrids) and their deep physico-chemical characterizations; ii) engineering the gas sensor device; and iii) evaluating the sensing performances at both high and mild temperatures (also exploiting the UV light) towards gaseous ethanol, acetone and ethylbenzene. Starting from pure graphite, graphene oxide (GO) powder was synthesized by adopting the Hummer\u2019s modified method [5]. The synthetic route was deeply investigated by modulating both the starting carbon material (powder or flakes graphite) and the concentration of the H2O2 (i.e. the quenching/oxidizing agent), thus tailoring the final GO surface/structural properties (TEM images in Fig. 1a and 1b). Once optimized this step, SnO2 or ZnO were grown on its surface by a hydrothermal method, varying the starting salt precursor/GO weight ratio between 4 and 32 (Fig. 1c and 1d). For comparison, pure SnO2 and ZnO (both commercial and home-made) were also tested. Several physico-chemical techniques have been used to characterize all the as-prepared nanopowders, such as XRPD, Raman, FTIR, XPS and TEM analyses. Subsequently, a homogeneous layer was deposited by spraying technique onto Pt-Interdigitated Electrodes (IDEs) starting from an ethanol suspension of each sample (2.0\u20132.5 mg mL-1). Then, gaseous ethanol, acetone and the less studied ethylbenzene were sensed, obtaining very promising results (in terms of both response/recovery time and sensibility down to ppb levels) for either pure and hybrid materials at 350\ub0C, and at lower temperatures (150\ub0C to 30\ub0C) for the graphene-based samples. Hence, these powders may represent very potential candidates for the gas sensing of highly toxic VOCs traces, both for environmental [1] and medical [3] diagnosis purposes

Exploring SnxTi1-xO2 Solid Solutions Grown onto Graphene Oxide (GO) as Selective Toluene Gas Sensors

The major drawback of oxide-based sensors is the lack of selectivity. In this context, SnxTi1- xO2/graphene oxide (GO)-based materials were synthesized via a simple hydrothermal route, varying the titanium content in the tin dioxide matrix. Then, toluene and acetone gas sensing performances of the as-prepared sensors were systematically investigated. Specifically, by using 32:1 SnO2/GO and 32:1 TiO2/GO, a greater selectivity towards acetone analyte, also at room temperature, was obtained even at ppb level. However, solid solutions possessing a higher content of tin relative to titanium (as 32:1 Sn0.55Ti0.45O2/GO) exhibited higher selectivity towards bigger and non-polar molecules (such as toluene) at 350 \ub0C, rather than acetone. A deep experimental investigation of structural (XRPD and Raman), morphological (SEM, TEM, BET surface area and pores volume) and surface (XPS analyses) properties allowed us to give a feasible explanation of the different selectivity. Moreover, by exploiting the UV light, the lowest operating temperature to obtain a significant and reliable signal was 250 \ub0C, keeping the greater selectivity to the toluene analyte. Hence, the feasibility of tuning the chemical selectivity by engineering the relative amount of SnO2 and TiO2 is a promising feature that may guide the future development of miniaturized chemoresistors

Graphene Oxide-Based Hybrids for Chemiresistive VOCs Sensors

INTRODUCTION The sensing of gas molecules is of primary importance for environmental monitoring, control of chemical processes, medical applications, and so on1. In recent years, graphene-based gas sensors have attracted much attention due to enhanced graphene thermo-electric conductivity, surface area and mechanical strength. Thus, different structures have been developed and high sensing performances and room temperature working conditions were achieved1. However, they still suffer from several problems, which could be overcome by covering the graphene surface with metal oxide nanoparticles2. Furthermore, studies regarding the detection of Volatile Organic Compounds (VOCs) are still at the beginning1. Hence, the present work will be aimed at: i) optimizing the synthetic routes of ad hoc composite VOCs sensing materials (based on graphene oxide/SnO2 or ZnO hybrids) and their deep physico-chemical characterizations; ii) engineering the gas sensor device; and iii) evaluating the sensing performances at both high and mild temperatures (also exploiting the UV light) towards gaseous ethanol, acetone and ethylbenzene. EXPERIMENTAL/THEORETICAL STUDY Starting from pure graphite, graphene oxide (GO) powder was synthesized by adopting the Hummer\u2019s modified method2. The synthetic route was deeply investigated by modulating both the starting carbon material (powder or flakes graphite) and the concentration of the H2O2 (i.e. the quenching/oxidizing agent), thus tailoring the final GO surface/structural properties. Once optimized this step, SnO2 or ZnO were grown on its surface by a hydrothermal method, varying the starting salt precursor/GO weight ratio (ZnxGO or SnxGO, x = 4, 8, 16, 32). For comparison, pure SnO2 and ZnO (both commercial and home-made) were also tested. Several physico-chemical techniques have been used to characterize all the as-prepared nanopowders, such as XRPD, BET, Raman, FTIR, XPS, TEM and electrochemical analyses (CV and EIS). Subsequently, a homogeneous layer was deposited by spraying technique onto Pt-Interdigitated Electrodes (IDEs) starting from an ethanol suspension of each sample (2.5 mg mL-1). Then, gaseous ethanol, acetone and ethylbenzene (the more interesting one, being nowadays the less studied VOC) were sensed by using a Linkam Scientific stage, equipped with an electrochemical workstation for the chronoamperometric measurements. RESULTS AND DISCUSSION The effective synthesis of graphene oxide sheets and, subsequently, the growth of metal oxide nanoparticles on its surface were confirmed by exploiting different physico-chemical techniques. As concerns the VOCs sensing analyses, we obtained very promising results (in terms of both response/recovery time and sensibility down to ppb levels) for either pure and hybrid materials at 350\ub0C, and at lower temperatures (150\ub0C to RT, by exploiting UV light) for the graphene-based samples (Figure 1), thanks to the presence of the carbon material.Furthermore, a similar behavior has been noticed towards acetone and ethylbenzene pollutants. CONCLUSION Very promising results have been obtained with graphene oxide-based materials, which reveal to be more performing than the corresponding pure samples. Hence, these powders may represent very potential candidates for the gas sensing of highly toxic VOCs traces, both for environmental and medical diagnosis1 purposes

Durable Modified Polyacrylic Coatings for Cultural Heritage Protection

INTRODUCTION Deterioration phenomena of ancient and modern stone cultural heritage are natural and unrestrainable decay processes mainly arising from water adsorption and percolation into stone building materials1. Once water attacks and penetrates stone surfaces, several chemical, physical and biological degradation processes can occur altering significantly, and in some cases even irreversibly, the properties of stone materials. The application of hydrophobic coatings to stone surfaces is mandatory to protect stone artefacts from the deleterious effects occurring in the case of water exposition. The protective agent must possess several features, i.e. high compatibility with the substrate, high durability, transparency, easiness of application and removal, water-repellency, capability to avoid the attack of organic and inorganic contaminants; moreover, it should be permeable to water vapor. The aim of the present work was to synthesize new polymer coatings as stone protective with satisfactory water repellent properties and improved durability, thanks to the combined use of fluorinated and long alkyl chain monomers and without the use of any photo stabilizers agents. EXPERIMENTAL/THEORETICAL STUDY New types of polymer protectives were prepared via free radical polymerization between either 1H,1H,2H,2H-Perfluoro-octyl-methacrylate (POMA) or commercial stearyl methacrylate (STEA, Sigma Aldrich) and methacrylic monomers (methyl, MMA, and n-butyl, nBuMA, methacrylates)2,3. Specifically, POMA was synthesized via esterification reaction using methacryloyl chloride and 1H,1H,2H,2H-Perfluoro-1-octanol. RESULTS AND DISCUSSION The properties of the home-made hydrophobizing polymers in terms of macromolecular structure, molecular weights, thermal features and water repellency were determined. Furthermore, the long-term behavior of these polymeric protective agents was estimated by means of accelerated aging tests exploiting UV radiations (in according to UNI 10925:2001 standard method for 100h, 315-400 nm for UVA rays and 280-315 nm for UVB ones). Their behavior over time was checked via Size Exclusion Chromatography (SEC) by evaluating Mn and D data of aged polymeric samples (Table 1) and by Fourier Transform Infrared (FT-IR) spectroscopy. By evaluating Mn and D data reported in Table 1, all the synthesized polymers seem to be unaffected by UV aging. Thus, the present stable resins were applied on both natural (Botticino marble) and artificial (mortar) stone substrates and their wetting properties together with their absorption by capillarity and water vapour permeability were successfully assessed and compared. All the covered substrates show an increase of water contact angle of around 50\ub0 and a decrease in water absorption and permeation of about 50% and 20%, respectively. Lastly, in order to evaluate the stability of the applied coatings towards degradation induced by solar radiation and interaction with the atmospheric pollution, exposure to a typical polluted urban environment for some months have been carried out. For this purpose, the following analyses have been performed: contact angle measurements, SEM-EDS (Scanning Electron Microscopy with X-ray microanalysis), IC (Ion Chromatography), and colorimetric tests by CIELab elaboration. CONCLUSION The use of polymeric protectives is very advantageous in fields when the hydrophobic properties and high chemical stability are required. Within this context, the use of polymer resins bearing methacrylic and fluorinated monomers along the polymeric chain can be a way to create tailor-made water repellent materials with enhanced durability, without the addition of any stabilizing agent