Graphene-TiO2 hybrids for photocatalytic aided removal of VOCs and nitrogen oxides from outdoor environment.

Outdoor and indoor air pollution has become a global concern in modern society. Although many policies and regulations on air quality have been promulgated worldwide over the past decades, airborne pollution still negatively affects health and therefore the life-style of human beings. One of the strategies to challenge this problem might be reducing the amount of airborne pollutant by mineralising them via photoinduced reactions. Photocatalytic oxidation of gaseous pollutants via titanium dioxide is one of the most promising solar photochemical reactions. In this research work, by means of a green sol-gel procedure, we have coupled titania to graphene (0.5 and 1.0 wt%) aiming to increase the solar photocatalytic activity of the produced hybrid materials. Transient paramagnetic species formed upon UV-A irradiation were detected by means of EPR spectroscopy. The photocatalytic reactions were assessed by monitoring the removal of nitrogen oxides and two different volatile organic compounds (benzene and isopropanol), which has never been assessed before. Our results highlight the exceptional characteristics of the TiO2/graphene hybrid material synthesised with 1.0 wt% graphene, and its excellent suitability for multi-purpose applications in the field of environmental remediation. Compared to unmodified titania, it shows a clear enhancement in the photocatalytic removal of those hazardous pollutants, having a photocatalytic degradation rate twice higher. In addition, the same material is highly stable and shows fully recyclability over repeated tests. Hybrid titania-graphene materials could thus be exploited to grant safer outdoor and indoor environments, having thus a beneficial impact on public health and on the quality of our lives.

Synthesis of ceramic pigments from industrial wastes: Red mud and electroplating sludge.

The perception of industrial waste has changed, in the last decades, from an economic and environmental problem to a potential raw material. In this work, the synthesis of a stable pigment was prepared by combining two hazardous and unexplored wastes: red mud (RM, rich in Fe) and electroplating sludge (ES, rich in Ni/Cr). The wastes were mixed in different proportions and calcined at 1200 °C. Black and brown pigments were obtained from the mixture of RM/ES in 1:3 and 1:1 wt proportions, respectively. The color was given by the chrome-iron-nickel spinels, based on Ni2+ 3T1g(3F) transitions (≈13,000 cm-1), Cr3+ 4A2g → 4T1g(4F) transitions (≈24,400 cm-1) and Fe3+ (≈15,000-≈22,500 cm-1). The achieved coloring strength and thermal stability on various ceramic glazes render excellent prospects for the industrial application of such waste-based pigments.

Purely Visible-Light-Induced Photochromism in Ag-TiO2 Nanoheterostructures.

We report titania nanoheterostructures decorated with silver, exhibiting tuneable photochromic properties for the first time when stimulated only by visible white light (domestic indoor lamp), with no UV wavelengths. Photochromic materials show reversible color changes under light exposure. However, all inorganic photochromic nanoparticles (NPs) require UV light to operate. Conventionally, multicolor photochromism in Ag-TiO2 films involves a change in color to brownish-gray during UV-light irradiation (i.e., reduction of Ag+ to Ag0) and a (re)bleaching (i.e., (re)oxidation of Ag0 to colorless Ag+) upon visible-light exposure. In this work, on the contrary, we demonstrate visible-light-induced photochromism (ranging from yellow to violet) of 1-10 mol % Ag-modified titania NPs using both spectroscopic and colorimetric CIEL*a*b* analyses. This is not a bleaching of the UV-induced color but a change in color itself under exposure to visible light, and it is shown to be a completely different mechanism-driven by the interfacial charge transfer of an electron from the valence band of TiO2 to that of the AgxO clusters that surround the titania-to the usual UV-triggered photochromism reported in titania-based materials. The quantity of Ag or irradiation time dictated the magnitude and degree of tuneability of the color change, from pale yellow to dark blue, with a rapid change visible only after a few seconds, and the intensity and red shift of surface plasmon resonance induced under visible light also increased. This effect was reversible after annealing in the dark at 100 °C/15 min. Photocatalytic activity under visible light was also assessed against the abatement of nitrogen oxide pollutants, for interior use, therefore showing the coexistence of photochromism and photocatalysis-both triggered by the same wavelength-in the same material, making it a multifunctional material. Moreover, we also demonstrate and explain why X-ray photoelectron spectroscopy is an unreliable technique with such materials.

Effect of preparation and processing conditions on UV absorbing properties of hydroxyapatite-Fe2O3 sunscreen.

The development of innovative, safe and non-photocatalytic sunscreens is urgently needed, as it is essential to have sunscreen filters offering appropriate UV protection without damaging the environment and/or generating free radicals when in contact with the skin. Hydroxyapatite (Ca10(PO4)6(OH)2, HAp) when substituted with iron has UV protection properties and is not photocatalytic; HAp was used to make a sunscreen filter by treating cod fish bones in an iron-containing solution, and then calcining them at 700°C. Here we present a systematic and advanced study on this material, to obtain a sunscreen with improved UV absorbing properties. Bones were treated with three different iron salts - Fe(II) chloride, Fe(II) lactate and Fe(III) nitrate - under various pH conditions. Results showed that Fe(II) chloride in basic pH led to the most effective iron inclusion. High energy ball milling or ultrasound were investigated to increase surface area and corresponding UV absorption; high energy ball milling treatment led to the best optical properties. The optimum powders were used to formulate UV protection creams, which showed Sun Protection Factor (SPF) values significantly superior to the control cream (up to 4.1). Moreover the critical wavelength (λcrit) was >370nm (388-389nm) and UVA/UVB ratios were very close to 1. With these properties these sunscreens can be classified as broad UV protectors. Results also showed that combining these powders with other sunscreens (i.e. titanium dioxide), a synergic effect between the different components was also observed. This investigation showed that HAp-based sunscreens of marine origin are a valid alternative to commercial products, safe for the health of the customers and, being non-photocatalytic, do not pose a threat to the environment.

Novel porous fly-ash containing geopolymer monoliths for lead adsorption from wastewaters.

In this study novel porous biomass fly ash-containing geopolymer monoliths were produced using a simple and flexible procedure. Geopolymers exhibiting distinct total porosities (ranging from 41.0 to 78.4%) and low apparent density (between 1.21 and 0.44g/cm(3)) were fabricated. Afterwards, the possibility of using these innovative materials as lead adsorbents under distinct conditions was evaluated. Results demonstrate that the geopolymers' porosity and the pH of the ion solution strongly affect the lead adsorption capacity. Lead adsorption by the geopolymer monoliths ranged between 0.95 and 6.34mglead/ggeopolymer. More porous geopolymers presented better lead removal efficiency, while higher pH in the solution reduced their removal ability, since metal precipitation is enhanced. These novel geopolymeric monoliths can be used in packed beds that are easily collected when exhausted, which is a major advantage in comparison with the use of powdered adsorbents. Furthermore, their production encompasses the reuse of biomass fly-ash, mitigating the environmental impact associated with this waste disposal, while decreasing the adsorbents production costs.

Waste glass from end-of-life fluorescent lamps as raw material in geopolymers.

Nowadays the stunning volume of generated wastes, the exhaustion of raw materials, and the disturbing greenhouse gases emission levels show that a paradigm shift is mandatory. In this context, the possibility of using wastes instead of virgin raw materials can mitigate the environmental problems related to wastes, while reducing the consumption of the Earth's natural resources. This innovative work reports the incorporation of unexplored waste glass coming from end-of-life fluorescent lamps into geopolymers. The influence of the waste glass incorporation level, NaOH molarity and curing conditions on the microstructure, physical and mechanical properties of the geopolymers was evaluated. Results demonstrate that curing conditions are the most influential factor on the geopolymer characteristics, while the NaOH molarity is less important. Geopolymers containing 37.5% (wt) waste glass were successfully produced, showing compressive strength of 14MPa (after 28days of curing), suggesting the possibility of their use in non-structural applications. Porous waste-based geopolymers for novel applications were also fabricated.

Preparation of clinker from paper pulp industry wastes.

The production of paper pulp by the Kraft method generates considerable amounts of wastes. Namely, lime mud generated in the recovery circuit of chemical reagents, biological sludge from the wastewater treatment of wood digestion process and fly ash collected in the fluidized bed combustor used to generate electricity from biomass burning. The final destination of such wastes is an important concern, since environmental regulations are becoming stricter regarding their landfill. Driven by this fact, industries are looking for more sustainable solutions, such as the recycling in distinct products. This work tested these wastes as secondary raw materials to produce clinker/cement that was then experienced in mortar formulations. The first step involved the residues detailed characterization and a generated amounts survey. Then, specific but simple steps were suggested, aiming to facilitate transport and manipulation. Distinct blends were prepared and fired in order to get belitic and Portland clinkers. The Portland clinkers were processed at lower temperatures than the normally used in the industry due to the presence of mineralizing impurities in some wastes. Belite-based cements were used to produce mortars that developed satisfactory mechanical strength and did not reveal signs of deterioration or durability weaknesses.

Novel nanosynthesis of In2O3 and its application as a resistive gas sensor for sevoflurane anesthetic.

A novel non-aqueous sol-gel route for synthesizing pure indium oxide (In2O3) nanoparticles (NPs) using indium acetylacetonate and n-butylamine as the reactive solvent, under solvothermal conditions, is herein proposed. The samples were characterized by an advanced X-ray method, whole powder pattern modeling (WPPM) and high-resolution transmission electron microscopy (HR-TEM), showing the exclusive presence of pure In2O3. Diffuse reflectance spectroscopy (DRS) was used to determine the optical band gap (Eg) of the sample. Moreover, these investigations also revealed that the In2O3 nanoparticles are quasi-spherical in shape, with a diameter of around 7 nm as prepared and 9.5 nm after thermal treatment at 250 °C. In2O3 NPs worked as highly sensitive sensing interfaces to provide resistance changes during exposure to sevoflurane, a volatile anesthetic agent used in surgical wards. The developed sensor demonstrated a good response and fast response/recovery time towards very low concentrations of sevoflurane in air, suggesting a very attractive application as a real-time monitoring analyzer in a hospital environment.

A hydroxyapatite-Fe2O3 based material of natural origin as an active sunscreen filter.

The use of sunscreens as protective barriers against skin damage and cancer, by absorbing harmful UVA and UVB rays, is becoming an increasingly important issue. Such products are usually based on TiO2 or ZnO, although both Fe2O3 and hydroxyapatite (Ca10(PO4)6(OH)2, HAp) doped with metal ions have been reported as being ultraviolet (UV) absorbing materials. HAp is the main component of bone; it is, therefore, highly biocompatible. In the present work, an iron-doped HAp-based material, containing both Fe ions substituted into the HAp structure and iron oxide in hematite (α-Fe2O3) form, was successfully developed from waste cod fish bones. This was achieved through a simple process of treating the bones in a Fe(ii) containing solution, followed by heating at 700 °C. The material showed good absorption in the whole UV range and did not form radicals when irradiated. The sunscreen cream formulated with this material could be used as a broad sunscreen protector (λcrit > 370 nm), showing high absorption both in the UVA and UVB ranges. Because of its absorption properties it would be classified as 5 star protection according to the Boots UVA star rating system. The cream is also photostable, and does not cause irritation or erythema formation when in contact with the human skin. These results show that a food by-product such as fish bones could be converted into a valuable product, with potential applications in health care and cosmetics. This is the first time a HAp-based sunscreen cream has been developed and validated as a proof of concept.

Evaluation of metal-ions containing sludges in the preparation of black inorganic pigments.

Inorganic pigments were prepared from industrial wastes: galvanizing sludges resulting from Cr/Ni plating processes (S, G, and T) and a sludge generated from steel wiredraw process that is Fe-rich (F). These industrial wastes were characterized in order to determine the main compositional variations and discover their influence on the colour characteristics of pigments for glazes and ceramics. The toxic character was also investigated and established. Attempting to form the black spinel structure, several combinations of sludges were prepared and then calcined at 1000 °C. XRD and microscopy analysis confirmed the presence of nichromite for compositions with higher Ni amounts, while trevorite was detected in iron-rich formulations. The combination of S and F sludges (SF compositions) generates pigments with higher black colorimetric quality, which is similar to, and sometimes better than, a commercial black pigment. Pigments containing GF and TF sludges develop brown hues on glazes and on porcelain stoneware bodies, being this effect more evident upon industrial firing trials. The addition of minor amounts of cobalt or manganese enhances the black coloration, and might adjust some formulation deviations.

Photocatalytic decolouration of Orange II by ZnO active layers screen-printed on ceramic tiles.

In this work ZnO layers have been deposited by screen-printing in common ceramic tiles. These layers were characterized and tested for the photocatalytic degradation of the organic dye Orange II in aqueous solutions, using a batch photoreactor either under visible light provided by a Philips ML-160 W lamp or under direct exposure to sunlight. For sake of comparison, ZnO suspensions have also been evaluated for similar reacting conditions. The influence of experimental parameters such as (i) firing temperature of the printed layer; (ii) layer thickness; and (iii) operation time have been investigated. Screen-printed ZnO layers obtained in optimal processing conditions showed photocatalytic activity comparable to aqueous ZnO suspensions. The maximal attenuation degree is over 70% and decolourisation rate, assuming that reaction kinetics follows a pseudo-first order rate law, is over 0.015 min(-1). Thus these ZnO-layered ceramic tiles can be regarded as an alternative to photocatalytic suspensions of the same material with the advantage of avoiding the removal of the photocatalyst.

Leaching behaviour of a galvanic sludge in sulphuric acid and ammoniacal media.

Leaching studies of a sludge produced by the physico-chemical treatment of wastewaters generated by a Ni/Cr plating plant were carried out in both sulphuric acid and ammoniacal media aiming to decide which of them would be the best treatment for this kind of waste material. The dissolution behaviour of some metals (Cu, Ni, Cr and Zn) was studied in order to assure the best metal recovery conditions in subsequent processes by the use of some separation methods such as solvent extraction and precipitation techniques. Therefore, the study here presented deals with the first chemical stage of an integrated treatment process. For the sulphuric acid leaching, maximal conversions obtained were 88.6% Cu, 98.0% Ni and 99.2% Zn for the following experimental conditions: a 100 g L(-1) acid concentration, a 5:1 liquid-to-solid ratio (L/S), a particle size less than 1 mm, a digestion time of 1h, a stirring speed of 700 rpm (all at room temperature and under atmospheric pressure). As expected, no selectivity was achieved for the sulphuric acid leaching, despite this option yielding much higher metal ion dissolution when compared with that reached by ammoniacal leaching. The use of this latter medium allowed the extraction of Cu and Ni without Cr species, but rates of conversion were only about 70% for Cu and 50% for Ni, much lower than those obtained for sulphuric acid leaching.

Effect of experimental variables on the inertization of galvanic sludges in clay-based ceramics.

The incorporation of several industrial wastes in ceramic matrixes had been attempted as an effective low expense technique for the fixation of metallic species in usable products or simply to reduce the residue volume for further disposal. However, the dominant mechanism of the inertization process and the relevant influent parameters are still unknown, mostly due to the complexity of the systems. This work reports the effect of several processing parameters such as the mixing time, the calcination temperature and duration, the relative amount of sludge, and the physical aspect of the sample (powdered or pressed pellets) on the fixing level of relevant species (SiO2), SO4(2)-, Zn, Ni, Ca, Cu, Cr) by leaching in different media (aqueous, acetate, and citrate). Statistical tools were used to define the relevance of each experimental variable on the inertization process of the used galvanic sludge. The relative amount of sludge in the mixture, the calcination temperature and the agglomeration state of the sample were found to be the most influent parameters of the inertization process. The incipient reaction between sludge and ceramic matrix components points out for the dominance of a macro-encapsulation mechanism.

Role of the mixing conditions and composition of galvanic sludges on the inertization process in clay-based ceramics.

Hydroxide-metal sludges from electroplating industry are a potential source of environmental contamination due to their high content of heavy metals. The incorporation of these residues in a ceramic matrix can be a promising way to suppress the harmful effect of metals normally present in those sludges. This work reports the role of the mixing time between the waste and ceramic materials and of the calcination step on the fixing level of several metal-containing species (Al, Zn, Ni, Fe, Ca, Cu, Cr) after sequential leaching in different media (aqueous, acetate and citrate). A strong and/or long mixing process will promote the deagglomeration of the coarser agglomerates and then will increase the reactivity of remaining grains towards the ceramic material during the calcination. As a consequence, inertization is improved for fired samples. With non-calcined samples leaching increases as a result of increasing dispersability/availability of species.