In this work, iron ore tailing (IOT) was used for the production of two different materials: sodium silicate and geopolymers. Initially, reactions of IOT with NaOH were carried out by hydrothermal reaction in autoclave at 200 °C (1:1.5 and 1:2.5 SiO2:NaOH molar ratio) and reaction times of 4 and 8 h. X-ray fluorescence by dispersive energy (XRF), X-ray diffraction (XRD), Mössbauer spectroscopy, scanning electron microscopy (SEM-EDS) and titrations showed that IOT:NaOH ratios of 1:2.5 and reaction time 8 h completely dissolved the quartz from the IOT, obtaining a solid fraction consisting mainly of hematite and an aqueous phase of sodium silicate, which showed contents of ca. 23% SiO2 and 19% Na2O. This sodium silicate obtained was then combined with IOT (25 and 50 wt.%) to produce geopolimeric material with excellent physico-chemical properties, fast curing time and very good compressive strength results, which ranged from 41 to 58 MPa and many potential applications.

In this work, we describe a sustainable alternative to recover iron from two iron ore tailings (IOT) using hydrogen reduction at relatively low temperatures followed by magnetic separation. X-ray powder diffraction (XRD), inductively coupled plasma (ICP), atomic absorption (AA), Mössbauer, scanning electron microscopy (SEM/EDS), Raman and thermogravimetry (TG) analyses indicated that the Fe oxide present in the IOTs (sandy tailing (ST) and mud tailings (MT)), can be reduced with H2 at 500 ºC to produce α-Fe. Upon magnetic separation the mud tailing produced a 77 wt.% magnetic fraction increasing the Fe content from 19.2 to ca. 56 wt.% of Fe. On the other hand, the sandy tailing resulted in a 15 wt.% magnetic fraction increasing the Fe content from 19.2 to 70 wt.%. These results indicate that up to 86% of iron can be recovered from the IOT wastes already in the metallic form which can be very interesting for the steel industry.

According to the World Health Organization, amoxicillin (AMX) is the most widely consumed antibiotic in the world. Consequently, there is great interest in the development of new technologies that allow the removal of this type of contaminant, as exposure to antibiotic residues can cause a variety of adverse effects, such as toxicity and antimicrobial resistance. In this work, AMX adsorption from aqueous solution was investigated using nickel ferrite nanoparticles. The nanoadsorbents were prepared by the coprecipitation method, annealed at 300 to 700 °C, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Mössbauer spectroscopy (ME) and vibratory sample magnetometry (VSM). Nanoparticle size, pH and temperature were found to significantly affect the amount of adsorbed AMX. The pseudo-second order kinetic model described the adsorption process and the adsorption isotherm fitted to the Freundlich model. AMX adsorption capacity was 104-45 mg g−1 (miligram of AMX per gram of ferrite) for ferrite annealed at 300-700 °C, respectively. The nanoadsorbents employed showed higher AMX removal efficiency when compared to other iron oxides. Moreover, the good reuse results obtained showed their great potential for antibiotic removal by adsorption.

Zinc hexacyanoferrate (ZnHCF) is a Prussian Blue analog and can be intercalated by both monovalent and divalent ions. ZnHCF/multi-walled carbon nanotube (MWCNT) film could be used as a cathode for zinc ions battery. Carbon nanotubes improved significantly the electrochemical performance of the electrode. It is described the preparation of ZnHCF/MWCNT films by the interfacial method with cyclohexane/water mixture as solvent. The crystal structure, morphology, and microstructure of the as-prepared products were characterized by X-ray diffraction, scanning electron microscopy, Mossbaüer, Raman spectroscopy, and infrared spectroscopy. Results revealed that the MWCNTs extend the electrochemical properties of the ZnHCF and influence the structure and morphology of the hexacyanoferrate particles. If tested as cathode material for zinc ion batteries, the nanocomposite film exhibits a capacity of 25.81 mA h g-1, which is much higher than those obtained for a ZnHCF single-component film (3.28 mA h g-1). The physical characteristics and properties that allow good reversibility to a high potential difference, achieved with the ZnHCF/MWCNT film, suggest new developments in the manufacture of translucent, flexible and light energy storage devices, which can be used as a lower-cost, safer and environmentally friendly alternative to the currently existing technologies.

In this work, bio-oil (an organic matrix rich in oxygen functionalities) was used to efficiently dissolve and disperse Fe3+ which upon thermal treatment produced a carbon containing dispersed and encapsulated Fe oxide magnetic nanoparticles. These materials were prepared by dissolution of 8, 16 and 24 wt.% Fe3+ salt in bio-oil followed by treatment at 400, 450, 500 or 600 ºC in N2 atmosphere. X-ray diffraction (XRD), scanning (SEM) and transmission electron microscopies (TEM), elemental analysis, thermogravimetric-mass spectrometry (TG-MS), potentiometric titration, Raman and Mössbauer spectroscopies showed that Fe3+ species in bio-oil is reduced to produce magnetic nanoparticles phases: magnetite Fe3O4 and maghemite γ-Fe2O3. At low temperatures, the iron phases were less protected, and the carbon matrix was more reactive, while in temperatures above 500 ºC, the iron phases were more stable, however, the carbon matrix was less reactive. Reaction of these magnetic carbon materials with concentrated H2SO4 produced surface sulfonic acidic sites (ca. 1 mmol g-1), especially for the materials obtained at 400 and 450 ºC. The materials were used as catalysts on esterification reaction of oleic acid with methanol at 100 ºC and conversions of 90% were reached, however, after 2 consecutive uses, the conversion decreased to 30%, being required more studies to improve the material stability.

Although largely used in mobiles and electric vehicles applications, insertion batteries based on Li-ion technology are high-cost devices. These applications require high-performance energy storage systems with high-energy and high-power densities, which are better attained by Li-ion technology. However, stationary applications such as power plants and uninterruptible power supplies (UPS) mainly require low-cost energy storage devices. In this scenario Na-ion insertion batteries feature as a cheaper option for such applications. Among the several compounds for use as cathode in Na-batteries, a largely studied class of compounds are the sodium-carbonate-phosphates, Na3MCO3PO4 (M = Mn, Fe, Co or Ni), with structure analogue to the mineral sidorenkite. In this work, it was developed a new microwave-assisted hydrothermal method as an ultra-fast way to prepare sodium-carbonate-phosphate compounds. This methodology results in high-quality materials with general formula Na3MCO3PO4 (M = Mn, Fe, Co or Ni) upon only 5 min processing time. Characterization techniques indicate highly ordered materials with sidorenkite-like phase and different morphologies or crystal habits, including plates, rods, and a ‘starfruit’ shape. As a proof-of-application the Mn-based material was evaluated from electrochemical tests for Na+ insertion reactions. The obtained results evidence initial discharge capacity of 107 mA h g-1 with good reversible capacity (65 mA h g-1) after several charge/discharge cycles.

In this work, efficient adsorbents for β-lactam antibiotics based on mesoporous iron oxide containing surface [FeOx(OH)y] sites were produced by controlled precipitation of iron hydroxide and thermal treatment at 150, 200, 300 and 450 ºC (150FeOH, 200FeOH, 300FeOH and 450FeOH, respectively). Mössbauer, X-ray diffraction (XRD), thermogravimetry-mass spectrometry (TG-MS), Fourier transform infrared spectroscopy (FTIR), Raman, Brunauer-Emmett-Teller method (BET), scanning electron microscopy (SEM) and elemental analyses showed that the temperature caused a gradual dehydroxylation process with a significant increase of the mesoporous surface area (e.g., 114-142 m2 g-1 with 46-59% mesopores, i.e., 0.04-0.09 cm3 g-1) and approximate compositions of FeO1.06(OH)0.89 for 150FeOH up to FeO1.38(OH)0.26 for 450FeOH. The material 150FeOH showed high adsorption capacities of ca. 42 and 58 mg g-1 for amoxicillin and ceftriaxone, respectively. Experiments assessing the effect of NO3-, Cl-, competitive PO43- adsorption and H2O2 decomposition suggest that the [FeOx(OH)y] surface sites located in the mesopores are involved in the efficient adsorption by complexation of the β-lactam antibiotics.

A magnetic catalyst (sample MCat) consisting of KI supported on a mixture of silica and maghemite (γ-Fe2O3) was prepared and used in the transesterification reaction for the synthesis of biodiesel. The energy dispersive X-ray spectrum of the catalyst showed signals due to Si, Fe, K, and I. Powder X-ray diffraction data revealed the amorphous nature of the SiO2 and the duly impregnation of the support with KI. 57Fe Mössbauer spectroscopy and magnetization measurements confirmed the ferrimagnetic iron oxide in the catalyst to be maghemite. N2 adsorption-desorption data indicated that the silica is mesoporous with a specific area of 352 m2 g-1, enabling the impregnation of 40 and 11 wt.% of KI and maghemite, respectively, according to the chemical composition obtained by the X-ray fluorescence measurements. The MCat was found to be efficient in the transesterification reaction in the macaúba and soybean oils. The MCat was easily removed from the reaction medium, with a hand magnet, and efficiently reused for more four consecutive reaction cycles. The good catalytic activity along with its magnetic behavior, high chemical stability and recyclability make the MCat a suitable material for the green synthesis of biodiesel.

This paper describes the synthesis of four new organotin compounds of general formula: (Ph4P)[Sn(Cy)3(RSO2N=CS2)] [Ph4P = tetraphenylphosphonium cation, Cy = cyclohexyl, R = C6H5 (1), 4-ClC6H4 (2), 4-BrC6H4 (3) and 4-IC6H4 (4)]. They were obtained by the reaction between four different potassium N-R-sulfonyldithiocarbimate salts and tricyclohexyltin chloride in methanol, and were isolated as tetraphenylphosphonium salts. The elemental analyses of C, H, N and the data of high-resolution mass spectrometry were consistent with the proposed formulae. The 119Sn NMR spectra and 119Sn Mössbauer spectroscopic data were consistent with the presence of tetracoordinated tin(IV) species in solution and in the solid state. The electrolytic molar conductance and the integration curves in the 1H NMR spectra are in accord with the 1:1 proportion between the tetraphenylphosphonium cations and the complex anions. The activity of the new compounds in the vulcanization of nitrile rubber was evaluated and the results were compared to those achieved with the commercial accelerators: N-tert-butyl-2-benzothiazolesulfenamide (TBBS), tetramethylthiuram disulfide (TMTD) and zinc diethyldithiocarbamate (ZEDC).

Six new salts of organometallic complexes of tin(IV) with the general formulae: (Ph4P)2[Sn(Bu)2(RSO2N=CS2)2] and [Fe(phen)3][Sn(Bu)2(RSO2N=CS2)2] [Ph4P = tetraphenylphosphonium, R = CH3 (1), C2H5 (2) and C4H9 (3); Fe(phen)3 = tris(1,10-phenanthroline)iron(II), R = CH3 (4), C2H5 (5) and C4H9 (6)] were synthetized from potassium dithiocarbimates (RSO2N=CS2K2.H2O) in reaction with dichlorobis-n-butyltin(IV) and tetraphenylphosphonium chloride (1-3) in N,N-dimethylformamide or tris(1,10-phenanthroline)iron(II) (4-6) in methanol. The new compounds were characterized by elemental analysis of Fe and Sn, and by vibrational, Mössbauer and nuclear magnetic resonance of 1H, 13C and 119Sn spectroscopies. High-resolution mass spectra in the negative and positive modes were also obtained. The elemental analyses and the exact masses obtained for the cations and the complex anions were consistent with the proposed formulae. The Mössbauer spectroscopic data were consistent with the presence of tin(IV) with coordination numbers between 4 and 5 (compounds 1-6), and of hexacoordinated iron(II) (compounds 4-6). The 1H and 13C NMR spectra presented all the expected signals for the cations and anions, and the signals observed in the 119Sn NMR spectra indicated an equilibrium between tetra- and pentacoordination around the tin atoms in solution. The in vitro activity of the new compounds was evaluated against Botrytis cinerea and Colletotrichum acutatum.

In this work, composites based on carbon (1, 10 and 20 wt.%) interfaced with Fe3O4 (magnetite) have been studied as catalysts for the oxidation of aqueous sulfide. The composites were prepared by assembling cellulose nanocrystals surrounding Fe3O4 followed by a controlled thermal decomposition at 400, 600 and 800 ºC. Mössbauer, X-ray diffractometry (XRD), Raman, thermogravimetry (TG), elemental analysis CHN, scanning electron microscopy (SEM/EDS), Fourier transform infrared spectroscopy (FTIR) and potentiometric titration indicated that at 400 and 600 ºC the cellulose nanocrystals decompose to different carbon forms, i.e., films, filaments and particles attached to the Fe3O4 crystals. At higher temperature, i.e., 800 ºC, this carbon on the magnetite surface further reacted to produce Fe0. UV-Vis, Raman and electrospray ionization mass spectrometry (ESI-MS) measurements showed that these composites catalyze the oxidation of aqueous sulfide to convert S2-aq to polysulfides Sn2- (where n = 2-9) and also oxygen containing polysulfides HOSn-. Simple kinetic experiments showed very low sulfide oxidation activities for pure Fe3O4 and pure carbon. On the other hand, the composites, especially with 10% C obtained at 600 ºC, were remarkably active. These results are discussed in terms of a possible participation of oxygen based redox groups present on the carbon surface and an electron transfer from the carbon to the Fe3O4 phase.

In this work, a bulky Fe0/carbon matrix obtained by a low cost and simple reduction/carbonization of Fe3+ salt with sucrose was treated with CO2 to selectively oxidize the amorphous carbon to release the graphite like carbon coated magnetic Fe0 particles. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman, X-ray diffraction (XRD), BET, thermogravimetric analysis (TG) (in CO2) and particle size analyses showed that the treatment with CO2 of the Fe/carbon bulky composite led to the selective oxidation of the more amorphous carbon with the formation of 125-132 nm Fe@C nanoparticles with surface areas of 217 m2 g−1.

In this work, Ricinus communis L. press cake waste from biodiesel production was used to produce a versatile reactive material for environmental applications. The biodiesel cake waste was impregnated with FeIII at different concentrations (19-45 wt.%) and treated at 400, 600 and 800 °C. Mössbauer, X-ray diffraction (XRD), thermogravimetric analysis (TG/DTA), scanning electron microscope (SEM), elemental analysis CHN, Raman, potentiometric titration, saturation magnetization and Brunauer-Emmett-Teller (BET) analyses showed that the materials prepared at 400 °C are composed mainly of a graphitic and amorphous carbon containing dispersed magnetite (Fe3O4). At higher temperatures, metallic iron (Fe0) and iron carbide (Fe3C) are the predominant phases well dispersed in the carbon porous structure. These reduced iron species, Fe3O4 and Fe0, are active for the reduction of different hazardous contaminants. Preliminary experiments showed very high activities for the reduction and removal of aqueous CrVI.

Ferro é um elemento versátil que forma várias fases com diferentes estados de oxidação e estruturas, tais como Feº, FeO, Fe3O4, γ-Fe2O3, α-Fe2O3 e FeOOH. Todas estas fases têm propriedades físico-químicas únicas que podem ser usadas para diferentes aplicações. Neste trabalho, descreve-se o uso de diferentes compostos de ferro, sintéticos e também naturais ou de rejeitos, em aplicações ambientais e tecnológicas. Duas áreas principais de pesquisa são descritas. A primeira é relacionada às estratégias para aumentar a reatividade de fases de ferro pela formação de compósitos Feº/Fe óxido e pela introdução de novos metais na estrutura de óxidos de ferro para promover novas reações superficiais. A segunda área de pesquisa é o uso das propriedades magnéticas de algumas fases de ferro para produzir materiais magnéticos versáteis com aplicações focadas em adsorção, catálise e emulsões.

Iron is a versatile element forming several phases with different oxidation states and structures, such as Feº, FeO, Fe3O4, γ-Fe2O3, α-Fe2O3 and FeOOH. All these phases have unique physicochemical properties which can be used for different applications. In this work, it is described the use of different iron compounds, synthetic and also from natural and waste sources, in environmental and technological applications. Two main research areas are described. The first one is related to strategies to increase the reactivity of Fe phases, mainly by the formation of Feº/iron oxide composites and by the introduction of new metals in the iron oxide structure to promote new surface reactions. The second area is the use of the magnetic properties of some iron phases to produce versatile magnetic materials with focus in adsorption, catalysis and emulsions.

As reações de meso-1,2-bis(fenilsulfinil)etano (meso-bpse) com Ph2SnCl2, de 2-fenil-1,3-ditiona trans-1-trans-dióxido (pdtd) com n-Bu2SnCl2 e de 1,2-cis-bis-(phenylsulfinyl)ethene (rac-,cis-cbpse) com Ph2SnCl2, na proporção molar 1:1, levaram à formação de [{Ph2SnCl2(meso-bpse)}n], [{n-Bu2SnCl2(pdtd)}2] e [{Ph2SnCl2(rac,cis-cbpse)}x] (x = 2 ou n), respectivamente. Na investigação das propriedades estruturais dos produtos foram empregadas as espectroscopias de absorção no infravermelho, Mössbauer e RMN de 119Sn, além de análise elementar e difratometria de raios X em monocristal. O estudo de [{Ph2SnCl2(meso-bpse)}n] por difratometria de raios X revelou a ocorrência de um encadeamento infinito no qual os átomos de tin(IV) apresentam uma geometria octaédrica distorcida com os átomos de Cl em posições cis e os grupos Ph em trans. A estrutura cristalina de [{n-Bu2SnCl2(pdtd)}2] revelou a presença de espécies diméricas centrossimétricas nas quais os átomos de tin(IV) possuem geometria octaédrica distorcida com dissulfóxidos em ponte ocupando posições cis e grupos n-butila ocupando posições trans. Os dados espectroscópicos indicaram que o produto contendo o ligante rac,cis-cbpse pode ser dimérico ou polimérico. O estudo por difratometria de raios X do sulfóxido rac-,cis-cbpse livre revelou que os cristais pertencem ao grupo espacial C2/c.

The reactions of meso-1,2-bis(phenylsulfinyl)ethane (meso-bpse) with Ph2SnCl2, 2-phenyl-1,3-dithiane trans-1-trans-3-dioxide (pdtd) with n-Bu2SnCl2 and 1,2-cis-bis-(phenylsulfinyl)ethene (rac-,cis-cbpse) with Ph2SnCl2, in 1:1 molar ratio, yielded [{Ph2SnCl2(meso-bpse)}n], [{n-Bu2SnCl2(pdtd)}2] and [{Ph2SnCl2(rac,cis-cbpse)}x] (x = 2 or n), respectively. All adducts were studied by IR, Mössbauer and 119Sn NMR spectroscopic methods, elemental analysis and single crystal X-ray diffractometry. The X-ray crystal structure of [{Ph2SnCl2(meso-bpse)}n] revealed the occurrence of infinite chains in which the tin(IV) atoms appear in a distorted octahedral geometry with Cl atoms in cis and Ph groups in trans positions. The X-ray crystal structure of [{n-Bu2SnCl2(pdtd)}2] revealed discrete centrosymmetric dimeric species in which the tin(IV) atoms possess a distorted octahedral geometry with bridging disulfoxides in cis and n-butyl moieties in trans positions. The spectroscopic data indicated that the adduct containing the rac,cis-cbpse ligand can be dimeric or polymeric. The X-ray structural analysis of the free rac-,cis-cbpse sulfoxide revealed that the crystals belong to the C2/c space group.