Márcio C. Pereira

δ-FeOOH: a superparamagnetic material for controlled heat release under AC magnetic field

Experimental evidences on its in vitro use reveal that δ-FeOOH is a material that release-controlled amount of heat if placed under an AC magnetic field. δ-FeOOH nanoparticles were prepared by precipitating Fe(OH)2 in alkaline solution followed by fast oxidation with H2O2. XRD and 57Fe Mössbauer spectroscopy data confirmed that δ-FeOOH is indeed the only iron-bearing compound in the produced sample. TEM images evidence that the averaged particle sizes for this δ-FeOOH sample is 23xa0nm. Magnetization measurements indicate that these δ-FeOOH particles behave superparamagnetically at 300xa0K; its saturation magnetization was found to be 13.2xa0emuxa0g−1; the coercivity and the remnant magnetization were zero at 300xa0K. The specific absorption rate values at 225xa0kHz were 2.1, 6.2, and 34.2xa0Wxa0g−1, under 38, 64, and 112xa0mT, respectively. The release rate of heat can be directly controlled by changing the mass of δ-FeOOH nanoparticles. In view of these findings, the so-prepared δ-FeOOH is a real alternative to be further tested as a material for medical practices in therapies involving magnetic hyperthermia as in clinical oncology.

Bismuth Vanadate Photoelectrodes with High Photovoltage as Photoanode and Photocathode in Photoelectrochemical Cells for Water Splitting

Using dual-photoelectrode photoelectrochemical (PEC) devices based on earth-abundant metal oxides for unbiased water splitting is an attractive means of producing green H2 fuel, but is challenging, owing to low photovoltages generated by PEC cells. This problem can be solved by coupling n-type BiVO4 with n-type Bi4 V2 O11 to create a virtual p/n junction due to the formation of a hole-inversion layer at the semiconductor interface. Thus, photoelectrodes with high photovoltage outputs were synthesized. The photoelectrodes exhibited features of p- and n-type semiconductors when illuminated under an applied bias, suggesting their use as photoanode and photocathode in a dual-photoelectrode PEC cell. This concept was proved by connecting a 1u2005molu2009% W-doped BiVO4 /Bi4 V2 O11 photoanode with an undoped BiVO4 /Bi4 V2 O11 photocathode, which produced a high photovoltage of 1.54u2005V, sufficient to drive stand-alone water splitting with 0.95u2009% efficiency.

Magnetic iron species highly dispersed over silica: use as catalysts for removal of pollutants in water

AbstractFe2O3-SiO2 composites were prepared by impregnation (sample FeIMP) or doping (sample FeDOP) in the structure of porous silica. The dye removal capacity of the materials was investigated through adsorption and oxidation studies of methylene blue and rhodamine B. N2 adsorption/desorption measurements on FeIMP and FeDOP resulted in specific areas of 27 and 235xa0m2xa0g−1, respectively. Mössbauer spectroscopy and XRD data detected hematite and maghemite as the iron phases in the samples FeIMP and FeDOP, respectively. Adsorption isotherms and kinetic studies of the dyes were better fitted in DKR model for FeDOP, where the process follows a pseudo-second order with the interparticle diffusion step being the rate-limiting step. On the other hand, FeIMP has better fit in the Langmuir model. Photocatalytic activity was observed in FeDOP under UV irradiation by the presence of reaction-hydroxylated intermediates for MB (m/zu2009=u2009301) and RhB (m/zu2009=u2009459). However, the photocatalytic activity was strongly influenced by the adsorption affinity between dye/catalyst. Photogenerated holes are the species responsible for the dye degradation when the adsorption is too strong, while hydroxyl radical action will be favored when the adsorption is not vigorous as detected by ESI-MS.n Graphical AbstractAction of photogenerated holes and free electrons into the photocatalytically mechanism of methylene blue degradation over a semiconductor

Purification of arsenic-contaminated water with K-jarosite filters

The high toxicity and potential arsenic accumulation in several environments have encouraged the development of technologies for its removal from contaminated waters. However, the arsenic released into aquatic environment comes mainly from extremely acidic mining effluents, making harder to find stable adsorbents to be used in these conditions. In this work, K-jarosite particles were synthesized as a stable adsorbent in acidic medium for eliminating arsenic from contaminated water. The adsorption capacities of K-jarosite for As3+, As5+, and monomethylarsonic acid were 9.45, 12.36, and 8.21xa0mgxa0g−1, respectively. Most arsenic in water was adsorbed within the first 10xa0min, suggesting the fast arsenic adsorption kinetics of K-jarosite particles. Because of that, a K-jarosite filter was constructed for purifying water at a constant flow. The K-jarosite filter was highly efficient to treat arsenic-contaminated water from a Brazilian river, reducing the concentration of arsenic in water to near zero. These data suggest the K-jarosite filter can be used as a low-cost technology for purifying arsenic-contaminated water in acidic medium.

Validation of a robust LLE-GC-MS method for determination of trihalomethanes in environmental samples

An analytical liquid-liquid extraction-gas chromatography-mass spectrometry (LLE-GC-MS) method was developed and validated for the determination of trihalomethanes (THMs) in environmental samples. The compounds studied were trichloromethane (TCM), bromodichloromethane (BDCM), dibromochloromethane (DBCM), and tribromomethane (TBM). The calibration curves for the THMs showed high linearity in the range of 1–1000xa0μgxa0L−1. Studies of intra-day and inter-day precision, limit of detection (LOD), limit of quantification (LOQ), accuracy, and recovery were performed with low (10xa0μgxa0L−1), medium (40xa0μgxa0L−1), and high (200xa0μgxa0L−1) concentrations of THMs. The intra-day and inter-day precision RSD varied in the ranges of 0.17–6.95% and 0.26–15.70%, respectively. No statistical differences were observed between the analysis of the concentration of certified reference materials (CRM 4M8140-U) and the values reported by CRM, indicating the good accuracy of the proposed method. The recovery was 88.75–119.21%. The LOD and LOQ were smaller than 0.13 and 0.40xa0μgxa0L−1. Compared with reported LLE-GC-MS methods, the validated method had similar LOD and enhanced LOQ, precision, accuracy, and recovery. Also, the method is robust, selective to THMs, and the total time for the extraction and GC separation of THMs is about 18xa0min. The method was useful for detecting and quantifying low concentrations of TCM (40–80xa0μgxa0L−1) formed by water chlorination in the presence of Microcystis aeruginosa cyanobacteria, thus demonstrating its applicability for monitoring THMs in real samples.

Electrocatalytic performance of different cobalt molybdate structures for water oxidation in alkaline media

Cobalt molybdates with different crystalline structures, i.e., α, β, and hydrated (H)-CoMoO4, were synthesized, and their electrocatalytic activities were thoroughly examined for catalyzing the oxygen evolution reaction (OER) in alkaline media. The material characteristics were associated with the electrocatalytic properties by evaluating the CoMoO4 crystal structures (XRD and Raman), morphologies (TEM), and electrochemical features (electrochemically active surface area, roughness factor, electrochemical impedance, Tafel analysis, and controlled-current electrolysis). These combined findings revealed that the electrocatalytic performance is greatly influenced by the crystalline structures of CoMoO4, following the order α-CoMoO4 > H-CoMoO4 > β-CoMoO4. The H-CoMoO4 catalysts crystallized in the triclinic space group, P (#2), with Z = 4. On the other hand, the α- and β-CoMoO4 catalysts exhibited a monoclinic structure, C2/m (#12), with Z = 8. In the OER experiments, α-CoMoO4 showed an overpotential of 0.43 ± 0.05 V compared to the 0.51 ± 0.05 V and 0.56 ± 0.04 V exhibited by the H-CoMoO4 and β-CoMoO4 catalysts, respectively, to achieve 10 mA cm−2. All CoMoO4 structures displayed stability for at least 6 h at a controlled current density of 10 mA cm−2. Finally, computational simulations indicate that the coexistence of Co and Mo ions in edge-shared octahedral sites of α-CoMoO4 may favor the interaction between the O atom of the water molecule and the metal adsorption sites due to its surface being electronically less dense than β- and H-CoMoO4 surfaces, thus resulting in its higher performance for OER.