Novel Ni-Mg-Al-Ca catalyst for enhanced hydrogen production for the pyrolysis-gasification of a biomass/plastic mixture

A Ni-Mg-Al-Ca catalyst was prepared by a co-precipitation method for hydrogen production from polymeric materials. The prepared catalyst was designed for both the steam cracking of hydrocarbons and for the in situ absorption of CO2 via enhancement of the water-gas shift reaction. The influence of Ca content in the catalyst and catalyst calcination temperature in relation to the pyrolysis-gasification of a wood sawdust/polypropylene mixture was investigated. The highest hydrogen yield of 39.6molH2/g Ni with H2/CO ratio of 1.90 was obtained in the presence of the Ca containing catalyst of molar ratio Ni:Mg:Al:Ca=1:1:1:4, calcined at 500°C. In addition, thermogravimetric and morphology analyses of the reacted catalysts revealed that Ca introduction into the Ni-Mg-Al catalyst prevented the deposition of filamentous carbon on the catalyst surface. Furthermore, all metals were well dispersed in the catalyst after the pyrolysis-gasification process with 20-30nm of NiO sized particles observed after the gasification without significant aggregation.

Investigação da rota biohidrometalúrgica com Acidithiobacillus ferrooxidans/thiooxidans para recuperação do cobalto de baterias de íons lítio descartadas

The recycling of metals from secondary sources can be advantageous. Among the metals of interest, we have cobalt, a metal used for various purposes. As regards the secondary sources of cobalt, the lithium-ion batteries can be considered, since they contain cobalt oxide in their composition (LiCoO2). This way, the objective of this work was to use the microorganism strains (Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans) to bioleach the LiCoO2 extracted from discarded lithium ion batteries with emphasis on the recovery of cobalt for synthesis of new materials of interest. The lineage growth occurred in T&K medium and the growth investigation was made by observing the media, by platelet growth and microscope analysis. Then, the inoculum was standardized on 5 x 106 cells mL-1 and used in bioleaching tests. The bioleaching was investigated: the microorganism nature: separate strains and A. ferrooxidans and A. thiooxidans consortium, bioleaching time (0 to 40 days), inoculum proportion (5 to 50% v/v), energy source (iron and sulfur) and residue concentration (1063 to 8500 mg L-1 of cobalt). The cobalt concentration in the media was found by atomic absorption spectrometry and the medium pH was monitored during the bioleaching. The results show that the amount of bioleached cobalt increases with time and the iron concentration. The bioleaching with A. thiooxidans was not influenced by the addition of sulfur. The use of the two lineages together did not improve the bioleaching rates. Among the lineages, the A. thiooxidans presented better results and was able to bioleach cobalt amounts above 50% in most of the experiments. A. thiooxidans presented lower bioleaching rates, with a maximum of 50% after 24 days of experiment. After reprocessing by bioleaching, the cobalt in solution was used for synthesis of new materials: such as LiCoO2 cathode and as adsorbent pesticide double lamellar hydroxide (HDL Co-Al-Cl) by the Pechini and co-precipitation methods. The reprocessed LiCoO2 presented a unique stoichiometric phase relative to the HT-LiCoO2 structure similar to the JCPDS 44-0145, presenting electrochemical activity when tested as a cathode material. The double lamellar hydroxide Co-Al-Cl was tested as pesticide adsorbent, being possible to adsorb around 100% of the pesticide. The bioleaching was efficient in the recovery of cobalt present in lithium-ion batteries and microorganisms presented high tolerance to the residue, being able to bioleach even at higher LiCoO2 concentrations. The cobalt bioleaching medium did not impair the synthesis phases and the obtained materials presented structure and activity similar to the sintered materials from the reagents containing cobalt.

Elettrodeposizione di catalizzatori a base di Rh su schiume e fibre metalliche di FeCrAlloy per la produzione di syngas

The preparation of structured catalysts active in the catalytic partial oxidation of methane to syngas, was performed by electrosynthesis of hydroxides on FeCrAlloy foams and fibers. Rh/Mg/Al hydrotalcite-type compounds were prepared by co-precipitation of metallic cations on the support and successive calcination. Electrochemical reactions have been studied during the electrodeposition by linear sweep voltammetry. The experiments were performed at supports immersed in KNO3, KCl, Mg2+ and Al3+ aqueous solutions, starting by different precursors (nitrate and chlorides salts) and modifying the Mg/A ratio. Rh/Mg/Al hydrotalcite-type compounds were deposited on metal foams by applying a -1.2V vs SCE potential for 2000s with a nitrate solution of 0.06M total metal concentration. Firstly it was studied the effect of Mg on the coating propierties, modifying the Rh/Mg/Al atomic ratio (5/70/25, 5/50/45, 5/25/70 e 5/0/95). Then the effect of the amount of Rh was later investigated in the sample with the largest Mg content (Rh/Mg/Al = 5/70/25 and 2/70/28).The results showed that magnesium allowed obtaining the most homogeneous and well adherent coatings, wherein rhodium was well dispersed. The sample with the Rh/Mg /Al ratio equal to5/70/25 showed the best catalytic performances. Decreasing the Rh content, the properties of the coating were not modified, but the catalytic activity was lower, due to a not enough number of active sites to convert the methane. The work on metal fibers focused on the effect of precursor concentration, keeping constant composition, potential and synthesis time at the values of Rh/Mg/Al =5/70/25, -1.2V vs SCE and 1000s. However fibers geometry did not allow to obtain a high quality coating, even if results were quite promising.

Síntese e caracterização de nanocompósitos de carbon-dot e lantanídeos

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, 2015.

Platinum–rhodium–tin/carbon electrocatalysts for ethanol oxidation in acid media: effect of the precursor addition order and the amount of tin

Carbon-supported Pt x –Rh y –Sn z catalysts (x:y:z = 3:1:4, 6:2:4, 9:3:4) are prepared by Pt, Rh, and Sn precursors reduction in different addition order. The materials are characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy techniques and are evaluated for the electrooxidation of ethanol in acidic media by cyclic voltammetry, chronoamperometry, and anode potentiostatic polarization. The influence of both the order in which the precursors are added and the composition of metals in the catalysts on the electrocatalytic activity and physico-chemical characteristics of Pt x –Rh y –Sn z /C catalysts is evaluated. Oxidized Rh species prevail on the surface of catalysts synthesized by simultaneous co-precipitation, thus demonstrating the influence of synthesis method on the oxidation state of catalysts. Furthermore, high amounts of Sn in composites synthesized by co-precipitation result in very active catalysts at low potentials (bifunctional effect), while medium Sn load is needed for sequentially deposited catalysts when the electronic effect is most important (high potentials), since more exposed Pt and Rh sites are needed on the catalyst surface to alcohol oxidation. The Pt3–Rh1–Sn4/C catalyst prepared by co-precipitation is the most active at potentials lower than 0.55 V (related to bifunctional effect), while the Pt6–Rh2–Sn4/C catalyst, prepared by sequential precipitation (first Rh and, after drying, Pt + Sn), is the most active above 0.55 V.

Filmes formados pelo copolímero SEBS e nanopartículas de óxidos de ferro : preparação e caracterização

Dissertação (mestrado)—Universidade de Brasília, Instituto de Física, Programa de Pós-Graduação em Física, 2016.

Impact of biohybrid magnetite nanoparticles and moroccan propolis on adherence of methicillin resistant strains of staphylococcus aureus

Biofilm bacteria are more resistant to antibiotics than planktonic cells. Propolis possesses antimicrobial activity. Generally, nanoparticles containing heavy metals possess antimicrobial and antibiofilm properties. In this study, the ability of adherence of Methicillin Resistant Strains of Staphylococcus aureus (MRSA) to catheters treated with magnetite nanoparticles (MNPs), produced by three methods and functionalized with oleic acid and a hydro-alcoholic extract of propolis from Morocco, was evaluated. The chemical composition of propolis was established by gas chromatography mass spectrometry (GC-MS), and the fabricated nanostructures characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Mossbauer spectroscopy and Fourrier transform infrared spectroscopy (FTIR). The capacity for impairing biofilm formation was dependent on the strain, as well as on the mode of production of MNPs. The co-precipitation method of MNPs fabrication using Fe(3+) and Na₂SO₃ solution and functionalized with oleic acid and propolis was the most effective in the impairment of adherence of all MRSA strains to catheters (p < 0.001). The adherence of the strain MRSA16 was also significantly lower (p < 0.001) when the catheters were treated with the hybrid MNPs with oleic acid produced by a hydrothermal method. The anti-MRSA observed can be attributed to the presence of benzyl caffeate, pinocembrin, galangin, and isocupressic acid in propolis extract, along with MNPs. However, for MRSA16, the impairment of its adherence on catheters may only be attributed to the hybrid MNPs with oleic acid, since very small amount, if any at all of propolis compounds were added to the MNPs.

Newly developed electrosynthesis of Layered Double Hydroxides: application to sensing, energy storage and conversion

Layered Double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, it does not usually allow for a fine control of the M(II)/M(III) ratio in the synthesized material and it is not suitable for large anions intercalation. Therefore, in this work a novel protocol has been proposed with the aim to overcome all these constraints using a method based on potentiodynamic synthesis. LDHs of controlled composition were prepared using different molar ratios of the trivalent to bivalent cations in the electrolytic solution ranging from 1:1 to 1:4. Moreover, we were able to produce electrochemically LDHs intercalated with carbon nanomaterials for the first time. A one-step procedure which contemporaneously allows for the Ni/Al-LDH synthesis, the reduction of graphene oxide (GO) and its intercalation inside the structure has been developed. The synthesised materials have been applied in several fields of interest. First of all, LDHs with a ratio 3:1 were exploited, and displayed good performances as catalysts for 5-(hydroxymethyl)furfural electro-oxidation, thus suggesting to carry out further investigation for applications in the field of industrial catalysis. The same materials, but with different metals ratios, were tested as catalysts for Oxygen Evolution Reaction, obtaining results comparable to LDHs synthesised by the classical co-precipitation method and also a better activity with respect to LDHs obtained by the potentiostatic approach. The composite material based on LDH and reduced graphene oxide was employed to fabricate a cathode of a hybrid supercapacitor coupled with an activated carbon anode. We can thus conclude that, to date, the potentiodynamic method has the greatest potential for the rapid synthesis of reproducible films of Co and Ni-based LDHs with controlled composition.

Nuovi processi catalitici per la produzione di syngas

The study of the combined Steam/Dry Reforming (S/DR) process for the production of syngas (CO + H2) from clean biogas was carried out using Ni/Ir bimetallic catalysts on Mg and Al mixed-oxides, obtained by calcination of hydrotalcite-type precursors (Ht) prepared by co-precipitation. The presence of small amounts of Ir promoted the catalytic activity and limited the deactivation phenomena through the formation of a bimetallic alloy, which does the catalyst very active even at lowest temperature and in lack of steam. By integrating a High Temperature–WGS unit (HTS) after the S/DR reactor it was possible to increase the H2 yield of the process. The performance of the Zn/Al/Cu-based catalyst was improved using a templating agent during the synthesis of the catalyst, which increased the catalyst’s structural properties and activity especially at lowest temperatures and at highest contact times. Finally, starting from the laboratory data, it was possible to simulate the S/DR process on industrial scale, evaluating its scalability and environmental impact. The results showed that, using the S/DR technology instead of the current processes, it was possible to reduce the energy costs and the atmospheric emissions of the plant.

Synthesis and Characterization of Double Metal Hexacyanoferrates

Manganese Hexacyanoferrate (MnHCF) and nickel doped manganese hexacyanoferrate were synthesized by simple co-precipitation method. The water content and chemical formula was obtained by TGA and MP-AES measurements, functional groups by FT-IR analysis, the crystal structure by PXRD and a local geometry by XAS. Elemental species of cycled samples were further investigated by TXM and 2D XRF. Electrochemical tests were performed in the glass cell. With addition of nickel, vacancies and water content increased in the sample. Crystal structure changed from monoclinic to cubic. Ni disturbed the local structure of Mn, site, however, almost no change was observed in Fe site. After charge/discharge cycling of MnHCF intercalation was already found in the peripheries of charged species after 20 cycle in 2D XRF analysis and randomly distributed intercalated regions after 50 cycles in TXM analysis. Cyclic voltammetry showed that peak-to-peak separation is increasing in case of the addition of Ni to MnHCF.

Synthesis and characterization of defective PBAs electrode material

Sodium manganese hexacyanoferrate (NaMnHCF) and its derivatives have been synthesized by simple co-precipitation method with addition of the citric and ascorbic acids respectively. The correspondent crystal structure, water content, chemical formula and a deep structural investigation of prepared samples have been performed by means of the combination of the laboratory and synchrotron techniques (PXRD, FT-IR, TGA, MP-AES and XAS). Electrochemical tests have been done using three-electrode system in sodium nitrate solution at different concentration. From cyclic voltammetry curves, Fe3+/2+ redox peak has been observed, whereas Mn3+/2+ peak was not always evident. Structural stability of the cycled samples has then been tested using 2D XRF imaging and Transmission X-ray microscopy (TXM) techniques. The intercalation of NaMnHCF after 20 cycles has been found by micro-XANES analysis of the highlighted spots which have been found in the XRF images. TXM has also confirmed the appearance of the intercalated particles after 50 cycles comparing the spectra between charged and discharged materials at three different edges (Mn, Fe and N). However, by comparison with lithium samples, it seems obvious that sodium samples are more homogeneous and intercalation is at the very beginning indicating the relative structural stability of sodium manganese hexacyanoferrate electrode material.

Synthesis and characterization of prussian blue analogue materials for post-Li ion batteries

Energy issues have always been a subject of concern to people. During the past 30 years, rechargeable Li-ion batteries (LIBs) have been widely used in portable electronic devices and power tools because of their high energy density and efficiency among practical secondary batteries. While the unevenly distribution of Lithium sources and the increasing cost of lithium-raw material can not satisfy the requirement for further cost reduction, especially for the grid-scale energy storage. Post-lithium ion batteries as promising replacement for LIBs have attracted wide attention, owing to their high abundant resources and adequate insertion potential. Similar with Li-ion batteries, finding a suitable electrode material is the key for the research and application of the post-Li ion batteries. In our project, we focus our study on Prussian blue analogues (PBAs), with formula AxM[M’(CN)6]1-y□y•zH2O (0≤x≤2, 0co-precipitation method, and their electrochemical properties were tested in both aqueous Na+, K+, Mg2+, Zn2+ and organic Li+, Na+ electrolytes. Various X-ray techniques were employed to study their electronic and structural properties of electrodes and electrochemical reaction mechanism during cycling.

Optimization of aqueous Zn-ion batteries

MnHCF was synthesized by simple co-precipitation method. In this work we investigate the electrochemical behavior of manganese hexacyanoferrate in zinc sulfate (ZnSO4), ZnSO4+MnSO4 and zinc triflate (Zn(OTF)2) aqueous electrolytes. Electrochemical tests were performed by both El-cell which is designed for reflection investigation and coin cell. In cyclic voltammetry curves, we observed redox peaks of both Fe3+/2+ and Mn3+/2+ pairs. The results based on current shows that the capacity of battery is controlled by diffusion process in aqueous electrolyte system. MnHCF undergoes severe dissolution and zinc displacement during cycling. Compared to ZnSO4, anions of Zn (OTF)2 electrolyte are strongly adsorbed on the electrolyte surface, in turn hindering the water oxidation reaction and reducing the decomposition of MnHCF. The MnHCF/Zn battery using 3M Zn (OTF)2 delivers a specific capacity of 41 mAhg-1 at 50 mAg-1 while by using 3M ZnSO4+1M MnSO4 the specific capacity reaches to 400 mAhg-1 for the pure sample and around 250 mAhg-1 for the MnHCF+A. Our results suggest that the anions in the aqueous electrolyte are of great importance to optimize the electrochemical performance of metal hexacyanoferrates. The pre-addition of MnSO4 into ZnSO4 solution is capable of easing the Mn2+ dissolution from the cathode.

Co-variation of temperature and precipitation in CMIP5 models and satellite observations

Current variability of precipitation (P) and its response to surface temperature (T) are analysed using coupled(CMIP5) and atmosphere-only (AMIP5) climate model simulations and compared with observational estimates. There is striking agreement between Global Precipitation Climatology Project (GPCP) observed and AMIP5 simulated P anomalies over land both globally and in the tropics suggesting that prescribed sea surface temperature and realistic radiative forcings are sufficient for simulating the interannual variability in continental P. Differences between the observed and simulated P variability over the ocean, originate primarily from the wet tropical regions, in particular the western Pacific, but are reduced slightly after 1995. All datasets show positive responses of P to T globally of around 2 %/K for simulations and 3-4 %/K in GPCP observations but model responses over the tropical oceans are around 3 times smaller than GPCP over the period 1988-2005. The observed anticorrelation between land and ocean P, linked with El Niño Southern Oscillation, is captured by the simulations. All data sets over the tropical ocean show a tendency for wet regions to become wetter and dry regions drier with warming. Over the wet region (75% precipitation percentile), the precipitation response is ~13-15%/K for GPCP and ~5%/K for models while trends in P are 2.4%/decade for GPCP, 0.6% /decade for CMIP5 and 0.9%/decade for AMIP5 suggesting that models are underestimating the precipitation responses or a deficiency exists in the satellite datasets.

Combining Satellite And Gauge Precipitation Data With Co-Kriging Method For Jakarta Region

Jakarta is vulnerable to flooding mainly caused by prolonged and heavy rainfall and thus a robust hydrological modeling is called for. A good quality of spatial precipitation data is therefore desired so that a good hydrological model could be achieved. Two types of rainfall sources are available: satellite and gauge station observations. At-site rainfall is considered to be a reliable and accurate source of rainfall. However, the limited number of stations makes the spatial interpolation not very much appealing. On the other hand, the gridded rainfall nowadays has high spatial resolution and improved accuracy, but still, relatively less accurate than its counterpart. To achieve a better precipitation data set, the study proposes cokriging method, a blending algorithm, to yield the blended satellite-gauge gridded rainfall at approximately 10-km resolution. The Global Satellite Mapping of Precipitation (GSMaP, 0.1⁰×0.1⁰) and daily rainfall observations from gauge stations are used. The blended product is compared with satellite data by cross-validation method. The newly-yield blended product is then utilized to re-calibrate the hydrological model. Several scenarios are simulated by the hydrological models calibrated by gauge observations alone and blended product. The performance of two calibrated hydrological models is then assessed and compared based on simulated and observed runoff.