Formation of TiO2 photoanodes by simultaneous electrophoretic deposition of anatase and rutile particles for photoassisted electrolytic copper ions removal

The influence of Anatasa/Rutile ratio on TiO2 films, grown by electrophoretic deposition was studied in the photoassisted electrolytic copper ions removal from cyanide solutions. The proper dispersant dosage allowing the simultaneous electrophoretic deposition of Anatase and Rutile was chosen based on electrokinetic measurements; evidenced by the XRD spectra of the formed films. The evaluation of films photoassisted electrolytic copper ion removal showeds that it is possible to enhance the activity of Anatase films by adding some Rutile exploiting the synergetic interaction between these two materials, achieve by its proper deposition.

Nanocompósitos semicondutores ZnO/TiO2: testes fotocatalíticos

Titanium dioxide is an efficient photocatalist, being possible to improve its efficiency with better charge separation which occurs when it is coupled with other semiconductors. Nanometric particles of ZnO were used to impregnate TiO2 P25 in order to optimize its photocatalytic properties. ZnO/TiO2 composites were obtained at different proportions and were characterized by X-ray diffraction (XRD), micro-Raman and diffuse reflectance spectroscopies, measurement of surface area (BET) and scanning electron microscopy (SEM). Raman spectroscopy data revealed a change on the TiO2 surface due the presence of ZnO which was observed by an enlargement of TiO2 peaks and a change on the relation rate between anatase and rutile phases of the composites. The photodegradation of azo-dye Drimaren red revealed better efficiency for ZnO/TiO2 3% nanocomposite and for ZnO pure.

Highlands of the upper Jequitinhonha valley, Brazil: II - mineralogy, micromorphology, and landscape evolution¹

Palm swanp formations, the so-called veredas, typically occur in the Brazilian biome known as "Cerrado" (savanna-like vegetation), especially on flattened areas or tablelands (chapadas). The aim of this study was to characterize the mineralogy and micromorphology of soil materials from a representative toposequence of the watershed of the vereda Lagoa do Leandro, located in Minas Novas, state of Minas Gerais, Brazil, on plains in the region of the upper Jequitinhonha valley, emphasizing essential aspects of their genesis and landscape evolution. The toposequence is underlain by rocks of the Macaúbas group and covered with detrital and metamorphic rocks (schists of Proterozoic diamictites). The soil profiles were first pedologically described; samples of the disturbed and undisturbed soils were collected from all horizons for further micromorphological and mineralogical analyses. The mineralogical analysis was mainly based on powder X ray diffractometry (XRD) and micromorphological descriptions of thin sections under a petrographic microscope. The soils from the bottom to the top of this toposequence were classified as: Typic Albaquult (GXbd), Xanthic Haplustox, gray color, here called "Gray Haplustox" ("LAC"), Xanthic Haplustox (LA) and Typic Haplustox (LVA). The clay mineralogy of all soils was found to be dominated by kaolinite. In soil of LA and LVA, the occurrence of goethite, gibbsite, and anatase was evidenced; "LAC" also contained anatase and the GXbd, illite, anatase, and traces of vermiculite. The micromorphological analyses of the LVA, LA and "LAC" soils showed the prevalence of a microaggregate-like or granular microstructure, and aggregate porosity has a stacked/packed structure, which is typical of Oxisols. A massive structure was observed in GXbd material, with the presence of illuviation cutans of clay minerals and iron compounds. Paleogleissolos, which are strongly weathered, due to the action of the excavating fauna , and resulted in the present "LAC". The GXbd at the base of the vereda preserved the physical, mineralogical and micromorphological properties that are typical of a pedogenesis with a strong influence of long dry periods.

INFLUÊNCIA DO TRATAMENTO TÉRMICO NO NANOCOMPÓSITO FOTOCATALISADOR ZnO/TiO2

ZnO/TiO2 nanocomposites were prepared by impregnating zinc acetate dihydrate on the surface of titanium dioxide P25, followed by thermal treatment at 350, 600, 750, and 900 °C, in order to investigate the TiO2 phase and titanate formation and the role of the latter in the photocatalytic activity of the nanocomposite. In the nanocomposites, the anatase-to-rutile transition is favored due to the presence of Zn2+, and the conversion is nearly complete at 750 °C. The presence of zinc metatitanate in the sample heated at 600 °C had no significant effect on the nanocomposite photocatalytic activity.

The ceramic artifacts in archaeological black earth (terra preta) from lower Amazon region, Brazil: mineralogy

Several archaeological black earth (ABE) sites occur in the Amazon region. They contain fragments of ceramic artifacts, which are very important for the archaeological purpose. In order to improve the archaeological study in the region we carried out a detailed mineralogical and chemical study of the fragments of ceramic artifacts found in the two ABE sites of Cachoeira-Porteira, in the Lower Amazon Region. Their ceramics comprise the following tempers: cauixi, cariapé, sand, sand +feldspars, crushed ceramic and so on and are composed of quartz, clay equivalent material (mainly burned kaolinite), feldspars, hematite, goethite, maghemite, phosphates, anatase, and minerals of Mn and Ba. Cauixi and cariapé, siliceous organic compounds, were found too. The mineralogical composition and the morphology of their grains indicate a saprolite (clayey material rich on quartz) derived from fine-grained felsic igneous rocks or sedimentary rocks as source material for ceramic artifacts, where silica-rich components such cauixi, cariapé and/or sand (feldspar and rock fragments) were intentionally added to them. The high content of (Al,Fe)-phosphates, amorphous to low crystalline, must be product of the contact between the clayey matrix of pottery wall and the hot aqueous solution formed during the daily cooking of animal foods (main source of phosphor). The phosphate crystallization took place during the discharge of the potteries put together with waste of organic material from animal and vegetal origin, and leaving to the formation of the ABE-soil profile.

Análise por difração de raios x de filmes de óxidos cerâmicos compostos por IrO2/TiO2/CeO2

Independent of the sample form (powder or film), XRD analysis of Ir0,3Ti(0,7-x)Ce xO2, (nominal) mixtures, for x=0, shows the formation of a solid solution phase between IrO2 and TiO2, as well as the rutile phases of IrO2 and TiO2. The presence of the anatase phase of TiO2 is also confirmed. The introduction of 30 mol% CeO2 in the mixture reveals the presence of the CeO2 and Ce2O3 phases, besides the already mentioned ones, in the powder. In the film form, however, an amorphous phase is identified. When all of the TiO2 is substituded by CeO2, for both sample forms, the only phases found are IrO2, CeO2 and Ce2O3. This result suggests cerium oxides are not capable of forming solid solutions with either IrO2 or (Ir,Ti)O2 acting solely as a dispersant matrix for these phases. These results are consistent with the much higher electrochemically active surface area when CeO2 is introduced in the binary Ti/Ir0,3Ti0,7O2 mixture. It was possible to establish a relationship between the electrochemical stability of the supported films and their crystalline structure. The unexpected presence of TiO2 and Ti2O3 in the Ti/Ir0,3Ce0,7O2 (film sample) is attributed to oxidation of the Ti support during the calcination step.

Caracterização textural e estrutural de V2O5/TiO2 obtidos via sol-gel: comparação entre secagem convencional e supercrítica

This work describes a modified sol-gel method for the preparation of V2O5/TiO2 catalysts. The samples have been characterized by N2 adsorption at 77K, x-ray diffractometry (XRD) and Fourier Transform Infrared (FT-IR). The surface area increases with the vanadia loading from 24 m² g-1, for pure TiO2, to 87 m² g-1 for 9wt.% of V2O5. The rutile form is predominant for pure TiO2 but became enriched with anatase phase when vanadia loading is increased. No crystalline V2O5 phase was observed in the catalysts diffractograms. Two species of surface vanadium observed by FT-IR spectroscopy a monomeric vanadyl and polymeric vanadates, the vanadyl/vanadate ratio remains practically constant.

Oxochloroalkoxide of the Cerium (IV) and Titanium (IV) as oxides precursor

The Cerium (IV) and Titanium (IV) oxides mixture (CeO2-3TiO2) was prepared by thermal treatment of the oxochloroisopropoxide of Cerium (IV) and Titanium (IV). The chemical route utilizing the Cerium (III) chloride alcoholic complex and Titanium (IV) isopropoxide is presented. The compound Ce5Ti15Cl16O30 (iOPr)4(OH-Et)15 was characterized by elemental analysis, FTIR and TG/DTG. The X-ray diffraction patterns of the oxides resulting from the thermal decomposition of the precursor at 1000 °C for 36 h indicated the formation of cubic cerianite (a = 5.417Å) and tetragonal rutile (a = 4.592Å) and (c = 2.962 Å), with apparent crystallite sizes around 38 and 55nm, respectively.

A new experimental procedure to obtain titania powders as anatase phase by a sol-gel process

Titania powders were synthesized by a sol-gel process using titanium tetrabutoxide as precursor. The syntheses were performed in water or in solutions of dimethylformamide (dmf) or dimethylsulfoxide (dmso). It is demonstrated, by X-ray diffraction patterns of the synthesized powders, that the samples obtained in dmf or dmso solutions are crystalline (anatase phase) with some minor amount of brookite phase, whereas the sample synthesized in water is amorphous. The anatase phase can be obtained independently of any previous or further treatment of the synthesized powder, such as hydrothermal or heat treatment, providing a new, simple, quick and inexpensive route to synthesize anatase powders. From the peak broadening of the anatase (101) diffraction, the crystallite sizes were calculated as 6 nm.

Propriedades estruturais e eletrônicas de nanofilmes de TiO2 anatase: cálculos B3LYP-D* em sistemas periódicos bidimensionais

Structural and electronic properties of titanium dioxide (TiO2) thin films, in anatase phase, were investigated using periodic 2D calculations at density functional theory (DFT) level with B3LYP hybrid functional. The Grimme dispersion correction (DFT/B3LYP-D*) was included to better reproduce structural features. The electronic properties were discussed based on the band gap energy, and proved dependent on surface termination. Surface energies ranged from 0.80 to 2.07 J/m², with the stability orders: (101) > (100) > (112) > (110) ~ (103) > (001) >> (111), and crystal shape by Wulff construction in accordance with experimental data.

Synthesis and characterization of Fe(III)-doped ceramic membranes of titanium dioxide and its application in photoelectrocatalysis of a textile dye

Pure and Fe(III)-doped TiO2 suspensions were prepared by the sol gel method with the use of titanium isopropoxide (Ti(OPri)4) as precursor material. The properties of doped materials were compared to TiO2 properties based on the characterization by thermal analysis (TG-DTA and DSC), X-ray powder diffractometry and spectroscopy measurements (FTIR). Both undoped and doped TiO2 suspensions were used to coat metallic substrate as a mean to make thin-film electrodes. Thermal treatment of the precursors at 400ºC for 2 h in air resulted in the formation of nanocrystalline anatase TiO2. The thin-film electrodes were tested with respect to their photocatalytic performance for degradation of a textile dye in aqueous solution. The plain TiO2 remains as the best catalyst at the conditions used in this report.