Katalizatory złotowo-miedziowe na nośnikach cerowych, cyrkonowych i cerowo-cyrkonowych – preparatyka, charakterystyka i zastosowanie w procesach utleniania

Wydział Chemii

A comparative study of N2O conversion to N-2 over Co/AC and Cu/AC catalysts

Catalytic conversion of N2O to N-2 over Cu- and Co-impregnated activated carbon catalysts (Cu/AC and Co/AC) was investigated. Catalytic activity measurements were carried out in a fixed-bed flow reactor at atmospheric pressure. The catalysts were characterized by N-2 adsorption, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). This study aimed to provide insights into the following aspects: the metal dispersion, changes in pore structure, influence of catalyst loading on reaction, and reaction mechanism. Increasing loading of Co or Cu led to decreasing dispersion, but 20 wt % loading was an upper limit for optimal activities in both cases, with too high loading causing sintering of metal. Co exhibited a relatively better dispersion than Cu. Impregnation of metal led to a large decrease in surface area and pore volume, especially for 30 wt % of loading. 20 wt % of loading has proved to be the optimum for both Cu and Co, which shows the highest activity. Both N2O-Co/AC and -Cu/AC reactions are based upon a redox mechanism, but the former is limited by the oxygen transfer from catalysts to carbon, while N2O chemisorption on the surface of Cu catalyst controls the latter. The removal of oxygen from cobalt promotes the activity of Co/AC, but it is beneficial for Cu/AC to keep plenty of oxygen to maintain the intermediate oxidation of copper-Cu1+. The different nature of the two catalysts and their catalytic reaction mechanisms are closely related to their different electronegativities.

In-situ XPS study on the reducibility of Pd-promoted Cu/CeO2 catalysts for the oxygen-assisted water-gas-shift reaction

Cu/CeO2, Pd/CeO2, and CuPd/CeO2 catalysts were prepared and their reduction followed by in-situ XPS in order to explore promoter and support interactions in a bimetallic CuPd/CeO2 catalyst effective for the oxygen-assisted water-gas-shift (OWGS) reaction. Mutual interactions between Cu, Pd, and CeO2 components all affect the reduction process. Addition of only 1 wt% Pd to 30 wt% Cu/CeO2 greatly enhances the reducibility of both dispersed CuO and ceria support. In-vacuo reduction (inside XPS chamber) up to 400 °C results in a continuous growth of metallic copper and Ce3+ surface species, although higher temperatures results in support reoxidation. Supported copper in turn destabilizes metallic palladium metal with respect to PdO, this mutual perturbation indicating a strong intimate interaction between the Cu–Pd components. Despite its lower intrinsic reactivity towards OWGS, palladium addition at only 1 wt% loading significantly improved CO conversion in OWGS reaction over a monometallic 30 wt% Cu/CeO2 catalysts, possibly by helping to maintain Cu in a reduced state during reaction.

Electronic And Structural Study Of Pt-modified Au Vicinal Surfaces: A Model System For Pt-au Catalysts.

Two single crystalline surfaces of Au vicinal to the (111) plane were modified with Pt and studied using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) in ultra-high vacuum environment. The vicinal surfaces studied are Au(332) and Au(887) and different Pt coverage (θPt) were deposited on each surface. From STM images we determine that Pt deposits on both surfaces as nanoislands with heights ranging from 1 ML to 3 ML depending on θPt. On both surfaces the early growth of Pt ad-islands occurs at the lower part of the step edge, with Pt ad-atoms being incorporated into the steps in some cases. XPS results indicate that partial alloying of Pt occurs at the interface at room temperature and at all coverage, as suggested by the negative chemical shift of Pt 4f core line, indicating an upward shift of the d-band center of the alloyed Pt. Also, the existence of a segregated Pt phase especially at higher coverage is detected by XPS. Sample annealing indicates that the temperature rise promotes a further incorporation of Pt atoms into the Au substrate as supported by STM and XPS results. Additionally, the catalytic activity of different PtAu systems reported in the literature for some electrochemical reactions is discussed considering our findings.

Geological setting of the Guelb Moghrein Fe oxide-Cu-Au-Co mineralization, Akjoujt area, Mauritania

The Guelb Moghrein Fe oxide-Cu-Au-Co deposit is located at the western boundary of the West African craton in NW Mauritania. The wall rocks to the mineralization represent a meta-volcanosedimentary succession typical of Archaean greenstone belts. Two types of meta-volcanic rocks are distinguished: (1) volcanoclastic rocks of rhyodacite-dacite composition (Sainte Barbe volcanic unit), which form the stratigraphic base; (2) tholeiitic andesites-basalts (Akjoujt meta-basalt unit). The trace element signature of both types is characteristic of a volcanic arc setting. A small meta-pelitic division belongs to the Sainte Barbe volcanic unit. A meta-carbonate body, which contains the mineralization, forms a tectonic lens in the Akjoujt meta-basalt unit. It can be defined by the high X(mg) (=36) of Fe-Mg carbonate, the REE pattern and the delta(13)C values of -18 to -17 parts per thousand as a marine precipitate similar to Archaean banded iron formation (BIF). Additionally, small slices of Fe-Mg clinoamphibole-chlorite schist in the meta-carbonate show characteristics of marine shale. This assemblage, therefore, does not represent an alteration product, but represents an iron formation unit deposited on a continental shelf, which probably belongs to the Lembeitih Formation. The hydrothermal mineralization at 2492 Ma was contemporaneous with regional D(2) thrusting of the Sainte Barbe volcanic unit and imbrications of the meta-carbonate in the upper greenschist facies. This resulted in the formation of an ore breccia in the meta-carbonate, which is enriched in Fe, Ni, Co, Cu, Bi, Mo, As and Au. Massive sulphide ore breccia contains up to 20 wt% Cu. The ore fluid was aqueous-carbonic in nature and either changed its composition from a Mg-rich oxidizing to an Fe-rich reducing fluid or the two fluid types mixed at the trap site. All lithologies at Guelb Moghrein were deformed by D(3) thrusting to the east in the lower greenschist facies. The mobility of REE in the retrogressed rocks explains the formation of a second generation of hydrothermal monazite, which was dated at c. 1742 Ma. Archaean rocks of the West African craton extend to the west to Guelb Moghrein. The active continental margin was deformed and mineralized in the Late Archaean-Early Proterozoic and again reactivated in the Mid-Proterozoic and Westphalian, showing that the western boundary of the craton was reactivated several times.

Methanol steam reforming over Cu/CeO2 catalysts: influence of zinc addition

Methanol steam reforming reaction was studied over Cu(5 wt.%)/CeO2 with and without the presence of Zn. The Zn addition decreased the Cu+2 reducibility and increased the oxygen mobility of ceria. The main products were CO2 and H2 with small amount of CO. Selectivity to CO decreased with the Zn addition and it was lower at lower reaction temperatures and lower space velocities. At 230 ºC and W/F MeOH = 648 g min mol-1 selectivities to H2 and to CO2 were 100% on Zn/Cu/Ce. The catalytic results indicated that CO was mainly a secondary product formed from reverse water gas shift reaction.

Geocronologia e evolução crustal da área do depósito de Cu-Au Gameleira, Província Mineral de Carajás (Pará), Brasil

O depósito de Cu-Au Gameleira está hospedado nas rochas do Grupo Igarapé Pojuca, pertencente ao Supergrupo Itacaiúnas, Província Mineral de Carajás, SE do Cráton Amazônico. Esse grupo está representado principalmente por rochas metavulcânicas máficas (RMV), anfibolitos, biotita xistos, formações ferríferas e/ou hidrotermalitos, cortadas por rochas intrusivas máficas (RIM), bem como por granitos arqueanos (2,56 Ga, Granito Deformado Itacaiúnas) e paleoproterozóicos (1,87 - 1,58 Ga, Granito Pojuca e Leucogranito do Gameleira). Cristais de zircão de um saprolito (2615 ± 10 Ma e 2683 ± 7 Ma) e de uma amostra de RIM (2705 ± 2 Ma), mostraram ser contemporâneos aos dos gabros do depósito Águas Claras. Datações Pb-Pb em rocha total e calcopirita de RMV indicaram idades de 2245 ± 29 Ma e 2419 ± 12 Ma, respectivamente, enquanto lixiviados de calcopirita indicaram idades de 2217 ± 19 Ma e 2180 ± 84 Ma. Essas idades são interpretadas como rejuvenescimento parcial provocado pelas intrusões graníticas proterozóicas (1,58 e 1,87 Ga) ou pelas reativações tectônicas associadas aos Sistemas Transcorrentes Carajás e Cinzento, ou total, provocada pelas últimas. As idades-modelo T_DM de 3,12 e 3,33 Ga para as RMV e RIM e os valores de _εNd (t) de -0,89 a -3,26 sugerem contribuição continental de rochas mais antigas e magmas gerados possivelmente em um ambiente de rifte continental ou de margem continental ativa.

Depósito Cu-Au Visconde, Carajás (PA): geologia e alteração hidrotermal das rochas encaixantes

Distante 15 km a leste da mina Sossego (Canaã de Carajás, no Pará), o depósito Visconde jaz na zona de contato entre o Supergrupo Itacaiúnas (2,76 Ga) e o embasamento (> 3.0 Ga). No depósito e arredores, ocorrem, principalmente, o granito Serra Dourada, riodacitos e gabrodioritos, variavelmente deformados e hidrotermalizados. A Suíte Intrusiva Planalto, também identificada, não mostra feições de alteração das demais rochas. Diques máficos e félsicos cortam o pacote rochoso. Sob condições dúctil-rúpteis iniciais a rúpteis, subsequentemente, a alteração hidrotermal evoluiu de sódico-cálcica (albita, escapolita e anfibólios) precoce e ubíqua para potássica (K-feldspato e Cl-biotita), retomando, em seguida, o caráter sódico-cálcico de efeito local (albita, epidoto, apatita, turmalina e fluorita), para, finalmente, assumir caráter cálcio-magnesiano (clinocloro, actinolita, carbonatos e talco subordinado). No granito Serra Dourada, albitização, epidotização e turmalinização são mais proeminentes e se contrapõem à escapolitização, biotitização, anfibolitização e magnetitização, muito expressivas nos gabros/quartzodioritos, e à K-feldspatização, mais comum nos riodacitos. Os principais corpos de minério são representados por veios e brechas, constituídos por calcopirita-bornita, além de disseminações (calcopirita + pirita ± molibdenita ± pentlandita). A suíte metálica básica é Fe-Cu-Au ± ETR. Abundante sulfeto foi precipitado na transição da alteração potássica para a cálcio-magnesiana, tendo apatita, escapolita, actinolita, epidoto, magnetita, turmalina, calcita, gipsita e fluorita como os principais minerais de ganga. Os metais foram transportados por fluidos hidrotermais ricos em Na, Ca, K, Fe e Mg, além de P, B, F e espécies de S. As similaridades se sobrepõem às diferenças, o que permite considerar os depósitos Visconde e Sossego cogenéticos.

Zircon U-Pb and Hf-O analysis of porphyries from the Duolong porphyry Cu-Au deposit in the Bangongco copper belt, central Tibet

The Duolong porphyry Cu-Au deposit (5.4 Mt at 0.72% Cu, 41 t at 0.23 g/t Au), which is related to the granodiorite porphyry and the quartz-diorite porphyry from the Bangongco copper belt in central Tibet, formed in a continental arc setting. Here, we present the zircon U-Pb ages, geochemical whole-rock, Sr-Nd whole-rock and zircon in-situ Hf-O isotopic data for the Duolong porphyries. Secondary ion mass spectrometry (SIMS) zircon U-Pb analyses for six samples yielded consistent ages of ~118 Ma, indicating a Cretaceous formation age. The Duolong porphyries (SiO2 of 58.81-68.81 wt.%, K2O of 2.90-5.17 wt.%) belong to the high-K calc-alkaline series. They show light rare earth element (LREE)-enriched distribution patterns with (La/Yb)N = 6.1-11.7, enrichment in large ion lithophile elements (e.g., Cs, Rb, and Ba) and depletion of high field strength elements (e.g., Nb), with negative Ti anomalies. All zircons from the Duolong porphyries share relatively similar Hf-O isotopic compositions (d18O=5.88-7.27 per mil; eHf(t)=3.6-7.3), indicating that they crystallized from a series of cogenetic melts with various degrees of fractional crystallization. This, along with the general absence of older inherited zircons, rules out significant crustal contamination during zircon growth. The zircons are mostly enriched in d18O relative to mantle values, indicating the involvement of an 18O-enriched crustal source in the generation of the Duolong porphyries. Together with the presence of syn-mineralization basaltic andesite, the mixing between silicic melts derived from the lower crust and evolved H2O-rich mafic melts derived from the metsomatizied mantle wedge, followed by subsequent fractional crystallization (FC) and minor crustal contamination in the shallow crust, could well explain the petrogenesis of the Duolong porphyries. Significantly, the hybrid melts possibly inherited the arc magma characteristics of abundant F, Cl, Cu, and Au elements and high oxidation state, which contributed to the formation of the Duolong porphyry Cu-Au deposit.

SiGe nanowires grown by LPCVD using Ga-Au catalysts

The use of Ga-Au alloys as metal catalysts for the growth of SiGe nanowires has been investigated. The grown nanowires are cylindrical and straight, with a defect-free crystalline structure, sharp nanowire-droplet interfaces and an almost constant Ge atomic fraction throughout all their length. These features represent significant improvements over the results obtained using pure Au