Estudio geológico del área de Peñacerrada (Alava) : petrografía y cristalografía de las silificaciones existentes

El estudio geológico de la zona de Peñacerrada (Alava) pone de manifiesto la existencia de diversas silicificaciones en el Dogger (Jurásico) y en el Thanetiense (Paleoceno). Se han levantado columnas estratigráficas en tres localidades: Montoria, Arroyo de Santiama (Peñacerrada) y Loza, habiéndose realizado una recogida de muestras sistemáticas tanto de la "roca caja" como de las silicificaciones, para poder establecer las posibles relaciones existentes entre las mismas. La fuente de la sílice probablemente sea biogénica debido a la presencia de espículas de esponjas. El ambiente de depósito de los sedimentos carbonatados del Dogger se debió producir en una plataforma de mar abierto (nerítica), mientras que los del Thanetiense lo hicieron en un "lagoon" de circulación restringuida. En este último ambiente los vaivenes de la línea de costa crearon secuencias de somerización hacia arriba "shallowing upward" donde la mezcla de aguas continentales y marinas jugaron un papel importante tanto para la formación de las silicificaciones como para la dolomitización observada en la localidad de Loza. Se han diferenciado cuatro tipos generales de silicificaciones: cuarzos autigénicos, silicificaciones en nódulos, silicificaciones irregulares y silicificaciones en bancos lenticulares. El estudio de la Cristalografía-Mineralogía de los sílex de las tres localidades confirma en líneas generales la dependencia existente entre los valores de cristalinidad (I.C.G.) en el sentido de que a mayor volumen de celda le corresponde una disminución de la cristalinidad. Esto se observa siempre que los datos obtenidos se comparen con valores de otros sílex de la Cuenca, ya que la misma naturaleza de los sílex aquí estudiados (microcuarzo) hace que las diferencias en cuanto al volumen de Celda e I.C.G. de los mismos no sean muy significativasThe geological study of the Peñacerrada (Alava) area shows the existence of different types of silicification in the Dogger (Jurassic) Age and in the Thanetian (Paleocene) Age. We have drawn stratigraphic sections in three places: Montoria, Arroyo de Santiama (Peñacerrada) and Loza, with relations between them. The silica soruce may be biogenci, because a big number of siliceous sponge spicules included in the nodular chert ara appreciated. The Dogger carbonate sediments were deposited in an open platform (neritic) while the Thanetian sediments were in a lagoon environment. The movements of the shoreface generated sequences of "shallowing upward" where the mixing continental and marine waters played an important role for silicification and dolomitization processes observed in Loza. We have differentiated foru types of general silicification: Äutigenic quartzs, nodular chert, irregular silidifications and lenticular chert bands. The Crystallographic and Mineralogic study of the cherts show the general relation between the Crystalinity index values of the cherts and the limestone or dolomitic replacement. The values obtained for the crystallinity and unit cell volume allows us to corfirm the inverse relation existing between the

Nota sobre la composición química y mineralógica de los piroxenos monoclínicos existentes en lso basaltos de Fruniz (Vizcaya)

Clinopyroxenes from the Fruniz (Vizcaya) basalts have been studied by chemical analysis and X-ray diffraction. The chemical analysis carried out by atomic absorption spectrography has led to the following structural composition Wo44,4 En 47,2 Fs  8,4 which is in agreement with the composition Wo 42  En 48 Fs 10 obtained irom the interpretation of the crystal powder patterns. According to these data the mineralogical composition of these pyroxenes is situated between endiopside and augite

Functionalization of Cu3BTC2@IL composites with Pd(II) for catalytic applications

Comunicación en forma de panel presentada en el congreso 2nd European Conference on Metal Organic Frameworks and Porous Polymers del 29 de octubre al 1 denoviembre de 2017 en Delft, HolandaMetal-organic frameworks could be excellent supports for active catalytic species in order to obtain heterogeneous and reusable catalysts, easily removable from the reaction media.[1,2] Additionally, the presence of unsaturated metal centres in their pores provides a superb opportunity to tackle with reactions that requires more than one type of metal centre.[3] In order to obtain heterometallic catalyst we have immobilized Pd(II) into the pores of the well studied Cu3BTC2 MOF (BTC= benzene-1,3,5-tricarboxilate) with the help of imidazolium derivated ionic liquids (IL). The preparation of the catalyst was made in two steps. Firstly, the Cu3BTC2 was charged with [BMIM][BF4] and [BMIM][PF6] ionic liquids(BMIM= 1-Butyl-3-methylimidazolium). The stability of the composite materials, both chemical and thermal, was studied. Then, the insertion of palladium was made in basic media. By means of EDX the presence of Pd into the structural pores was proved and the quantification was made by ICP-AES. The powder DRX of the Cu3BTC2@[BMIM][Cation]-Pd samples show no structural changes with respect to the pristine Cu3BTC2. The functionalized material was tested as heterogeneous catalyst for Suzuki-Miyaura coupling reactions. The reactions were made in methanol at 70 ºC and using K2CO3 as base. The Pd:substrate molar ratio was set at 0.1 %. The activity was firstly studied using 4-bromotoluene and phenylboronic acid as reagents. The total conversion of the reaction reached 91 % in 1.5 hours with a selectivity towards the cross-coupling product of 67 %. Afterwards, other substrates were tested to study the scope of the reaction. When using 4-bromoanisole and phenylboronic acid, 67% of conversion was reached after 4 hours with a 100 % of selectivity towards the cross-coupling product. References: [1] P. Valvekens, F. Vermoortele and D. D. Vos, Catal. Sci. Technol., 2013, 3, 1435–1445. [2] E. S. Larrea, R. Fernández de Luis, J. Orive, M. Iglesias and M. I. Arriortua, Eur. J. Inorg. Chem., 2015, 2015, 4699–4707. [3] D. Saha, R. Sen, T. Maity and S. Koner, Langmuir, 2013, 29, 3140–3151

Functionalization of Cu3BTC2@IL composites with Pd(II) for catalytic applications

Comunicación en forma de panel presentada en el congreso 2nd European Conference on Metal Organic Frameworks and Porous Polymers del 29 de octubre al 1 denoviembre de 2017 en Delft, HolandaMetal-organic frameworks could be excellent supports for active catalytic species in order to obtain heterogeneous and reusable catalysts, easily removable from the reaction media.[1,2] Additionally, the presence of unsaturated metal centres in their pores provides a superb opportunity to tackle with reactions that requires more than one type of metal centre.[3] In order to obtain heterometallic catalyst we have immobilized Pd(II) into the pores of the well studied Cu3BTC2 MOF (BTC= benzene-1,3,5-tricarboxilate) with the help of imidazolium derivated ionic liquids (IL). The preparation of the catalyst was made in two steps. Firstly, the Cu3BTC2 was charged with [BMIM][BF4] and [BMIM][PF6] ionic liquids(BMIM= 1-Butyl-3-methylimidazolium). The stability of the composite materials, both chemical and thermal, was studied. Then, the insertion of palladium was made in basic media. By means of EDX the presence of Pd into the structural pores was proved and the quantification was made by ICP-AES. The powder DRX of the Cu3BTC2@[BMIM][Cation]-Pd samples show no structural changes with respect to the pristine Cu3BTC2. The functionalized material was tested as heterogeneous catalyst for Suzuki-Miyaura coupling reactions. The reactions were made in methanol at 70 ºC and using K2CO3 as base. The Pd:substrate molar ratio was set at 0.1 %. The activity was firstly studied using 4-bromotoluene and phenylboronic acid as reagents. The total conversion of the reaction reached 91 % in 1.5 hours with a selectivity towards the cross-coupling product of 67 %. Afterwards, other substrates were tested to study the scope of the reaction. When using 4-bromoanisole and phenylboronic acid, 67% of conversion was reached after 4 hours with a 100 % of selectivity towards the cross-coupling product. References: [1] P. Valvekens, F. Vermoortele and D. D. Vos, Catal. Sci. Technol., 2013, 3, 1435–1445. [2] E. S. Larrea, R. Fernández de Luis, J. Orive, M. Iglesias and M. I. Arriortua, Eur. J. Inorg. Chem., 2015, 2015, 4699–4707. [3] D. Saha, R. Sen, T. Maity and S. Koner, Langmuir, 2013, 29, 3140–3151

Fe-Mg M1 site distribution in some clinopyroxenes from Santa Olalla (Huelva, Spain)

The crystal structures of two clinopyroxenes related to the skarns from Santa Olalla (Huelva. Spain) have been refined. From these refinements it is shown that pyroxene SO-1 of metamorphic origin is almost pure diopside. whereas for pyroxene SO-2 of metasomatic origin the following formula CaMg 0.64 Fe 0,34 Si2 O6. was found. These clinopyroxenes show cation ordering

Catalytic performance of a new 1D Cu(II) coordination polymer {Cu(NO3)(H2O)}(HTae)(4,4'-Bpy)

Abstract y comunicación en formato poster: 5th International Conference on Multifunctional, Hybrid and Nanomaterials (6-10 March 2017 | Lisbon, Portugal)There has been extensive interest in the synthesis and design of new porous coordination polymers [1] because of their potential applicability in different areas. One interesting crystal engineering approach to construct new coordination polymers is the selection of metal chelating ligands different from those commonly used. [2] In this regard, the β-diketonates, and concretely the metal β-diketonates, have been recently started to be used as structural building blocks in coordination polymers. [3] Deprotonated β-diketonates act as metal chelating agents; hence, in order to obtain extended structures other substituents are necessary to make them act as bridging ligands. This is the case of bis(β-diketonate) 1,1,2,2-tetraacetylethane (H2Tae) which can act as bischelating ligand bridging two metal centres. During the course of our research with the system Cu−Tae−4,4´-Bpy, we have obtained the 1D {Cu(NO3)(H2O)}(HTae)(4,4’-Bpy) coordination polymer.[4] The crystal structure consists in parallel and oblique {Cu(HTae)(4,4’-Bpy)} zig-zag metal-organic chains stacked along the [100] crystallographic direction. Copper atoms are in octahedral coordination environment linked to two nitrogen atoms of two bridging 4,4’-Bipy and to two oxygen atoms of one HTae molecule. The occupation of the other two positions varies from one copper atom to another with different combinations of water and nitrate molecules, giving rise to a commensurate super-structure. By means of thermal removal of water molecules we were able to obtain copper coordinatively unsaturated centres which could act as Lewis acid active sites in several heterogeneous catalytic reactions. Therefore, we have tested the anhydrous compound as heterogeneous catalyst for Knoevenagel condensation reactions. {Cu(NO3)(H2O)}(HTae)(4,4’-Bpy) is an efficient catalyst for the condensation of benzaldehyde and malonitrile in mild conditions (60 ºC in toluene, 5 % catalyst). The scope of the reaction was studied with various substrates. Recycling and leaching tests were also performed.Ministerio de Economía y Competitividad: MAT2013-42092-R Gobierno Vasco: IT-630-13 Dpto. Desarrollo Economico y Competitividad, programa ELKARTEK: ACTIMAT-KK-2015/0009

Fe-dolomite(teruelite) from the Keuper of the southern sector of the Iberian Mountain Range, Spain

En la parte meridional del Keuper de la Cordillera Ibérica una variedad de dolomita ferrosa es de interés como curiosidad mineralogica (teruelita). Los analisis quimicos y el estudio cristalografico por medio de las tecnicas de difraccion de rayos X de monocristales confirman que se trata de una variedad de la dolomita y no de la ankerita. Solo ligeras diferencias morfologicas han sido apreciadas entre dolomita y temelita. Asi, la teruelita cristaliza en la forma(4041) mientras que la dolomita cristaliza preferentemente en la forma (l0l 1)

Designing multifunctional pigments for an improved energy efficiency in buildings

Materials science offers solutions that when are combined can offer important energy savings in the building sector. In this study, high reflectance coating and thermal storage capacity are combined with the aim of improving energy efficiency in buildings. For this issue a multifunctional pigment having a phase change material adsorbed on its surface and a high total solar reflectance has been manufactured. The total solar reflectance of the pigment will make the paint to reflect the sunlight radiation in the infrared part of the spectrum reducing the amount of absorbed radiation. This high reflection provides a surface level effect as is a passive stimulus-responsive solution that acts with sunlight radiation. On the other hand, the thermal storage capability provides a bulk level effect as is passive stimulus-responsive solution acting by temperature changes, making it possible to use constructive materials as a thermal energy storage media. The preparation process is described and the pigment is characterized conveniently. The thermal performance of corresponding pigmented coatings was evaluated by an experiment simulation in which different boxes were covered with the coating containing the multifunctional pigment and traditional pigmented coating on their tops. The indoor air temperature and the interior temperature of the substrate were measured obtaining differences of 4–5°C.European Union Seventh Framework Programme, FP7-NMP-2010-Small-5 (under grant agreement no 280393) Dpto. Educación, Política Lingüística y Cultura of the Basque Goverment, IT-630-13 Ministerio de Ciencia e Innovación, MAT2013-42092-R Engineering and Physical Sciences Research Council, EP/I00393

Effect of synthesis conditions on electrical and catalytical properties of perovskites with high value of A-site cation size mismatch

et al.The perovskite La0.15Sm0.35Sr0.08Ba0.42FeO3-δ has been prepared by the glycine nitrate route, varying the calcination temperature, fuel/oxidizer ratio and cooling rate, in order to study the sample preparation influence on the properties in the context of their application as a electrode material for SOFCs. The obtained materials have been characterized by X-ray diffraction, scanning electron microscopy, electrical and BET surface area measurements, and also the reaction between oxygen and CO, which can occur in SOFCs during the conversion of chemical energy into electrical energy. As overall results, all the samples present a phase segregation showing two perovskites with rhombohedral structure. SEM images show a well-necked morphology of the powders which are composed of nanosized particles and agglomerations of grains. The BET specific surface area of the samples decreases as calcination temperature increases, as well as for the quenched sample. The measured electronic conductivity values (<50 S/cm) are characteristic for samples with these high values of σ(r) (A cation size disorder). The catalytic activity tests for the CO oxidation reaction showed a T50% (“light-off temperature”, defined as the temperature at which 50% conversion of CO is achieved) value about 440°C–450 °C, CO conversion reaching 100% at approximately 600 °C for all the prepared perovskites. Then, for the La0.15Sm0.35Sr0.08Ba0.42FeO3-δ perovskite, CO conversion temperature is lower than usual SOFCs operating temperature. This points out to the technological interest of these materials in the framework of reducing the operating temperature of SOFCs.This research has been funded by the Ministerio de Ciencia e Innovación (CONSOLIDER-INGENIO 2010 CSD2009-00013), Ministerio de Economía y Competitividad (MAT2013-42092-R and MAT2012-30763), the Feder program of the Europen Union and Dpto. Educación, Política Lingüística y Cultura of the Basque Goverment (IT-630-13). The authors thank for technical and human support provided by SGIker of UPV/EHU. K. Vidal thanks UPV/EHU for funding.Peer Reviewe