CO2 interactions with porous carbons: Is the surface stable at ambient conditions?

Interactions of CO2 with polymer derived carbon/rGO composites at ambient conditions were studied. Both, dynamic adsorption tests and equilibrium adsorption measurements were analyzed. The samples differed in the porosity, oxidation level and speciation of sulfur on the surface. Even though more CO2 was adsorbed on the oxidized sample than in the unmodified one, the surface chemistry of the latter was found as having more pronounced effect on attracting CO2 to the pore system. The results showed the marked changes in S-doped nanoporous carbon composite surface chemistry upon CO2 adsorption at ambient conditions. The changes were more pronounced for carbon with higher density of sulfur in thiophenic configurations on the surface emphasizing the role of these species in CO2 reduction. Even though CO could not be the target of our detection, identification of water, SO and SO2 as products of surface reactions supports our hypothesis that CO2 adsorption was accompanied by some extent of its reduction to CO. CO is formed in the process of electron transfer from thiophenes to CO2 in which the former are oxidized forming sulfones and sulfonic acids. Those species are likely thermodynamically unstable and decompose forming SO/SO2 and water providing additional electrons for CO2 reduction. Conductivity of carbon matrix and the local increase in this feature owing to the presence of the graphene-based phase facilitate this process. Based on the results collected, it is recommended that the stability of carbons towards carbon dioxide should be evaluated before it is used as CO2 sequestration medium

Nanocátalysts for oxygen removal from biomass derived biofuel

The use of bio-energy as a renewable alternative to fossil fuels is nowadays attracting more and more attention. Bio-fuel from biomass seems to be a potential energy substitute for fossil fuels since it is a renewable resource that could contribute to sustainable development and global environmental preservation and it appears to have significant economic potential. Liquid fuels can be obtained from fast pyrolysis of lignocellulosic biomass, where fast pyrolysis is a promising route because the process takes place at moderate temperatures, in absence of air and with a short hot vapor residence time. However, these liquid fuels have poor quality due to their low volatility, high viscosity, low heating value, a high oxygen content and poor chemical stability. This high oxygen is due to the presence of oxygen-containing compounds such as alcohols, aldehydes, ketones, furans and phenols. In this sense, catalytic hydrodeoxygenation (HDO) is one the most efficient processes to remove oxygen from these liquid fuels. In this context, the catalyst design is of upmost importance to achieve a high degree of deoxygenation, and bifunctional catalysts are required to achieve high degrees of activity. Noble metal and non-noble metal based catalysts will be evaluated in HDO of model molecules in order to get further insight about the important role of the active phase. Transition metal phosphides have shown excellent catalytic performances due to their good hydrogen transfer properties that diminishes the amount of metal exposed, avoiding, as much as possible, the deactivation, and modifies the electronic density of the catalyst leading to solids that favors the HDO. In addition these phosphides show bifunctional catalytic properties (metallic sites for hydrogenation and acid sites for cracking, methyl transfer reaction, dehydration and isomerization).Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Synthesis of type A zeolites from natural kaolinite for their application in CO2 capture processes

Climate change is the greatest environmental threat of the 21st century, with major economic, social and environmental consequences. The level of carbon dioxide (CO2) emissions has increased by 31%, therefore, both governments and the scientific community are taking steps to mitigate emissions into the atmosphere. The most economically sustainable method is the use of low cost adsorbents that perform a selective adsorption of CO2 with respect to other inert gases such as N2. Clay minerals are highly available materials on the planet, are a low cost raw material and have great versatility for various processes in the field of adsorption and catalysis. The present work describes the synthesis of type A zeolite from a hydrothermal process in basic medium using metacaolinite as a starting material. Several parameters such as temperature and time were modified to evaluate the relationship between the formation conditions of the zeolite and its CO2 adsorption capacity. Synthesized catalysts were characterized by X-ray diffraction (XRD), N2 adsorption-desorption at -196 ºC, nuclear magnetic resonance of solids (NMR) and infrared spectroscopy (IR). In addition, the absorption capacity of CO2 with type A zeolites has been evaluated, and all the results were compared with the commercial zeolites. With respect to the results obtained, it can be said that the bands obtained by IR for the synthesized Zeolites are similar to those of the commercial Zeolite. On the other hand, the NMR results show that the synthesized and commercial zeolite present the same chemical environment. Finally, the textural parameters corroborate that in all cases the surface area is low from 12 m2g-1 for kaolinite to 7 m2g-1 for commercial zeolite AUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Role of Mo in catalysts based on noble metals in hydrodeoxygenation reactions

The use of bio-energy as a renewable alternative to fossil fuels is nowadays attracting more and more attention. The bio-fuel from biomass seems to be a potential energy substitute for fossil fuels since it is a renewable resource that could contribute to sustainable development and global environmental preservation and it appears to have significant economic potential1. The problem is its high oxygen content, which gives undesirable properties for combustion. To remove oxygen, catalytic hydrodeoxygenation (HDO) reactions are carried out. Monometallic Mo/Si, Pt/Si as well as bimetallic PtMo/Si catalysts were prepared and evaluated in the hydrodeoxygenation (HDO)reaction of dibenzofurane (DBF) as a model molecule in biomass derived bio-oil.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Au-Cu/SBA(Ti) based catalysts for photocatalytic applications

Comunicación a congresoIn this work, it has been synthesized several Au and Au-Cu alloy photocatalysts supported on two different mesoporous supports: a non-commercial SBA-15 and a post-synthesis TiO2 modified SBA-15 (TiSBA-15), with which a high dispersion of TiO2 species have been achieved maintaining the SBA-15 structure. In addition, it has also been obtained highly dispersed Au nanoparticles confined in SBA-15 pore channels, as can be observed in Figure 1. The photocatalysts have been preliminary tested in the preferential CO oxidation in a H2-rich stream (CO-PROX) at room temperature and atmospheric pressure under simulated solar light irradiation. In spite of the very low gold and copper loading (1.5 wt% and 0.5wt% respectively), the catalysts resulted active and selective in the low temperature photo-CO-PROX.Universidad de Málaga, Campus de Excelencia Internacional Andalucía Tec

Synthesis of porous graphene/TiO2 by use of recycled graphite

Graphene-based nanomaterials are a kind of new technological materials with high interest for physicists, chemists and materials scientists. Graphene is a two-dimensional (2-D) sheet of carbon atoms in a hexagonal configuration with atoms bonded by sp2 bonds. These bonds and this electron configuration provides the extraordinary properties of graphene, such as very large surface area, a tunable band gap, high mechanical strength and high elasticity and thermal conductivity [1]. Graphene has also been investigated for preparation of composites with various semiconductors like TiO2, ZnO, CdS aiming at enhanced photocatalytic activity for their use for photochemical reaction as water splitting or CO2 to methanol conversion [2-3]. In this communication, the synthesis of porous graphene@TiO2 obtained from a powder graphite recycled, supplied by ECOPIBA, is presented. This graphite was exfoliated, using a nonionic surfactant (Triton X-100) and sonication. Titanium(IV) isopropoxide was used as TiO2 source. After removing the surfactant with a solution HCl/n-propanol, a porous solid is obtained with a specific area of 358 m2g-1. The solid was characterized by XRD, FTIR, XPS, EDX and TEM. Figure 1 shows the graphene 2D layer bonded with nanoparticles of TiO2. When a water suspension of this material is exposed with UV-vis radiation, water splitting reaction is carried out and H2/O2 bubbles are observed (Figure 2)Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Synthesis and characterization of silver vanadates thin films for photocatalytic applications

Silver vanadates thin films were deposited by a hybrid deposition system combining laser ablation and thermal evaporation. A high purity vanadium target was ablated using the third harmonic of a Nd:YAG laser whereas high purity silver pellets were evaporated. The as-deposited thin films were subjected to thermal treatments at 400 °C to obtain crystalline films. For films without Ag amorphous V2O5 thin films were deposited and as the Ag is incorporated in the material different silver vanadates were obtained. The effect of the silver load on the composition, structure, optical properties, surface morphology and photocatalytic response of the deposited films was studied. The film composition, determined by X-ray photoelectron spectroscopy, reveals Ag contents from 5.5 to 18.9 at.%. The crystalline phases formed were identified by micro-Raman Spectroscopy; the results indicate the formation of three silver vanadates depending on the silver content. The morphology was observed using scanning electron microscopy, the filmś surface changes from a smooth surface to belts covering the surface and finally Ag nanoparticles are observed at the higher Ag contens. Optical properties determined from UV–vis reveal the presence of the surface plasmon signal in films containing silver. The films were tested in the photocatalytic degradation of Malachite Green dye reaching maximum degradations degrees close to 53% under solar irradiation. Reactive species trapping experiments suggest that O2 − produced by the O2 reduction via the photogenerated electrons drives the photodegradation mechanismCB-168827 CB-240998 F. Gonzalez-Zavala thanks to CONACyT for the PhD and Beca Mixta grants, and also to the SIEA-UAEM for the beca movilidad para estudios avanzados 2016. E. Rodríguez-Castellón thanks to project CTQ2015-68951-C3-3-R of Ministerio de Economía y Competitividad (Spain) and FEDER funds

Pt-Fe2O3 based catalysts for anisole hydrodeoxygenation

The depletion of fossil fuels along with massive emissions of greenhouse gases (GHG) emissions are serious issues facing society nowadays. Considering that almost a quarter of fossil fuel consumption is associated with the transport sector, the scientific community has focused a great deal of its research to the quest of alternative environmentally friendly technologies and products with minimum GHG emissions derived from renewable energy sources. In this context, lignocellulosic biomass has demonstrated a great potential, since from its fast pyrolysis a bio-oil with interesting properties can be obtained to be used as liquid fuel for internal combustion engines. However, this bio-oil contains a considerable percentage of water and oxygenated compounds that impoverishes its quality making it unstable, acid, corrosive and with low calorific value. Thus, hydrotreating technologies like hydrodeoxygenation reaction are essential to upgrade bio-oil by means of removing oxygen from oxygenated compounds. The hydrodeoxygenation reaction usually takes places at high temperature and moderate hydrogen pressure, in the presence of a bifunctional catalyst that, on the one hand, promotes the oxygen removal with acid sites and, on the other hand, activates the hydrogen molecule in metallic hydrogenating sites. Regarding the latter function, noble metals like Pt, Ru or Pd have demonstrated outstanding hydrogenation capability even with low metal loading. To maximise metal dispersion, these noble metals are supported on mesoporous solids that in turn provide the moderate acidity necessary to remove oxygen heteroatom. In this work, supported Pt on Fe2O3-containing SBA-15 were tested in the HDO reaction of anisole at 275 ºC and 30 bar in a fixed-bed reactor in continuous down flow. Pt was added in 1 wt. % as the hydrogenating metal and different Fe2O3 loadings (5 wt. %, 15 wt. % and 30 wt. %) as the oxyphilic and acid counterpart.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Ni-Doped Ordered Nanoporous Carbon Prepared from Chestnut Wood Tannins for the Removal and Photocatalytic Degradation of Methylene Blue

In this work, Ni-doped ordered nanoporous carbon was prepared by a simple and green one-pot solvent evaporation induced self-assembly process, where chestnut wood tannins were used as a precursor, Pluronic® F-127 as a soft template, and Ni2+ as a crosslinking agent and catalytic component. The prepared carbon exhibited a 2D hexagonally ordered nanorod array mesoporous structure with an average pore diameter of ~5 nm. Nickel was found to be present on the surface of nanoporous carbon in the form of nickel oxide, nickel hydroxide, and metallic nickel. Nickel nanoparticles, with an average size of 13.1 nm, were well dispersed on the carbon surface. The synthesized carbon was then tested for the removal of methylene blue under different conditions. It was found that the amount of methylene blue removed increased with increasing pH and concentration of carbon but decreased with increasing concentration of methylene blue. Furthermore, photocatalytic tests carried out under visible light illumination showed that purple light had the greatest effect on the methylene blue adsorption/degradation, with the maximum percent degradation achieved at ~4 h illumination time, and that the percent degradation at lower concentrations of methylene blue was much higher than that at higher concentrations. The adsorption/degradation process exhibited pseudo second-order kinetics and strong initial adsorption, and the prepared carbon showed high magnetic properties and good recyclabilityThis research was funded by Junta de Andalucía, Consejería de Transformación Económica, Industria, Conocimiento y Universidades. Project P20_00375. Partial funding for open access charge: Universidad de Málag

Nanoestructuras de ceria-titania para fotodegradar azul de metileno con luz solar simulada

En los últimos años la protección ambiental y el uso de fuentes de energía renovables son dos objetivos principales en la investigación química. La energía solar se puede aprovechar para la degradación fotocatalítica de moléculas orgánicas contaminantes, hormonas o medicamentos, tanto en el aire, en el agua, como en las superficies, porque la luz solar es capaz de descomponerlas [1]. A pesar de la gran cantidad de aplicaciones fotocatalíticas de la titania (TiO2), fotocatalizador no tóxico, de bajo costo y muy prometedor [2], hay algunos factores críticos que limitan su fotoactividad. El principal es el valor de su salto de energía, que limita su uso como fotocatalizador en la región UV del espectro. Con el objetivo principal de extender su uso a la región visible del espectro, en literatura se ha propuesto el depósito de metales nobles en su superficie, modificaciones superficiales, así como el dopaje con iones de metales de transición o elementos de tierras raras. En este sentido, el uso de ceria (CeO2) ha atraído una gran atención debido a propiedades como su biocompatibilidad, inercia química así como su actividad en reacciones de oxidación, relacionada con la formación vacantes de oxígeno en su superficie [3]. Se ha comprobado que el sistema oxídico mixto CeO2-TiO2 es más fotoactivo que la titania pura debido a la disminución del salto de energía y a la mejora en la movilidad de los excitones. Este trabajo tiene como objetivo desarrollar fotocatalizadores basados en nanoestructuras de titania que sean activas en el visible, dopando la matriz de titania con cerio. Principalmente se pretende evaluar tanto el papel del cerio como la morfología del nanomaterial en la respuesta fotocatalítica bajo luz UV y solar.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech