Desarrollo de nuevos materiales nanoestructurados para la valorización de metano a hidrógeno y olefinas C2-C4

Principal Researcher: Alfonso Caballero and Gerardo Colón
Components: Juan Pedro Holgado, Rosa M. Pereñiguez, Francisco Platero
Ministerio de Ciencia, Innovación y Universidades
ENE2017-88818-C2-1-R
2018-2020

In the present project the preparation of a set of materials, including some with perovskite structure (Fe, Co, Mn, Cu and Bi in positions B; Ca, Mg, Ce and La in positions A), and the study of its application in different processes of heterogeneous catalysis and adsorption of pollutants has been proposed. For this purpose, a number of recently described preparation techniques will be used to obtain high surface specific and controlled nanostructure systems. In this way, and combining the metals in positions A and B to act both as promoters and precursors of metal alloys in the reduced systems, systems with very varied and versatile properties will be obtained.
Thus, we will study its catalytic properties in processes of great interest for the valorization of methane, the main component of natural gas and one of the most abundant energy sources today. In particular, and together with systems supported on mesoporous materials and others, the activity of nickel perovskites for the dry methane reforming reaction will be studied first in order to obtain synthesis gas. The aim will be to obtain active and above all stable systems in the face of the usual deactivation phenomena by deposition of coke. Secondly, systems based mainly on Fe and Co for the Fisher-Tropsch reaction to C2-C4 olefins will be studied, products of great economic interest as precursors to a large number of other high added value products.

Rational design of highly effective photocatalysts with atomic level control. RATOCAT

Principal Researcher: Gerardo Colón
Components: Alfonso Caballero, Angeles Martín
European Research Area
RATOCAT
2017-2020

Using the sun’s energy to generate hydrogen from water is probably the cleanest and most sustainable source of fuel that we can envisage. Unfortunately, catalysts that do this are currently too expensive to be commercially viable. The RATOCAT project aims to develop improved photocatalyst materials, along with the processes for their production. The catalytic performance of cheap TiO2 and C3N4 powders will be improved by tailoring their surface with nanostructured oxides as co-catalysts of highly-controlled composition, nanoarchitecture, size and chemical state. First principles simulations will be used to design the optimum nanostructures, which will then be deposited onto powders with the required precision using atomic layer deposition, again supported by simulation. Lab-scale tests of photocatalytic activity will provide feedback for the optimisation of the material and process, before the most promising materials are tested in the field on both pure water and wastewater.


Development of catalytic and photocatalytic processes for natural gas valorization: Activation and transformation of methane into light hydrocarbons. METANCAT

Principal Researcher: Alfonso Caballero and Gerardo Colón
Components: Juan Pedro Holgado, Rosa M. Pereñiguez, Alberto Rodríguez
Ministerio de Economía, Industria y Competitividad
CTQ2014-60524-R
2015-2017

 

The present project intends to study and develop different methane activation and transformation processes to obtain high value added molecules.
For this scope we propose to study well established processes of indirect conversion, through reforming reactions (RM) for syngas production, as well as those direct conversion ones, particularly the direct oxidation to methanol (DOM) and aromatization of methane (DAM).  
Regarding to the methane reforming reaction, we propose the development of catalytic systems with improved resistance against deactivation processes. In this case, we would prepare and characterize new nanostructured bimetallic catalysts based on nickel supported on ceria, alumina, or alumina/ceria, as well as mesoporous SBA-15 supports, doped with ceria and alumina. As a second metal we would use cobalt or iron. At the same time, we would perform the study of the reforming reaction by a photocatalytic process using Cu, Pt and Ni doped photoactive systems such as titania or ceria, and others recently proposed as Ga2O3, carbon nitride or graphene. In this case, we propose to explore the possibility of the photochemical activation for the preferential oxidation of CO (photo-PROX) in the presence of hydrogen, a very usefulness process for hydrogen purification from syngas synthesis. We will focus our attention in the preparation of systems with the appropriate band structure for the control of the selective oxidation of CO.
Concerning to direct conversion processes, we would study the direct oxidation of methane (DOM) using O2, H2O2, or N2O as reaction activators, in combination with systems based on Au/Pd, Fe, Cu and/or Ni deposited on different supports as ZSM-5, graphene and TiO2. In this later case, using Au/Pd as the active metallic phase in the presence of H2O2, we propose the possibility to combine the synthesis of H2O2 in situ with the subsequent direct oxidation of methane.
Moreover, we would explore the photocatalytic oxidation of methane to methanol as a novel and highly attractive alternative. In this case, the use of new photocatalytic materials as BiVO4 and the presence of redox mediators would allow us to control the selective photo-oxidation to methanol.
Other catalytic systems closely related to above mentioned, and in particular those based on Mo supported on ZSM-5 and MCM-22 zeolites, would be used for the methane aromatization reaction study. The aluminiun ratio, Mo loading and its activation in the microporous structure of the suport, as well as the addition of certain promoters as Ga, Tl or Pb would be some of the parameters to be optimized for this reaction. At the same time, recently reported photoinduced aromatization process would be studied.


New Bi3+ based highly visible active photocatalysts

Principal Researcher: Gerardo Colón
Components: M. Carmen Hidalgo, José A. Navío, Manuel Macías, Sebastián Murcia
Resultado de imagen de junta de andalucia innovacion y ciencia

 

Junta de Andalucía
Excellence Project P09-FQM-4570
2011-2015

 

The main objective of this project is the development of a new generation of nanostructured materials alternative to TiO2 with high photoactivity in the visible region that could be efficiently used in liquid or gaseous effluent treatment. The present project intent to develop new heterogeneous nanocatalytic systems based on Bi3+ (Bi2WO4, Bi2MoO6, BiVO4, Bi3O4Cl, CaBi2O4, PbBi2Nb2O9,…) exhibiting appropriated optoelectronic properties for the solar light use in the visible range (Solar Photocatalysis). Moreover, from the point of view of the photoinduced charge carriers diffusion and transfer, the improved physicochemical properties would optimize the photocatalytic process.


Development of nanostructured catalytic systems prepared by sol-gel and fotoassisted deposition (PAD) methods for energy and environmental applications

Principal Researcher: Alfonso Caballero
Components: Gerardo Colón, Juan Pedro Holgado, Sergio Obregón, Rosa María Pereñiguez, Fátima Ternero
Ministerio de Economía, Industria y Competitividad
ENE2011-24412
2012-2014

 

In the present project we propose the development of a series of nanostructured catalysts based on transition metals such as Ni, Cu, Au or Pd deposited in active supports (TiO2, CeO2, WO3, Fe2O3 and mesoporous supportslike SBA-15 doped with titania and ceria). Conventional methods of preparation will be used (impregnation, deposition-precipitation, etc.), along with procedures of synthesis of more recent development, like sol-gel and, very specially, the denominated Photochemical Assisted Deposition (PAD). In this way, we expect to control at the nanometric scale the size of the metallic and/or bimetallic particle, along with the interaction between the metal and support surface. In the case of the PAD method, one of the primary targets of the project is the study and optimization of the different parameters affecting the deposition process. So that, besides the control of the metallic particle size from diameters around 15nm to atomic dispersed systems on active supports like ceria or titania, it would allow us to design the distribution of metals in bimetallic particles, making use of consecutive and/or simultaneous controlled processes of fotodeposition of metals. Using this methodology, we will try to obtain metallic distributions of different kinds: core-shell, alloys, etc., which as it is well-known, can strongly affect the catalytic performances. These benefits will be verified in different catalytic reactions of energetic and/or environmental interest, both in gas and liquid phase. Thus, the systems based on nickel and gold will be used in the steam and dry reforming reactions of methane and the selective oxidation of CO (Preferential Oxidation of CO, PROX), respectively. The bimetallic catalytic systems based on palladium and palladium-gold will be used for the optimization of the reaction of direct synthesis of hydrogen peroxide from hydrogen and oxygen, made in liquid phase at high pressure. The correlation between the physical-chemistry state and the reactivity of the catalytic systems will allow us to clarify fundamental aspects of the mechanisms of the proposed heterogeneous reactions.


Development of new industrial processes based on catalytic systems for Sustainable production of base compounds of fragrances and aromas

Principal Researcher: Juan Pedro Holgado Vázquez
Components: Alfonso Caballero, Víctor Manuel González de la Cruz, Rosa Pereñíguez, Gerardo Colón
Ministerio de Economía, Industria y Competitividad
IPT-2011-1553-420000
2011-2014

 

Nowadays, most of the industrial processes used for transformations of many com-pounds used in the field of fragrances and aromas have low yields, and generate a lot of environmentally noxious products, being necessary to accomplish several stages of segregation and treatment during the process of production of these chemicals. Most of these processes are done by reduction or oxidation reactions using stoichiometric compounds, or are based in homogeneous catalysis, that present associated hitches associated with corrosion, recovery of the catalysts from reaction media and its regeneration for its possible recycle. In this “environmentally friendly” context, there is a growing interest in the use of oxidants less contaminants, such as molecular oxygen or hydrogen peroxide, and the integration of these oxidants into heterogeneous catalysis processes. Obviously, one of the big challenges for catalytic systems is to maximize the yield (conversion times selectivity), in order to reduce the consumption of reactants (raw material), and minimize the separation and elimination of undesired sub-products obtained as consequence of process inefficacy. In these type of reactions (with mainly organic products, many from natural sources), it is not, as a general rule, difficult to obtain a high conversion, but as the starting materials present many functionalities and/or points susceptible to be oxidized, the main challenge is to obtain a (very) high selectivity, in many cases even at enantiomer level.
In this project, we have selected processes and reactions with a direct interest in the food and cosmetic industry, with the scope to develop processes, at industrial scale, based on heterogeneous catalysts to obtain compounds with high added value in the aromas and fragrances fields, such as the production of l-carvone from catalytic oxidation of d-limonene.


Gold based nanostructured catalysts for selective oxidation reactions

Principal Researcher: Juan Pedro Holgado
Components: Alfonso Caballero, Víctor Manuel González de la Cruz, Fátima Ternero, Richard M. Lambert
Ministerio de Economía, Industria y Competitividad
CTQ2010-21348-C02-01
2011

 

The aim of the proposed project is the development of highly active gold-based catalysts for selective oxidation processes. In these context, benzyl alcohol oxidation (and derivatives) under mild conditions and low temperature CO oxidation in connection with applications in Environment Catalysis as the air control (CO-removal from air) and applications in Catalysis for Energy as the purification of H2 produced by reforming (CO removal from H2) will be considered.
The outstanding properties of gold, a biocompatible non-toxic metal, can be exploited in catalysis when used in highly dispersed form. In order to get elevated yields and selectivities, doubly nanostructured (considering both the active phase and support) gold-based catalysts deposited onto CeO2 and TiO2 (Al2O3 and SiO2 as references) will be prepared. Monometallic gold catalysts will be prepared with control of size and shape of the Au particles, taking advantage of the observed “structure sensitivity” of the proposed reactions.  In the same context, it has been recently reported that bimetallic composition based on Gold (AuPd, AuCu, etc) may enhance the performance of these catalysts. Therefore bimetallic catalysts such as AuPt, AuCu and AuNi, will be explored and tested.


Syngas and Hydrogen Production by Hydrocarbon Reforming on Nickel Nanostructured Catalysts (SYNANOCAT)

Principal Researcher: Alfonso Caballero
Components: Juan Pedro Holgado, Agustín R. González-Elipe, Victor Manuel González de la Cruz, Rosa Pereñiguez
Ministerio de Educación y Ciencia
ENE2007-67926-C02-01
2007-2011

 

The coordinated proposed research project, that seek to be an extension of the references ENE2004- 01660 and ENE2004-06176,pretends to prepare new catalytic systems, with a discrete crystallite size and a higher resistance to deactivation. The aim is to obtain catalysts for an optimum performance in the reforming reaction of hydrocarbons to yield H2(+CO), principally from methane and propane. These reactions being structure-sensitive, are affected by the size of metallic particles.
Nanoparticles of nickel with well controlled size and morphology will be prepared by ex-situ methods as microwave plasma irradiation, ionic liquid, reverse microemulsion or impregnation with external surface modification by silylation. These methods will allow us to obtain metal particles of a very different range of size: from less than 10nm to sizes about 100nm and a narrow particle size distribution. The catalytic activity of these nanoparticles, supported on different oxides as ZrO2 or Al2O3, will be evaluated in the reforming reactions of methane and propane to establish a structure-reactivity relationship. Special attention will be devoted to the carbon deposition over the catalyst in reaction conditions, the more important process hindering the performances of these kind of catalysts. The strict control of the morphology of the particles must allow us to correlate the kinetic of the deactivation process to the different type of nanoparticles. Also, we will evaluate the effect of different kind of additives, as Pt, Au, Sr, K, etc., reported in the literature as beneficial for the overall activity of these materials.
The reforming reactions of hydrocarbon will be alternatively studied in the presence of a microwave generated plasma. We expect finally to develop an integrated thermal-plasma reactor that could permit the reaction at a lower temperature and/or with less deposition of coke over the catalyst.


Design of photocatalytic systems highly active in the visible for environmental applications

Research head: Gerardo Colón
Components: José Antonio Navío, Manuel Macías, Carmen Hidalgo, Marina Maicu
Resultado de imagen de junta de andalucia innovacion y cienciaJunta de Andalucía
FQM-1406
2007-2010

 

 

The heterogeneous photocatalysis has demonstrated to be a promising and efficient technology for the oxidation of a large variety of toxic substrates in relatively short reaction times. It is widely known that the most used photocatalysts can be only activated by means of photons with wavelengths lower than 390 nm, being an important limitation for large scale use. The main objective of this project is based on previous development in our group of highly UV photoactive TiO2 powders able to completely remove different toxic species for the environment. Our challenge is to overcome the problems and limitations of the UV range in the solar spectrum. The core of our activity will be the development of new oxidic photoactive doped systems based on Ti and Zn, which could provide a shift in the absorption edge toward the visible range.
 Thus, under the point of view of the enhancement in the photon efficiencies of the photocatalytic processes, it is evident that the designing and development of alternative photocatalysts is of great interest.  We intend the obtention of highly efficient materials that can be used for the degradation of contaminants in water and gas effluents by the incorporation of cationic/anionic dopants and the immobilization in different adequate supports.The evaluation of the photocatalytic activity will be performed for the photooxidation of a great variety of toxic organic compounds and using solar simulation lamps.